TW201307069A - Method for producing polarizing laminate film - Google Patents

Method for producing polarizing laminate film Download PDF

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TW201307069A
TW201307069A TW101123697A TW101123697A TW201307069A TW 201307069 A TW201307069 A TW 201307069A TW 101123697 A TW101123697 A TW 101123697A TW 101123697 A TW101123697 A TW 101123697A TW 201307069 A TW201307069 A TW 201307069A
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Taiwan
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film
polyvinyl alcohol
layer
resin
based resin
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TW101123697A
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Chinese (zh)
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Yuichiro Kunai
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Sumitomo Chemical Co
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

Abstract

The present invention provides a method for producing polarizing laminate film having a base film comprising a thermoplastic resin in which a rubber component is dispersed and a polarizer layer which is laminated on one surface of the base film, wherein the method comprises: a step of obtaining a laminate film by forming a polyvinyl alcohol resin layer on one surface of a base film comprising a thermoplastic resin in which a rubber component is dispersed; a step of obtaining a stretched film by uniaxially stretching the laminate film; a step of obtaining a colored film by coloring the polyvinyl alcohol resin layer of the stretched film with a dichroic colorant; a step of obtaining a cross-linked film by forming a polarizer layer from the polyvinyl alcohol resin layer by immersing the polyvinyl alcohol resin layer in a solution containing a cross-linking agent and then cross-linking the polyvinyl alcohol resin; and a step of drying the cross-linked film.

Description

偏光性積層膜的製造方法 Method for producing polarizing laminated film

本發明係關於一種適於作為偏光板或其製造中間物而使用之偏光性積層膜的製造方法。 The present invention relates to a method for producing a polarizing laminated film which is suitable for use as a polarizing plate or an intermediate thereof.

偏光板係在液晶顯示裝置中作為偏光之供給元件、或偏光之偵測元件而廣泛使用。該偏光板已往以來係在由聚乙烯醇系樹脂所構成之偏光膜之單面或兩面上接著以三醋酸纖維素等所構成之保護膜者,近年來,伴隨著液晶顯示裝置之筆記型個人電腦及行動電話等行動機器方面之發展,以及大型電視之發展,偏光板又有更薄型輕量化之要求。 The polarizing plate is widely used as a polarizing supply element or a polarized detecting element in a liquid crystal display device. The polarizing plate has been a protective film composed of cellulose triacetate or the like on one surface or both surfaces of a polarizing film made of a polyvinyl alcohol-based resin. In recent years, a notebook personal person accompanying a liquid crystal display device has been used. With regard to the development of mobile devices such as computers and mobile phones, and the development of large-scale televisions, polarizers have been required to be thinner and lighter.

例如在:JP-2000-338329-A、JP-2009-93074-A、JP-2009-98653-A、及JP-2003-43257-A中,係揭示在由熱塑性樹脂所構成之基材膜之一邊面上形成由聚乙烯醇系樹脂所構成之樹脂層後,再施以延展處理及染色處理,得到含有薄層偏光件層的偏光性積層膜,並作為偏光板或其製造中間物使用。 For example, in JP-2000-338329-A, JP-2009-93074-A, JP-2009-98653-A, and JP-2003-43257-A, it is disclosed in a substrate film composed of a thermoplastic resin. A resin layer made of a polyvinyl alcohol-based resin is formed on one surface, and then subjected to a stretching treatment and a dyeing treatment to obtain a polarizing laminate film containing a thin polarizer layer, and used as a polarizing plate or an intermediate thereof.

以往之偏光性積層膜的製造中,特別在延展處理時之延展倍率高之情形,在聚乙烯醇系樹脂層之染色時,會有膜在由夾持輥(nip roll)等輥捲取時膜向延展方向碎裂之問題。 In the production of the polarizing laminated film of the related art, particularly in the case where the stretching ratio at the time of the stretching treatment is high, when the polyvinyl alcohol-based resin layer is dyed, the film may be taken up by a roll such as a nip roll. The problem of cracking of the film in the direction of extension.

因此,本發明之目的係提供一種可良好地抑制在染色步驟中向延展方向碎裂的偏光性積層膜之製造方法。 Accordingly, an object of the present invention is to provide a method for producing a polarizing laminated film which can satisfactorily suppress fragmentation in a stretching direction in a dyeing step.

本發明係包含以下之各項。 The present invention encompasses the following items.

[1]一種偏光性積層膜之製造方法,該偏光性積層膜具備在熱塑性樹脂中分散有橡膠成分而製得之基材膜、及在前述基材膜之一邊面上積層之偏光件層,該製造方法係包含:在熱塑性樹脂中分散有橡膠成分而構成之基材膜的一邊面上形成聚乙烯醇系樹脂層而得到積層膜之步驟;將前述積層膜向單軸延展得到延展膜之步驟;將前述延展膜之前述聚乙烯醇系樹脂層以二色性色素染色,而得到染色膜之步驟;將前述染色膜之前述聚乙烯醇系樹脂層浸漬於含交聯劑之溶液中,使前述聚乙烯醇系樹脂交聯,由前述聚乙烯醇系樹脂層形成偏光件層,而得到交聯膜之步驟;以及將前述交聯膜乾燥之步驟。 [1] A method for producing a polarizing laminated film comprising: a base film obtained by dispersing a rubber component in a thermoplastic resin; and a polarizer layer laminated on one side of the base film. The production method includes a step of forming a polyvinyl alcohol-based resin layer on one surface of a base film formed by dispersing a rubber component in a thermoplastic resin to obtain a laminated film, and stretching the laminated film to a uniaxial direction to obtain an expanded film. a step of dyeing the polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye to obtain a dyed film; and immersing the polyvinyl alcohol-based resin layer of the dyed film in a solution containing a crosslinking agent, a step of crosslinking the polyvinyl alcohol-based resin, forming a polarizer layer from the polyvinyl alcohol-based resin layer to obtain a crosslinked film, and drying the crosslinked film.

[2]如[1]中所載之偏光性積層膜的製造方法,其中前述熱塑性樹脂為聚丙烯系樹脂。 [2] The method for producing a polarizing laminate film according to [1], wherein the thermoplastic resin is a polypropylene resin.

[3]如[1]中所載之偏光性積層膜的製造方法,其中前述熱塑性樹脂為丙烯單獨之聚合物。 [3] The method for producing a polarizing laminate film as set forth in [1], wherein the thermoplastic resin is a polymer of propylene alone.

[4]如[1]至[3]中任一項所載之偏光性積層膜的製造方法,其中前述橡膠成分為含乙烯單元之共聚物。 [4] The method for producing a polarizing laminated film according to any one of [1] to [3] wherein the rubber component is a copolymer containing an ethylene unit.

[5]如[4]中所載之偏光性積層膜的製造方法,其中前述橡膠成分為含有由乙烯單元、丙烯單元、丁烯單元、辛烯單 元及苯乙烯單元所形成之群中選擇1種以上的單元之共聚物。 [5] The method for producing a polarizing laminate film as set forth in [4], wherein the rubber component contains ethylene unit, propylene unit, butene unit, octene unit A copolymer of one or more units selected from the group consisting of a unit and a styrene unit.

[6]如[4]或[5]中所載之偏光性積層膜的製造方法,其中前述共聚物中前述乙烯單元之含量超過10重量%且未達90重量%。 [6] The method for producing a polarizing laminate film as set forth in [4] or [5], wherein the content of the aforementioned ethylene unit in the copolymer exceeds 10% by weight and is less than 90% by weight.

[7]一種偏光性積層膜,其具備在熱塑性樹脂中分散有橡膠成分之基材膜、及在前述基材膜之一邊面上積層之厚度為10μm以下之偏光件層。 [7] A polarizing laminate film comprising a base material film in which a rubber component is dispersed in a thermoplastic resin, and a polarizer layer having a thickness of 10 μm or less laminated on one side of the base film.

根據本發明,除可提供含薄層之偏光件層的薄型偏光性積層膜,且因使用分散有橡膠成分之熱塑性樹脂膜為基材膜,因此可有效地抑制在染色步驟中向延展方向之破裂,可以優良產率且安定地製得偏光性積層膜。 According to the present invention, in addition to providing a thin polarizing layer film having a thin layer of a polarizer layer, and using a thermoplastic resin film in which a rubber component is dispersed as a base film, it is possible to effectively suppress the stretching direction in the dyeing step. The rupture can produce a polarizing laminate film with excellent yield and stability.

本發明之偏光性積層膜可適合使用於液晶顯示裝置,如使用作為在行動終端機等中之液晶顯示裝置用之偏光板或其製造中間物。 The polarizing laminated film of the present invention can be suitably used for a liquid crystal display device, for example, as a polarizing plate for a liquid crystal display device used in a mobile terminal device or the like, or an intermediate thereof.

<偏光性積層膜之製造方法> <Method for Producing Polarized Laminated Film>

本發明之偏光性積層膜的製造方法係包含下述步驟。 The method for producing a polarizing laminate film of the present invention comprises the following steps.

(a)在熱塑性樹脂中分散有橡膠成分製得之基材膜的一邊面上形成聚乙烯醇系樹脂層,而得到積層膜之積層步驟;(b)將積層膜單軸延展而得到延展膜之延展步驟;(c)將延展膜之聚乙烯醇系樹脂層以二色性色素染 色,得到染色膜之染色步驟;(d)將染色膜之聚乙烯醇系樹脂層浸漬於含交聯劑之溶液中,使前述聚乙烯醇系樹脂交聯,由聚乙烯醇系樹脂層形成偏光件層,而得到交聯膜之交聯步驟;及(e)將交聯膜乾燥之乾燥步驟。 (a) a step of forming a polyvinyl alcohol-based resin layer on one side of a base film obtained by dispersing a rubber component in a thermoplastic resin to obtain a laminated film; (b) uniaxially stretching the laminated film to obtain a stretched film The step of stretching; (c) dyeing the polyvinyl alcohol-based resin layer of the stretched film with dichroic dye a dyeing step of obtaining a dyed film; (d) immersing the polyvinyl alcohol-based resin layer of the dyed film in a solution containing a crosslinking agent to crosslink the polyvinyl alcohol-based resin to form a polyvinyl alcohol-based resin layer a polarizing member layer to obtain a crosslinking step of the crosslinked film; and (e) a drying step of drying the crosslinked film.

本發明中所使用之基材膜由於分散有橡膠成分,因此即使在延展步驟(b)中在以高倍率延展後亦可有高抗拉強度,因此可有效地改善延展膜染色之染色步驟(c)中向延展方向的膜之破裂耐性。本發明不會增加製造步驟亦可得到期望的效果,此點係有利的。以下,一邊參考第1至4圖一邊詳細說明本發明之偏光性積層膜之製造方法。 Since the base film used in the present invention has a rubber component dispersed therein, even if it has a high tensile strength after being stretched at a high magnification in the stretching step (b), the dyeing step of the dyeing of the stretched film can be effectively improved ( c) Crack resistance of the film in the direction of the medium extension. This is advantageous in that the present invention does not increase the number of manufacturing steps and also achieves the desired effect. Hereinafter, the method for producing the polarizing laminated film of the present invention will be described in detail with reference to the first to fourth drawings.

(a)積層步驟 (a) Lamination step

本步驟中,參考第1圖,係以在熱塑性樹脂中分散(混合分散)橡膠成分所構成之膜為基材膜10,在其一邊面上形成聚乙烯醇系樹脂層20而製得積層膜100。 In this step, referring to Fig. 1, a film composed of a rubber component dispersed (mixed and dispersed) in a thermoplastic resin is used as the base film 10, and a polyvinyl alcohol-based resin layer 20 is formed on one surface thereof to obtain a laminated film. 100.

(基材膜) (substrate film)

形成基材膜10之基底的熱塑性樹脂較佳為透明性、機械強度、熱安定性、延展性等均優良之熱塑性樹脂。此類熱塑性樹脂之具體例可列舉:直鏈聚烯烴系樹脂;環狀聚烯烴系樹脂;(甲基)丙烯酸系樹脂;聚酯系樹脂;纖維素酯系樹脂;聚碳酸酯系樹脂;聚乙烯醇系樹脂;醋酸乙烯酯系樹脂;聚芳酯系樹脂;聚苯乙烯系樹脂;聚醚碸系樹脂;聚碸系樹脂;聚醯胺系樹脂;聚醯亞胺系樹脂;及該等之混合物或共聚物等。 The thermoplastic resin forming the base of the base film 10 is preferably a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, and ductility. Specific examples of such a thermoplastic resin include a linear polyolefin resin; a cyclic polyolefin resin; a (meth)acrylic resin; a polyester resin; a cellulose ester resin; a polycarbonate resin; Vinyl alcohol resin; vinyl acetate resin; polyarylate resin; polystyrene resin; polyether oxime resin; polyfluorene resin; polyamine resin; polyimine resin; a mixture or a copolymer or the like.

由基材膜10之操作性之觀點來看,熱塑性樹脂較佳為在常溫常壓(25℃、101.3kPa)下為剛性(rigid)者。所謂剛性指在係非結晶性高分子時其玻璃轉移溫度Tg在常壓下高於常溫,在係結晶性高分子時其結晶化熔點Tm在常壓下高於常溫。若考慮供於延展步驟(b),則較佳為具有100℃以上之Tg或Tm之熱塑性樹脂。 From the viewpoint of the handleability of the base film 10, the thermoplastic resin is preferably rigid at normal temperature and normal pressure (25 ° C, 101.3 kPa). The rigidity means that the glass transition temperature Tg is higher than normal temperature at normal pressure in the case of a non-crystalline polymer, and the crystallization melting point Tm is higher than normal temperature at normal pressure in the case of a crystalline polymer. If it is considered to be supplied to the stretching step (b), it is preferably a thermoplastic resin having a Tg or Tm of 100 ° C or more.

直鏈聚烯烴系樹脂由於容易安定地以高倍率延展,較佳為使用聚丙烯系樹脂(丙烯之單獨聚合物的聚丙烯樹脂、及以丙烯為主體之共聚物等)、聚乙烯系樹脂(乙烯之單獨聚合物的聚乙烯樹脂、及以乙烯為主體之共聚物等)等。直鏈聚烯烴系樹脂以結晶性之情形為多,丙烯之單獨聚合物的聚丙烯樹脂其結晶化熔點Tm約在150至180℃之範圍。在乙烯之單獨聚合物的聚乙烯樹脂時,結晶化熔點Tm可因密度等而變動,但約在100至140℃之範圍。 The linear polyolefin resin is preferably stretched at a high rate, and it is preferably a polypropylene resin (a polypropylene resin of a single polymer of propylene, a copolymer mainly composed of propylene, or the like) or a polyethylene resin (for example). A polyethylene resin of a single polymer of ethylene, a copolymer mainly composed of ethylene, or the like). The linear polyolefin resin is mostly in the case of crystallinity, and the polypropylene resin of the individual polymer of propylene has a crystallization melting point Tm of about 150 to 180 °C. In the case of a polyethylene resin of a single polymer of ethylene, the crystallization melting point Tm may vary depending on the density or the like, but is in the range of about 100 to 140 °C.

藉由使用以丙烯為主體並與其他種單體共聚之聚丙烯系樹脂、或以乙烯為主體並與其他種單體共聚之聚乙烯系樹脂,而可提高基材膜10之耐熱性及柔軟性。 The heat resistance and softness of the base film 10 can be improved by using a polypropylene-based resin mainly composed of propylene and copolymerized with another monomer or a polyethylene-based resin mainly composed of ethylene and copolymerized with other kinds of monomers. Sex.

可與丙烯共聚之其他種單體例如可列舉:乙烯、α-烯烴。α-烯烴較佳為使用碳數4以上之α-烯烴,更佳為碳數4至10之α-烯烴。碳數4至10之α-烯烴之具體例可列舉:1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯等之直鏈單烯烴類;3-甲基-1-丁烯、3-甲基-1-戊烯、4-甲基-1-戊烯等之分支單烯烴類;乙烯環己烷等。丙烯與可與其共聚之其他單體的共聚物可為無規共聚物,也可為 嵌段共聚物。 Examples of other kinds of monomers copolymerizable with propylene include ethylene and α-olefin. The α-olefin is preferably an α-olefin having 4 or more carbon atoms, more preferably an α-olefin having 4 to 10 carbon atoms. Specific examples of the α-olefin having 4 to 10 carbon atoms include linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene. a branched monoolefin such as 3-methyl-1-butene, 3-methyl-1-pentene or 4-methyl-1-pentene; ethylene cyclohexane or the like. The copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or Block copolymer.

可與乙烯共聚之其他種單體例如可舉出α-烯烴。α-烯烴除丙烯之外,較佳為使用碳數4以上之α-烯烴為佳,更佳為丙烯,又更佳為碳數4至10之α-烯烴。 Other types of monomers copolymerizable with ethylene include, for example, an α-olefin. The α-olefin is preferably a olefin having 4 or more carbon atoms, more preferably propylene, and still more preferably an α-olefin having 4 to 10 carbon atoms, in addition to propylene.

上述之中,聚丙烯系樹脂較佳為使用:丙烯單獨聚合物、丙烯-乙烯無規共聚物、丙烯-1-丁烯無規共聚物、及丙烯-乙烯-1-丁烯無規共聚物。此外,聚乙烯系樹脂較佳為使用:乙烯單獨聚合物、乙烯-丙烯無規共聚物、乙烯-1-丁烯無規共聚物、及乙烯-丙烯-1-丁烯無規共聚物。 Among the above, the polypropylene resin is preferably used: a propylene individual polymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, and a propylene-ethylene-1-butene random copolymer. . Further, as the polyethylene resin, an ethylene individual polymer, an ethylene-propylene random copolymer, an ethylene-1-butene random copolymer, and an ethylene-propylene-1-butene random copolymer are preferably used.

聚丙烯系樹脂之立體規則性較佳為本質上為同排(isotactic)聚合物或間規(syndiotactic)聚合物。由該丙烯系樹脂所構成之基材膜,不僅其操作性較為良好,同時在高溫環境下之機械強度亦優異。 The stereoregularity of the polypropylene resin is preferably essentially an isotactic polymer or a syndiotactic polymer. The base film composed of the propylene resin is excellent not only in handleability but also in mechanical strength in a high temperature environment.

直鏈聚烯烴系樹脂係以主要之單體與其他種單體(共聚成分)的共聚物所構成時,較佳為其他種單體之含量(共聚比)為少量,具體來說較佳為10重量%以下,更佳為8重量%以下。共聚比為少量時,共聚物在常溫常壓下係形成含大量結晶化節段(segment)之狀態,因此易形成剛性樹脂。另一方面,若共聚比太高時,在常溫常壓下係形成液狀,相反地會有耐熱性降低之情形。共聚物中之其他種單體的共聚比,除可由聚合時物質之增減計算之外,亦可依照「高分子分析手冊」(1995年、紀伊國屋書電發行)之第616頁中所載之方法,以紅外線(IR)光譜進行測定而求出。 When the linear polyolefin resin is composed of a copolymer of a main monomer and another monomer (copolymerization component), the content (copolymerization ratio) of the other monomer is preferably a small amount, and specifically, it is preferably 10% by weight or less, more preferably 8% by weight or less. When the copolymerization ratio is small, the copolymer forms a state containing a large amount of crystallized segments at normal temperature and normal pressure, and thus a rigid resin is easily formed. On the other hand, when the copolymerization ratio is too high, a liquid form is formed under normal temperature and normal pressure, and conversely, heat resistance may be lowered. The copolymerization ratio of other kinds of monomers in the copolymer, in addition to the calculation of the increase or decrease of the substance during the polymerization, can also be carried out in accordance with the "Handbook of Polymer Analysis" (issued in 1995, issued by Kiyuki Ueya Electric Co., Ltd.). The method was determined by measuring with an infrared (IR) spectrum.

環狀聚烯烴系樹脂係將環狀烯烴作為聚合單位所聚合 之樹脂的總稱,例如JP-01-240517-A、JP-03-14882-A、JP-03-122137-A等中所載之樹脂。環聚烯系樹脂之具體例例如可列舉:環狀烯烴之開環(共)聚物、環狀烯烴之加成聚合物、環狀烯烴與乙烯、丙烯等直鏈烯烴之共聚物(其代表為無規共聚物)、以及該等經過不飽合羧酸及其衍生物所改質之崁段共聚物及該等之氫氧化物等。其中,環狀烯烴較佳為使用冰片烯(norbornene)或多環冰片烯系單體等之冰片烯系單體所得之冰片烯系樹脂。 Cyclic polyolefin resin is a polymerization of a cyclic olefin as a polymerization unit A general term for the resin, for example, a resin contained in JP-01-240517-A, JP-03-14882-A, JP-03-122137-A, or the like. Specific examples of the cycloolefin-based resin include a ring-opening (co)polymer of a cyclic olefin, an addition polymer of a cyclic olefin, and a copolymer of a cyclic olefin and a linear olefin such as ethylene or propylene (which is representative). It is a random copolymer), and the above-mentioned cyclic copolymers modified with unsaturated carboxylic acids and derivatives thereof, and the like. Among them, the cyclic olefin is preferably a borneol-based resin obtained by using a borneol-based monomer such as a norbornene or a polycyclic norbornene-based monomer.

環狀聚烯系樹脂之販售品之例子可列舉:「Topas」(TOPAS ADVANCED POLYMERS GmbH公司製造,可由日本Polyplastics公司購得)、「ARTON」(日本JSR公司製造)、「ZEONOR」(日本Zeon公司製造)、「ZEONEX」(日本Zeon公司製造)、「APEL」(日本三井化學公司製造)等,以上皆為商品名。 Examples of the products of the cyclic polyolefin resin are "Topas" (manufactured by TOPAS ADVANCED POLYMERS GmbH, available from Japan Polyplastics Co., Ltd.), "ARTON" (manufactured by Japan JSR Corporation), and "ZEONOR" (Japan Zeon). Manufactured by the company, "ZEONEX" (made by Zeon Corporation of Japan), "APEL" (manufactured by Mitsui Chemicals, Inc.), etc., all of which are trade names.

(甲基)丙烯酸系樹脂例如可列舉:聚甲基丙烯酸甲酯等之聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、含脂環族烴基之聚合物(如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸冰片酯共聚物等)。較佳為聚(甲基)丙烯酸甲酯等,其烷基部位為碳數1至6之聚(甲基)丙烯酸烷酯,更佳為以甲基丙烯酸甲酯為主成分(50至100重量%,較佳為70至100重量%)之甲基丙烯酸甲酯系樹脂更佳。 Examples of the (meth)acrylic resin include poly(meth)acrylate such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymer, and methyl methacrylate-(methyl). Acrylate copolymer, methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-styrene copolymer (MS resin, etc.), alicyclic hydrocarbon group-containing polymer ( For example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-methacrylate methacrylate copolymer, and the like. It is preferably poly(methyl) acrylate or the like, the alkyl moiety of which is a poly(meth)acrylic acid alkyl ester having 1 to 6 carbon atoms, more preferably methyl methacrylate as a main component (50 to 100 weight). More preferably, the methyl methacrylate resin is preferably from 70 to 100% by weight.

聚酯系樹脂係具有酯鍵結之聚合物,例如可藉由多元羧酸(含其酯化合物)與多元醇之聚縮合而獲得。多元羧酸主要使用2元羧酸,例如間苯二甲酸、對苯二甲酸、對苯二甲酸二甲酯、萘二羧酸二甲酯等。多元醇主要使用2元醇,例如丙二醇、丁二醇、新戊二醇、環己二甲醇等。聚酯系樹脂之具體例例如可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚對苯二甲酸三亞甲酯、聚萘二甲酸三亞甲酯、聚對苯二甲酸環己烷二甲酯、聚萘二甲酸環己烷二甲酯等。亦可適合使用該等之混合樹脂、或共聚物。 The polyester-based resin is a polymer having an ester bond, and can be obtained, for example, by polycondensation of a polyvalent carboxylic acid (including an ester compound thereof) with a polyhydric alcohol. The polycarboxylic acid mainly uses a divalent carboxylic acid such as isophthalic acid, terephthalic acid, dimethyl terephthalate or dimethyl naphthalate. The polyol mainly uses a dihydric alcohol such as propylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol or the like. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polybutylene terephthalate. Trimethyl ester, triamethylene naphthalate, dimethyl dimethyl terephthalate, cyclohexane dimethyl phthalate, and the like. These mixed resins or copolymers may also be suitably used.

纖維素酯系樹脂係纖維素與脂肪酸之酯。纖維素酯系樹脂之具體例除了可列舉三醋酸纖維素、二醋酸纖維素、三丙酸纖維素、二丙酸纖維素之外,亦可舉出其共聚物及一部分羥基被其他取代基等所修飾者等。其中特佳為三醋酸纖維素。三醋酸纖維素有多種市售製品,從易於取得及成本此點為有利的。三醋酸纖維素之販售品之例可列舉:「FUJITAC TD80」(富士軟片股份公司製造)、「FUJITAC TD80UF」(富士軟片股份公司製造)、「FUJITAC TD80UZ」(富士軟片股份公司製造)、「FUJITAC TD40UZ」(富士軟片股份公司製造)、「KC8UX2M」(Konica Minolta Opto Products股份公司製造)、「KC4UY」(日本Konica Minolta Opto Products股份公司製造)等,以上皆為商品名。 The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester-based resin include triacetate cellulose, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate, and examples thereof include copolymers and a part of hydroxyl groups thereof, and other substituents. Modifiers, etc. Among them, particularly preferred is cellulose triacetate. There are a variety of commercially available products of cellulose triacetate which are advantageous from the point of availability and cost. Examples of the sales of the cellulose triacetate include "FUJITAC TD80" (manufactured by Fujifilm Co., Ltd.), "FUJITAC TD80UF" (manufactured by Fujifilm Co., Ltd.), "FUJITAC TD80UZ" (manufactured by Fujifilm Co., Ltd.), " FUJITAC TD40UZ" (manufactured by Fujifilm Co., Ltd.), "KC8UX2M" (manufactured by Konica Minolta Opto Products Co., Ltd.), "KC4UY" (manufactured by Konica Minolta Opto Products Co., Ltd., Japan), etc., all of which are trade names.

聚碳酸酯系樹脂係由透過碳酸酯基鍵結單體單元之聚合物所構成的工程塑膠,為具有高耐衝擊性、耐熱性、阻 燃性之樹脂。同時因具有高透明性故適於使用在光學用途。在光學用途中為降低光彈性係數而有修飾聚合物骨架之類稱為改質聚碳酸酯之樹脂、及改良波長相關性之共聚聚碳酸酯,該等係於市面上有販售並可適宜地使用。聚碳酸酯樹脂販售品之例子可列舉:「Panlite」(帝人化成股份公司)、「Iupilon」(三菱工業塑膠股份公司)、「SD Polyca」(住友陶式股份公司)、「Calibre」(陶式化學股份公司)等,以上皆為商品名。 The polycarbonate resin is an engineering plastic composed of a polymer that permeates a monomer unit bonded through a carbonate group, and has high impact resistance, heat resistance, and resistance. Flammable resin. At the same time, it is suitable for use in optical applications because of its high transparency. In optical applications, in order to reduce the photoelastic coefficient, there are modified polymer skeletons, such as modified polycarbonate resins, and copolymerized polycarbonates with improved wavelength dependence, which are commercially available and suitable for use. Use. Examples of polycarbonate resin-selling products include "Panlite" (Emperor Chemical Co., Ltd.), "Iupilon" (Mitsubishi Industrial Plastics Co., Ltd.), "SD Polyca" (Sumitomo Ceramics Co., Ltd.), and "Calibre" (Tao) Chemical company), etc., all of which are trade names.

在熱塑性樹脂中分散之橡膠成分係具有橡膠彈性之樹脂成分,一般橡膠粒子係均勻分散在熱塑性樹脂中。藉由橡膠成分之混合分散,而可提高基材膜,甚至延展膜之抗拉強度。橡膠成分只要為具有橡膠彈性之樹脂即無特別限定,但由與熱塑性樹脂之互溶性之觀點來看,較佳為與所使用之熱塑性樹脂為同種或類似之樹脂所構成者。 The rubber component dispersed in the thermoplastic resin has a rubber-elastic resin component, and generally the rubber particles are uniformly dispersed in the thermoplastic resin. By mixing and dispersing the rubber component, the tensile strength of the substrate film and even the film can be increased. The rubber component is not particularly limited as long as it is a resin having rubber elasticity. However, from the viewpoint of compatibility with the thermoplastic resin, it is preferably one composed of the same or similar resin as the thermoplastic resin to be used.

例如熱塑性樹脂為直鏈聚烯系樹脂時,橡膠成分可為由乙烯及α-烯烴所選擇2種以上之單體的共聚物。在該情形時,構成該共聚物之各單體的含量(聚合比例)較佳為未達90重量%,更佳為未達80重量%。在1種單體單元之含量過度地高時,將使該單體單元容易生成連續節段並易於結晶化,而喪失橡膠彈性。 For example, when the thermoplastic resin is a linear polyolefin resin, the rubber component may be a copolymer of two or more monomers selected from ethylene and an α-olefin. In this case, the content (polymerization ratio) of each monomer constituting the copolymer is preferably less than 90% by weight, more preferably less than 80% by weight. When the content of one type of monomer unit is excessively high, the monomer unit is easily formed into a continuous segment and is easily crystallized, and the rubber elasticity is lost.

由上述2種以上之單體的共聚物所構成之橡膠成分,可適合使用在包括乙烯單元之各種共聚物中,其中較佳為使用含由乙烯單元、丙烯單元、丁烯單元、辛烯單元及苯乙烯單元所形成之群所選擇1種以上之單元的共聚物。該 共聚物中乙烯單元之含量(聚合比例)較佳為超過10重量%且未達90重量%為佳,更佳為20重量%以上80重量%以下,又更佳為25重量%以上70重量%以下。本發明中所使用之基材膜之1種較佳形態係為,使用聚丙烯系樹脂(如丙烯單獨聚合物)作為熱塑性樹脂,並在其中分散作為橡膠成分之共聚物,其中,該共聚物係以上述含量含有乙烯單元。 The rubber component composed of the copolymer of the above two or more kinds of monomers can be suitably used in various copolymers including ethylene units, and among them, ethylene units, propylene units, butene units, and octene units are preferably used. And a copolymer of one or more selected units selected from the group consisting of styrene units. The The content (polymerization ratio) of the ethylene unit in the copolymer is preferably more than 10% by weight and less than 90% by weight, more preferably 20% by weight or more and 80% by weight or less, still more preferably 25% by weight or more and 70% by weight or less. the following. A preferred embodiment of the substrate film used in the present invention is a polypropylene resin (for example, a propylene alone polymer) as a thermoplastic resin in which a copolymer as a rubber component is dispersed, wherein the copolymer The ethylene unit is contained in the above content.

共聚物中的乙烯單元之含量係除了可由聚合時物質之增減來計算之外,亦可以依照「高分子分析手冊」(1995年、紀伊國屋書店發行)之第616頁中所載之方法,藉由進行紅外線(IR)光譜測定而求出。 The content of the ethylene unit in the copolymer can be calculated by adding or subtracting the substance during the polymerization, and can also be borrowed according to the method described in the "Handbook of Polymer Analysis" (1995, issued by Kiyoshiya Shoten). It was determined by performing infrared (IR) spectrum measurement.

熱塑性樹脂係(甲基)丙烯酸系樹脂時,由互溶性之觀點來看,較佳為含作為橡膠成分且具有橡膠彈性的丙烯酸系聚合物。丙烯酸系聚合物只要為以丙烯酸烷酯為主體之聚合物即可,丙烯酸烷酯之單獨聚合物亦可,50重量%以上丙烯酸烷酯與50重量%以下其他單體之共聚物亦可。 In the case of a thermoplastic resin-based (meth)acrylic resin, from the viewpoint of mutual solubility, an acrylic polymer containing rubber rubber as a rubber component is preferable. The acrylic polymer may be a polymer mainly composed of an alkyl acrylate, and a single polymer of an alkyl acrylate may be a copolymer of 50% by weight or more of an alkyl acrylate and 50% by weight or less of another monomer.

丙烯酸烷酯一般使用烷基之碳數為4至8者。上述其他單體之例子除了可列舉甲基丙烯酸甲酯及甲基丙烯酸乙酯之類的甲基丙烯酸烷酯、苯乙烯及烷基苯乙烯之類的苯乙烯系單體、丙烯腈及甲基丙烯腈之類的不飽合腈等之單官能單體之外,可舉出:(甲基)丙烯酸丙烯酯及(甲基)丙烯酸甲基丙烯酯之類的不飽合羧酸之烯酯、順丁烯二酸二丙烯酯之類的二元酸之二烯酯、烷二醇二(甲基)丙烯酸酯之類的二醇類之不飽合羧酸二酯等之多官能單體。 The alkyl acrylate generally uses an alkyl group having a carbon number of 4 to 8. Examples of the other monomer mentioned above include alkyl methacrylate such as methyl methacrylate and ethyl methacrylate, styrene monomers such as styrene and alkyl styrene, acrylonitrile and methyl group. Examples of the monofunctional monomer such as an unsaturated nitrile such as acrylonitrile include an unsaturated carboxylic acid ester such as (meth)acrylic acid acrylate and (meth)acrylic acid methacrylic acid ester. a polyfunctional monomer such as a dibasic acid of a dibasic acid such as dipropylene maleate or an unsaturated carboxylic acid diester of a glycol such as an alkanediol di(meth)acrylate .

含有丙烯酸系聚合物之橡膠成分較佳為粒子狀,更佳 為含有丙烯酸系聚合物之層的多層構造之粒子。在丙烯酸系聚合物之層(核)之外側具有以甲基丙烯酸烷酯為主體之聚合物之層的2層構造者亦可,復在丙烯酸系聚合物之層之內側具有以甲基丙烯酸烷酯為主體之聚合物之層(核)的3層構造者亦可。多層構造之丙烯酸系橡膠粒子例如可以JP-55-27576-B中所載之方法製造。 The rubber component containing the acrylic polymer is preferably in the form of particles, preferably It is a particle of a multilayer structure containing a layer of an acrylic polymer. A two-layer structure having a layer of a polymer mainly composed of an alkyl methacrylate on the outer side of the layer (core) of the acrylic polymer may have an alkyl methacrylate on the inner side of the layer of the acrylic polymer. A three-layer structure of a layer (core) of a polymer in which an ester is a main component may also be used. The acrylic rubber particles having a multilayer structure can be produced, for example, by the method described in JP-55-27576-B.

橡膠成分之摻配量較佳為熱塑性樹脂之5至50重量%,更佳為10至45重量%。若橡膠成分之摻配量過少時,會有不易得到充分之提高抗拉強度之效果的傾向,若橡膠成分之摻配量過多時,會有基材膜之操作性減低的傾向。 The blending amount of the rubber component is preferably from 5 to 50% by weight, more preferably from 10 to 45% by weight, based on the thermoplastic resin. When the blending amount of the rubber component is too small, the effect of sufficiently improving the tensile strength tends to be insufficient, and when the blending amount of the rubber component is too large, the handleability of the base film tends to be lowered.

橡膠成分在熱塑性樹脂中之分散方法並無特別之限定,可例舉如將分別製作之熱塑性樹脂與橡膠成分(橡膠粒子)以擠出機(plastomill)等混拌使其分散之方法、及在調製熱塑性樹脂時在同一反應容器內亦調製橡膠成分而得到分散橡膠成分的熱塑性樹脂之反應器混合法等。反應器混合法,在提高橡膠成分之分散程度上為有利。 The method of dispersing the rubber component in the thermoplastic resin is not particularly limited, and examples thereof include a method in which a thermoplastic resin and a rubber component (rubber particles) produced separately are mixed by an plastomill or the like, and In the case of preparing a thermoplastic resin, a rubber component is prepared in the same reaction vessel to obtain a thermoplastic resin resin mixture method in which a rubber component is dispersed. The reactor mixing method is advantageous in increasing the degree of dispersion of the rubber component.

基材膜10中,在上述熱塑性樹脂及橡膠成分之外,亦可再添加任意適當之添加劑。此類添加劑可例舉如:使橡膠成分之分散性提高的互溶劑、紫外線吸收劑、抗氧化劑、滑劑、塑化劑、脫模劑、防著色劑、阻燃劑、成核劑、抗帶電劑、顏料、及著色劑等。基材膜中熱塑性樹脂及橡膠成分之合計含量較佳為50至100重量%,更佳為50至99重量%,又更佳為60至98重量%,特佳為70至97重量%。該合計含量未達50重量%時,會有熱塑性樹脂本來所具有 之高透明性等無法充分表現之虞。 In the base film 10, any appropriate additives may be added in addition to the thermoplastic resin and the rubber component. Such an additive may, for example, be a mutual solvent which improves the dispersibility of a rubber component, an ultraviolet absorber, an antioxidant, a slip agent, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, and an anti Chargers, pigments, and colorants. The total content of the thermoplastic resin and the rubber component in the substrate film is preferably from 50 to 100% by weight, more preferably from 50 to 99% by weight, still more preferably from 60 to 98% by weight, particularly preferably from 70 to 97% by weight. When the total content is less than 50% by weight, the thermoplastic resin may have The high transparency and the like cannot be fully expressed.

互溶劑亦可使用低分子者,但因為滲出等之顧慮,故較佳為使用高分子所構成之互溶劑。高分子所構成之互溶劑之例子可舉出嵌段共聚物等,具體可舉如苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物等。 The mutual solvent may also be a low-molecular one. However, it is preferable to use a mutual solvent composed of a polymer because of the concern of bleeding or the like. Examples of the mutual solvent composed of the polymer include a block copolymer and the like, and specific examples thereof include a styrene-ethylene-butylene-styrene block copolymer.

積層膜100中基材膜10之厚度(延展前)並無特別之限定,但由強度及操作性等之作業性之點方面較佳為1至500μm,更佳為1至300μm,又更佳為5至200μm,最佳為5至150μm最佳。 The thickness of the base film 10 in the laminated film 100 (before stretching) is not particularly limited, but is preferably from 1 to 500 μm, more preferably from 1 to 300 μm, and more preferably from the viewpoint of workability such as strength and workability. It is preferably 5 to 200 μm, preferably 5 to 150 μm.

在基材膜10之形成聚乙烯醇系樹脂層20側的表面上,為提高其與聚乙烯醇系樹脂層20之密接性,亦可施以電暈處理、電漿處理、火燄處理等處理使密接性提高,或形成底層(primer layer)、接著劑層等之薄層。 On the surface of the base film 10 on the side where the polyvinyl alcohol-based resin layer 20 is formed, in order to improve the adhesion to the polyvinyl alcohol-based resin layer 20, corona treatment, plasma treatment, flame treatment, or the like may be applied. The adhesion is improved, or a thin layer of a primer layer, an adhesive layer, or the like is formed.

(聚乙烯醇系樹脂層) (polyvinyl alcohol resin layer)

形成聚乙烯醇系樹脂層20之聚乙烯醇系樹脂例如可舉出聚乙烯醇樹脂及其衍生物。聚乙烯醇樹脂之衍生物之例子可舉出如聚乙烯甲醛、聚乙烯乙醛等之外,可舉出聚乙烯醇樹脂藉由乙烯、丙烯等之烯烴、丙烯酸、甲基丙烯酸、巴豆酸等之不飽合羧酸、不飽合羧酸之烷酯、丙烯醯胺等所改質之者。其中較佳為使用聚乙烯醇樹脂。 The polyvinyl alcohol-based resin forming the polyvinyl alcohol-based resin layer 20 is, for example, a polyvinyl alcohol resin or a derivative thereof. Examples of the derivative of the polyvinyl alcohol resin include, for example, polyethylene formaldehyde and polyvinyl acetaldehyde, and examples thereof include an olefin such as ethylene or propylene, acrylic acid, methacrylic acid or crotonic acid. Those which are not saturated with carboxylic acid, unsaturated carboxylic acid alkyl ester, acrylamide or the like. Among them, a polyvinyl alcohol resin is preferably used.

聚乙烯醇系樹脂較佳為完全皂化者。皂化度之範圍較佳為80.0至100.0莫耳%,更佳為90.0至99.5莫耳%更佳,又更佳為94.0至99.0莫耳%。若皂化度未達80.0莫耳%,則製成偏光性積層膜後會有耐水性及耐濕性顯著變差之不 良情形。同時,在使用其皂化度高於99.5莫耳%之聚乙烯醇系樹脂時,會有染色速度顯著地變緩,因此無法得到具有充分偏光性能的偏光性積層膜之情形,同時亦會有製造時須耗費一般之數倍時間的不良情形。 The polyvinyl alcohol-based resin is preferably a completely saponified one. The degree of saponification is preferably in the range of 80.0 to 100.0 mol%, more preferably 90.0 to 99.5 mol%, still more preferably 94.0 to 99.0 mol%. If the degree of saponification is less than 80.0 mol%, the water resistance and moisture resistance will be significantly deteriorated after the polarizing laminated film is formed. Good situation. At the same time, when a polyvinyl alcohol-based resin having a degree of saponification of more than 99.5 mol% is used, the dyeing speed is remarkably slowed, so that a polarizing laminated film having sufficient polarizing properties cannot be obtained, and there is also production. It takes a few times as much time as usual.

此處之皂化度,係表示聚乙烯醇系樹脂之原料聚醋酸乙烯酯系樹脂中所含之醋酸基藉由皂化步驟使羥基變化之比例,以單元比(莫耳%)表示,而可以下述式定義之數值。即可以JIS K 6726(1994)中所規定之方法求得。 Here, the degree of saponification is a ratio of a hydroxyl group which changes the acetic acid group contained in the polyvinyl acetate-based resin, which is contained in the polyvinyl acetate-based resin, by a saponification step, and is expressed by a unit ratio (% by mole). The value defined by the statement. That is, it can be obtained by the method specified in JIS K 6726 (1994).

皂化度(莫耳%)=(羥基數)÷(羥基數+醋酸基數)×100 Degree of saponification (% by mole) = (number of hydroxyl groups) ÷ (number of hydroxyl groups + number of acetate groups) × 100

聚乙烯醇系樹脂之平均聚合度並無特別之限定,但較佳為100至10000,更佳為1500至8000,又更佳為2000至5000。此處之平均聚合度係依照JIS K 6726(1994)所規定之方法求得之數值。 The average degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but is preferably from 100 to 10,000, more preferably from 1,500 to 8,000, still more preferably from 2,000 to 5,000. The average degree of polymerization herein is a value determined in accordance with the method specified in JIS K 6726 (1994).

上述之聚乙烯醇系樹脂亦可依照其須要再添加塑化劑、界面活性劑等添加劑。塑化劑方面可使用多元醇及其縮合物等,例如:丙三醇、二縮丙三醇、三縮丙三醇、乙二醇、丙二醇、聚乙二醇等。添加劑之摻配量並無特別之限定,但較佳為聚乙烯醇系樹脂之20重量%以下。 The above polyvinyl alcohol-based resin may be further added with an additive such as a plasticizer or a surfactant in accordance with the necessity. As the plasticizer, a polyhydric alcohol, a condensate thereof, or the like can be used, for example, glycerin, propylene glycol, triglycerol, ethylene glycol, propylene glycol, polyethylene glycol, or the like. The blending amount of the additive is not particularly limited, but is preferably 20% by weight or less of the polyvinyl alcohol-based resin.

較佳為使聚乙烯醇系樹脂在良溶劑中溶解所得之聚乙烯醇系樹脂溶液在基材膜10之一邊面上塗布,再經過乾燥使溶劑蒸發而形成聚乙烯醇系樹脂層20。根據此種方法即可形成薄的聚乙烯醇系樹脂層20。將聚乙烯醇系樹脂溶液塗布在基材膜10上之方法,可由線棒塗布法、逆向塗布法(reverse coating)、凹版塗布法等之輥塗法、旋轉塗布 法、網版印刷塗布法、噴注塗布法(fountain coating)、含浸法、噴塗法等一般已知之方法中適當地選擇。乾燥溫度例如為50至200℃,較佳為60至150℃。乾燥時間例如為2至20分鐘。 The polyvinyl alcohol-based resin solution obtained by dissolving a polyvinyl alcohol-based resin in a good solvent is preferably applied to one side of the base film 10, and dried to evaporate the solvent to form a polyvinyl alcohol-based resin layer 20. According to this method, the thin polyvinyl alcohol-based resin layer 20 can be formed. The method of applying the polyvinyl alcohol-based resin solution to the base film 10 can be carried out by a roll coating method such as a bar coating method, a reverse coating method, a gravure coating method, or the like. A method generally selected from the methods such as a method, a screen printing coating method, a fountain coating method, an impregnation method, and a spray coating method are appropriately selected. The drying temperature is, for example, 50 to 200 ° C, preferably 60 to 150 ° C. The drying time is, for example, 2 to 20 minutes.

如上所述,在聚乙烯醇系樹脂層20之形成前,亦可在基材膜10之形成聚乙烯醇系樹脂層20側之表面上,預先形成以提高密接性為目的之底層。例如可將含聚乙烯醇系樹脂及交聯劑之溶液,以與上述相同之方法塗布,再使其乾燥而形成底層。 As described above, before the formation of the polyvinyl alcohol-based resin layer 20, a primer layer for the purpose of improving the adhesion can be formed on the surface of the base film 10 on the side where the polyvinyl alcohol-based resin layer 20 is formed. For example, a solution containing a polyvinyl alcohol-based resin and a crosslinking agent can be applied in the same manner as described above and dried to form a primer layer.

此外,聚乙烯醇系樹脂層20係可以在基材膜10上貼著由聚乙烯醇系樹脂所構成之膜而形成,此時,膜之間的接著可使用接著劑。 Further, the polyvinyl alcohol-based resin layer 20 may be formed by laminating a film made of a polyvinyl alcohol-based resin on the base film 10, and in this case, an adhesive may be used in the film.

積層膜100中之聚乙烯醇系樹脂層20的厚度較佳為3μm以上50μm以下,更佳為5μm以上45μm以下。若為3μm以下則其延展後會過薄而使染色性顯著惡化,若超過50μm則會使其得到之偏光性積層膜變厚。 The thickness of the polyvinyl alcohol-based resin layer 20 in the laminated film 100 is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 45 μm or less. When it is 3 μm or less, the film is too thin after stretching, and the dyeability is remarkably deteriorated. When it exceeds 50 μm, the polarizing laminated film obtained is thickened.

(b)延展步驟 (b) Extension steps

本步驟係將具備基材膜10及聚乙烯醇系樹脂層20之積層膜100單軸延展並得到延展膜200之步驟(參考第2圖)。積層膜100之延展倍率,可依照期望之偏光特性而適當選擇,但較佳為相對於積層膜100之原長度為超過5倍且17倍以下,更佳為超過5倍且8倍以下。若延展倍率為5倍以下,則延展聚乙烯醇系樹脂層20’無法完全配向,結果使偏光件層之偏光度無法充分提高。另一方面,若延展 倍率高於17倍時延展時容易發生膜之斷裂,且同時使膜之厚度為必要以上地薄,會有使後面步驟中之加工性、操作性減低之虞。本發明中,由於係使用以如上述之橡膠成分分散的基材膜10,即使在延展倍率超過5倍時,所得之延展膜200對延展方向之破裂具有高耐性。因此,根據本發明可提供表現高偏光特性,同時具備高耐久性之偏光性積層膜。 This step is a step of uniaxially stretching the laminated film 100 including the base film 10 and the polyvinyl alcohol-based resin layer 20 to obtain the stretched film 200 (refer to FIG. 2). The stretching ratio of the laminated film 100 can be appropriately selected in accordance with the desired polarizing characteristics, but is preferably more than 5 times and 17 times or less, more preferably more than 5 times and 8 times or less with respect to the original length of the laminated film 100. When the stretching ratio is 5 or less, the stretched polyvinyl alcohol-based resin layer 20' cannot be completely aligned, and as a result, the degree of polarization of the polarizer layer cannot be sufficiently improved. On the other hand, if extended When the magnification is higher than 17 times, the film is likely to be broken at the time of stretching, and at the same time, the thickness of the film is made thinner than necessary, and the workability and workability in the subsequent step are reduced. In the present invention, since the base film 10 dispersed with the rubber component as described above is used, even when the expansion ratio exceeds 5 times, the obtained stretched film 200 has high resistance to cracking in the extending direction. Therefore, according to the present invention, it is possible to provide a polarizing laminated film which exhibits high polarization characteristics while having high durability.

單軸延展處理並不限定為一段延展,亦可以多段進行。此時,較佳為以延展處理之全階段合計為超過5倍之延展倍率進行延展處理。 The uniaxial extension processing is not limited to one extension, and may be performed in multiple stages. In this case, it is preferable to carry out the stretching treatment at a stretching ratio of more than 5 times in total of all the stages of the stretching treatment.

單軸延展較佳為向積層膜100之長度方向(膜輸送方向)進行延展之縱向延展。縱向延展方式之例可列舉:輥間延展方法、壓縮延展方法、使用拉幅機之延展方法等。同時,單軸延展亦不限定於縱向延展處理,亦可為斜向延展等。 The uniaxial stretching is preferably a longitudinal extension of the extension to the longitudinal direction of the laminated film 100 (film transport direction). Examples of the longitudinal stretching method include a roll stretching method, a compression stretching method, and a stretching method using a tenter. At the same time, the uniaxial stretching is not limited to the longitudinal stretching treatment, and may be oblique stretching or the like.

延展處理可採用濕潤式延展方法、乾式延展方法任一者,但使用乾式延展方法時,由於其延展時溫度可由廣泛範圍中選擇,此點係較佳。 The stretching process may be either a wet stretching method or a dry stretching method, but when the dry stretching method is used, it is preferable since the temperature during stretching can be selected from a wide range.

延展溫度可設定在基材膜之玻璃轉移溫度Tg或結晶化熔點Tm附近,較佳為[(Tg或Tm)-30℃]至[(Tg或Tm)+15℃]之範圍,更佳為[(Tg或Tm)-25℃]至[Tg或Tm]之範圍。若延展溫度比[(Tg或Tm)-30℃]低,則會使超過5倍之高倍率延展變得困難。若延展溫度超過[(Tg或Tm)+15℃],則會使基材膜10之流動性過大因此有延展困難 之傾向。又,延展溫度在上述範圍內,又更佳為在120℃。延展溫度為120℃以上時,即使以超過5倍之高延展倍率延展進行延展處理亦沒有困難性。一般係藉由加熱爐之溫度調整而進行延展處理之溫度調整。 The stretching temperature may be set in the vicinity of the glass transition temperature Tg or the crystallization melting point Tm of the substrate film, preferably in the range of [(Tg or Tm) -30 ° C] to [(Tg or Tm) + 15 ° C], more preferably [(Tg or Tm) - 25 ° C] to the range of [Tg or Tm]. If the extension temperature is lower than [(Tg or Tm) -30 °C], it will be difficult to extend the magnification of more than 5 times. If the elongation temperature exceeds [(Tg or Tm) + 15 ° C], the fluidity of the base film 10 is too large, so that it is difficult to extend. The tendency. Further, the stretching temperature is in the above range, and more preferably at 120 °C. When the stretching temperature is 120 ° C or more, it is not difficult to extend the stretching treatment at a stretching ratio of more than 5 times. Generally, the temperature adjustment of the elongation treatment is performed by the temperature adjustment of the heating furnace.

在積層膜100之厚度在上述範圍時,延展膜200中之單軸延展之基材膜10’的厚度一般為1至300μm,更佳為1至100μm。此外,延展膜200中之單軸延展之聚乙烯醇系樹脂層20’的厚度較佳為1至10μm,更佳為2至8μm。延展聚乙烯醇系樹脂層20’的厚度若為1μm以下則過薄而會使染色性顯著惡化,若超過10μm則會使所得之偏光性積層膜變厚。 When the thickness of the laminated film 100 is in the above range, the thickness of the uniaxially stretched base film 10' in the stretched film 200 is generally from 1 to 300 μm, more preferably from 1 to 100 μm. Further, the thickness of the uniaxially stretched polyvinyl alcohol-based resin layer 20' in the stretched film 200 is preferably from 1 to 10 μm, more preferably from 2 to 8 μm. When the thickness of the expanded polyvinyl alcohol-based resin layer 20' is 1 μm or less, the dyeability is remarkably deteriorated, and when it exceeds 10 μm, the obtained polarizing laminated film is made thick.

(c)染色步驟 (c) Dyeing step

本步驟係使延展膜200之聚乙烯醇系樹脂層20’以二色性色素染色而得到染色膜300之步驟(參考第3圖)。二色性色素例如可舉出碘及有機染料等。有機染料例如可使用:紅色染料BR、紅色染料LR、紅色染料R、粉紅染料LB、紅寶石色染料BL、紅葡萄酒色染料GS、天空藍色染料LG、檸檬黃色染料、藍色染料BR、藍色染料2R、海軍藍色染料RY、綠色染料LG、紫色染料LB、紫色染料B、黑色染料H、黑色染料B、黑色染料GSP、黃色染料3G、黃色染料R、橙色染料LR、橙色染料3R、猩紅色染料GL、猩紅色染料KGL、剛果紅色染料、明紫色染料BK、超藍色染料G(suprablue G)、超藍色染料GL、超橘色染料GL、直接藍色染料、直接耐光橙色染料S(direct fast orange S)、耐光黑色染料 等。該等二色性物質可只單獨使用1種單獨,亦可併用2種以上。 This step is a step of dyeing the polyvinyl alcohol-based resin layer 20' of the stretched film 200 with a dichroic dye to obtain a dyed film 300 (refer to Fig. 3). Examples of the dichroic dye include iodine and an organic dye. For the organic dye, for example, red dye BR, red dye LR, red dye R, pink dye LB, ruby dye BL, red wine dye GS, sky blue dye LG, lemon yellow dye, blue dye BR, blue Dye 2R, Navy Blue Dye RY, Green Dye LG, Purple Dye LB, Purple Dye B, Black Dye H, Black Dye B, Black Dye GSP, Yellow Dye 3G, Yellow Dye R, Orange Dye LR, Orange Dye 3R, Gorilla Red dye GL, scarlet dye KGL, Congo red dye, bright purple dye BK, ultra blue dye G (suprablue G), ultra blue dye GL, super orange dye GL, direct blue dye, direct light orange dye S (direct fast orange S), light fast black dye Wait. These dichroic substances may be used alone or in combination of two or more.

例如可將延展膜200全部浸漬在含上述二色性色素之溶液(染色溶液)中,藉此而進行染色步驟。染色溶液可使用將上述二色性色素溶解在溶劑中之溶液。染色溶液之溶劑一般可使用水,但可再添加與水具互溶性之有機溶劑。二色性色素之濃度較佳為0.01至10重量%,更佳為0.02至7重量%,特佳為0.025至5重量%。 For example, the entire stretch film 200 can be immersed in a solution (dye solution) containing the above-described dichroic dye, whereby the dyeing step can be carried out. As the dyeing solution, a solution in which the above dichroic dye is dissolved in a solvent can be used. The solvent of the dyeing solution can generally be water, but an organic solvent which is miscible with water can be further added. The concentration of the dichroic dye is preferably from 0.01 to 10% by weight, more preferably from 0.02 to 7% by weight, particularly preferably from 0.025 to 5% by weight.

由於二色性色素使用碘時可使其染色效率更為提高,故較佳為復將碘化物添加在含碘之染色溶液中。該碘化物例如可列舉:碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等。染色溶液中碘化物之濃度較佳為0.01至20重量%。在碘化物中,較佳為添加碘化鉀。添加碘化鉀時,碘與碘化鉀之比例以重量比較佳為在1:5至1:100之範圍,更佳為在1:6至1:80之範圍,特佳為在1:7至1:70之範圍。 Since the dyeing efficiency can be further improved by using iodine in the dichroic dye, it is preferred to add the iodide to the dyeing solution containing iodine. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, cesium iodide, calcium iodide, tin iodide, and titanium iodide. The concentration of the iodide in the dyeing solution is preferably from 0.01 to 20% by weight. Among the iodides, potassium iodide is preferably added. When potassium iodide is added, the ratio of iodine to potassium iodide is preferably in the range of 1:5 to 1:100, more preferably in the range of 1:6 to 1:80, and particularly preferably in the range of 1:7 to 1:70. The scope.

延展膜200浸漬在染色溶液之時間並無特別限定,較佳為在15秒至15分鐘之範圍,更佳為30秒至3分鐘之範圍。又,染色溶液之溫度較佳為在10至60℃之範圍,更佳為20至40℃之範圍。 The time during which the stretched film 200 is immersed in the dyeing solution is not particularly limited, and is preferably in the range of 15 seconds to 15 minutes, more preferably in the range of 30 seconds to 3 minutes. Further, the temperature of the dyeing solution is preferably in the range of 10 to 60 ° C, more preferably in the range of 20 to 40 ° C.

另外,染色步驟在延展步驟之前或同時進行均可,但為使聚乙烯醇系樹脂層上吸著之二色性色素可良好地配向,較佳為在積層膜100實施延展步驟之後進行。 Further, the dyeing step may be performed before or at the same time as the stretching step, but the dichroic dye adsorbed on the polyvinyl alcohol-based resin layer may be favorably aligned, and it is preferred to carry out the stretching step after the laminated film 100 is subjected to the stretching step.

(d)交聯步驟 (d) Cross-linking step

本步驟係對於以二色性色素染色所得到之染色膜300之聚乙烯醇系樹脂層30進行交聯處理,以使該聚乙烯醇系樹脂交聯,藉此而可由聚乙烯醇系樹脂層形成偏光件層40並得到交聯膜400之步驟(參考第4圖)。交聯步驟例如可藉由使染色膜300浸漬在含交聯劑之溶液(交聯溶液)中而進行。交聯劑可使用已往已知之物質。例如硼酸、硼砂等硼化合物,及乙二醛、戊二醛等。可只單獨使用該等物種之1種,亦可併用2種以上。 In this step, the polyvinyl alcohol-based resin layer 30 of the dyed film 300 obtained by dyeing the dichroic dye is subjected to a crosslinking treatment to crosslink the polyvinyl alcohol-based resin, whereby the polyvinyl alcohol-based resin layer can be used. The step of forming the polarizer layer 40 and obtaining the crosslinked film 400 (refer to Fig. 4). The crosslinking step can be carried out, for example, by immersing the dyed film 300 in a solution containing a crosslinking agent (crosslinking solution). As the crosslinking agent, those known in the art can be used. For example, a boron compound such as boric acid or borax, and glyoxal or glutaraldehyde. One type of these species may be used alone, or two or more types may be used in combination.

交聯溶液可使用將交聯劑溶解在溶劑中之溶液。溶劑可使用如水,但可復含與水為互溶性之有機溶劑。交聯溶液中交聯劑之濃度較佳為在1至20重量%之範圍,更佳為6至15重量%。 As the crosslinking solution, a solution in which a crosslinking agent is dissolved in a solvent can be used. The solvent may be used, for example, water, but may contain an organic solvent which is miscible with water. The concentration of the crosslinking agent in the crosslinking solution is preferably in the range of 1 to 20% by weight, more preferably 6 to 15% by weight.

交聯溶液可添加碘化物。藉由碘化物之添加可使偏光件層40之面內側之偏光特性更為均勻化。碘化物例如可列舉:碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等。碘化物之濃度較佳為0.05至15重量%,更佳為0.5至8重量%。 The cross-linking solution can be added with iodide. The polarization characteristics inside the surface of the polarizer layer 40 can be made more uniform by the addition of iodide. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, cesium iodide, calcium iodide, tin iodide, and titanium iodide. The concentration of the iodide is preferably from 0.05 to 15% by weight, more preferably from 0.5 to 8% by weight.

染色膜300浸漬在交聯溶液中之時間較佳為15秒至20分鐘,更佳為30秒至15分鐘。又,交聯溶液之溫度較佳為在10至90℃之範圍。 The time during which the dyed film 300 is immersed in the crosslinking solution is preferably from 15 seconds to 20 minutes, more preferably from 30 seconds to 15 minutes. Further, the temperature of the crosslinking solution is preferably in the range of 10 to 90 °C.

又,可藉由將交聯劑摻配在染色溶液中摻配,而使交聯步驟與染色步驟同時進行。此外,交聯步驟與延展步驟亦可同時進行。 Further, the crosslinking step and the dyeing step can be carried out simultaneously by blending the crosslinking agent in the dyeing solution. In addition, the crosslinking step and the stretching step can also be carried out simultaneously.

(e)乾燥步驟 (e) drying step

所得到之交聯膜400一般在進行洗淨後乾燥。藉此可得到偏光性積層膜(參考第5圖)。洗淨可藉由將交聯膜400浸漬在離子交換水、蒸餾水等之純水中而進行。水洗淨溫度一般為3至50℃,較佳為在4至20℃之範圍。浸漬時間一般為2至300秒,較佳為5至240秒。洗淨,可組合以碘化物溶液之洗淨處理及水洗淨處理,亦可適當地使用摻配甲醇、乙醇、異丙醇、丁醇、丙醇等之液體醇之溶液。 The obtained crosslinked film 400 is generally dried after being washed. Thereby, a polarizing laminated film can be obtained (refer to Fig. 5). The washing can be carried out by immersing the crosslinked film 400 in pure water such as ion-exchanged water or distilled water. The water washing temperature is usually from 3 to 50 ° C, preferably from 4 to 20 ° C. The immersion time is generally from 2 to 300 seconds, preferably from 5 to 240 seconds. The washing may be carried out by washing with an iodide solution and washing with water, and a solution of a liquid alcohol blended with methanol, ethanol, isopropanol, butanol or propanol may be suitably used.

乾燥方法可採用任意適當之方法(如自然乾燥、吹風乾燥、加熱乾燥)。例如,加熱乾燥時之乾燥溫度一般為20至95℃,乾燥時間一般為1至15分鐘左右。 The drying method may be any suitable method (such as natural drying, air drying, and heat drying). For example, the drying temperature during heat drying is generally from 20 to 95 ° C, and the drying time is usually from about 1 to 15 minutes.

偏光性積層膜係具備由吸著配向二色性色素之聚乙烯醇系樹脂層所構成的偏光件層40,其本身可作為偏光板使用。根據本發明之方法可使偏光件層40之厚度在10μm以下,因此可得到薄型之偏光性積層膜。此外,本發明之偏光性積層膜其偏光性能及耐久性均優異。 The polarizing laminated film system includes a polarizer layer 40 composed of a polyvinyl alcohol-based resin layer that adsorbs a dichroic dye, and can be used as a polarizing plate itself. According to the method of the present invention, the thickness of the polarizer layer 40 can be made 10 μm or less, so that a thin polarizing laminated film can be obtained. Further, the polarizing laminated film of the present invention is excellent in both polarizing performance and durability.

<附有保護膜之偏光板之製造方法> <Method of Manufacturing Polarizing Plate with Protective Film>

上述之偏光性積層膜作為用以製造貼著保護膜之偏光板的中間物亦為有用的,藉由使用此偏光性積層膜,可使附有保護膜之偏光板之製造有效率且產率佳。附有保護膜之偏光板之一例可如第6圖所示。該圖所示之附有保護膜之偏光板600,在偏光件層40中與延展基材膜10’所積層之面的相反側上具有保護膜50。在第6圖之例中基材膜10’係已剝離去除,附有保護膜之偏光板亦可具有基材膜10’。 The above polarizing laminated film is also useful as an intermediate for producing a polarizing plate attached to a protective film, and by using the polarizing laminated film, the polarizing plate with the protective film can be efficiently manufactured and produced. good. An example of a polarizing plate with a protective film can be as shown in Fig. 6. The polarizing plate 600 with a protective film shown in the figure has a protective film 50 on the side opposite to the surface on which the layered substrate film 10' is laminated in the polarizer layer 40. In the example of Fig. 6, the base film 10' is peeled off, and the polarizing plate with the protective film may have the base film 10'.

使用上述偏光性積層膜並藉由含有下述步驟之方法而 可製作附有保護膜之偏光板。 Using the above polarizing laminate film and by the method comprising the following steps A polarizing plate with a protective film can be produced.

(A)在偏光性積層膜500之偏光件層40中與基材膜10’側的相反側之面上貼合保護膜50之步驟、(B)將基材膜10’剝離去除之步驟。又,步驟(B)係如上述般任意之步驟。 (A) a step of bonding the protective film 50 to the surface of the polarizer layer 40 of the polarizing laminated film 500 on the side opposite to the side of the base film 10', and (B) a step of peeling off the base film 10'. Further, the step (B) is a step as described above.

保護膜50,其構成基材膜之熱塑性樹脂可由與上述之樹脂相同的樹脂構成。保護膜50即使為藉由單軸延展或雙軸延展賦予其位相差者亦可。 The protective film 50 whose thermoplastic resin constituting the base film can be composed of the same resin as the above-mentioned resin. The protective film 50 may be imparted to the phase difference by uniaxial stretching or biaxial stretching.

保護膜50較佳為較薄者,但若過薄會使強度減低並使加工性變差。另一方面,若過厚時則會有透明性減低或積層後所需要之固化(curing)時間變長等之問題。因此,保護膜50之厚度較佳為80μm以下,更佳為5至60μm。又,由附有保護膜之偏光板之薄型化之觀點來看,偏光件層40及保護膜50之合計厚度較佳為100μm以下,更佳為90μm以下,又更佳為80μm以下。 The protective film 50 is preferably thinner, but if it is too thin, the strength is lowered and the workability is deteriorated. On the other hand, when it is too thick, there is a problem that the transparency is reduced or the curing time required after lamination is lengthened. Therefore, the thickness of the protective film 50 is preferably 80 μm or less, more preferably 5 to 60 μm. Moreover, the total thickness of the polarizer layer 40 and the protective film 50 is preferably 100 μm or less, more preferably 90 μm or less, and still more preferably 80 μm or less from the viewpoint of the thickness reduction of the polarizing plate with a protective film.

在保護膜50之與偏光件層40為相反側之表面上,亦可形成硬化膜層、抗眩光層、光擴散層、抗反射層等之光學層。 On the surface of the protective film 50 opposite to the polarizer layer 40, an optical layer such as a cured film layer, an anti-glare layer, a light-diffusing layer, an anti-reflection layer or the like may be formed.

偏光件層40及保護膜50之貼合可使用接著劑或黏著劑而進行。接著劑例如可舉如聚乙烯醇系樹脂水溶液、水系二液型胺甲酸乙酯(urethane)系乳液接著劑等水系接著劑。保護膜50使用經皂化處理等親水化處理之纖維素酯系樹脂膜時,接著劑適合使用聚乙烯醇系樹脂水溶液。作為接著劑使用之聚乙烯醇系樹脂中,除了將醋酸乙烯酯之單 獨聚合物的聚醋酸乙烯酯經過皂化處理所得之乙烯醇均聚物(homopolymer)之外,亦有將醋酸乙烯酯與可與其共聚的其他單體之共聚物經過皂化處理所得之乙烯醇系共聚物、復有該等之部分羥基經過改質之改質聚乙烯醇系聚合物等。水系接著劑中亦可添加多元醛、水溶性環氧化合物、三聚氰胺系化合物、氧化鋯化合物、鋅化合物等添加劑。 The bonding of the polarizer layer 40 and the protective film 50 can be carried out using an adhesive or an adhesive. The subsequent agent may, for example, be a water-based adhesive such as a polyvinyl alcohol-based resin aqueous solution or an aqueous two-component urethane-based emulsion adhesive. When the cellulose ester-based resin film hydrophilized by a saponification treatment or the like is used as the protective film 50, a polyvinyl alcohol-based resin aqueous solution is suitably used as the adhesive. In the polyvinyl alcohol-based resin used as an adhesive, in addition to the single vinyl acetate The polyvinyl acetate of the sole polymer is subjected to a saponification treatment of a vinyl alcohol homopolymer, and a vinyl alcohol copolymer obtained by subjecting a copolymer of vinyl acetate and another monomer copolymerizable therewith to a saponification treatment. And a modified polyvinyl alcohol-based polymer obtained by modifying a part of the hydroxyl groups. Additives such as a polyvalent aldehyde, a water-soluble epoxy compound, a melamine-based compound, a zirconia compound, and a zinc compound may be added to the aqueous binder.

使用水系接著劑貼合偏光件層40及保護膜50之方法並無特別限定,可舉出以下方法:例如藉由流延法、線棒塗布法、凹版塗布法、刮刀塗布法(comma coating)、刮刀塗布法、鑄模塗布法、含浸塗布法、噴霧法等,在偏光件層40及/或保護膜50之表面上均一地塗布接著劑,在塗布面上重疊另一方之膜並以輥等使其貼合,再加以乾燥。流延法係被塗物之偏光件層40或保護膜50一邊向略垂直方向、略水平方向或兩者之間之斜向方向移動,一邊在其表面流下接著劑以使其擴散之方法。 The method of bonding the polarizer layer 40 and the protective film 50 with a water-based adhesive is not particularly limited, and examples thereof include a casting method, a bar coating method, a gravure coating method, and a comma coating method. , a doctor blade coating method, a die coating method, an impregnation coating method, a spray method, or the like, and an adhesive is uniformly applied to the surface of the polarizer layer 40 and/or the protective film 50, and the other film is superposed on the coated surface to be a roller or the like. Make it fit and dry. The casting method is a method in which the polarizer layer 40 or the protective film 50 of the object to be coated is moved in an oblique direction slightly in the vertical direction, in the horizontal direction, or in the oblique direction therebetween, and an adhesive is applied to the surface thereof to diffuse.

在偏光件層40與保護膜50貼合後,為了去除水系接著劑中所含之水而乾燥積層之膜。乾燥溫度較佳為30至90℃。若未達30℃則偏光件層40與保護膜50有易於剝離之傾向。此外,若在90℃以上則會有因熱而使偏光性能劣化之虞。乾燥時間可為10至1000秒,特別是由生產性之觀點來看較佳為60至750,更佳為150至600秒。乾燥後再以室溫或比室溫稍高之溫度,如可在20至45℃左右之溫度下固化12至600小時左右。固化溫度一般係設定比乾燥時所採用之溫度為低。 After the polarizer layer 40 is bonded to the protective film 50, the laminated film is dried in order to remove water contained in the aqueous adhesive. The drying temperature is preferably from 30 to 90 °C. If it is less than 30 ° C, the polarizer layer 40 and the protective film 50 tend to be easily peeled off. Further, when the temperature is 90 ° C or more, the polarizing performance is deteriorated due to heat. The drying time may be from 10 to 1,000 seconds, and particularly preferably from 60 to 750, more preferably from 150 to 600 seconds from the viewpoint of productivity. After drying, it may be cured at room temperature or slightly higher than room temperature, for example, at a temperature of about 20 to 45 ° C for about 12 to 600 hours. The curing temperature is generally set to be lower than the temperature used for drying.

貼合偏光件層40與保護膜50時之接著劑亦可使用光硬化性接著劑。光硬化性接著劑可例舉如光硬化性環氧樹脂與光陽離子聚合起始劑之混合物。 A photocurable adhesive can also be used as the adhesive for bonding the polarizer layer 40 and the protective film 50. The photocurable adhesive may, for example, be a mixture of a photocurable epoxy resin and a photocationic polymerization initiator.

使用光硬化性接著劑時,偏光件層40與保護膜50以與上述相同操作貼合後,再以活性能量射線照射使光硬化性接著劑硬化。活性能量射線之光源並無特別限定,但較佳為具有在波長400nm以下之發光分布之活性能量射線,具體來說適合使用低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、化學燈、黑光燈、微波激發汞燈、金屬鹵化物燈等。 When a photocurable adhesive is used, the polarizer layer 40 and the protective film 50 are bonded together in the same manner as described above, and then cured by an active energy ray to cure the photocurable adhesive. The light source of the active energy ray is not particularly limited, but is preferably an active energy ray having a light-emitting distribution at a wavelength of 400 nm or less, and specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, Chemical lamps, black lamps, microwave excited mercury lamps, metal halide lamps, and the like.

對光硬化性接著劑之光照射強度可依照光硬化性接著劑之組成而適當地決定,並無特別限定,但較佳為對於活化聚合起始劑有效之波長範圍的照射強度為0.1至6000mW/cm2。照射強度為0.1mW/cm2以上時則不會使反應時間過長,照射強度為6000mW/cm2以下時,因光源輻射熱及光硬化性接著劑硬化時之發熱而產生環氧樹脂黃變及偏光件層劣化之顧慮較少。對於光硬化性接著劑之光照時間,可依照所硬化之光硬化性接著劑而適當使用並無特別限定,但較佳為以使上述照射強度及照射時間之積所表示之累計光量為10至10000mJ/cm2之方式設定。對於光硬化性接著劑之累計光量在10mJ/cm2以上時,可使由聚合起始劑而來之活性種的產生量充分並使硬化反應確實地進行,在10000mJ/cm2以下時,可使照射時間不致過長並可維持良好之生產性。 The light irradiation intensity of the photocurable adhesive can be appropriately determined depending on the composition of the photocurable adhesive, and is not particularly limited, but it is preferably 0.1 to 6000 mW in the wavelength range effective for activating the polymerization initiator. /cm 2 . When the irradiation intensity is 0.1 mW/cm 2 or more, the reaction time is not excessively long, and when the irradiation intensity is 6,000 mW/cm 2 or less, yellowing of the epoxy resin occurs due to heat generation of the radiant heat of the light source and hardening of the photocurable adhesive. There are fewer concerns about degradation of the polarizer layer. The light irradiation time of the photocurable adhesive agent is not particularly limited as long as it can be suitably used in accordance with the cured photocurable adhesive, but it is preferable that the integrated light amount represented by the product of the irradiation intensity and the irradiation time is 10 to Set in the mode of 10000mJ/cm 2 . When the total amount of light of the photocurable adhesive is 10 mJ/cm 2 or more, the amount of active species produced by the polymerization initiator can be sufficiently increased, and the curing reaction can be surely performed. When the amount is 10000 mJ/cm 2 or less, The irradiation time is not too long and good productivity can be maintained.

此外,在偏光件層40與保護膜50之貼合中,為提高接著性,可預先在偏光件層40及/或保護膜50之接著面視需要實施電漿處理、電暈處理、紫外線照射處理、火燄(flame)處理、皂化處理等表面處理。皂化處理可舉出浸漬在氫氧化鈉及氫氧化鉀之類之鹼水溶液中之方法。 Further, in the bonding of the polarizer layer 40 and the protective film 50, in order to improve the adhesion, the plasma treatment, the corona treatment, and the ultraviolet irradiation may be performed on the surface of the polarizer layer 40 and/or the protective film 50 as needed. Surface treatment such as treatment, flame treatment, saponification treatment, and the like. The saponification treatment may be carried out by immersing in an aqueous alkali solution such as sodium hydroxide or potassium hydroxide.

另一方面,貼合偏光件層40與保護膜50所使用之黏著劑一般為:以丙烯酸系樹脂、苯乙烯系樹脂、聚矽氧系樹脂等為基底聚合物,再於其中加入異氰酸酯化合物、環氧化合物、氮丙啶(aziridine)化合物等交聯劑之組成物所構成。復可含有微粒子並作為顯示光散射性之黏著劑層。 On the other hand, the adhesive used for bonding the polarizer layer 40 and the protective film 50 is generally an acrylic resin, a styrene resin, a polyoxymethylene resin or the like as a base polymer, and an isocyanate compound is added thereto. A composition of a crosslinking agent such as an epoxy compound or an aziridine compound. The composite may contain fine particles and serve as an adhesive layer for exhibiting light scattering properties.

黏著劑層之厚度較佳為1至40μm,但在不損及加工性、耐久性等之範圍下較佳為形成薄層,更佳為3至25μm。黏著劑層之厚度若未達1μm則會使黏著性降低,若超過40μm則易發生黏著劑漏出等不良情形。 The thickness of the adhesive layer is preferably from 1 to 40 μm, but it is preferably a thin layer, more preferably from 3 to 25 μm, insofar as the workability, durability, and the like are not impaired. If the thickness of the adhesive layer is less than 1 μm, the adhesiveness is lowered. If it exceeds 40 μm, the adhesive may leak.

以黏著劑貼合偏光件層40與保護膜50之方法並無特別限定,可以在保護膜之面上或偏光件層之面上,塗布含以上述基底聚合物為始之各成分的溶液(黏著劑組成物),再使其乾燥形成黏著劑層後,使偏光件層40與保護膜50貼合,亦可在分隔層(剝離膜)上形成黏著劑層後,再轉印至保護膜之面上或偏光件層之面上,使偏光件層40與保護膜50貼合。 The method of bonding the polarizer layer 40 and the protective film 50 with an adhesive is not particularly limited, and a solution containing the components of the base polymer may be applied to the surface of the protective film or the surface of the polarizer layer ( After the adhesive composition is dried to form an adhesive layer, the polarizer layer 40 is bonded to the protective film 50, and an adhesive layer may be formed on the separation layer (release film), and then transferred to a protective film. The polarizer layer 40 is bonded to the protective film 50 on the surface or on the surface of the polarizer layer.

同時,為了提高密接性,可視需要在偏光件層40及/或保護膜50之貼合面、或在黏著劑層之單面或兩面上預先進行電暈處理等之表面處理。 At the same time, in order to improve the adhesion, it is necessary to perform surface treatment such as corona treatment on the bonding surface of the polarizer layer 40 and/or the protective film 50 or on one or both sides of the adhesive layer.

上述步驟(B)係由步驟(A)中所得具備基材膜10’/偏光件層40/保護膜50之積層物將基材膜10’剝離去除之步驟。可在貼合保護膜50之後直接立即將基材膜10’剝離,亦可在貼合保護膜50之後,先暫時捲起成輥狀後,在於之後之步驟中一邊繞開一邊將基材膜10’剝離。 The above step (B) is a step of peeling off the base film 10' by the laminate comprising the base film 10'/polarizer layer 40/protective film 50 obtained in the step (A). The base film 10' may be directly peeled off immediately after the protective film 50 is bonded, or may be temporarily rolled up into a roll shape after the protective film 50 is bonded, and then the substrate film may be circumscribed in the subsequent step. 10' peel off.

(實施例) (Example)

以下,以實施例再具體說明本發明,但本發明並不受該等例之限定。 Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples.

[偏光性積層膜之製作] [Production of polarizing laminated film] <實施例1> <Example 1>

(1)基材膜之製作 (1) Fabrication of substrate film

係以反應器混合物法,在相同反應器內依序調製熱塑性樹脂及橡膠成分。具體來說係使用齊格勒-納塔催化劑(Ziegler-Natta catalyst),將作為第一步驟之丙烯單體在氣相中進行進料並製造熱塑性樹脂之丙烯單獨聚合物。之後終止丙烯單體進料並停止反應後,在該反應容器直接將作為第二步驟之乙烯單體及丙烯單體在氣相中進行進料,而製造橡膠成分之乙烯-丙烯共聚物,並製得由橡膠成分之乙烯-丙烯共聚物以粒子狀分散之丙烯單獨聚合物。由聚合時物質之增減計算時,共聚物中所占乙烯單元之含量為35重量%。此外,樹脂全體(熱塑性樹脂及橡膠成分之合計)中所占乙烯單元之含量可依照「高分子手冊」(1995年,紀伊國屋書店發行)之第616頁中所記載之方法求出,以該值計算樹脂全體中所占乙烯-丙烯共聚物的含量時結果為 29重量%,(亦即乙烯-丙烯共聚物之含量為熱塑性樹脂之40.8重量%)。 The thermoplastic resin and the rubber component were sequentially adjusted in the same reactor by a reactor mixture method. Specifically, a propylene monomer as a first step is fed in a gas phase using a Ziegler-Natta catalyst and a propylene-individual polymer of a thermoplastic resin is produced. After the propylene monomer feed is terminated and the reaction is stopped, the ethylene monomer and the propylene monomer as the second step are directly fed in the gas phase in the reaction vessel to produce an ethylene-propylene copolymer of a rubber component. A propylene individual polymer obtained by dispersing an ethylene-propylene copolymer of a rubber component in the form of particles. The content of the ethylene unit in the copolymer was 35 wt% as calculated from the increase or decrease of the substance at the time of polymerization. In addition, the content of the ethylene unit in the total resin (total of the thermoplastic resin and the rubber component) can be obtained by the method described in the "Handbook of Polymers" (published by Kiyoshiya Shoten, 1995) on page 616. When calculating the content of the ethylene-propylene copolymer in the entire resin, the result is 29% by weight, (that is, the content of the ethylene-propylene copolymer is 40.8% by weight of the thermoplastic resin).

該製得之混合樹脂以250℃熔融混拌後,再於T-型模頭中於280℃之溫度下進行熔融壓出,即可製得厚度100μm之基材膜。 The obtained mixed resin was melt-mixed at 250 ° C, and then melt-extruded in a T-type die at a temperature of 280 ° C to obtain a substrate film having a thickness of 100 μm.

(2)底層之形成 (2) Formation of the bottom layer

先將聚乙烯醇粉末(日本合成化學工業股份公司製造「Z-200」,平均聚合度1100,平均皂化度99.5%)溶解在95℃之熱水中,調製成為濃度3重量%之聚乙烯醇水溶液。之後在製得之水溶液中,相對於6重量份之聚乙烯醇粉末而混合5重量份交聯劑(日本住友化學股份公司製造「SUMIREZ Resin 650」)。在實施電暈處理之上述基材膜之電暈處理面上以微凹版塗布機塗布所得混合水溶液,之後於80℃下乾燥10分鐘,即可形成厚度0.2μm之底層。 First, polyvinyl alcohol powder ("Z-200" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1100, average saponification degree 99.5%) was dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol having a concentration of 3% by weight. Aqueous solution. Then, 5 parts by weight of a crosslinking agent ("SUMIREZ Resin 650" manufactured by Sumitomo Chemical Co., Ltd.) was mixed with 6 parts by weight of the polyvinyl alcohol powder in the obtained aqueous solution. The resulting mixed aqueous solution was applied to a corona-treated surface of the substrate film subjected to corona treatment by a micro gravure coater, and then dried at 80 ° C for 10 minutes to form a bottom layer having a thickness of 0.2 μm.

(3)聚乙烯醇系樹脂層之形成 (3) Formation of a polyvinyl alcohol-based resin layer

先將聚乙烯醇粉末(日本Kuraray股份公司製造之「PVA124」,平均聚合度2400,平均皂化度98.0至99.0莫耳%)溶解在95℃之熱水中,調製成濃度為8重量%之聚乙烯醇水溶液。於上述底層上以噴嘴塗布機塗布所得水溶液,再以80℃下2分鐘、70℃下2分鐘、之後為60℃下4分鐘之條件下進行乾燥,藉此製作在基材膜上介置有底層並積層聚乙烯醇系樹脂層之積層膜。聚乙烯醇系樹脂層之厚度係9.8μm。 First, polyvinyl alcohol powder ("PVA124" manufactured by Kuraray Co., Ltd., average polymerization degree 2400, average saponification degree: 98.0 to 99.0 mol%) was dissolved in hot water at 95 ° C to prepare a concentration of 8 wt%. Aqueous vinyl alcohol solution. The obtained aqueous solution was applied to the above-mentioned underlayer by a nozzle coater, and dried at 80 ° C for 2 minutes, at 70 ° C for 2 minutes, and then at 60 ° C for 4 minutes, thereby preparing a substrate film. A laminate film of a polyvinyl alcohol-based resin layer is laminated on the bottom layer. The thickness of the polyvinyl alcohol-based resin layer was 9.8 μm.

(4)延展膜之製作 (4) Production of stretch film

將上述積層膜在160℃之延展溫度下進行5.8倍由自由端縱軸單軸延展,而製得延展膜。所得之延展膜之厚度為28.5μm,聚乙烯醇系樹脂層之厚度為4.2μm。 The laminated film was stretched uniaxially at a stretching temperature of 160 ° C by 5.8 times from the longitudinal axis of the free end to obtain an expanded film. The thickness of the obtained stretched film was 28.5 μm, and the thickness of the polyvinyl alcohol-based resin layer was 4.2 μm.

(5)偏光性積層膜之製作 (5) Production of polarizing laminated film

將上述延展膜在60℃之溫浴下浸漬60秒鐘之後,浸漬在含有碘及碘化鉀之水溶液的30℃染色溶液150秒鐘左右,進行聚乙烯醇系樹脂層之染色,之後再以10℃之純水沖洗多餘之碘液。其次,於含硼酸及碘化鉀之水溶液的76℃交聯溶液中浸漬600秒鐘。之後,再以10℃之純水洗淨4秒鐘,最後以50℃乾燥300秒鐘,藉此得到偏光性積層膜。 After immersing the above-mentioned stretched film in a warm bath of 60 ° C for 60 seconds, it was immersed in a 30 ° C dyeing solution containing an aqueous solution of iodine and potassium iodide for about 150 seconds to dye the polyvinyl alcohol-based resin layer, and then 10 ° C. Rinse excess iodine solution with pure water. Next, it was immersed in a 76 ° C crosslinking solution containing an aqueous solution of boric acid and potassium iodide for 600 seconds. Thereafter, the film was further washed with pure water of 10 ° C for 4 seconds, and finally dried at 50 ° C for 300 seconds to obtain a polarizing laminated film.

在至製作偏光性積層膜為止之各步驟中,並未發生延展後之膜破裂等不良,因此可安定地製作偏光性積層膜。 In each step up to the production of the polarizing laminated film, defects such as film breakage after stretching do not occur, and thus a polarizing laminated film can be produced stably.

<實施例2> <Example 2>

除了在實施例1之「(1)基材膜之製作」的第二步驟中,以乙烯單體及1-丁烯單體進料,而調製作為橡膠成分為乙烯-丁烯共聚物以外,以與實施例1同樣操作製作得厚度100μm之基材膜。共聚物中所占乙烯單元之含量為35重量%。樹脂整體中所占乙烯單元之含量為30重量%(即乙烯-丙烯共聚物之含量為熱塑性樹脂之42.9重量%)。 In addition to the ethylene monomer and the 1-butene monomer, the ethylene component and the 1-butene monomer are fed in the second step of the "(1) production of the base film" of the first embodiment, and the rubber component is prepared as an ethylene-butene copolymer. A substrate film having a thickness of 100 μm was produced in the same manner as in Example 1. The content of the ethylene unit in the copolymer was 35% by weight. The content of the ethylene unit in the entire resin was 30% by weight (that is, the content of the ethylene-propylene copolymer was 42.9% by weight of the thermoplastic resin).

使用如此所得之基材膜,以與實施例1相同操作製作偏光性積層膜。在至製作偏光性積層膜為止之各步驟中,並未發生延展後之膜破裂等不良,可安定地製作偏光性積層膜。 Using the thus obtained base film, a polarizing laminated film was produced in the same manner as in Example 1. In each step up to the production of the polarizing laminated film, defects such as film breakage after stretching do not occur, and a polarizing laminated film can be produced stably.

<比較例1> <Comparative Example 1>

除了使用丙烯單獨聚合物(日本住友化學股份公司製造之「住友Noblen FLX80E4」,熔點Tm=163℃)所構成厚度為100μm之基材膜(無橡膠成分)以外,以與實施例1同樣操作而製作積層膜。之後,以與實施例1同樣之條件進行自由端縱軸單軸延展處理,可得厚度為30.1μm之延展膜。該所得之延展膜中聚乙烯醇系樹脂層之厚度為4.5μm。 The same operation as in Example 1 was carried out except that a base film (no rubber component) having a thickness of 100 μm was formed using propylene alone polymer (Sumitomo Noblen FLX80E4 manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 163 ° C). Make a laminate film. Thereafter, the free end longitudinal axis uniaxial stretching treatment was carried out under the same conditions as in Example 1 to obtain an expanded film having a thickness of 30.1 μm. The thickness of the polyvinyl alcohol-based resin layer in the obtained stretched film was 4.5 μm.

<比較例2> <Comparative Example 2>

除了使用含約5重量%之乙烯單元之丙烯-乙烯無規共聚物(日本住友化學股份公司製造之「住友Noblen W151」,熔點Tm=138℃)所構成厚度為100μm之基材膜(無橡膠成分)以外,以與實施例1同樣操作而製作積層膜。之後,以與實施例1同樣之條件進行自由端縱軸單軸延展處理,可得厚度為30.1μm之延展膜。該所得之延展膜中聚乙烯醇系樹脂層之厚度為4.5μm。 A substrate film having a thickness of 100 μm (without rubber) using a propylene-ethylene random copolymer (Sumitomo Noblen W151, manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 138 ° C) containing about 5% by weight of ethylene units A laminate film was produced in the same manner as in Example 1 except for the component. Thereafter, the free end longitudinal axis uniaxial stretching treatment was carried out under the same conditions as in Example 1 to obtain an expanded film having a thickness of 30.1 μm. The thickness of the polyvinyl alcohol-based resin layer in the obtained stretched film was 4.5 μm.

(延展膜拉張強度之測定) (Measurement of stretch film tensile strength)

以下之方法測定上述實施例及比較例中所得之延展膜的拉張強度。首先,由延展膜之短邊邊緣部之中央(膜之寬方向之中央),以刀片以與延展方向平行切開切口。其次使用萬能試驗機(日本島津製作股份公司製造之「Autograph AG-I」),由該切口之基點拉張延展膜,用同一裝置測定此時之拉張強度。膜拉張時之速度為300mm/min。以本測定之操作可測得在各拉張距離(即由切口之基點拉張膜時之距離)之拉張強度,但使用拉張試驗機測定拉張強度時,至 達到一定程度拉張距離而至膜之拉張角度安定為止,其拉張強度會高出許多。因此,本測定中係排除該部分,再求出在拉張強度安定之範圍的拉張強度之平均值,以其為拉張強度。其結果如表1所示。 The tensile strength of the stretched film obtained in the above Examples and Comparative Examples was measured by the following method. First, the slit is cut in parallel with the extending direction by the blade at the center of the short edge portion of the stretched film (the center in the width direction of the film). Next, using a universal testing machine ("Autograph AG-I" manufactured by Shimadzu Corporation, Japan), the stretched film was stretched from the base of the slit, and the tensile strength at this time was measured by the same apparatus. The speed at which the film was stretched was 300 mm/min. The tensile strength at each tensile distance (ie, the distance from the base point of the slit) can be measured by the operation of the measurement, but when the tensile strength is measured using a tensile tester, When the stretching distance is reached to a certain extent until the tensile angle of the film is stabilized, the tensile strength is much higher. Therefore, in this measurement, the portion was excluded, and the average value of the tensile strength in the range of the tensile strength stability was determined, and this was taken as the tensile strength. The results are shown in Table 1.

如表1所示,實施例1及2之延展膜,與比較例1及2比較,可確配向相對延展方向之開裂具有高耐性。 As shown in Table 1, in the stretched films of Examples 1 and 2, compared with Comparative Examples 1 and 2, it was confirmed that the film was highly resistant to cracking in the relative extension direction.

[附有保護膜之偏光板之製作] [Production of polarizing plate with protective film] <實施例3> <Example 3>

係使用實施例1及2所得之各偏光性積層膜,再以以下之順序製作附有保護膜之偏光板。先將聚乙烯醇粉末(日本Kuraray股份公司製造之「KL-318」,平均聚合度1800)溶解在95℃之熱水中,調製成濃度3重量%之聚乙烯醇水溶液。之後再於所得之水溶液中,以相對於2重量份之聚乙烯醇粉末,以1重量份混合交聯劑(日本住友化學股份公司製造「SUMIREZ Resin 650」),而作為接著劑溶液。 Using the polarizing laminate films obtained in Examples 1 and 2, a polarizing plate with a protective film was produced in the following order. Polyvinyl alcohol powder ("KL-318" manufactured by Kuraray Co., Ltd., Japan, average degree of polymerization 1800) was dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol aqueous solution having a concentration of 3% by weight. Then, the crosslinking agent ("SUMIREZ Resin 650" manufactured by Sumitomo Chemical Co., Ltd.) was mixed with 1 part by weight of the polyvinyl alcohol powder in the obtained aqueous solution to obtain an adhesive solution.

其次,在偏光性積層膜之聚乙烯醇系樹脂層上塗布上 述接著劑溶液後,再貼合於以三醋酸纖維素(TAC)所構成之保護膜(日本Konica Minolta Opto Products股份公司製造之「KC4UY」),製得由保護膜/接著劑層/偏光件層/底層/基材膜之5層所構成之偏光板。由該得到之偏光板將基材膜剝離,而製作由保護膜/接著劑層/偏光件層/底層之4層所構成之偏光板。基材膜可容易地剝離。 Next, it is coated on the polyvinyl alcohol-based resin layer of the polarizing laminated film. After the adhesive solution is applied to a protective film made of cellulose triacetate (TAC) ("KC4UY" manufactured by Konica Minolta Opto Products Co., Ltd., Japan), a protective film/adhesive layer/polarizer is obtained. A polarizing plate composed of 5 layers of a layer/underlayer/substrate film. The base film was peeled off from the obtained polarizing plate, and a polarizing plate composed of four layers of a protective film/adhesive layer/polarizer layer/underlayer was produced. The base film can be easily peeled off.

10‧‧‧基材膜 10‧‧‧Base film

10’‧‧‧延展基材膜 10'‧‧‧Extended base film

20‧‧‧聚乙烯醇系樹脂層 20‧‧‧Polyvinyl alcohol resin layer

20’‧‧‧延展聚乙烯醇系樹脂層 20'‧‧‧Extended polyvinyl alcohol resin layer

30‧‧‧二色性色素染色之聚乙烯醇系樹脂層 30‧‧‧Dichromatic pigment dyed polyvinyl alcohol resin layer

40‧‧‧偏光件層 40‧‧‧ polarizer layer

50‧‧‧保護膜 50‧‧‧Protective film

100‧‧‧積層膜 100‧‧‧ laminated film

200‧‧‧延展膜 200‧‧‧Extended film

300‧‧‧染色膜 300‧‧‧Stained film

400‧‧‧交聯膜 400‧‧‧crosslinked film

500‧‧‧偏光性積層膜 500‧‧‧Polarized laminated film

600‧‧‧附有保護膜之偏光板 600‧‧‧Polarizer with protective film

第1圖係表示積層步驟中所得積層膜的一例之概略斷面圖。 Fig. 1 is a schematic cross-sectional view showing an example of a laminated film obtained in a lamination step.

第2圖係表示延展步驟中所得延展膜的一例之概略斷面圖。 Fig. 2 is a schematic cross-sectional view showing an example of the stretched film obtained in the stretching step.

第3圖係表示染色步驟中所得染色膜的一例之概略斷面圖。 Fig. 3 is a schematic cross-sectional view showing an example of a dyed film obtained in the dyeing step.

第4圖係表示交聯步驟中所得交聯膜的一例之概略斷面圖。 Fig. 4 is a schematic cross-sectional view showing an example of a crosslinked film obtained in the crosslinking step.

第5圖係表示偏光性積層膜之一例的概略斷面圖。 Fig. 5 is a schematic cross-sectional view showing an example of a polarizing laminated film.

第6圖係表示附有保護膜之偏光板之一例的概略斷面圖。 Fig. 6 is a schematic cross-sectional view showing an example of a polarizing plate with a protective film.

10’‧‧‧延展基材膜 10'‧‧‧Extended base film

40‧‧‧偏光件層 40‧‧‧ polarizer layer

500‧‧‧偏光性積層膜 500‧‧‧Polarized laminated film

Claims (7)

一種偏光性積層膜的製造方法,該偏光性積層膜具備在熱塑性樹脂中分散有橡膠成分而製得之基材膜、及在前述基材膜之一邊面上積層之偏光件層,該製造方法係包含:在熱塑性樹脂中分散有橡膠成分而構成之基材膜的一邊面上形成聚乙烯醇系樹脂層而得到積層膜之步驟;將前述積層膜向單軸延展而得到延展膜之步驟;將前述延展膜之前述聚乙烯醇系樹脂層以二色性色素染色,而得到染色膜之步驟;將前述染色膜之前述聚乙烯醇系樹脂層浸漬於含交聯劑之溶液中,使前述聚乙烯醇系樹脂交聯而由前述聚乙烯醇系樹脂層形成偏光件層,而得到交聯膜之步驟;及將前述交聯膜乾燥之步驟。 A method for producing a polarizing laminate film comprising: a base film obtained by dispersing a rubber component in a thermoplastic resin; and a polarizer layer laminated on one side of the base film, the production method The step of forming a polyvinyl alcohol-based resin layer on one side of a base film formed by dispersing a rubber component in a thermoplastic resin to obtain a laminated film; and extending the laminated film to a uniaxial direction to obtain an expanded film; a step of dyeing the polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye to obtain a dyed film; and immersing the polyvinyl alcohol-based resin layer of the dyed film in a solution containing a crosslinking agent to cause the aforementioned A step of crosslinking a polyvinyl alcohol-based resin to form a polarizer layer from the polyvinyl alcohol-based resin layer to obtain a crosslinked film, and drying the crosslinked film. 如申請專利範圍第1項所述之偏光性積層膜的製造方法,其中前述熱塑性樹脂為聚丙烯系樹脂。 The method for producing a polarizing laminate film according to claim 1, wherein the thermoplastic resin is a polypropylene resin. 如申請專利範圍第1項所述之偏光性積層膜的製造方法,其中前述熱塑性樹脂為丙烯單獨聚合物。 The method for producing a polarizing laminate film according to claim 1, wherein the thermoplastic resin is a propylene individual polymer. 如申請專利範圍第1至第3項中任一項所述之偏光性積層膜的製造方法,其中前述橡膠成分為含乙烯單元之共聚物。 The method for producing a polarizing laminate film according to any one of claims 1 to 3, wherein the rubber component is a copolymer containing an ethylene unit. 如申請專利範圍第4項所述之偏光性積層膜的製造方 法,其中前述橡膠成分為含有由乙烯單元、丙烯單元、丁烯單元、辛烯單元及苯乙烯單元所形成之群中選擇1種以上的單元之共聚物。 The manufacturer of the polarizing laminated film described in claim 4 of the patent application scope The rubber component is a copolymer containing one or more selected from the group consisting of an ethylene unit, a propylene unit, a butene unit, an octene unit, and a styrene unit. 如申請專利範圍第4項或第5項所述之偏光性積層膜的製造方法,其中,前述共聚物中之前述乙烯單元之含量為超過10重量%、未達90重量%。 The method for producing a polarizing laminate film according to the fourth aspect of the invention, wherein the content of the ethylene unit in the copolymer is more than 10% by weight and less than 90% by weight. 一種偏光性積層膜,具備在熱塑性樹脂中分散有橡膠成分之基材膜、及在前述基材膜之一邊面上積層之厚度為10μm以下之偏光件層。 A polarizing laminate film comprising a base material film in which a rubber component is dispersed in a thermoplastic resin, and a polarizer layer having a thickness of 10 μm or less laminated on one side of the base film.
TW101123697A 2011-07-06 2012-07-02 Method for producing polarizing laminate film TW201307069A (en)

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