TWI564138B - Polarizing laminated film and manufacturing method thereof, polarizing laminated film roll, and method for manufacturing polarizing plate - Google Patents
Polarizing laminated film and manufacturing method thereof, polarizing laminated film roll, and method for manufacturing polarizing plate Download PDFInfo
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- TWI564138B TWI564138B TW102103271A TW102103271A TWI564138B TW I564138 B TWI564138 B TW I564138B TW 102103271 A TW102103271 A TW 102103271A TW 102103271 A TW102103271 A TW 102103271A TW I564138 B TWI564138 B TW I564138B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, 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
- G02B5/3041—Polarisers, 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 comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, 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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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Description
本發明是有關使用於顯示裝置的偏光板等的偏光性積層膜及其製造方法。 The present invention relates to a polarizing laminated film used for a polarizing plate or the like of a display device, and a method for producing the same.
偏光板已廣泛的使用作為液晶顯示裝置中的偏光之供應元件,或偏光的檢測元件。雖然此偏光板過去以來使用在聚乙烯醇系樹脂形成的偏光膜上接著有三醋酸纖維素形成的保護膜者,但近年來隨著朝液晶顯示裝置的筆記型電腦或行動電話等行動裝置的發展,以及朝大型電視的發展等,而有薄質輕量化的要求。 A polarizing plate has been widely used as a supply element for polarized light in a liquid crystal display device, or a polarizing detecting element. Although this polarizing plate has been used in the past, a polarizing film formed of a polyvinyl alcohol-based resin is followed by a protective film formed of cellulose triacetate, but in recent years, with the development of a mobile computer such as a notebook computer or a mobile phone. As well as the development of large-scale TVs, there are requirements for thin and light weight.
這種薄型偏光板的製方法,已提案有在基材膜表面塗布含有聚乙烯醇系樹脂的溶液而設置樹脂層之後,經由延伸、然後染色,而獲得具有偏光子層的積層膜,將保護膜貼合在其上而得偏光性積層膜之後,自該偏光性積層膜剝離基材膜而得偏光板的方法(例如,參照日本特開2000-338329號公報)。 In the method for producing such a thin polarizing plate, it has been proposed to apply a solution containing a polyvinyl alcohol-based resin to a surface of a base film to form a resin layer, and then to obtain a laminated film having a polarizing layer by stretching and then dyeing, thereby protecting After the film is bonded to the polarizing laminate film, the substrate film is peeled off from the polarizing laminate film to obtain a polarizing plate (see, for example, JP-A-2000-338329).
專利文獻1:日本特開2000-338329號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-338329
在具有基材膜與偏光子層的積層膜上隔著接著劑層而貼合保護膜以得偏光性積層膜之際,如使用貼合滾輪進行連續性貼合時,接著劑會由偏光性積層膜的端部溢出,而污染到貼合滾輪,接著劑徐徐的繞至偏光性積層膜的背面時,也會使膜自身受到污染之不良情形。如以這種狀態將積層膜捲取成輪狀時,將因繞至積層膜背面的接著劑之影響而產生結塊(blocking)的不良情形,至使下一步驟中容易產生不能安定捲出的不適情況。另一方面,如將接著劑之供應量減量以使接著劑不溢出時,則接著劑不能充分到達偏光子的端部,以致端部的接著不安定,故不適合。 When the protective film is bonded to the laminated film having the base film and the polarizer layer via the adhesive layer to obtain a polarizing laminated film, when the bonding roller is used for continuous bonding, the adhesive is polarized. When the end portion of the laminated film overflows and contaminates the bonding roller, and the adhesive is slowly wound around the back surface of the polarizing laminated film, the film itself is contaminated. When the laminated film is wound into a wheel shape in this state, a problem of blocking occurs due to the influence of the adhesive wound around the back surface of the laminated film, so that the next step is likely to cause unsatisfactory roll-out. Discomfort. On the other hand, if the supply amount of the adhesive is decreased so that the adhesive does not overflow, the adhesive does not sufficiently reach the end of the polarizer, so that the end portion is not stable, which is not suitable.
本發明的目的是提供一種偏光性積層膜,其是依序積層基材膜、偏光子層、接著劑層、保護膜的長條狀之偏光性積層膜,是以安定的接著力使偏光子層與保護膜貼合,且接著劑不溢出的偏光性積層膜,將其捲取而成的偏光性積層膜捲,及偏光性積層膜之製造方法。 An object of the present invention is to provide a polarizing laminated film which is a long-length polarizing laminated film in which a base film, a polarizing layer, an adhesive layer, and a protective film are sequentially laminated, and a polarizing element is stabilized by a bonding force. A polarizing laminated film in which a layer is bonded to a protective film and which does not overflow the adhesive, a polarizing laminated film roll obtained by winding the film, and a method for producing a polarizing laminated film.
本發明包含下述的發明。 The present invention encompasses the invention described below.
[1]一種偏光性積層膜,其是依序積層有基材膜、偏光子層、接著劑層、保護膜的長條狀偏光性積層膜,在偏光性 積層膜的寬度方向中,偏光子層的兩端是位於基材膜及保護膜之兩端的內側,接著劑層的兩端是位於偏光子層之兩端的外側,且位於基材膜及保護膜之兩端的內側。 [1] A polarizing laminated film which is a long polarizing laminated film in which a base film, a polarizing layer, an adhesive layer, and a protective film are sequentially laminated, and is polarized. In the width direction of the laminated film, both ends of the polarizing sub-layer are located inside the both ends of the substrate film and the protective film, and both ends of the adhesive layer are located outside the both ends of the polarizing sub-layer, and are located on the substrate film and the protective film. The inside of both ends.
[2]如[1]中所述之偏光性積層膜,其中,上述偏光子層是已吸附配向二色性色素的聚乙烯醇系樹脂層,厚度為10μm以下。 [2] The polarizing laminated film according to [1], wherein the polarizing layer is a polyvinyl alcohol-based resin layer to which a dichroic dye has been adsorbed, and has a thickness of 10 μm or less.
[3]一種偏光性積層膜捲,其是將[1]中所述之偏光性積層膜捲繞而成的偏光性積層膜捲。 [3] A polarizing laminated film roll obtained by winding the polarizing laminated film described in [1].
[4]一種偏光性積層膜的製造方法,依序具有:在長條狀基材膜的至少一方的面形成聚乙烯醇系樹脂層而得到積層膜的積層步驟;將上述積層膜單軸延伸的延伸步驟;將已單軸延伸的積層膜之樹脂層以二色性色素染色的染色步驟;將已染色的積層膜之樹脂層浸漬在含有交聯劑之溶液中進行交聯而形成偏光子層的交聯步驟;以及在已交聯的積層膜中之偏光子層之與基材膜側的面為相反側的面隔著接著劑層而貼合保護膜之貼合步驟;在上述積層步驟中,於基材膜的寬度方向的兩方端部,設置有未形成前述聚乙烯醇系樹脂層的部份;在上述貼合步驟中,是以下述方式進行貼合:在貼合後的積層膜之寬度方向中,偏光子層的兩端位於保護膜之兩端的內側,接著劑層的兩端位於偏光子層之兩端的外側,且位於基材膜及保護膜的兩端之內側。 [4] A method for producing a polarizing laminated film, comprising: a step of forming a laminated film by forming a polyvinyl alcohol-based resin layer on at least one surface of the elongated substrate film; and uniaxially stretching the laminated film An extending step; a dyeing step of dyeing the resin layer of the uniaxially stretched laminated film with a dichroic dye; immersing the resin layer of the dyed laminated film in a solution containing a crosslinking agent to form a polarizer to form a polarizer a step of crosslinking the layer; and a bonding step of bonding the protective film to the surface of the polarizing layer of the crosslinked laminated film on the side opposite to the surface on the substrate film side via the adhesive layer; In the step, the portions in which the polyvinyl alcohol-based resin layer is not formed are provided at both end portions in the width direction of the base film; in the bonding step, the bonding is performed in the following manner: after lamination In the width direction of the laminated film, both ends of the polarizing sub-layer are located inside the two ends of the protective film, and both ends of the adhesive layer are located outside the both ends of the polarizing sub-layer, and are located inside the both ends of the substrate film and the protective film. .
[5]如[4]中所述之偏光性積層膜的製造方法,在上述貼合步驟之後,具有將基材膜與保護膜隔著接著劑層而直接接著的部份,自偏光性積層膜切斷而去除的去除步驟。 [5] The method for producing a polarizing laminate film according to [4], after the bonding step, the portion directly following the substrate film and the protective film via the adhesive layer, and the self-polarizing layer A removal step of film removal.
[6]一種偏光板的製造方法,其具有自藉由[5]中所述之方法所製造的偏光性積層膜將基材膜剝離而去除的剝離步驟。 [6] A method for producing a polarizing plate, comprising a peeling step of removing a base film by removing the base film from the polarizing laminate film produced by the method described in [5].
應用本發明,即可提供一種偏光性積層膜,其是偏光子層與保護膜以安定的接著力貼合,且在捲取之際不產生結塊等不良情況,可由該偏光性積層膜獲得偏光板。 According to the present invention, it is possible to provide a polarizing laminated film which is obtained by bonding a polarizing sublayer and a protective film with a stable adhesive force, and which does not cause agglomeration at the time of winding, and can be obtained from the polarizing laminated film. Polarizer.
11‧‧‧基材膜 11‧‧‧Base film
11a‧‧‧未塗布部份 11a‧‧‧Uncoated part
12‧‧‧樹脂層(偏光子層) 12‧‧‧ resin layer (polarized sublayer)
13‧‧‧接著劑層 13‧‧‧ adhesive layer
14‧‧‧保護膜 14‧‧‧Protective film
第1圖示意性表示本發明的偏光性積層膜之寬度方向的剖面之圖。 Fig. 1 is a view schematically showing a cross section in the width direction of the polarizing laminate film of the present invention.
第2圖表示本發明的偏光性積層膜之製造方法的流程圖。 Fig. 2 is a flow chart showing a method of producing a polarizing laminated film of the present invention.
第3圖示意性表示本發明的偏光性積層膜之製造方法的各製造步驟後之積層膜的上面斜視圖。 Fig. 3 is a perspective view showing the upper surface of the laminated film after each manufacturing step of the method for producing a polarizing laminated film of the present invention.
第1圖是示意性表示本發明的偏光性積層膜之寬度方向的剖面之圖。本發明的偏光性積層膜,是依序積層基材膜11、偏光子層12、接著劑層13、保護膜14的長條狀之偏光性積層膜。偏光性積層膜中,將基材膜11的寬度方向之兩端設為P1、偏光子層12的寬度方向之兩端為P2、接著劑層13的寬度方向之兩端為P3、保護膜14的寬度方向之兩端為P4時,偏光子層12的兩端P2是位於 基材膜11之兩端P1及保護膜14之兩端P4的更內側,接著劑層13的兩端P3是位於偏光子層12之兩端P2的更外側,且位於基材膜11之兩端P1及保護膜14之兩端P4的更內側。 Fig. 1 is a view schematically showing a cross section in the width direction of the polarizing laminate film of the present invention. The polarizing laminate film of the present invention is a long-length polarizing laminate film in which the base film 11, the polarizing layer 12, the adhesive layer 13, and the protective film 14 are sequentially laminated. In the polarizing laminated film, both ends of the base film 11 in the width direction are P1, both ends of the polarizing sub-layer 12 in the width direction are P2, both ends of the adhesive layer 13 in the width direction are P3, and the protective film 14 is provided. When both ends of the width direction are P4, both ends P2 of the polarizing sub-layer 12 are located. Both ends P1 of the base film 11 and the both ends P4 of the protective film 14 are further inside, and both ends P3 of the adhesive layer 13 are located outside the both ends P2 of the polarizing sub-layer 12, and are located at the outer side of the base film 11 The inner side of the end P1 and the protective film 14 are further inside.
在這種構成中,偏光子層12與保護膜14是藉由接著劑層13而以安定的接著力貼合,且不會產生接著劑由偏光性積層膜溢出而污染貼合滾輪等不良情形。 In such a configuration, the polarizer layer 12 and the protective film 14 are bonded together with a stable adhesive force by the adhesive layer 13, and there is no problem that the adhesive agent overflows from the polarizing laminated film and contaminates the bonding roller. .
基材膜11中使用的樹脂,可使用例如透明性、機械強度、熱安定性、延伸性等優異的熱可塑性樹脂,可配合該等樹脂的玻璃轉移溫度(Tg)或熔點(Tm)而選擇適宜的樹脂。熱可塑性樹脂之具體例,可列舉:例如聚烯烴系樹脂、聚酯系樹脂、環狀聚烯烴系樹脂(降冰片烯系樹脂)、(甲基)丙烯酸系樹脂、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,及此等樹脂的混合物、共聚合物等。 For the resin used for the base film 11, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, and elongation can be used, and the glass transition temperature (Tg) or melting point (Tm) of the resins can be selected. A suitable resin. Specific examples of the thermoplastic resin include, for example, a polyolefin resin, a polyester resin, a cyclic polyolefin resin (norbornene resin), a (meth)acrylic resin, a cellulose ester resin, and a poly Carbonate resin, polyvinyl alcohol resin, vinyl acetate resin, polyarylate resin, polystyrene resin, polyether oxime resin, polyfluorene resin, polyamine resin, polyimine A resin, a mixture of such resins, a copolymer, and the like.
基材膜11,可以是僅使用1種上述樹脂之單層,也可以是2種以上的樹脂摻混而成者。當然,也可以不是單層而是形成多層膜。 The base film 11 may be a single layer using only one type of the above resin, or may be a mixture of two or more types of resins. Of course, it is also possible to form a multilayer film instead of a single layer.
聚烯烴系樹脂,可列舉:例如聚乙烯、聚丙烯等,並宜為安定且易於高倍率延伸的樹脂。又,也可使用乙烯與丙烯共聚合而得的乙烯-聚丙烯共聚合物等。共 聚合也可為其他種類的單體,就可與丙烯共聚合的其他種單體而言,可列舉:例如乙烯、α-烯烴。α-烯烴,宜使用碳數4以上的α-烯烴,並以碳數4至10的α-烯烴更佳。碳數4至10的α-烯烴之具體例,可列舉:例如1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯等直鏈狀單烯烴類;3-甲基-1-丁烯、3-甲基-1-戊烯、4-甲基-1-戊烯等分枝狀單烯烴類;乙烯環己烷等。丙烯及可與丙烯共聚合的其他單體之共聚合物,可以是無規共聚合物,也可以是嵌段共聚合物。共聚合物中來自該其他單體的構成單元之含有率,可依照「高分子分析手冊」(1995年,紀伊國屋書店發行)的第616頁中所述之方法,進行紅外線(IR)光譜測定而求得。 The polyolefin-based resin may, for example, be polyethylene or polypropylene, and is preferably a resin which is stable and easily stretched at a high rate. Further, an ethylene-polypropylene copolymer obtained by copolymerizing ethylene and propylene or the like can also be used. Total The polymerization may be another type of monomer, and examples of other monomers copolymerizable with propylene include, for example, ethylene and an α-olefin. The α-olefin is preferably an α-olefin having 4 or more carbon atoms, and 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 chains such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene. a monoolefin; 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 with propylene may be a random copolymer or a block copolymer. In the copolymer, the content of the constituent unit derived from the other monomer can be measured by infrared (IR) spectroscopy according to the method described in the "Handbook of Polymer Analysis" (published by Kiyoshiya Shoten, 1995) on page 616. Seek.
在上述之中,構成丙烯系樹脂膜的丙烯系樹脂,宜使用丙烯的同元聚合物、丙烯-乙烯無規共聚合物、丙烯-1-丁烯無規共聚合物及丙烯-乙烯-1-丁烯無規共聚合物。 Among the above, the propylene-based resin constituting the propylene-based resin film preferably uses a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, and propylene-ethylene-1. - Butene random copolymer.
又,構成丙烯系樹脂膜的丙烯系樹脂之立體規則性,宜為實質的等規(isotactic)或間規(syndiotactic)。由具有實質的等規或間規之立體規則性的丙烯系樹脂形成之丙烯系樹脂膜,其使用性比較良好,同時在高溫環境下的機械強度亦優。 Further, the stereoregularity of the propylene resin constituting the propylene resin film is preferably a substantially isotactic or syndiotactic. The propylene-based resin film formed of a propylene-based resin having substantial isotactic or syndiotactic stereoregularity is relatively good in workability and excellent in mechanical strength in a high-temperature environment.
聚酯系樹脂,是具有酯鍵的聚合物,主要是多元羧酸與多元醇的聚縮合物。可使用的多元羧酸,主要是使用2價的二羧酸,可列舉:例如對苯二甲酸、間苯 二甲酸、對苯二甲酸二甲酯、萘二羧酸二甲酯等。又,可使用的多元醇,主要也是使用2價的二元醇,可列舉:例如丙二醇、丁二醇、新戊二醇、環己烷二甲醇等。 The polyester resin is a polymer having an ester bond, and is mainly a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. The polycarboxylic acid which can be used is mainly a divalent dicarboxylic acid, and examples thereof include terephthalic acid and m-benzene. Dicarboxylic acid, dimethyl terephthalate, dimethyl naphthalate or the like. Further, as the polyol which can be used, a divalent diol is mainly used, and examples thereof include propylene glycol, butanediol, neopentyl glycol, and cyclohexane dimethanol.
聚酯系樹脂的代表例,可舉出對苯二甲酸與乙二醇的共聚合物之聚對苯二甲酸乙二酯。聚對苯二甲酸乙二酯雖然是結晶性的樹脂,但結晶化處理前的狀態較易於進行延伸等處理。如有必要,可藉由延伸時或延伸後的熱處理等而結晶化處理。又,也可使用藉由復使聚對苯二甲酸乙二酯的骨架與其他種單體共聚合而使結晶性較為下降(或成為非晶性)的共聚合聚酯。這種樹脂之例,可適用例如將環己烷二甲醇、間苯二甲酸等共聚合者等。此等樹脂也因延伸性優異而適用。 A typical example of the polyester resin is polyethylene terephthalate which is a copolymer of terephthalic acid and ethylene glycol. Although polyethylene terephthalate is a crystalline resin, the state before the crystallization treatment is easier to handle and the like. If necessary, it can be crystallized by heat treatment or the like after stretching or stretching. Further, a copolymerized polyester in which the crystallinity of the polyethylene terephthalate is copolymerized with another monomer to reduce the crystallinity (or become amorphous) can be used. As an example of such a resin, for example, a copolymer of cyclohexanedimethanol or isophthalic acid can be applied. These resins are also suitable for their excellent elongation.
聚對苯二甲酸乙二酯及其共聚合物以外的具體的樹脂,可列舉:例如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、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸環己烷二甲酯、聚對萘二甲酸環己烷二甲酯等。也可適用此等的混合樹脂或共聚合物。 Specific examples of the resin other than polyethylene terephthalate and a copolymer thereof include, for example, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polypair. Propylene phthalate, poly(propylene naphthalate), poly(cyclohexanedimethylene terephthalate), poly(p-naphthalene dicarboxylate), and the like. These mixed resins or copolymers are also applicable.
環狀聚烯烴系樹脂,宜使用降冰片烯系樹脂。環狀聚烯烴系樹脂,是將環狀烯烴作為聚合單元而聚合之樹脂的總稱,可列舉:例如日本特開平1-240517號公報、日本特開平3-14882號公報、日本特開平3-122137號公報等中所述之樹脂。其具體例,可列舉:例如環狀烯烴的開環(共)聚合物、環狀烯烴的加成聚合物、環狀烯烴與 乙烯、丙烯等α-烯烴與其共聚合物(無規共聚合物為其代表)及此等樹脂經不飽和羧酸或其衍生物改質的接枝聚合物,以及此等樹脂的氫化物等。環狀烯烴之具體例,可列舉:例如降冰片烯系單體。 As the cyclic polyolefin resin, a norbornene-based resin is preferably used. The cyclic polyolefin-based resin is a general term for a resin obtained by polymerizing a cyclic olefin as a polymerization unit, and, for example, JP-A-1-240517, JP-A-3-14882, and JP-A 3-122137 The resin described in the publication No. Specific examples thereof include a ring-opened (co)polymer of a cyclic olefin, an addition polymer of a cyclic olefin, and a cyclic olefin. An α-olefin such as ethylene or propylene, a copolymer thereof (represented by a random copolymer), a graft polymer modified with an unsaturated carboxylic acid or a derivative thereof, and a hydride of the resin . Specific examples of the cyclic olefin include, for example, a norbornene-based monomer.
市面上已有販售環狀聚烯烴系樹脂的各種製品。其具體例,可列舉:例如Topas(註冊商標)(Ticona公司製)、Arton(註冊商標)(JSR(股)製)、ZEONOR(註冊商標)(日本Zeon(股)製)、ZEONEX(註冊商標)(日本Zeon(股)製)、Apel(註冊商標)(三井化學(股)製)。 Various products of cyclic polyolefin-based resins have been sold on the market. Specific examples thereof include, for example, Topas (registered trademark) (manufactured by Ticona Co., Ltd.), Arton (registered trademark) (manufactured by JSR), ZEONOR (registered trademark) (made by Zeon, Japan), and ZEONEX (registered trademark) (Japan Zeon Co., Ltd.), Apel (registered trademark) (Mitsui Chemical Co., Ltd.).
(甲基)丙烯酸系樹脂,可採用任何適切的(甲基)丙烯酸系樹脂。可列舉:例如聚甲基丙烯酸甲酯等聚(甲基)丙烯酸酯,甲基丙烯酸甲酯-(甲基)丙烯酸共聚合物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚合物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚合物、(甲基)丙烯酸甲酯-苯乙烯共聚合物(MS樹脂等)、具有脂環族烴基的聚合物(例如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚合物、甲基丙烯酸甲酯-(甲基)丙烯酸降冰片酯共聚合物等)。理想的是聚(甲基)丙烯酸甲酯等聚(甲基)丙烯酸C1至6烷酯。(甲基)丙烯酸系樹脂,是以使用甲基丙烯酸甲酯為主成分(50至100重量%,並宜為70至100重量%)的甲基丙烯酸甲酯系樹脂更佳。 As the (meth)acrylic resin, any suitable (meth)acrylic resin can be used. For example, poly(meth)acrylate such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymer, methyl methacrylate-(meth)acrylate copolymer, Methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methacrylic acid) Methyl ester-cyclohexyl methacrylate copolymer, methyl methacrylate-(meth)acrylic acid norbornene ester copolymer, etc.). Desirable is a poly(meth)acrylic acid C1 to 6 alkyl ester such as poly(methyl) acrylate. The (meth)acrylic resin is preferably a methyl methacrylate-based resin using methyl methacrylate as a main component (50 to 100% by weight, and preferably 70 to 100% by weight).
纖維素酯系樹脂,是纖維素與脂肪酸之酯。此種纖維素酯系樹脂之具體例,可列舉:例如纖維素三醋酸酯、纖維素二醋酸酯、纖維素三丙酸酯、纖維素二 丙酸酯等。又,可舉出此等樹脂的共聚合物或部份羥基經他種取代基等修飾之樹脂等。此等樹脂之中,以纖維素三醋酸酯尤佳。已有多種纖維素三醋酸酯的市售製品,在容易取得性或成本上亦有利。纖維素三醋酸酯的市售品,可列舉:例如Fujitac(註冊商標)TD80(富士軟片(股)製)、Fujitac(註冊商標)TD80UF(富士軟片(股)製)、Fujitac(註冊商標)TD80UZ(富士軟片(股)製)、Fujitac(註冊商標)TD40UZ(富士軟片(股)製)、KC8UX2M(Konica Minolta Opto(股)製)、KC4UY(Konica Minolta Opto(股)製)等。 A cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of such a cellulose ester-based resin include, for example, cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose II. Propionate and the like. Further, a copolymer of such a resin or a resin having a partial hydroxyl group modified with another substituent or the like may be mentioned. Among these resins, cellulose triacetate is particularly preferred. Commercially available products of various cellulose triacetates are also advantageous in terms of availability or cost. For the commercially available product of cellulose triacetate, for example, Fujitac (registered trademark) TD80 (made by Fujifilm Co., Ltd.), Fujitac (registered trademark) TD80UF (made by Fujifilm Co., Ltd.), Fujitac (registered trademark) TD80UZ (Fuji Film Co., Ltd.), Fujitac (registered trademark) TD40UZ (made by Fujifilm Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC4UY (Konica Minolta Opto Co., Ltd.), and the like.
聚碳酸酯系樹脂,是隔著碳酸酯基而使單體單元結合的聚合物形成之工程塑膠,是具有高耐衝擊性、耐熱性、難燃性的樹脂。又,因具有高透明性,故可適用於光學用途上。在光學用途中,為了降低光彈性係數,市面上也販售有已修飾聚合物骨架的稱為改質聚碳酸酯的樹脂,或已改良波長依存性的共聚合聚碳酸酯等,可適宜地使用。 The polycarbonate resin is an engineering plastic formed by a polymer in which a monomer unit is bonded via a carbonate group, and is a resin having high impact resistance, heat resistance, and flame retardancy. Moreover, since it has high transparency, it can be suitably used for optical use. In optical applications, in order to lower the photoelastic coefficient, a resin called modified polycarbonate having a modified polymer skeleton or a copolymerized polycarbonate having improved wavelength dependence may be commercially available. use.
此種聚碳酸酯樹脂已在市面上廣泛販售,例如Panlite(註冊商標)(帝人化成(股))、Iupilon(註冊商標)(三菱工程塑膠(股))、SD Polyca(註冊商標)(住友Dow(股))、Caliber(註冊商標)(Dow Chemical)等。 Such polycarbonate resins are widely sold in the market, such as Panlite (registered trademark) (Emperor Chemicals Co., Ltd.), Iupilon (registered trademark) (Mitsubishi Engineering Plastics Co., Ltd.), SD Polyca (registered trademark) (Sumitomo) Dow (share), Caliber (registered trademark) (Dow Chemical), and the like.
基材膜11中,除了上述熱可塑性樹脂之外,也可添加其他任何適切的添加劑。此種添加劑,可列舉:例如紫外線吸收劑、抗氧化劑、潤滑劑、可塑劑、離型劑、防著色劑、難燃劑、核劑、抗靜電劑、顏料及著色 劑等。上述例示的熱可塑性樹脂在基材膜中之含量,宜為50至100重量%,並以50至99重量%更佳,以60至98重量%又更佳,而以70至97重量%尤佳。如基材膜中的熱可塑性樹脂之含量未達50重量%時,有未能充分顯現熱可塑性樹脂原本具有的高透明性等之虞。 In the base film 11, in addition to the above thermoplastic resin, any other suitable additive may be added. Such additives may, for example, be ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, color preventives, flame retardants, nucleating agents, antistatic agents, pigments, and coloring. Agents, etc. The content of the above-exemplified thermoplastic resin 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, still more preferably from 70 to 97% by weight. good. When the content of the thermoplastic resin in the base film is less than 50% by weight, the high transparency and the like which the thermoplastic resin originally has may not be sufficiently exhibited.
基材膜11的厚度,雖然可適宜的決定,但一般就強度或使用性等作業性而言,其宜為1至500μm,並以1至300μm更佳,而以5至200μm又更佳。基材膜的厚度,是以5至150μm最佳。 The thickness of the base film 11 can be appropriately determined, but it is preferably from 1 to 500 μm, more preferably from 1 to 300 μm, even more preferably from 5 to 200 μm, in terms of workability such as strength and usability. The thickness of the substrate film is preferably 5 to 150 μm.
為了提高基材膜11與偏光子層12之間的密著性,可至少在形成偏光子層12之側的表面進行電暈處理、電漿處理、火焰處理等。又,也可在基材膜11的形成偏光子層12之側的表面設置底塗層(primer layer)、接著劑層等薄層,以提高密著性。在設置底塗層時,宜遍及基材膜11的表面整面而形成。又,此處所謂的基材膜11,是指不包含接著劑層或電暈處理層等者。 In order to improve the adhesion between the base film 11 and the polarizing sub-layer 12, at least the surface on the side on which the polarizing layer 12 is formed may be subjected to corona treatment, plasma treatment, flame treatment, or the like. Further, a thin layer such as a primer layer or an adhesive layer may be provided on the surface of the base film 11 on the side on which the polarizing layer 12 is formed to improve adhesion. When the undercoat layer is provided, it is preferably formed over the entire surface of the substrate film 11. Here, the base film 11 referred to herein means that the adhesive layer or the corona treatment layer is not included.
偏光子層12,宜為以二色性色素將聚乙烯醇系樹脂層染色而形成厚度10μm以下之層。偏光子層12中使用的聚乙烯醇系樹脂,適宜使用皂化度90至100莫耳%者,也可使用部份已經改質的改質聚乙烯醇。可列舉:例如以乙烯、丙烯等烯烴,丙烯酸、甲基丙烯酸、巴豆酸等不飽和羧酸,不飽和羧酸的烷酯、丙烯醯胺等將聚乙烯醇樹脂改質大約數%者等。聚乙烯醇系樹脂的平均聚合度 並無特別的限定,但宜為100至10,000,並以1,500至10,000更佳。 In the polarizing layer 12, it is preferable to dye the polyvinyl alcohol-based resin layer with a dichroic dye to form a layer having a thickness of 10 μm or less. The polyvinyl alcohol-based resin used in the polarizing layer 12 is preferably a saponification degree of 90 to 100 mol%, and a partially modified modified polyvinyl alcohol may also be used. For example, an olefin such as ethylene or propylene, an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, an alkyl ester of an unsaturated carboxylic acid or acrylamide may be used to modify the polyvinyl alcohol resin by about several %. Average polymerization degree of polyvinyl alcohol resin It is not particularly limited, but it is preferably from 100 to 10,000, and more preferably from 1,500 to 10,000.
可賦與這種特性的聚乙烯醇系樹脂,可列舉:例如Kuraray(股)製PVA124(皂化度:98.0至99.0莫耳%)、PVA117(皂化度:98.0至99.0莫耳%)、PVA624(皂化度:95.0至96.0莫耳%)、PVA617(皂化度:94.5至95.5莫耳%)等;例如日本合成化學工業(股)製的AH-26(皂化度:97.0至98.8莫耳%)、AH-22(皂化度:97.5至98.5莫耳%)、NH-18(皂化度:98.0至99.0莫耳%)、N-300(皂化度:98.0至99.0莫耳%)等;例如日本VAM&POVAL(股)的JF-17(皂化度:98.0至99.0莫耳%)、JF-17L(皂化度:98.0至99.0莫耳%)、JF-20(皂化度:98.0至99.0莫耳%)等可適宜使用。 Examples of the polyvinyl alcohol-based resin to which such a property can be imparted are, for example, PVA124 (saponification degree: 98.0 to 99.0 mol%) manufactured by Kuraray Co., Ltd., PVA117 (saponification degree: 98.0 to 99.0 mol%), PVA624 ( Saponification degree: 95.0 to 96.0 mol%), PVA617 (saponification degree: 94.5 to 95.5 mol%), etc.; for example, AH-26 (saponification degree: 97.0 to 98.8 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., AH-22 (saponification degree: 97.5 to 98.5 mol%), NH-18 (saponification degree: 98.0 to 99.0 mol%), N-300 (saponification degree: 98.0 to 99.0 mol%), etc.; for example, Japan VAM&POVAL ( JF-17 (saponification degree: 98.0 to 99.0 mol%), JF-17L (saponification degree: 98.0 to 99.0 mol%), JF-20 (saponification degree: 98.0 to 99.0 mol%), etc. use.
保護膜14,可以是不具有光學功能的單純保護膜,也可以是同時具有所謂相位差膜或亮度提高膜的光學功能之保護膜。保護膜14的材質雖然無特別的限定,但可列舉:例如環狀聚烯烴系樹脂膜,由如三醋酸纖維素、二醋酸纖維素的樹脂形成之醋酸纖維素系樹脂膜,由如聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯之樹脂形成的聚酯系樹脂膜,聚碳酸酯系樹脂膜、丙烯酸系樹脂膜、聚丙烯系樹脂膜等以往即廣泛使用在該領域中的膜。 The protective film 14 may be a simple protective film having no optical function, or may be a protective film having an optical function of a so-called retardation film or a brightness enhancement film. The material of the protective film 14 is not particularly limited, and examples thereof include a cyclic polyolefin resin film, and a cellulose acetate resin film formed of a resin such as cellulose triacetate or cellulose diacetate. Polyester resin film formed of resin of ethylene phthalate, polyethylene naphthalate or polybutylene terephthalate, polycarbonate resin film, acrylic resin film, polypropylene resin film Films in this field have been widely used in the past.
環狀聚烯烴系樹脂,可使用適宜的市售品,例如Topas(註冊商標)(Ticona公司製)、Arton(註冊商 標)(JSR(股)製)、ZEONOR(註冊商標)(日本Zeon(股)製)、ZEONEX(註冊商標)(日本Zeon(股)製)、Apel(註冊商標)(三井化學(股)製)。將此種環狀聚烯烴系樹脂製膜而成膜之時,可適宜使用溶劑鑄造法、熔融擠壓法等已知的方法。又,也可使用Esushina(註冊商標)(積水化學工業(股)製)、SCA40(積水化學工業(股)製)、ZEONOR(註冊商標)膜(Optes(股)製)等已預先製膜的環狀聚烯烴系樹脂製的膜之市售品。 As the cyclic polyolefin resin, a commercially available product such as Topas (registered trademark) (Ticona Co., Ltd.), Arton (registered company) can be used. Standard) (JSR (share) system), ZEONOR (registered trademark) (Japan Zeon), ZEONEX (registered trademark) (Japan Zeon), Apel (registered trademark) (Mitsui Chemical Co., Ltd.) ). When a film of such a cyclic polyolefin resin is formed into a film, a known method such as a solvent casting method or a melt extrusion method can be suitably used. In addition, pre-formed films such as Esushina (registered trademark) (made by Sekisui Chemical Co., Ltd.), SCA40 (made by Sekisui Chemical Co., Ltd.), and ZEONOR (registered trademark) (Optes) can be used. A commercially available product of a film made of a cyclic polyolefin resin.
環狀聚烯烴系樹脂膜,可以是已單軸延伸或二軸延伸的膜。因延伸,而可對環狀聚烯烴系樹脂膜賦與任意的相位差值。通常是一邊捲出膜捲(film roll)時一邊連續的進行延伸,可在加熱爐中使其朝滾輪的進行方向、垂直於該進行方向的方向,或其兩方向延伸。加熱爐的溫度,通常是由環狀聚烯烴系樹脂的玻璃轉移溫度附近至玻璃轉移溫度+100℃的範圍。延伸的倍率,通常在每一個方向上是1.1至6倍,並宜為1.1至3.5倍。 The cyclic polyolefin resin film may be a film that has been uniaxially stretched or biaxially stretched. Due to the extension, an arbitrary phase difference value can be imparted to the cyclic polyolefin resin film. Usually, the film roll is continuously stretched while being rolled up, and may be extended in the direction of the progress of the roller, in the direction perpendicular to the direction of progress, or both directions in the heating furnace. The temperature of the heating furnace is usually in the range from the vicinity of the glass transition temperature of the cyclic polyolefin resin to the glass transition temperature + 100 °C. The magnification of the extension is usually 1.1 to 6 times in each direction, and is preferably 1.1 to 3.5 times.
環狀聚烯烴系樹脂膜,因表面活性差,故一般在與偏光子層接著的表面上,宜為已經電漿處理、電暈處理、紫外線照射處理、火焰處理、皂化處理等表面處理者。其中並以可比較容易實施的電漿處理、電暈處理為理想。 Since the cyclic polyolefin-based resin film has poor surface activity, it is generally preferred that the surface of the cyclic polyolefin-based resin film is subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, or saponification treatment on the surface adjacent to the polarizing layer. Among them, plasma treatment and corona treatment which are relatively easy to implement are desirable.
醋酸纖維素系樹脂膜,可使用適宜的市售品,例如Fujitac(註冊商標)TD80(富士軟片(股)製)、Fujitac(註冊商標)TD80UF(富士軟片(股)製)、Fujitac(註冊商標) TD80UZ(富士軟片(股)製)、Fujitac(註冊商標)TD40UZ(富士軟片(股)製)、KC8UX2M(Konica Minolta Opto(股)製)、KC4UY(Konica Minolta Opto(股)製)等。 For the cellulose acetate-based resin film, a commercially available product such as Fujitac (registered trademark) TD80 (Fuji Film Co., Ltd.), Fujitac (registered trademark) TD80UF (Fuji Film Co., Ltd.), Fujitac (registered trademark) can be used. ) TD80UZ (Fuji Film Co., Ltd.), Fujitac (registered trademark) TD40UZ (Fuji Film Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC4UY (Konica Minolta Opto Co., Ltd.), and the like.
醋酸纖維素系樹脂膜的表面上也可形成液晶層等,以改良視野角特性。又,醋酸纖維素系樹脂膜也可以是已延伸之膜,以賦與相位差。醋酸纖維素系樹脂膜通常施予皂化處理,以提高與偏光膜的接著性。皂化處理,可採用將其浸漬在如氫氧化鈉或氫氧化鉀的鹼性水溶液中之方法。 A liquid crystal layer or the like may be formed on the surface of the cellulose acetate-based resin film to improve the viewing angle characteristics. Further, the cellulose acetate-based resin film may be an extended film to impart a phase difference. The cellulose acetate based resin film is usually subjected to a saponification treatment to improve adhesion to the polarizing film. The saponification treatment may be carried out by immersing it in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
在如上述的保護膜14之表面上,也可形成硬塗層、防眩層、防止反射層等光學層。在保護膜14的表面上形成此等光學層之方法,並無特別的限定,可使用已周知的方法。 On the surface of the protective film 14 as described above, an optical layer such as a hard coat layer, an antiglare layer, and an antireflection layer may be formed. The method of forming these optical layers on the surface of the protective film 14 is not particularly limited, and a well-known method can be used.
就薄型化的要求而言,保護膜14的厚度宜為薄者,宜為88μm以下,並以48μm以下更佳。但如其太薄時,則會使強度降低以致加工性差,故宜為5μm以上。 The thickness of the protective film 14 is preferably as thin as required for the thickness reduction, and is preferably 88 μm or less and more preferably 48 μm or less. However, if it is too thin, the strength is lowered to cause poor workability, and therefore it is preferably 5 μm or more.
形成使保護膜14與偏光子層12貼合的接著劑層13時使用的接著劑,可列舉:例如使用聚乙烯醇系樹脂水溶液、水系二液型胺酯系乳液接著劑等的水系接著劑。在使用藉皂化處理等而經親水化處理的醋酸纖維素系樹脂膜作為保護膜14時,可適宜使用聚乙烯醇系樹脂水溶液作為與偏光子層12貼合用的水系接著劑。在使用聚乙烯 醇系樹脂作為接著劑時,除了將醋酸乙烯酯的同元聚合物之聚醋酸乙烯酯進行皂化處理而得之乙烯醇同元聚合物之外,尚有將醋酸乙烯酯與可與其共聚合的他種單體之共聚合物進行皂化處理而得的乙烯醇系共聚合物,另外也有將此等的羥基經部份改質的改質聚乙烯醇系聚合物等。水系接著劑中,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、鋅化合物等作為添加劑。 In the adhesive agent used for forming the adhesive layer 13 which bonds the protective film 14 and the polarizer layer 12, water-based adhesive agent, such as a polyvinyl-alcohol-type resin aqueous solution, and an aqueous two-liquid type . When a cellulose acetate-based resin film which has been hydrophilized by a saponification treatment or the like is used as the protective film 14, a polyvinyl alcohol-based resin aqueous solution can be suitably used as a water-based adhesive for bonding to the polarizing sub-layer 12. Using polyethylene When an alcohol resin is used as an adhesive, in addition to a vinyl alcohol homopolymer obtained by saponifying a polyvinyl acetate of a homopolymer of vinyl acetate, vinyl acetate may be copolymerized therewith. A vinyl alcohol-based copolymer obtained by saponifying a copolymer of a monomer, and a modified polyvinyl alcohol-based polymer obtained by partially modifying such a hydroxyl group. A polyvalent aldehyde, a water-soluble epoxy compound, a melamine-based compound, a zirconia compound, a zinc compound or the like may be added as an additive to the aqueous binder.
又,使偏光子層12與保護膜14貼合之際的接著劑,也可使用光硬化性接著劑。此處所指的光硬化性接著劑,是可以紫外線等活性能量線照射而硬化的接著劑,可列舉:例如含有聚合性化合物及光聚合起始劑者、含有光反應性樹脂者、含有黏著劑(binder)樹脂及光反應***聯劑者等。前述聚合性化合物,可列舉:例如光硬化性環氧系單體、光硬化性丙烯酸系單體、光硬化性胺酯系單體等光聚合性單體,或來自該等單體的寡聚物等。前述光聚合起始劑,可列舉:例如含有經紫外線等活性能量線照射而產生所謂中性自由基、陰離子性自由基、陽離子性自由基的活性種之物質者。含有聚合性化合物及光聚合起始劑的光硬化性接著劑,宜為含有光硬化性環氧系單體及光陽離子聚合起始劑者。 Further, a photocurable adhesive can also be used as the adhesive for bonding the polarizing sub-layer 12 to the protective film 14. The photocurable adhesive agent to be used herein is an adhesive which can be cured by irradiation with an active energy ray such as ultraviolet rays, and includes, for example, a polymerizable compound and a photopolymerization initiator, and a photoreactive resin, and an adhesive. (binder) resin and photoreactive cross-linking agent, etc. The polymerizable compound may, for example, be a photopolymerizable monomer such as a photocurable epoxy monomer, a photocurable acrylic monomer or a photocurable amine ester monomer, or an oligomer derived from the monomers. Things and so on. The photopolymerization initiator may be, for example, a substance containing an active species which is irradiated with an active energy ray such as ultraviolet rays to generate a so-called neutral radical, an anionic radical or a cationic radical. The photocurable adhesive containing a polymerizable compound and a photopolymerization initiator is preferably a photocurable epoxy monomer and a photocationic polymerization initiator.
本發明的偏光性積層膜捲,是將長條狀的前述積層膜捲取而製作成。本發明的偏光性積層膜捲,由於不會自前述積層膜溢出接著劑,故可抑制因溢出的接著 劑的影響而產生的結塊。 The polarizing laminated film roll of the present invention is produced by winding up the long laminated film. In the polarizing laminated film roll of the present invention, since the adhesive agent does not overflow from the laminated film, the overflow due to the overflow can be suppressed. Agglomeration caused by the influence of the agent.
第2圖,是表示本發明的偏光性積層膜之製造方法的流程圖。第3圖,是示意性表示本發明的偏光性積層膜之製造方法中的各製造步驟後之積層膜的上面斜視圖。本發明的製造方法,是依序具有下述步驟的偏光性積層膜之製造方法:在長條狀基材膜11的至少一方之面形成聚乙烯醇系樹脂層12而得積層膜的積層步驟(S10)、將上述積層膜單軸延伸的延伸步驟(S20)、以二色性色素將已單軸延伸的積層膜之樹脂層染色的染色步驟(S30)、將已染色的積層膜之樹脂層浸漬在含有交聯劑之溶液中進行交聯而形成偏光子層的交聯步驟(S40),與已交聯的積層膜中之偏光子層的基材膜側之面相反側之面隔著接著劑層而貼合保護膜14之貼合步驟(S50)。貼合步驟(S50)中,宜在一對貼合滾輪間,進行以使積層膜與保護膜14重疊的方式進行送入貼合。 Fig. 2 is a flow chart showing a method of producing the polarizing laminated film of the present invention. Fig. 3 is a top perspective view schematically showing a laminated film after each manufacturing step in the method for producing a polarizing laminated film of the present invention. The production method of the present invention is a method for producing a polarizing laminate film which has the following steps: a step of forming a laminated film by forming a polyvinyl alcohol-based resin layer 12 on at least one surface of the elongated substrate film 11. (S10), a step (S20) of extending the laminated film uniaxially, a dyeing step of dyeing the resin layer of the laminated film which has been uniaxially stretched with a dichroic dye (S30), and a resin of the laminated film which has been dyed a layer is immersed in a solution containing a crosslinking agent to crosslink to form a polarizing layer, and a crosslinking step (S40) is formed on the side opposite to the surface of the substrate layer side of the polarizing layer in the laminated film. The bonding step of the protective film 14 is applied to the adhesive layer (S50). In the bonding step (S50), it is preferable to carry out the feeding and bonding so that the laminated film and the protective film 14 overlap each other between the pair of bonding rollers.
在積層步驟(S10)中,第3圖(a)中所示之基材膜11中,如同第3圖(b)所示僅在點線P2的更內側之區域中形成樹脂層12,在點線P2的更外側之區域設置不形成聚乙烯醇系樹脂層的部份11a。這種樹脂層12的形成法,可舉例如在基材膜11中的點線P2的更外側之區域不塗布含有聚乙烯醇系樹脂的溶液,而僅在點線P2的更內側之區域中塗布含有聚乙烯醇系樹脂的溶液之後,使其乾燥的方法。經由如此方式設置不形成樹脂層12的部份(未塗 布部份)11a後,可使接著劑在貼合步驟(S50)中充分的供給至偏光子層的端部而接著劑不會繞至背面,而得良好的偏光性積層膜。又,由於未塗布部份11a的設置,在使積層膜乾燥之際,可抑制使基材膜11的兩端反轉到含有前述樹脂的溶液之塗布面側的現象。規定未塗布部份11a的點線P2,宜決定在距離基材膜11的寬度方向之兩端0.5cm以上,並以1cm以上更佳,而以2cm以上的內側區域內又更佳。藉由決定在這樣的數值範圍,而可更確實獲得防止接著劑繞至背面之效果。又,點線P2的位置,宜為距離基材膜11的寬度方向之兩端50cm以下的區域內,並以30cm以下的區域內更佳,而以20cm以下的區域內又更佳。 In the lamination step (S10), in the base film 11 shown in Fig. 3(a), as shown in Fig. 3(b), the resin layer 12 is formed only in the region of the inner side of the dotted line P2. A portion 11a where the polyvinyl alcohol-based resin layer is not formed is provided in a region on the outer side of the dotted line P2. In the method of forming the resin layer 12, for example, a solution containing a polyvinyl alcohol-based resin is not applied to a region outside the dotted line P2 in the base film 11, but only in a region of the inner side of the dotted line P2. A method of applying a solution containing a polyvinyl alcohol-based resin and then drying it. The portion where the resin layer 12 is not formed is disposed in such a manner (uncoated After the cloth portion 11a, the adhesive can be sufficiently supplied to the end portion of the polarizer layer in the bonding step (S50), and the adhesive agent does not wrap around the back surface, and a good polarizing laminated film can be obtained. In addition, when the laminated film is dried, the phenomenon that the both ends of the base film 11 are reversed to the coated surface side of the solution containing the resin can be suppressed. The dotted line P2 of the uncoated portion 11a is preferably determined to be 0.5 cm or more from both ends in the width direction of the base film 11, and more preferably 1 cm or more, and more preferably 2 cm or more in the inner region. By determining such a numerical range, the effect of preventing the adhesive from being wound around the back surface can be more surely obtained. Further, the position of the dotted line P2 is preferably in a region of 50 cm or less from both ends in the width direction of the base film 11, and is preferably in a region of 30 cm or less, and more preferably in a region of 20 cm or less.
又,在貼合步驟(S50)中,如第3圖(c)所示,是將接著劑層如同覆蓋偏光子層12整體的方式並以直到偏光子層12的寬度方向之兩端的更外側之點線P3為止的方式設置,隔著此接著劑層而貼合保護膜14。規定接著劑層的區域之點線P3,宜決定在距離偏光子層的兩端之外側,例如0.5cm以上50cm以下的區域內。 Further, in the bonding step (S50), as shown in Fig. 3(c), the adhesive layer is formed so as to cover the entire polarizing layer 12 and is further outward from both ends in the width direction of the polarizing sub-layer 12. The protective film 14 is bonded to the dot line P3 so as to be interposed between the adhesive layers. The dotted line P3 defining the region of the adhesive layer is preferably determined to be outside the both ends of the polarizing sub-layer, for example, in a region of 0.5 cm or more and 50 cm or less.
在欲將接著劑層的塗布範圍調整至設定的寬度時,只要調整接著劑的供應量或塗布量、來自壓著裝置的外加壓力(使用貼合滾輪時,是貼合滾輪間的距離)、膜之搬送速度等即可。又,在以長條形的膜進行連續貼合時,可在膜之間連續供應接著劑,另一方面,一邊利用吸取(suction)裝置連續吸引從隔著接著劑層而積層的膜寬度方向端部所溢出的過量接著劑,一邊實施貼合步驟(S50), 此時,也可藉由調整接著劑的吸引量而調整接著劑層的寛度。 When the coating range of the adhesive layer is to be adjusted to the set width, the supply amount or the coating amount of the adhesive, the applied pressure from the pressing device (the distance between the bonding rollers when the bonding roller is used), The transport speed of the film can be used. Further, when the film is continuously bonded by the long film, the adhesive can be continuously supplied between the films, and the film width direction which is laminated from the adhesive layer is continuously suctioned by the suction device. The excess adhesive overflowing at the end portion is subjected to a bonding step (S50), At this time, the twist of the adhesive layer can also be adjusted by adjusting the amount of attraction of the adhesive.
保護膜14,是選擇寬度方向之長度比接著劑層的寬度方向之長度還長者,可以保護膜14覆蓋接著劑層整體。即,在貼合後的積層膜之寬度方向中,以使偏光子層的兩端位於保護膜之兩端的更內側,接著劑層的兩端位於偏光子層之兩端的更外側,且位於基材膜及保護膜的兩端的更內側的方式貼合。保護膜14的寬度方向之長度,只要是比接著劑層的寬度方向之長度更長即無限制,但宜選擇成比偏光子層的寬度方向之長度長0.5cm以上,並以1cm以上更佳,而以2cm以上又更佳。 The protective film 14 is selected such that the length in the width direction is longer than the length in the width direction of the adhesive layer, and the protective film 14 covers the entire adhesive layer. That is, in the width direction of the laminated film after bonding, both ends of the polarizer layer are located on the inner side of both ends of the protective film, and both ends of the adhesive layer are located outside the both ends of the polarizing layer, and are located at the base The material film and the protective film are bonded to each other on the inner side. The length of the protective film 14 in the width direction is not limited as long as it is longer than the length of the adhesive layer in the width direction, but is preferably selected to be longer than the length of the polarizing layer in the width direction by 0.5 cm or more, and more preferably 1 cm or more. , and more preferably 2cm or more.
藉由本發明的製造方法,在貼合步驟(S50)中,因以接著劑層覆蓋偏光子層整體,故可使偏光子層與保護膜以安定的接著力貼合,並且,由於接著劑層的寬度方向之兩端,是設置成位於基材膜及保護膜之兩端的更內側,故可使接著劑不溢出而可防止貼合滾輪及偏光性積層膜等受到接著劑之污染。 According to the manufacturing method of the present invention, in the bonding step (S50), since the entire polarizing layer is covered with the adhesive layer, the polarizing sub-layer and the protective film can be bonded with a stable adhesive force, and, due to the adhesive layer Both ends of the width direction are disposed on the inner side of both ends of the base film and the protective film, so that the adhesive can be prevented from being contaminated by the adhesive without causing the adhesive to overflow.
經由上述步驟而製造的偏光性積層膜,宜捲取並構成偏光性積層膜捲。偏光性積層膜中,由於抑制接著劑之污染,故可在捲取之際防止結塊的產生,所以也不會有在其後的步驟產生捲出困難等不良情形。 The polarizing laminated film produced through the above steps is preferably wound up to constitute a polarizing laminated film roll. In the polarizing laminated film, since the contamination of the adhesive is suppressed, the occurrence of agglomeration can be prevented at the time of winding, and therefore there is no problem that the winding step is difficult in the subsequent steps.
在貼合步驟(S50)之後,可復具有:以與偏光子層12的兩端相同的位置或比偏光子層12的兩端稍微內側的位置切斷偏光性積層膜而去除端部,並且將基材膜 剝離的剝離步驟。可利用由該剝離步驟而得的膜作為偏光板。偏光性積層膜的切斷,宜為可以滾輪等將長條連續處理的方法。雖然並無特別的限定方法,但一般可適宜使用例如稱為切割器(slitter)的方法等。 After the bonding step (S50), the polarizing laminated film may be cut at the same position as the both ends of the polarizing sub-layer 12 or a position slightly inside the both ends of the polarizing sub-layer 12 to remove the end portion, and Substrate film Stripping step of stripping. A film obtained by the peeling step can be used as a polarizing plate. The cutting of the polarizing laminated film is preferably a method in which a long strip can be continuously treated by a roller or the like. Although there is no particular limitation, a method called, for example, a slitter can be suitably used.
切割器之例,可舉出:例如利用稱為剃刀片(razor blade)的剃刀之方法。即使同樣是使用剃刀片之方法,也有特別不設置備用導溝(backup guide)而在空中切割的中空切器,或在切溝的滾輪上裝入刀片作為備用導溝(backup guide)以使切割的蛇行安定之溝滾輪法等。其他尚有使用二片稱為剪刀片(shear blade)的圓形刀,配合膜的運送一邊旋轉一邊以上刀接壓在下刀而切割的方法、或將剪刀片或稱為截痕刀(score blade)的刀壓附在燒附滾輪等而切割的方法,另外,可使用將二片剪刀片組合以如同剪刀般一邊裁剪一邊切割的方法等。其中,適宜使用可輕易變更膜的切割位置且容易安定行走的方法之「使用剃刀片的溝滾輪法」等。 An example of a cutter is, for example, a method using a razor called a razor blade. Even if the method of using the razor blade is used, there is a hollow cutter that is cut in the air without providing a backup guide, or a blade is placed on the roller of the groove as a backup guide to cut the blade. The serpent is a stable ditch roller method. Others use two circular knives called shear blades, which are used to rotate while the film is transported while the upper knives are pressed against the lower knives, or the scissor blades are called score blades. The knife press is attached to a method of cutting by burning a roller or the like, and a method of combining two scissor blades to cut while cutting like a scissors can be used. Among them, a "groove roller method using a razor blade" or the like which can easily change the cutting position of the film and is easy to move is suitable.
也可在上述的積層步驟(S10)中,使基材膜的兩面形成聚乙烯醇系樹脂層,在貼合步驟(S50)中,使二個偏光子層分別貼合保護膜。以下,詳細說明各步驟。 In the above-described lamination step (S10), a polyvinyl alcohol-based resin layer may be formed on both surfaces of the base film, and in the bonding step (S50), the two polarizing sub-layers may be bonded to the protective film. Hereinafter, each step will be described in detail.
此步驟中,是在基材膜的至少一面形成聚乙烯醇系樹脂層而得積層膜。前述樹脂層的形成方法,可舉出:例如在基材膜的至少一面塗布含有聚乙烯醇系樹脂的溶液之後,使其乾燥的方法。適於基材膜、聚乙烯醇系 樹脂的材料,是如偏光性積層膜的說明中所述者。基材膜,宜使用可在適於聚乙烯醇系樹脂的延伸之溫度範圍延伸者。 In this step, a polyvinyl alcohol-based resin layer is formed on at least one surface of the base film to obtain a laminated film. The method of forming the resin layer is, for example, a method in which a solution containing a polyvinyl alcohol-based resin is applied to at least one surface of a base film and then dried. Suitable for substrate film, polyvinyl alcohol The material of the resin is as described in the description of the polarizing laminated film. The substrate film is preferably one which can be extended in a temperature range suitable for elongation of the polyvinyl alcohol-based resin.
乾燥後的樹脂層之厚度,宜為超過3μm且在30μm以下之厚度,並且宜為5至20μm。如為3μm以下時,則延伸後變得過薄而使染色性明顯下降,如超過30μm時,有時會使最後獲得的偏光子層之厚度超過10μm,故不佳。 The thickness of the dried resin layer is preferably more than 3 μm and a thickness of 30 μm or less, and is preferably 5 to 20 μm. When it is 3 μm or less, the dyeability is remarkably lowered after stretching, and when it exceeds 30 μm, the thickness of the finally obtained polarizing layer may exceed 10 μm, which is not preferable.
樹脂層,宜將使聚乙烯醇系樹脂的粉末溶解在良溶劑中而得的聚乙烯醇系樹脂溶液塗布在基材膜的一表面上,使溶劑蒸發、乾燥而形成。藉由此方式而形成樹脂層,可能薄質的形成。將聚乙烯醇系樹脂溶液塗布在基材層的方法,可由線棒塗布法、逆向塗布(reverse coating)、凹板塗布等滾輪塗法,模壓塗布法、逗點式塗布法(comma coating)、唇嘴塗布(lip coat)法、旋轉塗布法、網版塗布法、噴泉塗布(fountain coat)法、浸塗法、噴塗法等已知的方法中適宜的選擇採用。乾燥溫度例如為50至200℃,並宜為60至150℃。乾燥時間例如為2至20分鐘。 In the resin layer, a polyvinyl alcohol-based resin solution obtained by dissolving a powder of a polyvinyl alcohol-based resin in a good solvent is applied onto one surface of a base film, and the solvent is evaporated and dried. By forming the resin layer in this way, it is possible to form a thin film. The method of applying the polyvinyl alcohol-based resin solution to the base material layer may be a roll coating method such as a bar coating method, a reverse coating method or a gravure coating method, a die coating method, a comma coating method, or the like. A known method such as a lip coat method, a spin coating method, a screen coating method, a fountain coat method, a dip coating method, or a spray coating method is suitably used. The drying temperature is, for example, 50 to 200 ° C, and preferably 60 to 150 ° C. The drying time is, for example, 2 to 20 minutes.
又,可在基材膜與聚乙烯醇系樹脂層之間設置底塗層,以提高基材膜與聚乙烯醇系樹脂之間的密著性。就密著性而言,底塗層宜為由在聚乙烯醇系樹脂中含有交聯劑等的組成物形成者。 Further, an undercoat layer may be provided between the base film and the polyvinyl alcohol-based resin layer to improve the adhesion between the base film and the polyvinyl alcohol-based resin. In terms of adhesion, the undercoat layer is preferably formed of a composition containing a crosslinking agent or the like in a polyvinyl alcohol-based resin.
此處,是將基材膜及樹脂層形成的積層膜 單軸延伸。並宜以成為超過5倍且17倍以下的延伸倍率之方式單軸延伸。而以成為超過5倍且8倍以下的延伸倍率之方式單軸延伸更佳。如延伸倍率為5倍以下時,則因聚乙烯醇系樹脂形成的樹脂層未能充分配向,結果有時會產生偏光子層的偏光度不夠高之不良情形。另一方面,如延伸倍率超過17倍時,容易使延伸時的積層膜產生破裂,同時使延伸膜的厚度成為必要以上的薄,而有後續步驟的加工性、處理性降低之虞。延伸步驟(S20)中的延伸處理,並不限定在一階段式的延伸,也可進行多階段式延伸。此時,雖然也可在延伸步驟(S20)中進行第二階段以後的延伸處理,但也可與染色步驟(S30)或交聯步驟(S40)中的處理同時進行。如此的以多階段進行延伸時,以延伸處理的所有階段總和成為超過5倍的延伸倍率之方式進行延伸處理。 Here, it is a laminated film in which a base film and a resin layer are formed. Single axis extension. It is preferable to uniaxially extend in such a manner that the stretching ratio is more than 5 times and 17 times or less. In the case of a stretching ratio of more than 5 times and 8 times or less, uniaxial stretching is more preferable. When the stretching ratio is 5 times or less, the resin layer formed of the polyvinyl alcohol-based resin is not sufficiently aligned, and as a result, the degree of polarization of the polarizing sub-layer may not be sufficiently high. On the other hand, when the stretching ratio is more than 17 times, the laminated film at the time of stretching is likely to be broken, and the thickness of the stretched film is made thinner than necessary, and the workability and handleability in the subsequent step are lowered. The extension processing in the extension step (S20) is not limited to the one-stage extension, and the multi-stage extension can also be performed. At this time, although the stretching process after the second stage may be performed in the extending step (S20), it may be performed simultaneously with the processing in the dyeing step (S30) or the crosslinking step (S40). When such a stretching is performed in multiple stages, the stretching process is performed in such a manner that the total of all the stages of the stretching process is more than 5 times the stretching ratio.
延伸步驟(S20)中,可實施針對積層膜的長度方向實施的縱向延伸處理,或針對寬度方向延伸的橫向延伸處理等。縱向延伸方式,可列舉:例如滾輪間延伸方法、壓縮延伸方法等,橫向延伸方式,可列舉:例如拉幅(tenter)法等。 In the stretching step (S20), a longitudinal stretching treatment for the longitudinal direction of the laminated film, a lateral stretching treatment for extending in the width direction, or the like can be performed. Examples of the longitudinal stretching method include, for example, a method of extending between rollers, a method of compressing and stretching, and the like, and examples of the lateral stretching method include, for example, a tenter method.
又,延伸處理可採用濕潤式延伸方法與乾式延伸方法的任何一種方式,但使用乾式延伸方法者,因可從廣範圍選擇延伸積層膜時的溫度而佳 Further, the stretching treatment may be any one of a wet stretching method and a dry stretching method, but a dry stretching method is preferred because the temperature at which the laminated film is extended can be selected from a wide range.
此時,是以二色性色素將延伸後的積層膜的樹脂層染色。二色性色素,可列舉:例如碘或有機染料 等。有機染料,可使用:例如紅BR、紅LR、紅R、粉紅LB、Rubin BL、Bordeaux GS、天空藍LG、檸檬黃、藍BR、藍2R、海軍藍RY、綠LG、紫LB、紫B、黑H、黑B、黑GSP、黃3G、黃R、橙LR、橙3R、深紅(scarlet)GL、深紅KGL、剛果紅、亮紫BK、Supra Blue G、Supra Blue GL、Supra Orange GL、直接天空藍、直接耐晒橙(Direct Fast Orange)S、耐晒黑等。此等二色性物質可使用一種,也可同時使用二種以上。 At this time, the resin layer of the laminated film after stretching is dyed with a dichroic dye. Dichroic dyes, for example, iodine or organic dyes Wait. Organic dyes, such as red BR, red LR, red R, pink LB, Rubin BL, Bordeaux GS, sky blue LG, lemon yellow, blue BR, blue 2R, navy blue RY, green LG, purple LB, purple B , Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Dark Red KGL, Congo Red, Bright Purple BK, Supra Blue G, Supra Blue GL, Supra Orange GL, Direct sky blue, Direct Fast Orange S, light fast black, etc. These dichroic substances may be used alone or in combination of two or more.
染色步驟,例如是將整個積層膜浸漬在含有上述二色性色素的溶液(染色溶液)中而進行。染色溶液,可使用已在溶劑中溶解有上述二色性色素的溶液。染色溶液之溶劑,雖然一般使用水,但也可復添加與水具有相溶性之有機溶劑。二色性色素的濃度,宜為0.01至10重量%,並以0.02至7重量%更佳,而以0.025至5重量%尤佳。 The dyeing step is carried out, for example, by immersing the entire laminated film in a solution (dyeing solution) containing the above-mentioned dichroic dye. As the dyeing solution, a solution in which the above-mentioned dichroic dye has been dissolved in a solvent can be used. As the solvent of the dyeing solution, although water is generally used, an organic solvent compatible with water may be 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, still more preferably from 0.025 to 5% by weight.
使用碘作為二色性色素時,因可使染色效率更進一步地提昇,故宜再添加碘化物。此碘化物,可列舉:例如碘化鉀、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。此等碘化物的添加比例,宜為染色溶液中的0.01至20重量%。在碘化物之中,尤其宜添加碘化鉀。在添加碘化鉀時,碘與碘化鉀的比例之重量比,宜為1:5至1:100的範圍,並以1:6至1:80的範圍更佳,而以1:7至1:70的範圍尤佳。 When iodine is used as the dichroic dye, the dyeing efficiency can be further improved, so that iodide should be further added. 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, titanium iodide, and the like. . The proportion of such iodide added is preferably from 0.01 to 20% by weight in the dyeing solution. Among the iodides, potassium iodide is particularly preferably added. When adding potassium iodide, the weight ratio of iodine to potassium iodide is preferably in the range of 1:5 to 1:100, and more preferably in the range of 1:6 to 1:80, but in the range of 1:7 to 1:70. The range is especially good.
積層膜在染色溶液中的浸漬時間並無特別的限定,但通常宜為15秒至15分鐘的範圍,並以30秒至3分鐘更佳。又,染色溶液的溫度宜為10至60℃的範圍,並以20至40℃的範圍更佳。 The immersion time of the laminated film in the dyeing solution is not particularly limited, but is usually preferably in the range of 15 seconds to 15 minutes, and more preferably 30 seconds to 3 minutes. Further, the temperature of the dyeing solution is preferably in the range of 10 to 60 ° C, and more preferably in the range of 20 to 40 ° C.
又,染色處理可在延伸步驟之前或同時進行,但為了能使吸附在聚乙烯醇系樹脂上的二色性色素顯現良好的配向,故宜在對未延伸膜施予延伸步驟之後進行染色處理。此時,可僅單純的將預先以目標倍率延伸的膜染色,也可將預先以低倍率延伸的膜於染色中再度延伸而合計達成目標倍率的方法。又,再於其後的交聯處理中延伸時,在此也可以停在低倍率延伸。此時,只要適時調整以使交聯處理後可達到目標倍率即可。 Further, the dyeing treatment may be carried out before or at the same time as the stretching step, but in order to allow the dichroic dye adsorbed on the polyvinyl alcohol-based resin to exhibit a good alignment, it is preferred to carry out the dyeing treatment after the stretching step is applied to the unstretched film. . In this case, it is possible to simply dye the film which has been stretched at the target magnification in advance, or to re-extend the film which has been stretched at a low magnification in advance in the dyeing to obtain a target magnification. Further, when extending in the subsequent crosslinking treatment, it is also possible to stop at a low magnification. At this time, it is only necessary to adjust in time so that the target magnification can be achieved after the crosslinking treatment.
繼染色步驟(S30)之後進行交聯步驟(S40)。交聯步驟,例如可將經過染色步驟(S30)的積層膜浸漬在含有交聯劑的溶液(交聯溶液)中而進行。交聯劑,可使用以往已知的物質。可列舉:例如硼酸、硼砂等硼化合物,或乙二醛、戊二醛等。此等交聯劑,可使用一種,也可同時使用二種以上。 The crosslinking step (S40) is carried out after the dyeing step (S30). The crosslinking step can be carried out, for example, by immersing the laminated film subjected to the dyeing step (S30) in a solution (crosslinking solution) containing a crosslinking agent. As the crosslinking agent, a conventionally known substance can be used. For example, a boron compound such as boric acid or borax, or glyoxal or glutaraldehyde may be mentioned. These crosslinking agents may be used alone or in combination of two or more.
交聯溶液,可使用已在溶劑中溶解有交聯劑的溶液。溶劑,例如可使用水,並且也可含有與水具有相溶性的有機溶劑。交聯溶液中的交聯劑之濃度,雖然無特別的限定,但宜為1至20重量%的範圍,並以6至15重量%更佳。 For the crosslinking solution, a solution in which a crosslinking agent has been dissolved in a solvent can be used. As the solvent, for example, water may be used, and an organic solvent compatible with water may also be contained. The concentration of the crosslinking agent in the crosslinking solution is preferably in the range of 1 to 20% by weight, and more preferably 6 to 15% by weight, although it is not particularly limited.
交聯溶液中也可添加碘化物。因碘化物的添加,而可使樹脂層面內中的偏光特性更為均勻。碘化物,可列舉:例如碘化鉀、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。碘化物之含量為0.05至15重量%,並以0.5至8重量%更佳。 Iodide may also be added to the crosslinking solution. Due to the addition of iodide, the polarization characteristics in the resin layer can be made more uniform. 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 content of the iodide is 0.05 to 15% by weight, and more preferably 0.5 to 8% by weight.
積層膜在交聯溶液中的浸漬時間,通常宜為15秒至20分鐘,並以30秒至15分鐘更佳。又,交聯溶液的溫度宜為10至90℃的範圍。 The immersion time of the laminated film in the crosslinking solution is usually from 15 seconds to 20 minutes, and 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,交聯步驟可藉由將交聯劑調配在染色溶液中,而與染色步驟同時進行。又,可僅單純的將預先以目標倍率延伸的膜交聯,也可同時進行交聯處理與延伸處理。可將預先在延伸步驟以低倍率延伸的延伸膜,在交聯處理中再度延伸,而合計達到目標倍率。 Further, the crosslinking step can be carried out simultaneously with the dyeing step by formulating the crosslinking agent in the dyeing solution. Further, the film which has been previously stretched at the target magnification may be simply cross-linked, or the crosslinking treatment and the stretching treatment may be simultaneously performed. The stretched film which has been previously stretched at a low magnification in the stretching step can be extended again in the crosslinking treatment to achieve the target magnification in total.
交聯步驟之後宜進行清洗步驟。清洗步驟,可施行水清洗處理。水清洗處理,通常可將延伸膜浸漬在離子交換水、蒸餾水等純水中而進行。水清洗溫度通常是3至50℃,並宜為4℃至20℃的範圍。浸漬時間通常是2至300秒,並宜為3至240秒。 A washing step is preferably carried out after the crosslinking step. The washing step can be performed by water washing. The water washing treatment can be usually carried out by immersing the stretched film in pure water such as ion-exchanged water or distilled water. The water washing temperature is usually from 3 to 50 ° C, and is preferably in the range of from 4 ° C to 20 ° C. The immersion time is usually from 2 to 300 seconds, and preferably from 3 to 240 seconds.
清洗步驟,可以是碘化物溶液的清洗處理與水清洗處理的組合,也可使用適宜調配甲醇、乙醇、異丙醇、丁醇、丙醇等液態醇的溶液。經過以上步驟之後,使樹脂層具有作為偏光子的功能。本說明書中,將具有作為偏光子的功能之樹脂層稱為偏光子層。 The washing step may be a combination of a washing treatment of an iodide solution and a water washing treatment, and a solution in which a liquid alcohol such as methanol, ethanol, isopropanol, butanol or propanol is appropriately formulated may be used. After the above steps, the resin layer has a function as a polarizer. In the present specification, a resin layer having a function as a polarizer is referred to as a polarizer layer.
在此,隔著接著劑層將保護膜貼合在與偏光子層之基材膜側的面相反側的面上,而得偏光性積層膜。適合保護膜的材料是如同偏光性積層膜的說明中所述之材料。又,適合接著劑的材料亦如同偏光性積層膜的說明中所述的材料,例如,可使用水系接著劑或光硬化性接著劑。 Here, the protective film is bonded to the surface on the side opposite to the surface on the side of the base film side of the polarizing sub-layer via the adhesive layer to obtain a polarizing laminated film. A material suitable for the protective film is a material as described in the description of the polarizing laminated film. Further, the material suitable for the adhesive is also the material described in the description of the polarizing laminate film, and for example, a water-based adhesive or a photocurable adhesive can be used.
使用水系接著劑而使偏光子層與保護膜貼合的方法,並無特別的限定,可舉出:例如在偏光子層及/或保護膜的表面均勻塗布接著劑,在塗布面重疊另一方的膜並以貼合滾輪等而貼合的方法等。將接著劑塗布在偏光子層及/或保護膜的表面之方法,可列舉:例如應用將接著劑進料用的噴嘴頭配置在偏光子層及保護膜之間,利用泵等由該噴嘴供應接著劑的方法,或藉由流延法、線棒塗布法、凹板塗布法、逗點式塗布法、刮刀(doctor blade)法、模壓塗布法、浸塗法、噴霧法等,將接著劑塗布在偏光子層及/或保護膜的表面上之方法等。 The method of bonding the polarizing layer to the protective film using a water-based adhesive is not particularly limited, and for example, an adhesive is uniformly applied to the surface of the polarizer layer and/or the protective film, and the other surface is overlapped on the coated surface. The film is bonded to a roller or the like, and the like. The method of applying the adhesive to the surface of the polarizer layer and/or the protective film may be, for example, a nozzle tip for feeding an adhesive agent disposed between the polarizing sublayer and the protective film, and supplied by the nozzle by a pump or the like. a method of a subsequent agent, or a casting agent by a casting method, a bar coating method, a gravure coating method, a comma coating method, a doctor blade method, a die coating method, a dip coating method, a spray method, or the like A method of coating on the surface of the polarizer layer and/or the protective film.
在使用水系接著劑時,將偏光子層與保護膜貼合之後,使積層膜乾燥,以去除水系接著劑中所含的水。乾燥爐的溫度宜為30℃至90℃。如未達30℃時,有使偏光子層面與保護膜面容易剝離的傾向。如為90℃以上時,有因熱而使光學性能劣化之虞。可使乾燥時間為10至1,000秒,特別就生產性而言,其宜為60至750秒,並以150至600秒更佳。 When a water-based adhesive is used, after the polarizing layer is bonded to the protective film, the laminated film is dried to remove water contained in the aqueous adhesive. The temperature of the drying oven is preferably from 30 ° C to 90 ° C. If it is less than 30 ° C, the polarizing layer and the protective film surface tend to be easily peeled off. When it is 90 ° C or more, there is a possibility that the optical properties are deteriorated by heat. The drying time can be from 10 to 1,000 seconds, and particularly in terms of productivity, it is preferably from 60 to 750 seconds, and more preferably from 150 to 600 seconds.
乾燥後,可再以室溫或稍高於室溫的溫 度,例如以20至45℃左右的溫度使其熟成(curing)大約12至600小時左右。熟成時的溫度,一般是設定在低於乾燥時採用的溫度。 After drying, it can be used at room temperature or slightly above room temperature. The degree is, for example, cured at a temperature of about 20 to 45 ° C for about 12 to 600 hours. The temperature at the time of ripening is generally set to a temperature lower than that used when drying.
以光硬化性接著劑將偏光子層與保護膜貼合的方法,可使用以往已知的方法,可舉例如流延法、線棒塗布法、凹板塗布法、逗點式塗布法、刮刀法、模壓塗布法、浸塗法、噴霧法等,將接著劑塗布在偏光子層及/或保護膜的接著面,使兩者重合之方法。流延法,是一邊使被塗物的偏光膜或保護膜朝向大概垂直方向、大概水平方向或兩者之間的斜向移動時,一邊在其表面流下接著劑而擴散塗布的方法。 A method of bonding the polarizing layer to the protective film with a photocurable adhesive can be a conventionally known method, and examples thereof include a casting method, a bar coating method, a gravure coating method, a comma coating method, and a doctor blade. A method in which a binder is applied to a bonding surface of a polarizing layer and/or a protective film by a method, a die coating method, a dip coating method, a spray method, or the like, and the two are superposed. The casting method is a method in which the polarizing film or the protective film of the article to be coated is diffused and coated by applying an adhesive to the surface in a direction perpendicular to the vertical direction, the horizontal direction, or the oblique direction therebetween.
在偏光子層或保護膜的表面塗布接著劑之後,隔著接著劑塗布面以壓輪(nip roll)等包挾偏光膜與保護膜,使其貼合而接著。又,也可適用使偏光子層與保護膜以部份重合的狀態,將接著劑滴到偏光子層與保護膜之間之後,以滾輪等加壓此積層膜而均勻的擴展的方法。此時,可使用金屬或橡膠等作為滾輪的材質。並且,也可適用將接著劑滴到偏光子層與保護膜之間之後,使此積層膜通過滾輪與滾輪之間而加壓,使其擴展的方法。此時,此等滾輪可使用相同的材質,也可使用不同的材質。使用上述壓輪等貼合之後的接著劑層,其乾燥或硬化前的厚度宜為5μm以下且0.01μm以上。 After applying an adhesive to the surface of the polarizer layer or the protective film, the polarizing film and the protective film are coated with a nip roll or the like via the adhesive application surface, and bonded together. In addition, a method in which the polarizer layer and the protective film are partially overlapped, and the adhesive is dropped between the polarizer layer and the protective film, and then the laminated film is pressed by a roller or the like to uniformly spread. At this time, metal, rubber, or the like can be used as the material of the roller. Further, a method in which the adhesive film is dropped between the polarizer layer and the protective film, and the laminated film is pressed between the roller and the roller to be expanded. In this case, these rollers can use the same material or different materials. The thickness of the adhesive layer after bonding using the above-described pressure roller or the like is preferably 5 μm or less and 0.01 μm or more before drying or hardening.
在偏光子層及/或保護膜的接著表面上,可適宜的施予電漿處理、電暈處理、紫外線照射處理、火 焰處理、皂化處理等表面處理,以提高其接著性。皂化處理,可舉出浸漬在如氫氧化鈉或氫氧化鉀的鹼性水溶液中的方法。 On the adhesive surface of the polarizer layer and/or the protective film, plasma treatment, corona treatment, ultraviolet irradiation treatment, fire may be suitably applied. Surface treatment such as flame treatment or saponification treatment to improve the adhesion. The saponification treatment may be exemplified by immersion in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
在使用光硬化性樹脂作為接著劑時,是將偏光膜與保護膜接合後,藉由照射活性能量線而使光硬化性接著劑硬化。活性能量線的光源雖然無特別的限定,但宜為波長400nm以下時具有發光分布的活性能量線,具體上宜使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激化水銀燈、金屬鹵素燈等。 When a photocurable resin is used as the adhesive, the photocurable adhesive is cured by irradiating the active energy ray after bonding the polarizing film and the protective film. Although the light source of the active energy ray is not particularly limited, it is preferably an active energy ray having a luminescent distribution when the wavelength is 400 nm or less. Specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black lamp, Microwave-activated mercury lamps, metal halide lamps, and the like.
對光硬化性接著劑照射的光強度,是依光硬化性接著劑的組成而適宜決定,雖然無特別的限定,但宜為對聚合起始劑之活性化有效的波長領域之照射強度0.1至6,000mW/cm2。如照射強度為0.1 mW/cm2以上時,不會使反應時間變得過長,如為6,000mW/cm2以下時,將使由光源的輻射熱及光硬化性接著劑硬化時的放熱所致之環氧樹脂黃變或偏光膜的劣化之虞較小。對光硬化性接著劑照射光的時間,配合欲硬化的光硬化性接著劑而適用者即無特別的限制,但宜設定成使表示上述照射強度與照射時間之積的累積光量成為10至10,000mJ/cm2。如對光硬化性接著劑照射的累積光量為10mJ/cm2以上時,可產生足夠量的來自聚合起始劑的活性種而使硬化反應更確實的進行,如為10,000mJ/cm2以下時,則可使照射時間不會過長,而維持良好的生產性。而且,活性能量線照射後的 接著劑層之厚度,通常是0.001至5μm左右,並宜為0.01μm以上且2μm以下,而以0.01μm以上且1μm以下更佳。 The light intensity of the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive, and is not particularly limited, but is preferably an irradiation intensity of 0.1 to a wavelength region effective for activation of the polymerization initiator. 6,000 mW/cm 2 . When the irradiation intensity is 0.1 mW/cm 2 or more, the reaction time is not excessively long, and when it is 6,000 mW/cm 2 or less, the radiant heat of the light source and the heat-curing adhesive are hardened. The yellowing of the epoxy resin or the deterioration of the polarizing film is small. The time when the photocurable adhesive is irradiated with light is not particularly limited as long as it is used in combination with the photocurable adhesive to be cured. However, it is preferable to set the cumulative light amount indicating the product of the irradiation intensity and the irradiation time to 10 to 10,000. mJ/cm 2 . When the cumulative amount of light to be irradiated to the photocurable adhesive is 10 mJ/cm 2 or more, a sufficient amount of the active species derived from the polymerization initiator can be generated to make the curing reaction more sure, for example, when it is 10,000 mJ/cm 2 or less. , so that the irradiation time is not too long, and good productivity is maintained. Further, the thickness of the adhesive layer after the active energy ray irradiation is usually about 0.001 to 5 μm, preferably 0.01 μm or more and 2 μm or less, and more preferably 0.01 μm or more and 1 μm or less.
藉由活性能量線的照射使光硬化性接著劑硬化時,宜在不使偏光膜的傓光度、透過率及色相,以及保護膜的透明性等偏光板的諸項功能降低之條件下進行硬化。 When the photocurable adhesive is cured by irradiation with an active energy ray, it is preferable to harden under the condition that the functions of the polarizing plate such as the luminosity, the transmittance, the hue, and the transparency of the protective film are lowered. .
本發明的製造方法中,可在將保護膜貼合在偏光子層上的貼合步驟(S50)之後,進行基材膜之剝離步驟。在基材膜之剝離步驟中,是使基材膜自積層膜剝離。基材膜的剝離方法並無特別的限定,可以與通常之附有黏著劑的偏光板進行的剝離膜之剝離步驟相同的方法進行。在貼合步驟(S50)之後,可直接立即就進行剝離,也可將其一度捲取成輪狀之後,再另外設置剝離步驟。 In the production method of the present invention, the step of peeling off the substrate film may be performed after the bonding step (S50) of bonding the protective film to the polarizing layer. In the peeling step of the base film, the base film is peeled off from the laminated film. The method of peeling the base film is not particularly limited, and it can be carried out in the same manner as the peeling step of the release film by a polarizing plate to which an adhesive is usually applied. After the bonding step (S50), the peeling may be performed immediately, or after it is once wound into a wheel shape, and a peeling step is additionally provided.
(1)基材膜之製作 (1) Fabrication of substrate film
藉由使用多層擠壓成形機的共擠壓成形,製作一種3層結構的基材膜捲,該基材膜是由在含有約5重量%乙烯單元的丙烯/乙烯之無規共聚合物(住友化學(股)製「住友Noburen W151」,熔點Tm=138℃)形成的樹脂層之兩側配置由丙烯的同元聚合物之均質聚丙烯(住友化學(股)製「住友Noburen FLX80E4」,熔點Tm=163℃)形 成的樹脂層而形成者。所得的基材膜捲之合計厚度為100μm,各層的厚度比(FLX80E4/W151/FLX80E4)是3/4/3。 A three-layered substrate film roll was produced by co-extrusion using a multilayer extrusion molding machine, which was composed of a random copolymer of propylene/ethylene containing about 5% by weight of ethylene units ( The Sumitomo Chemical Co., Ltd. "Sumitomo Noburen W151", melting point Tm = 138 ° C) is formed on the both sides of the resin layer by homopolymer polypropylene of propylene (Sumitomo Nobuen FLX80E4, manufactured by Sumitomo Chemical Co., Ltd.). Melting point Tm=163°C) Formed as a resin layer. The total thickness of the obtained base film roll was 100 μm, and the thickness ratio of each layer (FLX80E4/W151/FLX80E4) was 3/4/3.
(2)底塗層之形成 (2) Formation of undercoat layer
使聚乙烯醇粉末(日本合成化學工業(股)製「Z-200」,平均聚合度1,100,平均皂化度99.5莫耳%)溶解於95℃的熱水中,調製成濃度3重量%的聚乙烯醇水溶液。在所得的水溶液中,相對於聚乙烯醇粉末6重量份,混合交聯劑(住友化學(股)製,「Sumirez樹脂650」)5重量份。利用凹板塗布機,將所得的混合水溶液在已施予電暈處理的上述基材膜捲之電暈處理面上連續塗布,以80℃乾燥10分鐘後,形成厚度0.2μm的底塗層,作成由底塗層/基材膜的構成形成之膜。此時,底塗層是全面覆蓋基材膜而形成。 Polyvinyl alcohol powder ("Z-200" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1,100, average saponification degree: 99.5 mol%) was dissolved in hot water at 95 ° C to prepare a polycondensate having a concentration of 3% by weight. Aqueous vinyl alcohol solution. In the obtained aqueous solution, 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. The obtained mixed aqueous solution was continuously coated on the corona-treated surface of the above-mentioned substrate film roll subjected to corona treatment by a gravure coater, and dried at 80 ° C for 10 minutes to form an undercoat layer having a thickness of 0.2 μm. A film formed of a composition of an undercoat layer/base film is formed. At this time, the undercoat layer is formed by entirely covering the substrate film.
(3)積層步驟 (3) Lamination step
使聚乙烯醇粉末(Kuraray(股)製「PVA124」,平均聚合度2,400,平均皂化度98.0至99.0莫耳%)溶解於95℃的熱水中,調製成濃度8重量%的聚乙烯醇水溶液。利用逗點式塗布機,將所得的水溶液連續塗布在基材膜的一方之底塗層上,以80℃乾燥5分鐘後,製作成由基材膜/底塗層/聚乙烯醇系樹脂層形成的3層結構之積層膜捲。由聚乙烯醇系樹脂形成的樹脂層之厚度為10.6μm。塗布之際,在距離基材膜的兩端之各別3.0cm以內的區域內不塗布聚乙烯醇水溶液,作為未塗布部份。即,樹脂層 的寬度方向之長度比基材膜的寬度方向之長度還短6cm。 Polyvinyl alcohol powder ("PVA124" manufactured by Kuraray Co., Ltd., average polymerization degree 2,400, average saponification degree: 98.0 to 99.0 mol%) was dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol aqueous solution having a concentration of 8 wt%. . The obtained aqueous solution was continuously applied onto one of the undercoat layers of the substrate film by a comma coater, and dried at 80 ° C for 5 minutes to prepare a substrate film/undercoat layer/polyvinyl alcohol-based resin layer. A laminated film roll of a three-layer structure formed. The thickness of the resin layer formed of the polyvinyl alcohol-based resin was 10.6 μm. At the time of coating, a polyvinyl alcohol aqueous solution was not applied to a region within 3.0 cm from both ends of the base film as an uncoated portion. Namely, the resin layer The length in the width direction is shorter than the length in the width direction of the base film by 6 cm.
(4)延伸步驟 (4) Extension step
以160℃的延伸溫度,以滾輪間空中延伸裝置,使上述的積層膜朝縱方向以自由端單軸延伸至4.3倍之後捲取,獲得積層膜捲。所得的積層膜之厚度是55.2μm,聚乙烯醇系樹脂層的厚度是6.3μm。 The laminated film was stretched uniaxially by a free end to 4.3 times in the longitudinal direction at an extension temperature of 160 ° C by means of an inter-roller air extension device, and then wound up to obtain a laminated film roll. The thickness of the obtained laminated film was 55.2 μm, and the thickness of the polyvinyl alcohol-based resin layer was 6.3 μm.
(5)染色步驟、交聯步驟 (5) Dyeing step, cross-linking step
對於延伸後的積層膜捲,依下述方式進行染色步驟及交聯步驟。首先,將積層膜在30℃的含有碘與碘化鉀之水溶液的30℃染色溶液中以成為150秒左右的滯留時間之方式浸漬,進行聚乙烯醇系樹脂層的染色(染色步驟),接著以10℃的純水沖掉多餘的碘液。接著,在含有硼酸與碘化鉀的水溶液之72℃的交聯溶液中,以成為600秒左右的滯留時間之方式浸漬(交聯步驟),由樹脂層形成偏光子層。然後,以10℃的純水清洗4秒鐘之後,以80℃使其乾燥300秒,獲得積層膜捲。 For the stretched laminated film roll, the dyeing step and the crosslinking step were carried out in the following manner. First, the laminated film was immersed in a 30° C. dyeing solution containing an aqueous solution of iodine and potassium iodide at 30° C. for a residence time of about 150 seconds to carry out dyeing (dyeing step) of the polyvinyl alcohol-based resin layer, followed by 10 Pure water at °C washes away excess iodine. Next, in a crosslinking solution containing an aqueous solution of boric acid and potassium iodide at 72° C., it was immersed so as to have a residence time of about 600 seconds (crosslinking step), and a polarizing layer was formed from the resin layer. Then, it was washed with pure water of 10 ° C for 4 seconds, and then dried at 80 ° C for 300 seconds to obtain a laminated film roll.
(6)貼合步驟 (6) Fitting step
使聚乙烯醇粉末(Kuraray(股)製「KL-318_」,平均聚合度1,800)溶解於95℃的熱水中,調製成濃度3重量%的聚乙烯醇水溶液。在所得的水溶液中,相對於聚乙烯醇粉末2重量份,混合交聯劑(住友化學(股)製「Sumirez樹脂650」))1重量份,作為接著劑溶液。 Polyvinyl alcohol powder (KL-318_, manufactured by Kuraray Co., Ltd., average polymerization degree 1,800) was dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol aqueous solution having a concentration of 3 wt%. In the obtained aqueous solution, 1 part by weight of a crosslinking agent ("Sumirez Resin 650" manufactured by Sumitomo Chemical Co., Ltd.)) was mixed with 2 parts by weight of the polyvinyl alcohol powder to obtain an adhesive solution.
接著,在所得的積層膜之偏光子層側的面,將比偏光子層的寬度寬8.0cm之由三醋酸纖維素(TAC) 形成的保護膜(Konica Minolta Opto(股)製「KC4UY」),以使兩端分別比偏光子層更外側4.0cm之方式設置,將上述接著劑溶液進料在兩膜之間後,再以貼合滾輪貼合。此時,調整接著劑溶液之進料量以使接著劑層的寬度方向之兩端為偏光子層之兩端的更外側,且保護膜及基材膜之兩端的更內側。然後,將以80℃乾燥5分鐘後獲得的偏光性積層膜捲取,獲得偏光性積層膜捲。所得的偏光性積層膜,是由基材膜/底塗層/偏光子層/接著劑層/保護膜的5層形成之長條狀偏光性積層膜。 Next, on the side of the polarizing layer side of the obtained laminated film, cellulose triacetate (TAC) was 8.0 cm wider than the width of the polarizing sub-layer. The formed protective film ("KC4UY" manufactured by Konica Minolta Opto Co., Ltd.) was set so that both ends were respectively 4.0 cm outside the polarizing sub-layer, and the above-mentioned adhesive solution was fed between the two films, and then Fit the roller to fit. At this time, the feed amount of the adhesive solution is adjusted so that both ends of the adhesive layer in the width direction are more outward of both ends of the polarizer layer, and both ends of the protective film and the base film are further inside. Then, the polarizing laminated film obtained by drying at 80 ° C for 5 minutes was taken up to obtain a polarizing laminated film roll. The obtained polarizing laminate film is a long-length polarizing laminate film formed of five layers of a base film/undercoat layer/polarized sublayer/adhesive layer/protective film.
所得的偏光性積層膜,是接著劑不溢出,從而也使接著劑不漏出至偏光性積層膜的表面之良好狀態。 In the obtained polarizing laminated film, the adhesive does not overflow, and the adhesive does not leak to the surface of the polarizing laminated film.
所得的偏光性積層膜之寬度方向的剖面,是如第1圖中所示之剖面。接著劑層13之寬度方向的長度比基材膜11之寬度方向的長度還短3.2cm,接著劑層13的端部P3與基材膜11的端部P1之間隔為1.6cm。偏光子層12之寬度方向的長度比接著劑層13之寬度方向的長度還短2.0cm,偏光子層12的端部P2與接著劑層13的端部P3之間隔為1.0cm。又,接著劑層13之寬度方向的長度比保護膜14之寬度方向的長度還短8.0cm,接著劑層13的端部P3與保護膜14的端部P4之間隔為4.0cm。 The cross section in the width direction of the obtained polarizing laminated film is a cross section as shown in Fig. 1 . The length of the adhesive layer 13 in the width direction is shorter than the length of the base film 11 in the width direction by 3.2 cm, and the distance between the end portion P3 of the adhesive layer 13 and the end portion P1 of the base film 11 is 1.6 cm. The length of the polarizing sub-layer 12 in the width direction is shorter than the length of the adhesive layer 13 in the width direction by 2.0 cm, and the interval between the end portion P2 of the polarizing sub-layer 12 and the end portion P3 of the adhesive layer 13 is 1.0 cm. Further, the length of the adhesive layer 13 in the width direction is shorter than the length of the protective film 14 in the width direction by 8.0 cm, and the distance between the end portion P3 of the adhesive layer 13 and the end portion P4 of the protective film 14 is 4.0 cm.
將所得的偏光性積層膜捲設置在複捲機(rewinder)而捲出偏光性積層膜時,尤其無結塊等,且在下一步驟的捲出時可平順的捲出。又,就一邊直接連續的捲 出,一邊以剃刀片切割兩端部,保護膜與基材膜隔著接著劑層直接接著,雖然將偏光子層的未積層部份去除,因切割刀安定,故可將端部平整的去除。 When the obtained polarizing laminated film roll is placed in a rewinder and the polarizing laminated film is wound out, in particular, there is no agglomeration or the like, and it can be smoothly rolled out at the time of winding out in the next step. Again, directly on one side of the volume When the both ends are cut by the razor blade, the protective film and the substrate film are directly adhered to each other via the adhesive layer. Although the unlaminated portion of the polarizing sub-layer is removed, the end portion can be removed due to the stability of the cutting blade. .
並且,將基材膜自切割後獲得的偏光性積層膜剝離。由於已切割端部,故可平順的進行剝離,而獲得由保護膜/接著劑層/偏光子層/底塗層形成的偏光板。 Further, the polarizing laminated film obtained by cutting the base film from the base film was peeled off. Since the end portion has been cut, peeling can be smoothly performed, and a polarizing plate formed of a protective film/adhesive layer/polarized sub-layer/undercoat layer is obtained.
使用由1,4-環己烷二甲醇、對苯二甲酸、乙二醇的3種單體共聚合而成的聚酯基材(帝人(股)製:PETG)作為基材。基材膜的厚度是70μm。以與實施例1相同的方法設置底塗層及聚乙烯醇系樹脂層,作成由基材膜/底塗層/聚乙烯醇系樹脂層之構成形成的積層膜(積層步驟)。底塗層的厚度是0.2μm,聚乙烯醇系樹脂層的厚度是10.4μm。在此,也在距離基材膜之端部3.0cm以內的兩端部之區域中,不塗布聚乙烯醇水溶液而設置未塗布部份。 A polyester substrate (manufactured by Teijin Co., Ltd.: PETG) obtained by copolymerization of three kinds of monomers of 1,4-cyclohexanedimethanol, terephthalic acid, and ethylene glycol was used as a substrate. The thickness of the base film was 70 μm. The undercoat layer and the polyvinyl alcohol-based resin layer were provided in the same manner as in Example 1 to form a laminated film formed of a base film/undercoat layer/polyvinyl alcohol-based resin layer (layering step). The thickness of the undercoat layer was 0.2 μm, and the thickness of the polyvinyl alcohol-based resin layer was 10.4 μm. Here, in the region of both end portions within 3.0 cm from the end portion of the base film, an uncoated portion was provided without applying a polyvinyl alcohol aqueous solution.
以滾輪間空中延伸裝置,以110℃的延伸溫度將上述積層膜朝縱方向以自由端單軸延伸4.0倍(延伸步驟),獲得積層膜捲。所得的積層膜捲之厚度是40.5μm,聚乙烯醇系樹脂層的厚度是6.2μm。 The laminated film was uniaxially stretched 4.0 times in the longitudinal direction at a free end in the longitudinal direction of the roller at an elongation of 110 ° C (extension step) to obtain a laminated film roll. The thickness of the obtained laminated film roll was 40.5 μm, and the thickness of the polyvinyl alcohol-based resin layer was 6.2 μm.
將所得的積層膜進行與實施例1相同的染色步驟,清洗、乾燥後,獲得積層膜。將所得的積層膜以與實施例1相同的方式貼合保護膜(貼合步驟),獲得由基 材膜/底塗層/偏光子層/接著劑層/保護膜的5層形成的長條狀偏光性積層膜。 The obtained laminated film was subjected to the same dyeing step as in Example 1, and washed and dried to obtain a laminated film. The obtained laminated film was bonded to the protective film in the same manner as in Example 1 (bonding step) to obtain a base layer. A strip-shaped polarizing laminated film formed of five layers of a material film/undercoat layer/polarized sublayer/adhesive layer/protective film.
所得的偏光性積層膜之寬度方向的剖面,是如同第1圖中所示的剖面。接著劑層13的寬度方向之長度比基材膜11的寬度方向之長度短3.0cm,接著劑層13的端部P3與基材膜11的端部P1之間隔是1.5cm。偏光子層12的寬度方向之長度比接著劑層13的寬度方向之長度短2.0cm,偏光子層12的端部P2與接著劑層13的端部P3之間隔是1.0cm。又,接著劑層13的寬度方向之長度比保護膜14的寬度方向之長度短8.0cm,接著劑層13的端部P3與保護膜14的端部P4之間隔是4.0cm。 The cross section in the width direction of the obtained polarizing laminated film is a cross section as shown in Fig. 1 . The length of the adhesive layer 13 in the width direction is shorter than the length of the base film 11 in the width direction by 3.0 cm, and the distance between the end portion P3 of the adhesive layer 13 and the end portion P1 of the base film 11 is 1.5 cm. The length of the polarizing sub-layer 12 in the width direction is shorter than the length of the adhesive layer 13 by 2.0 cm, and the distance between the end portion P2 of the polarizing layer 12 and the end portion P3 of the adhesive layer 13 is 1.0 cm. Further, the length of the adhesive layer 13 in the width direction is shorter than the length of the protective film 14 in the width direction by 8.0 cm, and the distance between the end portion P3 of the adhesive layer 13 and the end portion P4 of the protective film 14 is 4.0 cm.
將所得的偏光性積層膜捲設置於複捲機上並捲出偏光性積層膜時,不僅無結塊等,且可使其在下一步驟捲出時平順的捲出。又,就一邊直接連續的捲出,一邊以剃刀片切割兩端部,保護膜與基材膜隔著接著劑層直接接著,雖然已將偏光子層的未積層部份去除,因切割刀安定,故可平整的將端部去除。 When the obtained polarizing laminated film roll is placed on a rewinder and the polarizing laminated film is wound up, it is not only agglomerated or the like, but can be smoothly rolled out when it is unwound in the next step. Further, while directly and continuously rolling out, both ends are cut by a razor blade, and the protective film and the base film are directly adhered to each other via the adhesive layer. Although the unlaminated portion of the polarizing sub-layer is removed, the cutting blade is stabilized. Therefore, the ends can be removed flat.
並且,自切割後獲得的偏光性積層膜將基材膜剝離。由於已切割端部,故可平順的進行剝離,而獲得由保護膜/接著劑層/偏光子層/底塗層形成的偏光板。 Further, the polarizing laminate film obtained after the dicing peels off the base film. Since the end portion has been cut, peeling can be smoothly performed, and a polarizing plate formed of a protective film/adhesive layer/polarized sub-layer/undercoat layer is obtained.
在與實施例1相同的基材膜上,以與實施例1相同的方法形成底塗層與樹脂層。以剃刀片將端部的未 塗布部份切割去除,使樹脂層與基材膜之兩端一致。然後,以與實施例1相同的方法進行延伸、染色、交聯、乾燥後,由樹脂層形成偏光子層。調整實施例1中使用的保護膜的寬度,以使其與所得的積層膜之偏光子層及基材膜相同寬度,將其設置在積層膜的偏光子層側,將接著劑溶液進料至兩膜之間再以貼合滾輪使其貼合。此時,是將接著劑溶液的進料量調整成以使接著劑層充分到達偏光子層的端部。然後,以80℃使其乾燥5分鐘,獲得由基材膜/底塗層/偏光子層/接著劑層/保護膜的5層形成長條狀偏光性積層膜。連續的調整接著劑之進料量,因膜之蛇行或進料量的變動,而使接著劑從膜的端部少量擠出而附著在貼合滾輪上。在使數十m的膜流出時,附著在貼合滾輪的接著劑開始附著在基材膜及保護膜的背面(與偏光子層側之表面相反的面),而開始明顯的污染背面。 On the same base film as in Example 1, an undercoat layer and a resin layer were formed in the same manner as in Example 1. With the razor blade will the end of the The coating portion is removed by cutting to make the resin layer coincide with both ends of the substrate film. Then, after stretching, dyeing, crosslinking, and drying in the same manner as in Example 1, a polarizing layer was formed from a resin layer. The width of the protective film used in Example 1 was adjusted so as to be the same width as the polarizing layer and the base film of the obtained laminated film, and it was set on the side of the polarizing layer of the laminated film, and the adhesive solution was fed to The two films are then attached to each other by a bonding roller. At this time, the feed amount of the adhesive solution is adjusted so that the adhesive layer sufficiently reaches the end portion of the polarizing layer. Then, it was dried at 80 ° C for 5 minutes to obtain a long polarizing laminated film formed of five layers of a base film/undercoat layer/polarized sublayer/adhesive layer/protective film. The feed amount of the adhesive is continuously adjusted, and the adhesive is slightly extruded from the end of the film to adhere to the bonding roller due to variations in the meandering or feeding amount of the film. When the film of several tens of meters is discharged, the adhesive adhering to the bonding roller starts to adhere to the back surface of the substrate film and the protective film (the surface opposite to the surface on the side of the polarizing layer), and starts to significantly contaminate the back surface.
在測定所得的偏光性積層膜之剖面中的各層之端部位置時,雖然基材膜、偏光子層、接著劑層、保護膜之兩端略為相同的位置,但在接著劑層的端部之位置上則有變動,而存在有些地方從膜的端部進入內側或溢出外側的部份。 When measuring the end position of each layer in the cross section of the obtained polarizing laminate film, the base film, the polarizer layer, the adhesive layer, and the protective film are slightly at the same position, but at the end of the adhesive layer. There is a change in the position, and there are places where the inside of the film enters the inside or overflows the outside.
將所得的偏光性積層膜再捲取成輪狀。雖然為了切割而捲出此膜捲,但因繞到背面的接著劑,而在膜的端部附近的區域膜彼此貼附,在捲出時接著劑層凝聚破壞而殘留下白色的凝聚破壞痕跡。同時,捲出時的張力亦不安定。 The obtained polarizing laminated film was further wound into a wheel shape. Although the film roll is wound up for cutting, the film in the vicinity of the end portion of the film adheres to each other due to the adhesive which is wound around the back surface, and the adhesive layer is agglomerated and broken when the film is unwound, leaving a white condensed damage mark. . At the same time, the tension when unwinding is also unsettled.
再者,在下一步驟中以剃刀片切割之際,因捲出不良所致之端部歪斜之影響與端部的接著劑層之厚度不均,而使切刀不能一定的切入,而使端部產生毛邊的不良情形。藉由切割而得的膜之端部是噴洒有白粉的狀態,又,因厚度增生而致產生邊端高之捲狀態等不良情形。 Further, in the next step, when the razor blade is cut, the influence of the end portion skew due to the unwinding failure and the thickness of the adhesive layer at the end portion are not uniform, so that the cutter cannot be cut in necessarily, and the end is made The bad situation that caused the burrs. The end portion of the film obtained by the cutting is in a state in which white powder is sprayed, and the thickness is increased to cause a problem such as a state in which the edge is high.
另外,雖然自切割而得的偏光性積層膜剝離取出基材膜,但因端部產生毛邊而未能平順的進行剝離,故端部是呈鋸齒狀。又,產生粉附著在膜背面的不良情形。再者,在觀察端部時,有部份的接著劑不足,而有保護膜與偏光子層之間產生間隔的不良情形。 Further, although the polarizing laminated film obtained by cutting is peeled off and the base film is peeled off, the end portion is burred and peeling is not smoothly performed, so that the end portion has a zigzag shape. Further, there is a problem that the powder adheres to the back surface of the film. Further, when the end portion is observed, a part of the adhesive is insufficient, and there is a problem that a gap is formed between the protective film and the polarizing sub-layer.
表1,是表示實施例1至3、比較例1的偏光性積層膜的概要及貼合後的端部之狀態。 Table 1 shows the outlines of the polarizing laminated films of Examples 1 to 3 and Comparative Example 1, and the state of the end portions after bonding.
本發明的偏光性積層膜,可有效適用於以 液晶顯示裝置為首的各種顯示裝置上。 The polarizing laminated film of the present invention can be effectively applied to The liquid crystal display device is the first of various display devices.
11‧‧‧基材膜 11‧‧‧Base film
12‧‧‧樹脂層(偏光子層) 12‧‧‧ resin layer (polarized sublayer)
13‧‧‧接著劑層 13‧‧‧ adhesive layer
14‧‧‧保護膜 14‧‧‧Protective film
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