TWI661238B - Method for producing polarizable laminated film - Google Patents
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- TWI661238B TWI661238B TW103111404A TW103111404A TWI661238B TW I661238 B TWI661238 B TW I661238B TW 103111404 A TW103111404 A TW 103111404A TW 103111404 A TW103111404 A TW 103111404A TW I661238 B TWI661238 B TW I661238B
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- 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
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Abstract
一種偏光性積層膜的製造方法,其係具備:於基材膜上形成聚乙烯醇系樹脂層而得到積層膜之步驟;使積層膜延伸而得到延伸膜之步驟;以及沿著通過染色槽之運送路徑而運送延伸膜,以雙色性色素染色聚乙烯醇系樹脂層之步驟;染色步驟係包含:沿著上述運送路徑而運送第1膜並浸漬在染色槽之步驟;接合第1膜的終端部與第2膜的起端部而形成接合部之步驟;以及沿著上述運送路徑而運送接合部並浸漬在染色槽之步驟;第1及第2膜中的至少任一者為延伸膜。 A method for manufacturing a polarizing laminated film, comprising: a step of forming a polyvinyl alcohol-based resin layer on a base film to obtain a laminated film; a step of extending the laminated film to obtain an extended film; and The step of conveying the stretched film and dyeing the polyvinyl alcohol-based resin layer with a dichroic dye by the conveying path; the dyeing step includes the steps of conveying the first film along the conveying path and immersing it in the dyeing tank; and joining the terminal of the first film A step of forming a bonding portion with the starting portion of the second film and the second film; and a step of transporting the bonding portion along the transport path and immersing the bonding portion in the dyeing tank; at least one of the first and second films is an stretched film.
Description
本發明係關於在基材膜的單面或雙面具備偏光器層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 having a polarizer layer on one or both sides of a base film.
偏光板為具備:具有偏光功能之偏光器層、以及用以保護此之保護膜之光學元件,並廣泛地使用來作為液晶顯示裝置中之偏光的供給元件或是偏光的檢測元件。以往,偏光板主要是採用:以從聚乙烯醇系樹脂的膜胚材所製造之偏光膜作為偏光器層,並將由三乙醯基纖維素等所構成之保護膜黏接於其單面或雙面者。近年來,伴隨著液晶顯示裝置朝向筆記型個人電腦或行動電話等之可攜式機器之進展,以及朝向大型電視之進展等,乃尋求偏光板的薄層輕量化。 The polarizing plate is provided with a polarizer layer having a polarizing function, and an optical element for protecting the protective film, and is widely used as a polarizing light supplying element or a polarizing light detecting element in a liquid crystal display device. In the past, polarizing plates have mainly used a polarizing film made of a film blank of a polyvinyl alcohol resin as a polarizer layer, and a protective film composed of triethylfluorinated cellulose or the like was adhered to one side or Duplex. In recent years, with the progress of liquid crystal display devices toward portable devices such as notebook personal computers and mobile phones, and progress toward large-scale televisions, thinner and lighter polarizing plates have been sought.
在使聚乙烯醇系樹脂的膜胚材(一般厚度約為75μm)延伸後,進行染色所製造之偏光膜的厚度,一般厚度約為30μm。此程度以上的薄膜化,由於存在著延伸時的膜容易斷裂等之生產性的問題,故難以達成。 The thickness of the polarizing film produced by stretching the film blank (typically about 75 μm) of the polyvinyl alcohol-based resin and then dyeing it is generally about 30 μm. Thinning above this level is difficult to achieve due to productivity problems such as easy breakage of the film during stretching.
另一方面,當連續地製造偏光板來作為長 條的多層膜時,例如在上述般之先前的偏光板中,必須連續地製造作為偏光板的構件之一之偏光膜。偏光膜的連續製造,一般包含一邊從膜捲中連續地捲出長條膜一邊浸漬在槽內的染色溶液以進行染色之步驟,並且以可進行偏光膜的連續製造之方式,在被捲出之長條膜即將用盡時,進行包含將該長條膜的終端部與預先準備的其他膜捲之長條膜的起端部予以接合之操作之膜捲的切換操作,接著對新的長條膜實施染色步驟。 On the other hand, when the polarizing plate is continuously manufactured as a long In the case of a multi-layered film, for example, in the conventional polarizing plate as described above, it is necessary to continuously manufacture a polarizing film as one of the members of the polarizing plate. The continuous production of polarizing films generally includes the steps of continuously dipping the long film from the film roll while dipping the dyeing solution in the tank to perform the dyeing, and the continuous production of the polarizing film is performed on the roll. When the long film is about to be used up, the switching operation of the film roll including the operation of joining the terminal portion of the long film with the beginning of the long film of another film roll prepared in advance is performed, and then the new long film is operated. The strip film is subjected to a dyeing step.
但於上述偏光膜的連續製造時,將膜的接合部(連接部)浸漬在染色溶液時,有時會產生膜於接合部斷裂,或是接合部剝離之缺失。解決此問題之方法,於日本特開2006-350224號公報(專利文獻1)中,已提出一種在從聚乙烯醇系樹脂的膜胚材連續地製造偏光膜之方法中,於膜的接合部通過染色步驟等之各種處理步驟時,藉由將製造裝置的升降輥全部上升以使膜的運送路徑成為直線狀,以免接合部浸漬在染色溶液等的藥液之方法。 However, in the continuous production of the above-mentioned polarizing film, when the joint portion (connection portion) of the film is immersed in the dyeing solution, the film may be broken at the joint portion, or the joint portion may be missing. As a method for solving this problem, Japanese Patent Application Laid-Open No. 2006-350224 (Patent Document 1) has proposed a method for continuously manufacturing a polarizing film from a film blank of a polyvinyl alcohol-based resin at a joint portion of the film. When passing through various processing steps such as the dyeing step, the method of raising all the elevating rollers of the manufacturing apparatus to make the film conveying path linear, so as to prevent the joint portion from being immersed in a chemical solution such as a dyeing solution.
然而,專利文獻1所記載之方法中,由於在膜的接合部結束通過處理步驟為止前無法對膜進行任何處理,所以產生相應量的膜損失。此外,在接合部通過處理步驟後,即使藉由將升降輥降下而再次建構用以實施處理步驟之運送路徑,在此之後至膜的狀態達到穩定為止,仍需耗費時間。就算對未回復穩定狀態之膜實施處理步驟,亦無法期待可製造出良好品質的偏光膜,所以至回復穩定狀態為止之間,亦會產生膜損失。 However, in the method described in Patent Document 1, since the film cannot be subjected to any treatment until the joint portion of the film has passed through the treatment step, a corresponding amount of film loss occurs. In addition, even after the joint passes the processing step, even if the conveying path for implementing the processing step is constructed again by lowering the elevating roller, it takes time until the state of the film reaches a stable state. Even if a processing step is performed on the film that has not returned to a stable state, it cannot be expected that a good-quality polarizing film can be produced, so that film loss will occur until the stable state is restored.
於日本特開2007-171897號公報(專利文獻2)中,係記載在對聚乙烯醇系樹脂的膜胚材依序施以染色處理、交聯處理、延伸處理以連續地製造偏光膜之方法中,藉由55至90℃之溫度範圍中的熱封,來實施先行的膜胚材的終端部與接續的膜胚材的起端部之接合,如此可抑制因往長度方向的單軸延伸所造成之膜的斷裂或接合部的剝離。然而,即使採用該專利文獻2所記載之接合方法時,在浸漬在容易使於膜的接合部產生變形之藥液,例如溫度高之藥液時,有時產生膜的斷裂或接合部的剝離。 Japanese Patent Application Laid-Open No. 2007-171897 (Patent Document 2) describes a method for continuously producing a polarizing film by sequentially applying a dyeing treatment, a crosslinking treatment, and an extension treatment to a film base material of a polyvinyl alcohol resin. In the middle, the heat sealing in the temperature range of 55 to 90 ° C is used to join the terminal part of the preceding film blank and the start of the continuous film blank, so that uniaxial extension in the longitudinal direction can be suppressed. The resulting film is broken or the joint is peeled off. However, even when the bonding method described in Patent Document 2 is used, when the chemical solution which is liable to deform the bonding portion of the film is immersed, for example, when the temperature is high, the film may be broken or the bonding portion may be peeled off. .
本發明係鑒於上述先前技術的問題而創作出,該目的在於提供一種其本身可使用作為偏光板,且亦有用於作為具備保護膜之偏光板的製造中間體之具備偏光器層之偏光性積層膜的製造方法,並且為即使藉由染色步驟中的浸漬處理,於先行的膜胚材的終端部與接續的膜胚材的起端部之接合部不會產生膜的斷裂或接合部的剝離,可穩定地連續製造具備薄膜的偏光器層之偏光性積層膜的方法。 The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a polarizing laminated layer with a polarizer layer that can be used as a polarizing plate by itself and also as a manufacturing intermediate for a polarizing plate with a protective film The method of manufacturing a film is such that even if the dipping process in the dyeing step is performed, the film is not cracked or peeled off at the joint between the terminal portion of the preceding film blank and the beginning of the subsequent film blank. A method for continuously and stably manufacturing a polarizing laminated film including a polarizer layer having a thin film.
本發明如下所述。 The present invention is as follows.
[1]一種偏光性積層膜的製造方法,其係依序具備:於基材膜之至少一面形成聚乙烯醇系樹脂層而得到積層膜之樹脂層形成步驟;將前述積層膜延伸而得到延伸膜之延伸步驟;以及沿著通過含有雙色性色素之染色槽之運送路徑而運送 前述延伸膜,藉此,以前述雙色性色素將前述延伸膜的聚乙烯醇系樹脂層染色而形成偏光器層之染色步驟;前述染色步驟係包含:沿著前述運送路徑而運送第1膜,藉此浸漬在前述染色槽之步驟;接合前述第1膜的終端部與第2膜的起端部而形成接合部之步驟;以及沿著前述運送路徑而運送前述接合部,藉此浸漬在前述染色槽之步驟;前述第1膜及前述第2膜中的至少任一者為前述延伸膜。 [1] A method for manufacturing a polarizing laminated film, comprising: sequentially forming a resin layer on which a polyvinyl alcohol resin layer is formed on at least one side of a base film to obtain a laminated film; and extending the laminated film to obtain an extension Film stretching step; and transport along a transport path through a dyeing tank containing a dichroic pigment The stretching film, thereby dyeing the polyvinyl alcohol-based resin layer of the stretching film with the dichroic dye to form a polarizer layer; the dyeing step includes: transporting the first film along the transport path, A step of immersing in the dyeing tank by this; a step of joining the terminal portion of the first film and the beginning of the second film to form a joint; and transporting the joint along the transport path to immerse in the aforementioned Step of dyeing tank; at least one of the first film and the second film is the stretched film.
[2]如上述[1]所述之方法,其中在浸漬於前述染色槽之步驟中,實質上未進行延伸處理。 [2] The method according to the above [1], wherein in the step of immersing in the aforementioned dyeing tank, substantially no stretching treatment is performed.
[3]如上述[1]或[2]所述之方法,其中前述運送路徑進一步通過被配置在前述染色槽後,且含有交聯劑之交聯槽。 [3] The method according to the above [1] or [2], wherein the transport path further passes through a cross-linking tank arranged behind the dyeing tank and containing a cross-linking agent.
[4]如上述[1]至[3]中任一項所述之方法,其中前述第1膜及前述第2膜任一者均為前述延伸膜。 [4] The method according to any one of the above [1] to [3], wherein any one of the first film and the second film is the stretched film.
[5]如上述[1]至[3]中任一項所述之方法,其中前述第1膜及前述第2膜中的任一者為前述延伸膜,另一方為導引膜。 [5] The method according to any one of the above [1] to [3], wherein any one of the first film and the second film is the stretched film, and the other is a guide film.
[6]如上述[1]至[5]中任一項所述之方法,其中在前述延伸步驟中,前述積層膜以超過5倍的延伸倍率進行延伸。 [6] The method according to any one of the above [1] to [5], wherein in the aforementioned stretching step, the laminated film is stretched at a stretching ratio exceeding 5 times.
[7]如上述[1]至[6]中任一項所述之方法, 其中前述積層膜之聚乙烯醇系樹脂層的厚度為3至30μm。 [7] The method according to any one of the above [1] to [6], The thickness of the polyvinyl alcohol-based resin layer of the aforementioned laminated film is 3 to 30 μm.
根據本發明之方法,被提供至染色步驟之偏光膜,為對每一基材膜施以延伸處理之延伸薄膜,且預先進行充分的延伸,故即使將第1膜與第2膜之接合部浸漬在染色槽或交聯槽,亦可抑制該接合部的變形,並且可有效地抑制該接合部上之膜的斷裂或剝離。 According to the method of the present invention, the polarizing film provided to the dyeing step is a stretched film that is subjected to a stretching treatment for each base film, and is sufficiently stretched in advance. Therefore, even if the first film is bonded to the second film, The immersion in the dyeing tank or the cross-linking tank can also suppress the deformation of the joint portion, and can effectively suppress the cracking or peeling of the film on the joint portion.
在浸漬於染色槽之步驟中若實質上未對膜進行延伸處理,可更有效地抑制因上述浸漬處理所造成之接合部的變形,並且可防止因使該接合部延伸所造成之皺褶的發生。 If the film is not substantially stretched in the step of immersing in the dyeing tank, the deformation of the joint portion caused by the above-mentioned dipping treatment can be more effectively suppressed, and the wrinkle caused by extending the joint portion can be prevented. occur.
偏光性積層膜的連續製造,必然會伴隨著膜捲的切換,伴隨此,而必然會產生先行的膜與接續的膜之接合。根據本發明之方法,即使對於該接合部,亦可在不產生膜的斷裂或剝離下,直接通過用以進行染色步驟之一般的運送路徑(通過染色槽等之運送路徑)。因此,可穩定且有效率地連續製造偏光性積層膜。 The continuous production of polarized laminated film will inevitably be accompanied by the switching of the film roll, and with this, the bonding of the preceding film and the succeeding film will inevitably occur. According to the method of the present invention, it is possible to directly pass through a general conveying path for carrying out the dyeing step (through a conveying path such as a dyeing tank) without causing breakage or peeling of the film to the joint portion. Therefore, a polarizing laminated film can be continuously and efficiently manufactured.
此外,根據本發明之方法,由於可藉由塗佈液的塗佈而形成偏光器層,故可製造具備薄膜的偏光器層之偏光性積層膜及偏光板。 In addition, according to the method of the present invention, since a polarizer layer can be formed by application of a coating liquid, a polarizing laminated film and a polarizing plate having a polarizer layer including a thin film can be manufactured.
1‧‧‧導引輥 1‧‧‧Guide roller
10‧‧‧延伸膜 10‧‧‧ stretch film
15‧‧‧接合部 15‧‧‧Joint
15a‧‧‧接合部的黏接區 15a‧‧‧ Adhesive area of the joint
20‧‧‧偏光性積層膜 20‧‧‧Polarized laminated film
40‧‧‧染色槽 40‧‧‧dyeing tank
41‧‧‧染色溶液 41‧‧‧ dyeing solution
50‧‧‧交聯槽 50‧‧‧ Crosslinking tank
51‧‧‧交聯溶液 51‧‧‧ Cross-linking solution
100‧‧‧第1膜的終端部 100‧‧‧ Terminal of the first film
200‧‧‧第2膜的起端部 200‧‧‧ the beginning of the second film
第1圖為顯示本發明之偏光性積層膜的製造方法之流程圖。 FIG. 1 is a flowchart showing a method for manufacturing a polarizing laminated film of the present invention.
第2圖為顯示染色步驟之實施樣態的一例之概略側視 圖。 Fig. 2 is a schematic side view showing an example of an embodiment of a dyeing step. Illustration.
第3圖為顯示第1膜的終端部與第2膜的起端部之接合部中之接合形態的一例之概略上方圖。 FIG. 3 is a schematic upper view showing an example of a bonding form in a bonding portion between a terminal portion of the first film and a starting end portion of the second film.
第4圖為顯示第1膜的終端部與第2膜的起端部之接合部中之接合形態的其他一例之概略上方圖。 FIG. 4 is a schematic upper view showing another example of a bonding form in a bonding portion between a terminal portion of the first film and a starting end portion of the second film.
第5圖為顯示偏光板的製造方法之流程圖。 FIG. 5 is a flowchart showing a method of manufacturing a polarizing plate.
〈偏光性積層膜的製造方法〉 <Manufacturing method of polarizing laminated film>
第1圖為顯示本發明之偏光性積層膜的製造方法之流程圖。如第1圖所示,本發明之偏光性積層膜的製造方法,係依序包含下列步驟[1]至[3]。 FIG. 1 is a flowchart showing a method for manufacturing a polarizing laminated film of the present invention. As shown in FIG. 1, the method for manufacturing a polarizing laminated film of the present invention includes the following steps [1] to [3] in sequence.
[1]於基材膜之至少一面形成聚乙烯醇系樹脂層而得到積層膜之樹脂層形成步驟S10。 [1] A resin layer forming step S10 in which a polyvinyl alcohol-based resin layer is formed on at least one side of the base film to obtain a laminated film.
[2]將積層膜延伸而得到延伸膜之延伸步驟S20。 [2] Step S20 of extending the laminated film to obtain an extended film.
[3]以雙色性色素將延伸膜的聚乙烯醇系樹脂層染色而形成偏光器層,藉此得到偏光性積層膜之染色步驟S30。 [3] The polarizing layer is formed by dyeing the polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye, thereby obtaining a dyeing step S30 of the polarizing laminated film.
如後述般,具備偏光器層與積層於其上方之保護膜之偏光板,可藉由:將保護膜貼合於實施至染色步驟S30為止所得之偏光性積層膜的偏光器層上而得到貼合膜(貼合步驟S40),然後從貼合膜剝離基材膜並去除(剝離步驟S50)而得到。 As will be described later, a polarizing plate having a polarizer layer and a protective film laminated thereon can be pasted by attaching the protective film to the polarizer layer of the polarizing laminated film obtained up to the dyeing step S30. The film is laminated (laminating step S40), and then the base film is peeled from the laminated film and removed (peeling step S50).
以下更詳細說明偏光性積層膜的製造方法具備之S10至S30的各步驟。 Hereinafter, each of steps S10 to S30 included in the method for manufacturing a polarizing laminated film will be described in more detail.
[1]樹脂層形成步驟S10 [1] Resin layer forming step S10
本步驟為於基材膜之至少一面形成聚乙烯醇系樹脂層而得到積層膜之步驟。此聚乙烯醇系樹脂層係經過延伸步驟S20及染色步驟S30而成為偏光器層之層。聚乙烯醇系樹脂層較佳係藉由將含有聚乙烯醇系樹脂之塗佈液塗佈於基材膜的單面或雙面,並使塗佈層乾燥而形成。根據如此之方法,可減少聚乙烯醇系樹脂層甚至偏光器層的厚度,所以有利於偏光性積層膜及偏光板的薄膜輕量化。雖可藉由將預先製膜之聚乙烯醇系樹脂膜貼合於基材膜而形成聚乙烯醇系樹脂層,但從偏光器層的薄膜化之觀點來看,如上述般,較佳係藉由塗佈液的塗佈而形成聚乙烯醇系樹脂層。 This step is a step of obtaining a laminated film by forming a polyvinyl alcohol-based resin layer on at least one side of the base film. This polyvinyl alcohol-based resin layer is a layer that becomes a polarizer layer after the stretching step S20 and the dyeing step S30. The polyvinyl alcohol-based resin layer is preferably formed by applying a coating solution containing a polyvinyl alcohol-based resin to one or both sides of the base film, and drying the coating layer. According to this method, the thickness of the polyvinyl alcohol-based resin layer and even the polarizer layer can be reduced, so it is advantageous for reducing the weight of the polarizing laminated film and the polarizing plate. Although a polyvinyl alcohol-based resin layer can be formed by bonding a polyvinyl alcohol-based resin film formed in advance to a base film, from the viewpoint of thinning the polarizer layer, as described above, it is preferred A polyvinyl alcohol-based resin layer is formed by application of a coating liquid.
樹脂層形成步驟S10典型上係從長條之基材膜的膜捲將基材膜連續地捲出,並一邊運送一邊進行。膜運送係可使用導輥等而進行。 The resin layer forming step S10 is typically performed by continuously rolling out a base film from a long roll of the base film, and transporting the base film. The film conveyance system can be performed using a guide roller or the like.
(基材膜) (Base film)
基材膜係可由熱塑性樹脂構成,其中,較佳是由透明性、機械強度、熱穩定性、延伸性等優異之熱塑性樹脂構成。如此之熱塑性樹脂的具體例,例如包含:鏈狀聚烯烴系樹脂、環狀聚烯烴系樹脂(降莰烯系樹脂等)之聚烯烴系樹脂;聚酯系樹脂;(甲基)丙烯酸系樹脂;纖維素三乙酸酯、纖維素二乙酸酯之纖維素酯系樹脂;聚碳酸酯系樹脂;聚乙烯醇系樹脂;聚乙酸乙烯酯系樹脂;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;及此等之混合物、共聚物等。 The base film may be made of a thermoplastic resin. Among them, it is preferably made of a thermoplastic resin that is excellent in transparency, mechanical strength, thermal stability, and extensibility. Specific examples of such thermoplastic resins include, for example, polyolefin resins including chain polyolefin resins and cyclic polyolefin resins (such as norbornene resins); polyester resins; (meth) acrylic resins ; Cellulose ester resins of cellulose triacetate and cellulose diacetate; polycarbonate resins; polyvinyl alcohol resins; polyvinyl acetate resins; polyarylate resins; polystyrene resins Resins; Polyether fluorene-based resins; Polyfluorene-based resins; Polyfluorene-based resins; Polyfluorene-imide-based resins; and mixtures and copolymers thereof.
基材膜可為由1種或2種以上的熱塑性樹脂所構成之1層樹脂層所形成之單層構造,或是積層複數層由1種或2種以上的熱塑性樹脂所構成之樹脂層之多層構造。 The base film may have a single-layer structure formed of one resin layer composed of one or two or more thermoplastic resins, or a laminate of a plurality of resin layers composed of one or two or more thermoplastic resins. Multi-layer construction.
鏈狀聚烯烴系樹脂係除了聚乙烯樹脂、聚丙烯樹脂等之鏈狀烯烴的單聚物之外,亦可列舉出由2種以上的鏈狀烯烴所構成之共聚物。由鏈狀聚烯烴系樹脂所構成之基材膜,就容易穩定且高倍率地延伸之觀點來看為較佳。當中,基材膜尤佳係由聚丙烯系樹脂(丙烯的單聚物之聚丙烯樹脂,或是以丙烯為主體之共聚物)、聚乙烯系樹脂(乙烯的單聚物之聚乙烯樹脂,或是以乙烯為主體之共聚物)等所構成。 The chain polyolefin resin is a copolymer of a chain olefin such as a polyethylene resin, a polypropylene resin, or the like, and a copolymer composed of two or more kinds of chain olefins. A base film made of a chain polyolefin resin is preferred from the viewpoint of easy and stable stretching at a high rate. Among them, the base film is particularly preferably made of polypropylene resin (polypropylene resin of propylene monopolymer or copolymer mainly composed of propylene), polyethylene resin (polyethylene resin of ethylene monopolymer, Or a copolymer mainly composed of ethylene).
可適當地使用來作為構成基材膜之熱塑性樹脂的一例之以丙烯為主體之共聚物,為丙烯及可與此共聚合之其他單體之共聚物。 As an example of the thermoplastic resin constituting the base film, a copolymer mainly composed of propylene, and a copolymer of propylene and other monomers copolymerizable therewith can be suitably used.
可與丙烯共聚合之其他單體,例如可列舉出乙烯、α-烯烴。α-烯烴較佳為使用碳數4以上的α-烯烴,尤佳為碳數4至10的α-烯烴。碳數4至10的α-烯烴的具體例,例如包含:1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯之直鏈狀單烯烴類;3-甲基-1-丁烯、3-甲基-1-戊烯、4-甲基-1-戊烯之分枝狀單烯烴類;乙烯基環己烷等。丙烯及可與此共聚合之其他單體之共聚物,可為隨機共聚物或嵌段共聚物。 Examples of other monomers copolymerizable with propylene include ethylene and α-olefins. The α-olefin is preferably an α-olefin having 4 or more carbon atoms, and particularly preferably an α-olefin having 4 to 10 carbon atoms. Specific examples of α-olefins having 4 to 10 carbon atoms include, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene linear monomers Alkenes; 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene branched monoolefins; vinyl cyclohexane, etc. Copolymers of propylene and other monomers copolymerizable therewith may be random copolymers or block copolymers.
上述其他單體的含量,於共聚物中例如為 0.1至20重量%,較佳為0.5至10重量%。共聚物中之其他單體的含量,可依循「高分子分析手冊(原文:高分子分析手冊)」(1995年,紀伊國屋書店發行)的第616頁所記載之方法,藉由進行紅外線(IR)光譜測定來求取。 The content of the other monomers in the copolymer is, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight. The content of other monomers in the copolymer can be determined by infrared (IR) according to the method described on page 616 of the "Handbook of Polymer Analysis (Original: Handbook of Polymer Analysis)" (1995, issued by Kii Kokuya Bookstore). Obtain by spectrum measurement.
上述中,聚丙烯系樹脂較佳係使用丙烯的單聚物、丙烯-乙烯隨機共聚物、丙烯-1-丁烯隨機共聚物或丙烯-乙烯-1-丁烯隨機共聚物。 Among the above, the polypropylene-based resin is preferably a propylene monopolymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, or a propylene-ethylene-1-butene random copolymer.
聚丙烯系樹脂的立體規則性較佳係實質為同排或對排。由具有實質上為同排或對排的立體規則性之聚丙烯系樹脂所構成之基材膜,其處理性比較佳,並且在高溫環境下之機械強度優異。 The three-dimensional regularity of the polypropylene-based resin is preferably substantially the same or opposite. A base film made of a polypropylene-based resin having substantially regular or opposite rows of three-dimensional regularity has good handling properties and excellent mechanical strength in a high-temperature environment.
基材膜可由1種鏈狀聚烯烴系樹脂所構成,或是由2種以上的鏈狀聚烯烴系樹脂之混合物所構成,或是由2種以上的鏈狀聚烯烴系樹脂之共聚物所構成。 The base film may be composed of one type of chain polyolefin resin, or a mixture of two or more types of chain polyolefin resins, or a copolymer of two or more types of chain polyolefin resins. Make up.
環狀聚烯烴系樹脂係以環狀烯烴作為聚合單位所聚合之樹脂的總稱,例如可列舉出日本特開平1-240517號公報、日本特開平3-14882號公報、日本特開平3-122137號公報等所記載之樹脂。若列舉出環狀聚烯烴系樹脂的具體例,有: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、丙烯般的鏈狀烯烴之共聚物(代表性者有隨機共聚物)、以及以不飽和羧酸或該衍生物將此等予以改質之接枝聚合物、以及此等之氫化物等。當中,較佳係使用:使用降莰烯或多環降莰烯系單體等之降莰烯系單體作為環狀烯烴之降莰烯系樹脂。 Cyclic polyolefin resin is a generic term for a resin polymerized by using a cyclic olefin as a polymerization unit, and examples thereof include Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 3-14882, and Japanese Patent Laid-Open No. 3-122137. Resin described in bulletins and the like. Specific examples of cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, and copolymerization of cyclic olefins with ethylene and propylene-like chain olefins. Polymers (typically random copolymers), graft polymers modified with unsaturated carboxylic acids or derivatives thereof, and hydrides thereof. Among them, a norbornene-based resin using norbornene or a polycyclic norbornene-based monomer as the cyclic olefin is preferably used.
環狀聚烯烴系樹脂市面上有販售各種製品。環狀聚烯烴系樹脂之市售品的例子,任一者均以商品名稱表示,包含「Topas」(TOPAS ADVANCED POLYMERS GmbH公司製,可從Polyplastics股份有限公司取得)、「ARTON」(JSR股份有限公司製)、「ZEONOR」(Zeon股份有限公司製)、「ZEONEX」(Zeon股份有限公司製)、「APEL」(三井化學股份有限公司製)。 Various products of cyclic polyolefin resins are commercially available. Examples of commercially available products of cyclic polyolefin resins, each of which is represented by a trade name, include "Topas" (manufactured by TOPAS ADVANCED POLYMERS GmbH, available from Polyplastics Co., Ltd.), "ARTON" (JSR Shares Limited Company), "ZEONOR" (Zeon Corporation), "ZEONEX" (Zeon Corporation), "APEL" (Mitsui Chemical Co., Ltd.).
亦可使用:任一者均以商品名稱表示,「S-SINA」(積水化學工業股份有限公司製)、「SCA40」(積水化學工業股份有限公司製)、「ZEONOR FILM」(Zeon股份有限公司製)等之經製膜後之環狀聚烯烴系樹脂膜的市售品作為基材膜。 Can also be used: Each is represented by a trade name, "S-SINA" (made by Sekisui Chemical Industry Co., Ltd.), "SCA40" (made by Sekisui Chemical Industry Co., Ltd.), "ZEONOR FILM" (Zeon Corporation) A commercially available cyclic polyolefin-based resin film, such as a film), is used as a base film.
基材膜可由1種環狀聚烯烴系樹脂所構成,或是由2種以上的環狀聚烯烴系樹脂之混合物所構成,或是由2種以上的環狀聚烯烴系樹脂之共聚物所構成。 The base film may be composed of one type of cyclic polyolefin resin, or a mixture of two or more types of cyclic polyolefin resin, or a copolymer of two or more types of cyclic polyolefin resin. Make up.
聚酯系樹脂為具有酯鍵之樹脂,一般是由多元羧酸或其衍生物與多元醇之聚縮合物所構成者。多元羧酸或其衍生物係可使用2價的二羧酸或其衍生物,例如可列舉出對苯二甲酸、間苯二甲酸、對苯二甲酸二甲酯、萘二羧酸二甲酯等。多元醇可使用2價的二醇,例如可列舉出乙二醇、丙二醇、丁二醇、新戊二醇、環己烷二甲醇等。 The polyester resin is a resin having an ester bond, and is generally composed of a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. The polyvalent carboxylic acid or a derivative thereof may be a divalent dicarboxylic acid or a derivative thereof. Examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalate. Wait. As the polyhydric alcohol, a divalent diol can be used, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol.
聚酯系樹脂的代表例,可列舉出對苯二甲酸與乙二醇之聚縮合物之聚對苯二甲酸乙二酯。聚對苯二 甲酸乙二酯雖為結晶性的樹脂,但結晶化處理前的狀態者,容易施以延伸等處理。若有必要,可藉由延伸時或延伸後的熱處理等而進行結晶化處理。此外,亦可較佳地使用:藉由使其他種類的單體共聚合於聚對苯二甲酸乙二酯的骨架以降低結晶性(或是成為非晶性)之共聚合聚酯。如此之聚酯的例子,例如可列舉出使環己烷二甲醇或間苯二甲酸共聚合者等。此等樹脂由於延伸性優異,亦可適宜使用。 Typical examples of the polyester-based resin include polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol. Parylene Although ethylene formate is a crystalline resin, it is easy to apply a treatment such as stretching to a state before the crystallization treatment. If necessary, a crystallization treatment may be performed by heat treatment or the like during or after stretching. In addition, a copolymerized polyester that reduces the crystallinity (or becomes amorphous) by copolymerizing other types of monomers on the backbone of polyethylene terephthalate can also be preferably used. Examples of such a polyester include a copolymer of cyclohexanedimethanol and isophthalic acid. These resins are also suitable for use because they are excellent in extensibility.
列舉出聚對苯二甲酸乙二酯及其共聚物以外之聚酯系樹脂的具體例,可列舉出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等。 Specific examples of polyester resins other than polyethylene terephthalate and its copolymers are listed, and examples include polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Esters, polytrimethylene terephthalate, polytrimethylene naphthalate, cyclohexanedimethyl terephthalate, and the like.
基材膜可由1種聚酯系樹脂所構成,或是由2種以上的聚酯系樹脂之混合物所構成,或是由2種以上的聚酯系樹脂之共聚物所構成。 The base film may be composed of one type of polyester resin, or a mixture of two or more types of polyester resins, or a copolymer of two or more types of polyester resins.
(甲基)丙烯酸系樹脂是以具有(甲基)丙烯醯基之化合物為主要構成單體之樹脂。(甲基)丙烯酸系樹脂的具體例,例如包含:聚甲基丙烯酸甲酯之聚(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);甲基丙烯酸甲酯與具有脂環族烴基之化合物之共聚物(例如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚 物、甲基丙烯酸甲酯-(甲基)丙烯酸降莰酯共聚物等)。較佳係使用以聚(甲基)丙烯酸甲酯般之聚(甲基)丙烯酸C1-6烷酯為主成分之聚合物,尤佳為使用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。 The (meth) acrylic resin is a resin having a (meth) acrylfluorenyl group as a main constituent monomer. Specific examples of the (meth) acrylic resin include, for example, poly (meth) acrylate of polymethyl methacrylate; methyl methacrylate- (meth) acrylic copolymer; and methyl methacrylate- ( (Meth) acrylate copolymer; methyl methacrylate-acrylate- (meth) acrylic copolymer; methyl (meth) acrylate-styrene copolymer (MS resin, etc.); methyl methacrylate and having Copolymers of alicyclic hydrocarbon-based compounds (such as methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth) acrylate copolymer, etc.). It is preferable to use a polymer containing poly (meth) acrylic acid C 1-6 alkyl ester as a polymethyl (meth) acrylate as a main component, and it is more preferable to use a polymer containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) of a methyl methacrylate resin.
基材膜可由1種(甲基)丙烯酸系樹脂所構成,或是由2種以上的(甲基)丙烯酸系樹脂之混合物所構成,或是由2種以上的(甲基)丙烯酸系樹脂之共聚物所構成。 The base film may be composed of one (meth) acrylic resin, or a mixture of two or more (meth) acrylic resins, or may be composed of two or more (meth) acrylic resins. Copolymer.
纖維素酯系樹脂為纖維素與脂肪酸之酯。纖維素酯系樹脂的具體例,例如包含:纖維素三乙酸酯、纖維素二乙酸酯、纖維素三丙酸酯、纖維素二丙酸酯等。此外,亦可列舉出此等之共聚物,或是羥基的一部分由其他取代基所改質者等。此等當中,特佳為纖維素三乙酸酯(三乙醯纖維素)。纖維素三乙酸酯有許多製品於市面上販售,就取得容易性或成本之觀點來看亦有利。纖維素三乙酸酯之市售品的例子,任一者均以商品名稱表示,可列舉出「Fujitac TD80」(Fuji Film股份有限公司製)、「Fujitac TD80UF」(Fuji Film股份有限公司製)、「Fujitac TD80UZ」(Fuji Film股份有限公司製)、「Fujitac TD40UZ」(Fuji Film股份有限公司製)、「KC8UX2M」(Konica Minolta Opto股份有限公司製)、「KC4UY」(Konica Minolta Opto股份有限公司製)等。 The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester-based resin include, for example, cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. In addition, copolymers such as those mentioned above, or those in which a part of the hydroxyl group is modified by another substituent, and the like can also be mentioned. Among these, cellulose triacetate (triethylammonium cellulose) is particularly preferred. Many products of cellulose triacetate are commercially available, and it is also advantageous from the viewpoint of availability or cost. Examples of commercially available products of cellulose triacetate are each represented by a trade name, and examples include "Fujitac TD80" (manufactured by Fuji Film Co., Ltd.) and "Fujitac TD80UF" (manufactured by Fuji Film Co., Ltd.) , "Fujitac TD80UZ" (manufactured by Fuji Film Co., Ltd.), "Fujitac TD40UZ" (manufactured by Fuji Film Co., Ltd.), "KC8UX2M" (manufactured by Konica Minolta Opto Co., Ltd.), "KC4UY" (Konica Minolta Opto Co., Ltd.制) and so on.
基材膜可由1種纖維素酯系樹脂所構成,或 是由2種以上的纖維素酯系樹脂之混合物所構成,或是由2種以上的纖維素酯系樹脂之共聚物所構成。 The base film may be composed of one type of cellulose ester resin, or It is composed of a mixture of two or more cellulose ester resins or a copolymer of two or more cellulose ester resins.
聚碳酸酯系樹脂係由單體單元介由碳酸酯基鍵結之聚合物所構成之工程塑膠,且為具有高耐衝擊性、耐熱性、難燃性、透明性之樹脂。構成基材膜之聚碳酸酯系樹脂,亦可為用以降低光彈性係數而將聚合物骨架改質之被稱為改質聚碳酸酯之樹脂,或是改良波長依存性之共聚合聚碳酸酯等。 Polycarbonate resins are engineering plastics composed of polymers whose monomer units are bonded via carbonate groups, and are resins with high impact resistance, heat resistance, flame resistance, and transparency. The polycarbonate-based resin constituting the substrate film may also be a resin called modified polycarbonate for modifying the polymer skeleton to reduce the photoelastic coefficient, or a copolymerized polycarbonate having improved wavelength dependence. Esters, etc.
聚碳酸酯系樹脂有許多製品於市面上販售。聚碳酸酯系樹脂之市售品的例子,任一者均以商品名稱表示,可列舉出「Panlite」(Teijin Chemicals股份有限公司製)、「Iupilon」(Mitsubishi Engineering Plastics股份有限公司製)、「SD Polyca」(Sumitomo Dow股份有限公司製)、「Calibre」(Dow Chemical股份有限公司製)等。 Many polycarbonate-based resins are commercially available. Examples of commercially available polycarbonate resins are each represented by a trade name, and examples thereof include "Panlite" (manufactured by Teijin Chemicals Co., Ltd.), "Iupilon" (manufactured by Mitsubishi Engineering Plastics Co., Ltd.), " "SD Polyca" (manufactured by Sumitomo Dow Co., Ltd.), "Calibre" (manufactured by Dow Chemical Co., Ltd.), etc.
基材膜可由1種聚碳酸酯系樹脂所構成,或是由2種以上的聚碳酸酯系樹脂之混合物所構成,或是由2種以上的聚碳酸酯系樹脂之共聚物所構成。 The base film may be composed of one type of polycarbonate-based resin, or a mixture of two or more types of polycarbonate-based resin, or a copolymer of two or more types of polycarbonate-based resin.
以上之中,從延伸性或耐熱性等觀點來看,較佳係使用聚烯烴系樹脂、聚酯系樹脂、(甲基)丙烯酸系樹脂、或聚碳酸酯系樹脂,尤佳為聚丙烯系樹脂或聚酯系樹脂,特佳為聚丙烯系樹脂。 Among the above, from the viewpoints of extensibility and heat resistance, it is preferable to use a polyolefin resin, a polyester resin, a (meth) acrylic resin, or a polycarbonate resin, and a polypropylene resin is particularly preferred. The resin or polyester resin is particularly preferably a polypropylene resin.
於基材膜中,除了上述熱塑性樹脂之外,亦可添加任意的適當添加劑。該添加劑例如可列舉出紫外線吸收劑、抗氧化劑、潤滑劑、可塑劑、脫模劑、抗著色 劑、難燃劑、成核劑、抗帶電劑、顏料、及著色劑等。基材膜中之熱塑性樹脂的含量,較佳為50至100重量%,尤佳為50至99重量%,更佳為60至98重量%,特佳為70至97重量%。當基材膜中之熱塑性樹脂的含量未達50重量%時,會有無法充分地顯現熱塑性樹脂本來所具有之高透明性等之疑慮。 Any appropriate additives may be added to the base film in addition to the above-mentioned thermoplastic resin. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, and coloring resistance. Agents, flame retardants, nucleating agents, anti-charge agents, pigments, and coloring agents. The content of the thermoplastic resin in the base film is preferably 50 to 100% by weight, particularly preferably 50 to 99% by weight, more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the base film is less than 50% by weight, there is a concern that the high transparency originally possessed by the thermoplastic resin cannot be sufficiently exhibited.
基材膜的厚度可適當地決定,一般從強度和處理性等之作業性的觀點來看,較佳為1至500μm,尤佳為1至300μm,更佳為5至200μm,最佳為5至150μm。 The thickness of the substrate film can be appropriately determined. Generally, from the viewpoints of workability such as strength and handleability, it is preferably 1 to 500 μm, particularly preferably 1 to 300 μm, more preferably 5 to 200 μm, and most preferably 5 Up to 150 μm.
(含有聚乙烯醇系樹脂之塗佈液) (Coating liquid containing polyvinyl alcohol resin)
塗佈液較佳為使聚乙烯醇系樹脂的粉末溶解於良溶劑(例如水)所得之聚乙烯醇系樹脂溶液。聚乙烯醇系樹脂,例如可列舉出聚乙烯醇系樹脂及其衍生物。聚乙烯醇系樹脂的衍生物,除了聚乙烯甲醛、聚乙烯縮醛等之外,可列舉出以乙烯、丙烯等之烯烴類將聚乙烯醇系樹脂予以改質者;以丙烯酸、甲基丙烯酸、巴豆酸般之不飽和羧酸類予以改質者;以不飽和羧酸的烷酯予以改質者;以丙烯醯胺予以改質者等。改質的比率,較佳為未達30莫耳%,尤佳為未達10莫耳%。當進行超過30莫耳%之改質時,難以吸附雙色性色素,可能產生偏光性能降低之缺失。上述聚乙烯醇系樹脂中,較佳係使用聚乙烯醇樹脂。 The coating liquid is preferably a polyvinyl alcohol-based resin solution obtained by dissolving a powder of the polyvinyl alcohol-based resin in a good solvent (for example, water). Examples of the polyvinyl alcohol resin include a polyvinyl alcohol resin and a derivative thereof. In addition to polyvinyl alcohol-based resin derivatives, in addition to polyvinyl formaldehyde, polyvinyl acetal, etc., examples include those modified with polyvinyl alcohol-based olefins such as ethylene and propylene; acrylic acid and methacrylic acid 2. Those who are modified by crotonic acid-like unsaturated carboxylic acids; those who are modified by alkyl esters of unsaturated carboxylic acids; those who are modified by acrylamide. The modification ratio is preferably less than 30 mole%, and even more preferably less than 10 mole%. When the modification exceeds 30 mol%, it is difficult to adsorb the dichroic pigment, and the lack of polarization performance may occur. Among the polyvinyl alcohol-based resins, a polyvinyl alcohol resin is preferably used.
聚乙烯醇系樹脂的平均聚合度,較佳係位於100至10000的範圍,尤佳係位於1000至10000的範圍, 更佳係位於1500至8000的範圍,最佳係位於2000至5000的範圍。平均聚合度係可依據JIS K 6726-1994「聚乙烯醇試驗方法」所規定之方法來求取。當平均聚合度未達100時,難以得到偏光性能,超過10000時,對溶劑之溶解性變差,而難以形成聚乙烯醇系樹脂層。 The average degree of polymerization of the polyvinyl alcohol resin is preferably in the range of 100 to 10,000, and more preferably in the range of 1000 to 10,000. The better line is in the range of 1500 to 8000, and the best line is in the range of 2000 to 5000. The average degree of polymerization can be determined in accordance with the method specified in JIS K 6726-1994 "Test Method for Polyvinyl Alcohol". When the average polymerization degree is less than 100, it is difficult to obtain polarizing performance, and when it exceeds 10,000, the solubility in a solvent is deteriorated, and it is difficult to form a polyvinyl alcohol-based resin layer.
聚乙烯醇系樹脂較佳為聚乙酸乙烯酯系樹脂的皂化品。皂化度的範圍較佳為80莫耳%以上,更佳為90莫耳%以上,特佳為94莫耳%以上。當皂化度過低時,於形成偏光性積層膜或偏光板時之耐水性或耐濕熱性可能會不足。此外,雖可為完全皂化品(皂化度100莫耳%),但當皂化度過高時,染色速度變慢,用以賦予充分的偏光性能之製造時間增長,因情況的不同,有時無法得到具有充分的偏光性能之偏光器層。因此,該皂化度較佳為99.5莫耳%以下,更佳為99.0莫耳%以下。 The polyvinyl alcohol-based resin is preferably a saponified product of a polyvinyl acetate-based resin. The range of the saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 94 mol% or more. When the degree of saponification is too low, the water resistance or moist heat resistance may be insufficient when forming a polarizing laminated film or a polarizing plate. In addition, although it can be completely saponified (saponification degree of 100 mol%), when the saponification degree is too high, the dyeing speed becomes slower, and the manufacturing time required to impart sufficient polarizing performance increases. Depending on the situation, it may not be possible. A polarizer layer having sufficient polarization performance was obtained. Therefore, the saponification degree is preferably 99.5 mol% or less, and more preferably 99.0 mol% or less.
所謂皂化度,是指以單位比(莫耳%)來表示藉由皂化處理使作為聚乙烯醇系樹脂的原料之聚乙酸乙烯酯系樹脂中所含有之乙酸基(乙醯氧基:-OCOCH3)轉化為羥基之比率,且由下列式所定義。 The degree of saponification refers to the acetic acid group (acetoxy: -OCOCH) contained in the polyvinyl acetate-based resin as a raw material of the polyvinyl alcohol-based resin by saponification treatment in a unit ratio (mol%). 3 ) The ratio of conversion to a hydroxyl group and is defined by the following formula.
皂化度(莫耳%)=[(羥基數)÷(羥基數+乙酸基數)]×100 Saponification degree (mol%) = [(hydroxyl number) ÷ (hydroxyl number + acetate number)] × 100
皂化度愈高,意味著羥基的比率愈多,因而意味著阻礙結晶化之乙酸基的比率少。皂化度可依據JIS K 6726-1994「聚乙烯醇試驗方法」所規定之方法來求取。 The higher the degree of saponification, the higher the ratio of hydroxyl groups, and therefore the smaller the ratio of acetic acid groups that hinder crystallization. The degree of saponification can be determined in accordance with the method specified in JIS K 6726-1994 "Test Method for Polyvinyl Alcohol".
聚乙酸乙烯酯系樹脂,除了乙酸乙烯酯的單聚物之聚乙酸乙烯酯之外,可例示出可與乙酸乙烯酯共 聚合之其他單體之共聚物等。可與乙酸乙烯酯共聚合之其他單體,例如可列舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基之丙烯醯胺類等。 Examples of polyvinyl acetate resins other than polyvinyl acetate, which is a single polymer of vinyl acetate, include copolymers with vinyl acetate. Copolymers of other monomers, etc. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
可適合地使用之聚乙烯醇系樹脂之市售品的例子,任一者均以商品名稱表示,包含:Kuraray股份有限公司製的「PVA124」(皂化度:98.0至99.0莫耳%)、「PVA117」(皂化度:98.0至99.0莫耳%)、「PVA117H」(皂化度:99.5莫耳%以上)、「PVA624」(皂化度:95.0至96.0莫耳%)及「PVA617」(皂化度:94.5至95.5莫耳%);日本合成化學工業股份有限公司製的「AH-26」(皂化度:97.0至98.0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%)及「N-300」(皂化度:98.0至99.0莫耳%);Japan Vam and Poval股份有限公司製的「JC-33」(皂化度:99.0莫耳%以上)、「JM-33」(皂化度:93.5至95.5莫耳%)、「JM-26」(皂化度:95.5至97.5莫耳%)、「JP-45」(皂化度:86.5至89.5莫耳%)、「JF-17」(皂化度:98.0至99.0莫耳%)、「JF-17L」(皂化度:98.0至99.0莫耳%)及「JF-20」(皂化度:98.0至99.0莫耳%)。 Examples of commercially available polyvinyl alcohol-based resins that can be suitably used are each represented by a trade name, and include "PVA124" (degree of saponification: 98.0 to 99.0 mol%) manufactured by Kuraray Co., Ltd., " "PVA117" (degree of saponification: 98.0 to 99.0 mole%), "PVA117H" (degree of saponification: 99.5 mole% or more), "PVA624" (degree of saponification: 95.0 to 96.0 mole%), and "PVA617" (degree of saponification: 94.5 to 95.5 mol%); "AH-26" (Saponification degree: 97.0 to 98.0 mol%), "AH-22" (Saponification degree: 97.5 to 98.5 mol%) made by Japan Synthetic Chemical Industry Co., Ltd. "NH-18" (degree of saponification: 98.0 to 99.0 mole%) and "N-300" (degree of saponification: 98.0 to 99.0 mole%); "JC-33" (made by Japan Vam and Poval Co., Ltd. Saponification degree: 99.0 mol% or more), "JM-33" (Saponification degree: 93.5 to 95.5 mol%), "JM-26" (Saponification degree: 95.5 to 97.5 mol%), "JP-45" ( Saponification degree: 86.5 to 89.5 mol%), "JF-17" (Saponification degree: 98.0 to 99.0 mol%), "JF-17L" (Saponification degree: 98.0 to 99.0 mol%), and "JF-20" (Saponification degree: 98.0 to 99.0 mole%).
塗佈液可依需要而含有可塑劑、界面活性劑等之添加劑。可塑劑可使用多元醇或其縮合物等,例如可例示出甘油、二甘油、三甘油、乙二醇、丙二醇、聚乙二醇等。添加劑的調配量,較適合為聚乙烯醇系樹脂的20重量%以下。 The coating liquid may contain additives such as a plasticizer and a surfactant, as needed. As the plasticizer, a polyhydric alcohol or a condensate thereof can be used, and examples thereof include glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, and polyethylene glycol. The blending amount of the additive is more preferably 20% by weight or less of the polyvinyl alcohol resin.
(塗佈液的塗佈及塗佈層的乾燥) (Coating of coating liquid and drying of coating layer)
將上述塗佈液塗佈於基材膜之方法,可適當地選自線棒塗佈法;如逆式滾輪塗佈、凹版塗佈般之輥塗佈法;模頭塗佈法;缺角輪塗佈法;模唇塗佈法;旋轉塗佈法;網版塗佈法;噴泉式塗佈法;浸漬法;噴塗法等之一般所知的方法。 The method for applying the coating liquid to the substrate film may be appropriately selected from a wire rod coating method; a roll coating method such as reverse roller coating or gravure coating; a die coating method; Wheel coating method; die lip coating method; spin coating method; screen coating method; fountain coating method; dipping method; spraying method and other commonly known methods.
在將塗佈液塗佈於基材膜的雙面時,可使用上述方法而單面單面地依序進行,亦可使用浸漬法或噴塗塗佈法或其他特殊裝置等,同時塗佈於基材膜的雙面。 When the coating solution is applied to both sides of the base film, the above method can be used to sequentially perform one-sided and one-sided order, or it can be applied to the substrate film simultaneously by dipping method, spray coating method, or other special equipment. Both sides of the base film.
塗佈層(乾燥前的聚乙烯醇系樹脂層)的乾燥溫度及乾燥時間,可依照塗佈液所含有之溶劑的種類來設定。乾燥溫度例如為50至200℃,較佳為60至150℃。當溶劑含有水時,乾燥溫度較佳為80℃以上。乾燥時間例如為2至20分鐘。 The drying temperature and drying time of the coating layer (the polyvinyl alcohol-based resin layer before drying) can be set in accordance with the type of the solvent contained in the coating liquid. The drying temperature is, for example, 50 to 200 ° C, and preferably 60 to 150 ° C. When the solvent contains water, the drying temperature is preferably 80 ° C or higher. The drying time is, for example, 2 to 20 minutes.
聚乙烯醇系樹脂層可僅形成於基材膜之一面或是形成於雙面。形成於雙面時,可抑制偏光性積層膜或偏光板的製造時可能產生之膜的捲曲,並且可從1片偏光性積層膜得到2片偏光板,就偏光板的生產效率方面來看亦為有利。 The polyvinyl alcohol-based resin layer may be formed on only one side of the base film or on both sides. When formed on both sides, curling of the film that may occur during the manufacture of polarizing laminated film or polarizing plate can be suppressed, and two polarizing plates can be obtained from one polarizing laminated film, also in terms of production efficiency of polarizing plate. As favorable.
積層膜中之聚乙烯醇系樹脂層的厚度,較佳為3至30μm,尤佳為5至20μm。若是具有此範圍內的厚度之聚乙烯醇系樹脂層,經過後述之延伸步驟S20及染色步驟S30,可得到雙色性色素的染色性良好且偏光性能優異,並且厚度極小之偏光器層。若聚乙烯醇系樹脂層的厚度超過30μm,偏光器層的厚度有時超過10μm。此 外,若聚乙烯醇系樹脂層的厚度未達3μm,延伸後變得過薄,有染色性變差之傾向。 The thickness of the polyvinyl alcohol-based resin layer in the laminated film is preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. If the polyvinyl alcohol-based resin layer has a thickness within this range, a polarizer layer having excellent dyeability, excellent polarizing performance, and extremely small thickness of the dichroic pigment can be obtained through the extension step S20 and the dyeing step S30 described later. When the thickness of the polyvinyl alcohol-based resin layer exceeds 30 μm, the thickness of the polarizer layer may exceed 10 μm. this In addition, if the thickness of the polyvinyl alcohol-based resin layer is less than 3 μm, it becomes too thin after stretching, and there is a tendency that the dyeability is deteriorated.
在塗佈液的塗佈之前,為了提升基材膜與聚乙烯醇系樹脂層之密著性,可於至少形成有聚乙烯醇系樹脂層之側的基材膜表面,施予電暈處理、電漿處理、火焰處理等。 Before the application of the coating liquid, in order to improve the adhesion between the base film and the polyvinyl alcohol-based resin layer, a corona treatment may be applied to the surface of the base film at least on the side where the polyvinyl alcohol-based resin layer is formed. , Plasma treatment, flame treatment, etc.
此外,為了提升基材膜與聚乙烯醇系樹脂層之密著性,可介由底漆(primer)層或黏接劑層將聚乙烯醇系樹脂層形成於基材膜上。 In addition, in order to improve the adhesion between the substrate film and the polyvinyl alcohol-based resin layer, the polyvinyl alcohol-based resin layer may be formed on the substrate film via a primer layer or an adhesive layer.
(底漆層) (Primer layer)
底漆層可藉由將底漆層形成用塗佈液塗佈於基材膜表面後,使之乾燥而形成。底漆層形成用塗佈液係包含可發揮對於基材膜與聚乙烯醇系樹脂層之兩者具有某種程度的強密著力之成分。底漆層形成用塗佈液一般含有可賦予如此之密著力之樹脂成分以及溶劑。樹脂成分較佳係使用透明性、熱穩定性、延伸性等優異之熱塑性樹脂,例如可列舉出(甲基)丙烯酸系樹脂、聚乙烯醇系樹脂等。當中,較佳為使用可賦予良好的密著力之聚乙烯醇系樹脂。 The primer layer can be formed by applying a coating liquid for forming a primer layer on the surface of a substrate film and then drying it. The coating liquid system for forming a primer layer contains a component that exhibits a certain degree of strong adhesion to both the substrate film and the polyvinyl alcohol-based resin layer. The coating liquid for forming a primer layer generally contains a resin component and a solvent capable of imparting such adhesion. The resin component is preferably a thermoplastic resin excellent in transparency, thermal stability, and extensibility, and examples thereof include (meth) acrylic resins and polyvinyl alcohol resins. Among them, it is preferable to use a polyvinyl alcohol-based resin that can impart good adhesion.
聚乙烯醇系樹脂例如可列舉出聚乙烯醇系樹脂及其衍生物。聚乙烯醇系樹脂的衍生物除了聚乙烯甲醛、聚乙烯縮醛等之外,可列舉出以乙烯、丙烯等之烯烴類將聚乙烯醇系樹脂予以改質者;以丙烯酸、甲基丙烯酸、巴豆酸之不飽和羧酸類予以改質者;以不飽和羧酸的烷酯予以改質者;以丙烯醯胺予以改質者等。上述聚乙烯醇系 樹脂中,較佳係使用聚乙烯醇樹脂。 Examples of the polyvinyl alcohol-based resin include a polyvinyl alcohol-based resin and a derivative thereof. In addition to polyvinyl alcohol-based resin derivatives other than polyvinyl formaldehyde, polyvinyl acetal, etc., examples include those modified with polyvinyl alcohol-based olefins such as ethylene and propylene; acrylic acid, methacrylic acid, Those who have been modified with unsaturated carboxylic acids of crotonic acid; those who have been modified with alkyl esters of unsaturated carboxylic acids; those who have been modified with acrylamide. Polyvinyl alcohol Among the resins, a polyvinyl alcohol resin is preferably used.
溶劑一般係使用可溶解上述樹脂成分之一般的有機溶劑或水系溶劑。列舉出溶劑的例子,例如有苯、甲苯、二甲苯之芳香族烴類;如丙酮、甲乙酮、甲基異丁酮之酮類;如乙酸乙酯、乙酸異丁酯之酯類;二氯甲烷、三氯乙烯、三氯甲烷般之氯化烴類;乙醇、1-丙醇、2-丙醇、1-丁醇般之醇類。惟,當使用含有有機溶劑之底漆層形成用塗佈液而形成底漆層時,亦有時會溶解基材膜,故較佳係考量基材膜的溶解性而選擇溶劑。若亦考量到對環境之影響,較佳是由以水為溶劑之塗佈液形成底漆層。 The solvent is generally a general organic solvent or an aqueous solvent that can dissolve the resin component. Examples of solvents are listed, such as aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; such as ethyl acetate and isobutyl acetate; dichloromethane , Trichloroethylene, chloroform-like chlorinated hydrocarbons; ethanol, 1-propanol, 2-propanol, 1-butanol-like alcohols. However, when a primer layer is formed using a coating liquid for forming a primer layer containing an organic solvent, the base film may be dissolved. Therefore, the solvent is preferably selected in consideration of the solubility of the base film. If the environmental impact is also considered, it is preferable to form the primer layer from a coating liquid using water as a solvent.
為了提升底漆層的強度,可於底漆層形成用塗佈液添加交聯劑。交聯劑可依照所使用之熱塑性樹脂的種類,而從有機系、無機系等之一般所知者當中適當地選擇。列舉出交聯劑的例子,例如有環氧系、異氰酸酯系、二醛系、金屬系之交聯劑。 In order to increase the strength of the primer layer, a crosslinking agent may be added to the coating liquid for forming a primer layer. The cross-linking agent can be appropriately selected from generally known organic and inorganic systems in accordance with the type of thermoplastic resin used. Examples of the crosslinking agent include epoxy-based, isocyanate-based, dialdehyde-based, and metal-based crosslinking agents.
環氧系交聯劑係單液硬化型及雙液硬化型之任一者均可使用,可列舉出乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二或三縮水甘油醚、1,6-己二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二縮水甘油基胺等。 The epoxy-based cross-linking agent can be used in either a single-liquid curing type or a two-liquid curing type, and examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycerol, and triglycidyl. Ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diglycidylamine, and the like.
異氰酸酯系交聯劑可列舉出甲苯二異氰酸酯、氫化甲苯二異氰酸酯、三羥甲基丙烷-甲苯二異氰酸酯加成物、三苯基甲烷三異氰酸酯、亞甲雙(4-苯基甲烷)三異氰酸酯、異佛爾酮二異氰酸酯、及此等之酮肟封端物或 酚封端物等。 Examples of the isocyanate-based crosslinking agent include toluene diisocyanate, hydrogenated toluene diisocyanate, trimethylolpropane-toluene diisocyanate adduct, triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate, Isophorone diisocyanate, and ketoxime end caps or Phenol end caps, etc.
二醛系交聯劑可列舉出乙二醛、丙二醛、琥珀二醛、戊二醛、順丁烯二醛、鄰苯二甲醛等。 Examples of the dialdehyde-based crosslinking agent include glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, malealdialdehyde, and o-phthalaldehyde.
金屬系交聯劑例如可列舉出金屬鹽、金屬氧化物、金屬氫氧化物、有機金屬化合物。金屬鹽、金屬氧化物、金屬氫氧化物例如可列舉出鎂、鈣、鋁、鐵、鎳、鋯、鈦、矽、硼、鋅、銅、釩、鉻、錫般之具有二價以上的原子價之金屬的鹽、氧化物及氫氧化物。 Examples of the metal-based crosslinking agent include metal salts, metal oxides, metal hydroxides, and organic metal compounds. Examples of the metal salt, metal oxide, and metal hydroxide include magnesium, calcium, aluminum, iron, nickel, zirconium, titanium, silicon, boron, zinc, copper, vanadium, chromium, and tin. Valence metal salts, oxides and hydroxides.
有機金屬化合物為於分子內具有至少1個之有機基直接鍵結於金屬原子、或是有機基介由氧原子或氮原子等鍵結於金屬原子之結構之化合物。有機基係意味著至少包含碳元素之一價或多價之基,例如可為烷基、烷氧基、醯基等。此外,鍵結並不僅意味著共價鍵,亦可為螯合狀化合物等之以配位所形成的配位鍵。 The organometallic compound is a compound having a structure in which at least one organic group is directly bonded to a metal atom, or an organic group is bonded to a metal atom via an oxygen atom or a nitrogen atom. The organic group means a group containing at least a monovalent or polyvalent carbon element, and examples thereof include an alkyl group, an alkoxy group, and a fluorenyl group. In addition, the bonding does not only mean a covalent bond, but also a coordination bond formed by coordination of a chelate compound or the like.
有機金屬化合物的較適合例子,包含有機鈦化合物、有機鋯化合物、有機鋁化合物、有機矽化合物。有機金屬化合物可僅單獨使用1種或併用2種以上。 Examples of suitable organometallic compounds include organic titanium compounds, organic zirconium compounds, organic aluminum compounds, and organic silicon compounds. The organometallic compound may be used alone or in combination of two or more.
有機鈦化合物例如可列舉出鈦酸四正丁酯、鈦酸四異丙酯、鈦酸丁酯二聚物、鈦酸四(2-乙基己基)酯、鈦酸四甲酯等之鈦原酸酯;乙醯丙酮酸鈦、四乙醯丙酮酸鈦、聚乙醯丙酮酸鈦、羥乙酸辛酯鈦、乳酸酯鈦、三乙醇胺化鈦、乙醯乙酸乙酯鈦般之鈦螯合物類;聚羥基硬脂酸鈦般之鈦醯化物類等。 Examples of the organic titanium compound include tetra-n-butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, and tetramethyl titanate. Acid esters; titanium acetoacetate, titanium tetraacetate pyruvate, titanium polyacetate pyruvate, titanium octyl glycolate, titanium lactate, titanium triethanolamine, titanium acetate ethyl acetate Substances: Titanium halides such as polyhydroxystearate.
有機鋯化合物例如可列舉出正丙酸酯鋯、 正丁酸酯鋯、四乙醯丙酮酸鋯、單乙醯丙酮酸鋯、雙乙醯丙酮酸鋯、乙醯丙酮酸鋯乙醯乙酸雙乙酯等。 Examples of the organic zirconium compound include zirconium n-propionate, Zirconium n-butyrate, zirconium tetraacetamidine pyruvate, zirconium monoacetamidine pyruvate, zirconium diacetamidine pyruvate, zirconium acetamidine pyruvate, diethyl acetate diacetate, and the like.
有機鋁化合物例如可列舉出乙醯丙酮酸鋁、有機酸螯合鋁等。有機矽化合物例如可列舉出先前於有機鈦化合物及有機鋯化合物所例示之配位基鍵結於矽之化合物。 Examples of the organoaluminum compound include aluminum acetopyruvate and organic acid chelate aluminum. Examples of the organic silicon compound include compounds in which the ligands previously exemplified for the organic titanium compound and the organic zirconium compound are bonded to silicon.
除了以上的低分子系交聯劑之外,亦可使用羥甲基化三聚氰胺樹脂、聚醯胺環氧樹脂般之高分子系交聯劑。列舉出聚醯胺環氧樹脂之市售品的例子,係有由田岡化學工業股份有限公司所販售之「Sumirez Resin 650(30)」或「Sumirez Resin 675」(任一者均為商品名稱)等。 In addition to the above low-molecular-weight cross-linking agents, polymer-type cross-linking agents such as methylolated melamine resins and polyamine epoxy resins can also be used. Examples of commercially available products of polyamide epoxy resins are "Sumirez Resin 650 (30)" or "Sumirez Resin 675" (Either of which is a trade name) sold by Taoka Chemical Industry Co., Ltd. )Wait.
當使用聚乙烯醇系樹脂作為形成底漆層之樹脂成分時,可適合地使用聚醯胺環氧樹脂、經甲基化三聚氰胺樹脂、二醛系交聯劑、金屬螯合化合物系交聯劑等作為交聯劑。 When a polyvinyl alcohol-based resin is used as a resin component for forming the primer layer, polyamine epoxy resin, methylated melamine resin, dialdehyde-based crosslinking agent, and metal chelate compound-based crosslinking agent can be suitably used. And so on as a crosslinking agent.
底漆層形成用塗佈液中之樹脂成分與交聯劑之比率,相對於樹脂成分100重量份,從交聯劑約0.1至100重量份的範圍中,只要依樹脂成分的種類或交聯劑的種類等而適當地決定即可,尤佳從約0.1至50重量份的範圍中選擇。此外,底漆層形成用塗佈液較佳係使其固體成分濃度成為約1至25重量%。 The ratio of the resin component to the cross-linking agent in the coating liquid for forming the primer layer ranges from about 0.1 to 100 parts by weight of the cross-linking agent relative to 100 parts by weight of the resin component. The type of the agent and the like may be appropriately determined, and it is particularly preferably selected from a range of about 0.1 to 50 parts by weight. Moreover, it is preferable that the coating liquid for primer layer formation is so that solid content concentration may become about 1 to 25 weight%.
底漆層的厚度較佳為0.05至1μm,尤佳為0.1至0.4μm。若較0.05μm更薄,基材膜與聚乙烯醇系樹脂層之密著力提升的效果小,若較1μm更厚,不利於 偏光性積層膜或偏光板的薄膜化。 The thickness of the primer layer is preferably 0.05 to 1 μm, and more preferably 0.1 to 0.4 μm. If it is thinner than 0.05 μm, the effect of improving the adhesion between the substrate film and the polyvinyl alcohol resin layer is small. If it is thicker than 1 μm, it is not good for it. Thinning of a polarizing laminated film or a polarizing plate.
將底漆層形成用塗佈液塗佈於基材膜之方法,可與聚乙烯醇系樹脂層形成用塗佈液之情形時相同。底漆層被塗佈於塗佈有聚乙烯醇系樹脂層形成用塗佈液之面(基材膜的單面或雙面)。由底漆層形成用塗佈液所構成之塗佈層的乾燥溫度及乾燥時間,可依塗佈液所含有之溶劑的種類而設定。乾燥溫度例如為50至200℃,較佳為60至150℃。當溶劑含有水時,乾燥溫度較佳為80℃以上。乾燥時間例如為30秒至20分鐘。 The method for applying the coating liquid for forming a primer layer to a base film may be the same as in the case of the coating liquid for forming a polyvinyl alcohol-based resin layer. The primer layer is applied to the surface (one or both sides of the base film) on which the coating liquid for forming a polyvinyl alcohol resin layer is applied. The drying temperature and drying time of the coating layer composed of the coating liquid for forming a primer layer can be set according to the type of the solvent contained in the coating liquid. The drying temperature is, for example, 50 to 200 ° C, and preferably 60 to 150 ° C. When the solvent contains water, the drying temperature is preferably 80 ° C or higher. The drying time is, for example, 30 seconds to 20 minutes.
當設置底漆層時,塗佈於基材膜之順序並無特別限制,例如在將聚乙烯醇系樹脂層形成於基材膜的雙面時,可在將底漆層形成於基材膜的雙面後,於雙面形成聚乙烯醇系樹脂層,或是於基材膜之一面依序形成底漆層、聚乙烯醇系樹脂層之後,於基材膜之另一面依序形成底漆層、聚乙烯醇系樹脂層。 When the primer layer is provided, the order of coating the base film is not particularly limited. For example, when a polyvinyl alcohol-based resin layer is formed on both sides of the base film, the primer layer may be formed on the base film. After double-sided, a polyvinyl alcohol-based resin layer is formed on both sides, or a primer layer and a polyvinyl alcohol-based resin layer are sequentially formed on one side of the base film, and then a base is sequentially formed on the other side of the base film. Lacquer layer and polyvinyl alcohol resin layer.
本發明之偏光性積層膜的製造方法中所得之積層膜,典型上為長條的膜。該長條之積層膜,可藉由在形成聚乙烯醇系樹脂層後依序捲取,暫時成為膜捲之形態,或是不捲取,而將所得之積層膜連續地供給至接續的延伸步驟S20,並接著進行延伸處理。 The laminated film obtained by the manufacturing method of the polarizing laminated film of this invention is typically a long film. The long laminated film can be sequentially wound up after forming a polyvinyl alcohol-based resin layer to temporarily become the form of a film roll, or the obtained laminated film can be continuously supplied to a continuous extension without being wound up. Step S20 is followed by an extension process.
[2]延伸步驟S20 [2] Extending step S20
本步驟係將由基材膜及聚乙烯醇系樹脂層所構成之積層膜延伸而得到延伸膜之步驟。延伸步驟S20典型係一邊運送長條的積層膜,或是從長條的積層膜的膜捲連續地捲 出積層膜,一邊運送此而連續地進行。膜運送可使用導引輥等來進行。 This step is a step of obtaining a stretched film by extending a laminated film composed of a base film and a polyvinyl alcohol resin layer. The stretching step S20 is typically to carry a long laminated film or to continuously roll it from a film roll of the long laminated film The laminated film is taken out continuously while being conveyed. Film conveyance can be performed using a guide roll or the like.
積層膜的延伸倍率可依所期望的偏光特性而適當地選擇,較佳係相對於積層膜的原長度而為超過5倍且為17倍以下,尤佳為超過5倍且為8倍以下。當延伸倍率為5倍以下時,構成聚乙烯醇系樹脂層之聚乙烯醇系樹脂的高分子鏈未充分地配向,有時使偏光器層的偏光度無法達到充分地高。另一方面,當延伸倍率超過17倍時,延伸時容易產生膜的斷裂,並且延伸膜的厚度被薄化至所需以上,而有在後續步驟中的加工性及處理性降低之疑慮。延伸處理一般為單軸延伸。 The stretch ratio of the laminated film can be appropriately selected depending on desired polarization characteristics, and is preferably more than 5 times and 17 times or less, and more preferably more than 5 times and 8 times or less with respect to the original length of the laminated film. When the stretching ratio is 5 times or less, the polymer chains of the polyvinyl alcohol-based resin constituting the polyvinyl alcohol-based resin layer are not sufficiently aligned, and the degree of polarization of the polarizer layer may not be sufficiently high in some cases. On the other hand, when the stretching ratio exceeds 17 times, film breakage is likely to occur during stretching, and the thickness of the stretched film is reduced to more than necessary, and there is a concern that the workability and handling properties in the subsequent steps are reduced. Stretching is generally uniaxial.
延伸處理除了可為在膜長度方向(膜運送方向)上延伸之縱向延伸之外,亦可為在膜寬度方向上延伸之橫向延伸或斜向延伸等。縱向延伸方式可列舉出:使用輥進行延伸之輥間延伸[一邊在隔著距離所設置之2個夾輥間運送,一邊藉由此等2個夾輥間的周速差而進行縱向單軸延伸之方式];熱輥延伸[藉由通過表面被加熱至可延伸之期望溫度之熱輥、以及周速與熱輥不同(周速較大)之導引輥(或者亦可為熱輥)之間,在與熱輥接觸所產生之加熱狀態下,於與熱輥接觸時(熱輥上)或其附近進行縱向單軸延伸之方式];壓縮延伸;使用卡盤(夾鉗)之延伸等,橫向延伸方式可列舉出拉幅法等。延伸處理係濕潤式延伸方法及乾式延伸方法之任一者均可採用,但使用乾式延伸方法者,從可廣範圍地選擇延伸溫度之點來看為較佳。 The stretching treatment may be a longitudinal extension extending in the film length direction (film transport direction), or a lateral extension or oblique extension extending in the film width direction. Longitudinal stretching methods include: roll-to-roll stretching [while conveying between two nip rollers set apart at a distance, while performing the vertical uniaxial by waiting for the peripheral speed difference between the two nip rollers Extension method]; heat roller extension [by heating the surface of the heat roller to a desired temperature that can be extended, and a guide roller with a peripheral speed different from the thermal roller (larger peripheral speed) (or a thermal roller) In the heating state generated by contact with the heat roller, the method of longitudinal uniaxial extension when contacting the heat roller (on the heat roller) or near it]; compression extension; extension using a chuck (clamp) The lateral stretching method includes a tenter method and the like. The stretching treatment can be performed by either a wet stretching method or a dry stretching method. However, a dry stretching method is preferred from the viewpoint that a wide range of stretching temperatures can be selected.
延伸溫度係被設定在聚乙烯醇系樹脂層及基材膜全體顯示流動性至可延伸之程度的溫度以上,較佳為[基材膜的相轉移溫度(熔點或玻璃轉移溫度)-30]℃至[基材膜的相轉移溫度+30]℃的範圍,尤佳為[基材膜的相轉移溫度-30]℃至[基材膜的相轉移溫度+5]℃的範圍,更佳為[基材膜的相轉移溫度-25]℃至[基材膜的相轉移溫度]℃的範圍。當基材膜為由複數層樹脂層所構成時,上述相轉移溫度係意指該複數層樹脂層顯示之相轉移溫度之中最高的相轉移溫度。 The elongation temperature is set to a temperature at which the entire polyvinyl alcohol-based resin layer and the base film exhibit fluidity to such an extent that it can be stretched, and is preferably [phase transition temperature (melting point or glass transition temperature) of the base film-30] ℃ to [phase transition temperature of substrate film +30] ° C, particularly preferably [phase transition temperature of substrate film -30] ° C to [phase transition temperature of substrate film +5] ° C, more preferably The range is [phase transition temperature of the base film -25] ° C to [phase transition temperature of the base film] ° C. When the substrate film is composed of a plurality of resin layers, the above-mentioned phase transition temperature means the highest phase transition temperature among the phase transition temperatures displayed by the plurality of resin layers.
當將延伸溫度設為低於[基材膜的相轉移溫度-30]℃時,難以達成超過5倍的高倍率延伸,或是基材膜的流動性過低,而有難以進行延伸處理之傾向。當延伸溫度超過[基材膜的相轉移溫度+30]℃時,基材膜的流動性過大,而有難以延伸之傾向。為了更容易達成超過5倍的高倍率延伸,延伸溫度為於上述範圍內,更佳為120℃以上。當延伸溫度為120℃以上時,即使是超過5倍的高倍率延伸,於延伸處理亦不會伴隨困難性之故。 When the stretching temperature is lower than [phase transition temperature of the base film -30] ° C, it is difficult to achieve a high-rate stretching of more than 5 times, or the fluidity of the base film is too low, and it is difficult to perform the stretching treatment. tendency. When the elongation temperature exceeds [phase transition temperature of the base material film + 30] ° C, the fluidity of the base material film becomes too large, and it tends to be difficult to extend. In order to more easily achieve a high magnification extension of more than 5 times, the extension temperature is within the above range, and more preferably 120 ° C or higher. When the stretching temperature is 120 ° C or higher, even if it is stretched at a high rate of more than 5 times, there is no difficulty in the stretching process.
延伸處理中之積層膜的加熱方法,係有:熱區加熱法(例如在藉由吹送熱風而調整至既定溫度之加熱爐般的延伸熱區內加熱之方法);在藉由熱輥延伸而進行延伸時,加熱輥本身之方法;加熱器加熱法(將紅外線加熱器、鹵素加熱器、平板加熱器等設置在積層膜的上下方並以輻射熱來加熱之方法)等。於輥間延伸方式中,從延伸溫度的均一性之觀點來看,較佳為熱區加熱法。此時,2個 夾輥可設置在經調溫後之延伸熱區內,或設置在延伸熱區外,但為了防止積層膜與夾輥之黏接,較佳係設置在延伸熱區外。 The heating method of the laminated film in the stretching treatment includes a hot zone heating method (for example, a heating method in a stretching hot zone like a heating furnace adjusted to a predetermined temperature by blowing hot air); and a stretching method using a heat roller. When stretching, the method of heating the roll itself; the heater heating method (a method of setting an infrared heater, a halogen heater, a flat plate heater, etc. above and below the laminated film and heating it with radiant heat) and the like. In the stretching method between rolls, a hot zone heating method is preferred from the viewpoint of uniformity of the stretching temperature. At this time, 2 The nip roller can be set in the extended hot zone after temperature adjustment, or outside the extended hot zone, but in order to prevent the laminated film and the nip roller from adhering, it is preferably set outside the extended hot zone.
所謂延伸溫度係於熱區加熱法時,意指熱區內(例如加熱爐內)的環境溫度,於加熱器加熱法中,在爐內亦進行加熱時,意指爐內的環境溫度。此外,於熱輥延伸時,意指輥的表面溫度。 The so-called extension temperature refers to the ambient temperature in the hot zone (for example, in a heating furnace) when the hot zone heating method is used. In the heater heating method, it means the ambient temperature in the furnace when heating is also performed in the furnace. In addition, when the hot roll is extended, it means the surface temperature of the roll.
延伸處理並不限定於以一段的延伸,亦可以多段進行。此時,較佳係以延伸處理的全段合計成為超過5倍的延伸倍率之方式進行延伸處理。 The extension processing is not limited to one-stage extension, and may be performed in multiple stages. In this case, it is preferable to perform the stretching process so that the entire length of the stretching process becomes a total stretching ratio of more than 5 times.
在延伸步驟S20之前,亦可設置將積層膜預熱之預熱處理步驟。預熱方法可使用與延伸處理的加熱方法相同之方法。當延伸處理方式為輥間延伸時,預熱可在通過上游側的夾輥前、通過中、及通過後的任一時機進行。當延伸處理方式為熱輥延伸時,預熱較佳係在通過熱輥前之時機進行。當延伸處理方式為使用卡盤之延伸時,預熱較佳係在擴展卡盤間距離前之時機進行。預熱溫度較佳為延伸溫度的-50℃至±0℃的範圍,尤佳為[延伸溫度-40]℃至[延伸溫度-10]℃的範圍。 Before the extending step S20, a preheating step for preheating the laminated film may be provided. As the preheating method, the same method as the heating method of the stretching treatment can be used. When the stretching treatment method is stretching between rolls, preheating can be performed before, during, and after passing through the nip roll on the upstream side. When the stretching treatment method is hot roll stretching, the preheating is preferably performed before the heat roller is passed. When the extension processing method is an extension using a chuck, the preheating is preferably performed at a time before the distance between the chucks is extended. The preheating temperature is preferably in a range of -50 ° C to ± 0 ° C of the extension temperature, and particularly preferably in a range of [drawing temperature-40] ° C to [extension temperature-10] ° C.
此外,於延伸步驟S20的延伸處理後,亦可設置熱固定處理步驟。熱固定處理為在以夾鉗握持延伸膜的端部之狀態下,一邊維持拉緊狀態一邊以結晶化溫度以上進行熱處理之處理。藉由此熱固定處理,可促進聚乙烯醇系樹脂層的結晶化。熱固定處理的溫度較佳為[延伸溫度] ℃至[延伸溫度-80]℃的範圍,尤佳為[延伸溫度]℃至[延伸溫度-50]℃的範圍。 In addition, after the stretching process in the stretching step S20, a heat fixing process step may also be provided. The heat-fixing treatment is a treatment in which the end of the stretched film is held by a clamp, and the heat treatment is performed at a temperature higher than the crystallization temperature while maintaining the tension. By this heat setting treatment, crystallization of the polyvinyl alcohol-based resin layer can be promoted. The temperature of the heat fixing treatment is preferably [elongation temperature] The range of ℃ to [elongation temperature-80] ℃, particularly preferably the range of [elongation temperature] ℃ to [elongation temperature -50] ℃.
本發明之偏光性積層膜的製造方法中所得之延伸膜,典型為長條的膜。一般是在延伸處理後依序捲取而以膜捲之形態得到。 The stretched film obtained by the manufacturing method of the polarizing laminated film of this invention is typically a long film. Generally, it is sequentially taken up after the stretching treatment and obtained in the form of a film roll.
[3]染色步驟S30 [3] Dyeing step S30
本步驟為以雙色性色素將延伸膜的聚乙烯醇系樹脂層染色並使其吸附及配向,而形成偏光器層之步驟。經過本步驟,可得到在基材膜的單面或雙面積層有偏光器層之偏光性積層膜。雙色性色素之染色係從長條的延伸膜之膜捲連續地捲出延伸膜,並沿著通過含有雙色性色素之染色槽之運送路徑(產線路徑)而運送延伸膜,以連續地浸漬在染色槽而進行。膜運送可使用導引輥等來進行。 This step is a step of forming a polarizer layer by dyeing a polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye, adsorbing and aligning the polyvinyl alcohol-based resin layer. After this step, a polarizing laminated film having a polarizer layer on one or both sides of the substrate film can be obtained. The dyeing of the dichromatic dye is to continuously roll out the stretched film from the long film roll of the stretched film, and transport the stretched film along the conveying path (production line path) through the dyeing tank containing the dichromatic dye to continuously immerse it. It is performed in a dyeing tank. Film conveyance can be performed using a guide roll or the like.
本發明中,染色步驟S30包含下列步驟[a]至[c]。 In the present invention, the dyeing step S30 includes the following steps [a] to [c].
[a]沿著通過上述染色槽之運送路徑而運送第1膜,藉此浸漬在染色槽之步驟。 [a] A step of immersing the first film in the dyeing tank by transporting the first film along the transport path passing through the dyeing tank.
[b]接合第1膜的終端部與第2膜的起端部而形成接合部之步驟。 [b] The step of joining the terminal portion of the first film and the starting end portion of the second film to form a joint portion.
[c]沿著上述運送路徑而運送接合部,藉此浸漬在染色槽之步驟。 [c] A step of immersing the joint in the dyeing tank by transporting the joint along the transport path.
第1膜及第2膜的至少任一者為於延伸步驟S20中所得之延伸膜。根據包含上述步驟[a]至[c]之染色步驟S30,藉由步驟[a],當沿著上述運送路徑而先行被運送 之長條的第1膜接近於結束時,可進行:包含將該第1膜的終端部與預先準備之另外的第2膜(第2膜一般作為膜捲而準備)的起端部接合之操作之膜捲的切換操作(步驟[b]),接著對被接合之第2膜實施染色處理,所以可連續地製造偏光性積層膜。本發明中,可依照期望之偏光性積層膜的製造量,將第3膜接合於第2膜,或更將第4膜(或進一步為第5膜、第6膜…)接合於第3膜。 At least one of the first film and the second film is an stretched film obtained in the stretching step S20. According to the dyeing step S30 including the above steps [a] to [c], in step [a], it is transported first along the transport path When the long first film is near the end, it may be performed by joining the terminal portion of the first film with the start portion of another second film prepared in advance (the second film is generally prepared as a film roll). The switching operation of the operated film roll (step [b]), and then the second film to be bonded is subjected to a dyeing treatment, so that a polarizing laminated film can be continuously manufactured. In the present invention, the third film can be bonded to the second film, or the fourth film (or further the fifth film, the sixth film, etc.) can be bonded to the third film according to the desired production amount of the polarizing laminated film. .
提供至染色步驟S30之第1膜及第2膜的至少任一者,為於延伸步驟S20中施以延伸處理後之延伸膜,已預先進行充分的延伸。因此,如專利文獻2所記載之方法般,在未延伸之狀態下將聚乙烯醇系樹脂的膜胚材浸漬在染色槽時不同,可有效地抑制在將第1膜與第2膜之接合部浸漬在染色槽時之接合部的變形。藉由對此變形之承受性,可有效地抑制起因於變形之接合部上之膜的斷裂或剝離。 At least one of the first film and the second film provided to the dyeing step S30 is sufficiently stretched in advance for the stretched film subjected to the stretching process in the stretching step S20. Therefore, as in the method described in Patent Document 2, when a film blank of a polyvinyl alcohol resin is immersed in a dyeing tank in an unstretched state, it is possible to effectively suppress the bonding of the first film and the second film Deformation of the joint when the part is immersed in the dyeing tank. By resisting this deformation, it is possible to effectively suppress the breakage or peeling of the film on the joint caused by the deformation.
由於接合部的耐變形性優異,所以在本發明中,可使接合部直接通過於上述通過染色槽之運送路徑(步驟[c])。亦即,不須如專利文獻1所記載之方法般擔心接合部的斷裂或剝離,而變更運送路徑以免接合部被浸漬在染色槽。根據本發明之方法,不僅可避免變更運送路徑之繁瑣作業,更可避免無法進行染色處理之膜部分發生,並且在以步驟[b]切換膜捲後,可顯著地縮短膜狀態達到穩定為止之時間,所以幾乎不會產生膜損耗,能夠以極高的製造效率連續地製造偏光性積層膜。 Since the joining portion is excellent in deformation resistance, in the present invention, the joining portion can be directly passed through the above-mentioned conveying path through the dyeing tank (step [c]). That is, it is not necessary to worry about breakage or peeling of the joint portion as in the method described in Patent Document 1, and the conveyance path is changed so that the joint portion is not immersed in the dyeing tank. According to the method of the present invention, not only the tedious work of changing the conveying path can be avoided, but also the part of the film that cannot be dyed can be avoided, and after the film roll is switched in step [b], the film state can be significantly shortened to reach a stable Therefore, almost no film loss occurs, and the polarizing laminated film can be continuously produced with extremely high production efficiency.
可想到作為用以抑制在染色步驟S30中之膜的斷裂或剝離之方法,可列舉出降低施加於膜之張力而運送膜之方法,但此時反而容易在染色槽或任意的膨潤槽中產生斷裂。此外,當張力較低時,容易產生膜的蛇行。此時,在回復張力後,至膜的行進達到穩定為止需耗費某些時間,膜的損耗增多,並且製造效率降低。當張力較低時,膜通過夾輥時流動性變差,故容易產生皺褶等缺失。 As a method for suppressing cracking or peeling of the film in the dyeing step S30, a method of conveying the film by reducing the tension applied to the film is conceivable, but in this case, it is likely to be generated in a dyeing tank or an arbitrary swelling tank. fracture. In addition, when the tension is low, the meandering of the film is liable to occur. At this time, after the tension is restored, it takes some time until the travel of the film reaches stability, the loss of the film increases, and the manufacturing efficiency decreases. When the tension is low, the fluidity of the film is deteriorated when it passes through the nip rolls, so wrinkles and the like are easily generated.
參考圖面而更具體說明染色步驟S30。第2圖為顯示染色步驟S30之實施樣態的一例之概略側視圖,係顯示出:作為先行的第1膜之延伸膜10依序通過染色槽40、交聯槽50(惟交聯槽50為任意設置之槽),藉此,連續地製作偏光性積層膜20,並且作為被接合於第1膜的終端部之第2膜之延伸膜10通過染色槽40之模樣。較接合部15更下游側為第1膜,上游側為第2膜。箭頭顯示膜的運送方向。如圖示般,根據本發明之方法,不須特意變更運送路徑,可使第1膜與第2膜之接合部15,直接通過用以實施至少包含染色槽40之染色步驟S30的運送路徑。 The dyeing step S30 will be described more specifically with reference to the drawings. FIG. 2 is a schematic side view showing an example of the implementation state of the dyeing step S30, which shows that the stretched film 10 as the first film in advance passes through the dyeing tank 40 and the cross-linking tank 50 (only the cross-linking tank 50). This is a slot provided arbitrarily), whereby the polarizing laminated film 20 is continuously produced, and the stretched film 10 as the second film bonded to the terminal portion of the first film passes through the dyeing tank 40. The first film is located further downstream than the bonding portion 15, and the second film is located upstream. The arrows show the transport direction of the film. As shown in the figure, according to the method of the present invention, it is not necessary to intentionally change the conveying path, and the joint portion 15 of the first film and the second film can be directly passed through the conveying path for performing the dyeing step S30 including at least the dyeing tank 40.
染色步驟S30中的膜運送,與其他步驟相同,可使用導引輥1等而進行。膜浸漬在容納於染色槽40之含有雙色性色素之染色溶液41或容納於交聯槽50之含有交聯劑之交聯溶液51,例如圖示般,在染色槽40或交聯槽50內,可於上下方設置複數個導引輥1,只要沿著此等而運送膜即可。導引輥1的設置數或導引輥間的距離等,可依照膜於溶液內期望滯留時間(浸漬時間)等而調整。 The film conveyance in the dyeing step S30 can be performed using the guide roller 1 or the like, as in the other steps. The film is immersed in the dyeing solution 41 containing the dichroic pigment contained in the dyeing tank 40 or the crosslinking solution 51 containing the crosslinking agent contained in the crosslinking tank 50, as shown in the figure, in the dyeing tank 40 or the crosslinking tank 50 A plurality of guide rollers 1 may be provided on the upper and lower sides, as long as the film is conveyed along these. The number of the guide rollers 1, the distance between the guide rollers, and the like can be adjusted according to the desired residence time (soak time) of the film in the solution.
染色槽40內的染色溶液41,可為將雙色性色素溶解於溶劑之溶液。染色溶液41所含有之雙色性色素,可列舉出碘或雙色性有機染料。雙色性有機染料的具體例,例如包含:Red BR、Red LR、Red R、Pink LB、Rubin BL、Bordeaux GS、Sky Blue LG、Lemon Yellow、Blue BR、Blue 2R、Navy RY、Green LG、Violet LB、Violet B、Black H、Black B、Black GSP、Yellow 3G、Yellow R、Orange LR、Orange 3R、Sky Red GL、Sky Red KGL、Congo Red、Brilliant Violet BK、Supra Blue G、Supra Blue GL、Supra Orange GL、Direct Sky Blue、Direct Fast Orange S、Fast Black等。雙色性色素,可僅單獨使用1種或併用2種以上。 The dyeing solution 41 in the dyeing tank 40 may be a solution in which a dichroic pigment is dissolved in a solvent. Examples of the dichroic dye contained in the dyeing solution 41 include iodine or a dichroic organic dye. Specific examples of dichroic organic dyes include: Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB , Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Sky Red GL, Sky Red KGL, Congo Red, Brilliant Violet BK, Supra Blue G, Supra Blue GL, Supra Orange GL, Direct Sky Blue, Direct Fast Orange S, Fast Black, etc. The dichroic pigment may be used alone or in combination of two or more.
染色溶液41中所含有之溶劑,一般係使用水,亦可進一步添加與水具有相溶性之有機溶劑。染色溶液41中之雙色性色素的濃度,較佳為0.01至10重量%,尤佳為0.02至7重量%,更佳為0.025至5重量%。 The solvent contained in the dyeing solution 41 is generally water, and an organic solvent compatible with water may be further added. The concentration of the dichroic pigment in the dyeing solution 41 is preferably 0.01 to 10% by weight, more preferably 0.02 to 7% by weight, and still more preferably 0.025 to 5% by weight.
當使用碘作為雙色性色素時,為了更進一步提升染色效率,較佳為進一步將碘化物添加於含有碘之染色溶液41。碘化物例如可列舉出碘化鉀、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41中之碘化物的濃度,較佳為0.01至20重量%。碘化物中,較佳係添加碘化鉀。添加碘化鉀時,碘與碘化鉀之比率,以重量比計,較佳為於1:5至1:100的範圍,尤佳為1:6至1:80的範圍,更佳為於1:7至1:70的範圍。 When using iodine as a dichroic pigment, in order to further improve the dyeing efficiency, it is preferable to further add iodide to the dyeing solution 41 containing iodine. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. The concentration of the iodide in the dyeing solution 41 is preferably 0.01 to 20% by weight. To the iodide, 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 by weight ratio, particularly preferably in the range of 1: 6 to 1:80, and more preferably in the range of 1: 7 to 1:70 range.
延伸膜10於染色溶液41中的浸漬時間,一般為15秒至15分鐘的範圍,較佳為30秒至3分鐘的範圍。此外,染色溶液41的溫度,較佳為於10至60℃的範圍,尤佳為20至40℃的範圍。 The immersion time of the stretch film 10 in the dyeing solution 41 is generally in the range of 15 seconds to 15 minutes, and preferably in the range of 30 seconds to 3 minutes. The temperature of the dyeing solution 41 is preferably in the range of 10 to 60 ° C, and more preferably in the range of 20 to 40 ° C.
如第2圖所示,於通過染色槽40之延伸膜10的運送路徑上,較佳係在染色槽40之後(下游側)設置交聯槽50。亦即,染色步驟S30較佳係包含:在染色槽40中的染色處理步驟後所實施之交聯處理步驟。交聯槽50內的交聯溶液51,可為將交聯劑溶解於溶劑之溶液。交聯劑可使用一般所知的物質,例如可列舉出硼酸、硼砂般的硼化物、乙二醛、戊二醛等。交聯劑可僅單獨使用1種或併用2種以上。 As shown in FIG. 2, on the conveyance path of the stretched film 10 passing through the dyeing tank 40, a cross-linking tank 50 is preferably provided after the dyeing tank 40 (downstream side). That is, the dyeing step S30 preferably includes a crosslinking treatment step performed after the dyeing treatment step in the dyeing tank 40. The crosslinking solution 51 in the crosslinking tank 50 may be a solution in which a crosslinking agent is dissolved in a solvent. As the crosslinking agent, generally known ones can be used, and examples thereof include boric acid, borax-like borides, glyoxal, and glutaraldehyde. The crosslinking agent may be used alone or in combination of two or more.
交聯溶液51中所含有之溶劑,一般係使用水,亦可進一步含有與水具有相溶性之有機溶劑。交聯溶液51中之交聯劑的濃度,較佳為1至20重量%,尤佳為6至15重量%。 The solvent contained in the crosslinking solution 51 generally uses water, and may further contain an organic solvent compatible with water. The concentration of the crosslinking agent in the crosslinking solution 51 is preferably 1 to 20% by weight, and particularly preferably 6 to 15% by weight.
交聯溶液51可含有碘化物。藉由碘化物的添加,可使偏光器層之面內的偏光性能更均一化。碘化物例如可列舉出碘化鉀、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。交聯溶液51中之碘化物的濃度,較佳為0.05至15重量%,尤佳為0.5至8重量%。 The crosslinking solution 51 may contain iodide. The addition of iodide can make the polarization performance in the plane of the polarizer layer more uniform. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. The concentration of the iodide in the crosslinking solution 51 is preferably 0.05 to 15% by weight, and particularly preferably 0.5 to 8% by weight.
浸漬在染色槽40後之膜於交聯溶液51的浸漬時間,一般為15秒至20分鐘,較佳為30秒至15分鐘。 此外,交聯溶液51的溫度,較佳為於10至90℃的範圍。 The immersion time of the film immersed in the dyeing tank 40 in the crosslinking solution 51 is generally 15 seconds to 20 minutes, preferably 30 seconds to 15 minutes. The temperature of the crosslinking solution 51 is preferably in the range of 10 to 90 ° C.
交聯處理亦可藉由將交聯劑調配於染色溶液41中而與染色處理同時處理。 The cross-linking treatment may be performed simultaneously with the dyeing treatment by blending the cross-linking agent in the dyeing solution 41.
染色步驟S30除了以上所說明之染色處理步驟與交聯處理步驟之外,亦可包含:在染色處理步驟之前,使延伸膜10膨潤之膨潤處理步驟;於染色處理步驟與交聯處理步驟之間所實施之第1洗淨步驟;於交聯處理步驟後,所實施之第2洗淨步驟。 The dyeing step S30 may include, in addition to the dyeing and cross-linking treatment steps described above, a swelling treatment step of swelling the stretch film 10 before the dyeing treatment step; between the dyeing treatment step and the cross-linking treatment step The first washing step performed; after the cross-linking treatment step, the second washing step performed.
膨潤處理步驟可藉由將延伸膜10浸漬在例如約0至40℃的水浴(離子交換水、蒸餾水般之純水浴)中進行。 The swelling treatment step can be performed by immersing the stretched film 10 in a water bath (ion-exchanged water, pure water bath such as distilled water) at about 0 to 40 ° C, for example.
第1及第2洗淨步驟一般包含水洗淨步驟。水洗淨步驟係可藉由將染色處理後或交聯處理後的膜浸漬在離子交換水、蒸餾水般之純水而進行。水洗淨溫度一般為3至40℃的範圍,較佳為於4至20℃的範圍。於水中的浸漬時間一般為2至300秒,較佳為3至240秒。 The first and second washing steps generally include a water washing step. The water washing step can be performed by immersing the membrane after the dyeing treatment or the crosslinking treatment in pure water such as ion-exchanged water or distilled water. The water washing temperature is generally in the range of 3 to 40 ° C, preferably in the range of 4 to 20 ° C. The immersion time in water is generally 2 to 300 seconds, preferably 3 to 240 seconds.
第1及第2洗淨步驟亦可為水洗淨步驟與以碘化物溶液所進行的洗淨步驟之組合。此外,水洗淨步驟及/或以碘化物溶液所進行的洗淨處理中使用之洗淨液,除了水之外,亦可適當地含有甲醇、乙醇、異丙醇、丁醇般之液態醇。 The first and second washing steps may be a combination of a water washing step and a washing step using an iodide solution. In addition, the washing liquid used in the water washing step and / or the washing treatment with the iodide solution may contain, in addition to water, a liquid alcohol such as methanol, ethanol, isopropanol, and butanol as appropriate. .
於將延伸膜10浸漬在染色槽之步驟及將接合部15浸漬在染色槽之步驟中,較佳係實質上任一者均未進行延伸處理。藉此,可更有效地抑制因在染色槽40之浸漬處理所造成之接合部15的變形。當浸漬在染色槽40中 實施延伸處理時,接合部15的變形量增加,有產生接合部上之膜的斷裂或剝離之疑慮。 In the step of immersing the stretched film 10 in the dyeing tank and the step of immersing the joint portion 15 in the dyeing tank, it is preferable that substantially no one is subjected to the stretching treatment. This makes it possible to more effectively suppress the deformation of the joint portion 15 caused by the dipping treatment in the dyeing tank 40. When immersed in the dyeing tank 40 When the stretching treatment is performed, the amount of deformation of the joint portion 15 increases, and there is a possibility that the film on the joint portion is cracked or peeled.
此外,藉由在將延伸膜10浸漬在染色槽40之步驟及將接合部15浸漬在染色槽之步驟中,實質上未進行延伸處理,可防止起因於對接合部15進行延伸處理而產生之皺褶的發生。若產生皺褶,為了解決此皺褶而需耗費某些時間,所以製造效率降低。在浸漬在交聯槽50之步驟中,亦可依需要而施以延伸處理。 In addition, in the step of immersing the stretched film 10 in the dyeing tank 40 and the step of immersing the bonding portion 15 in the dyeing tank, substantially no stretching treatment is performed, which can be prevented from being caused by the stretching processing of the bonding portion 15. The occurrence of wrinkles. If wrinkles occur, it takes some time to resolve the wrinkles, so the manufacturing efficiency decreases. In the step of immersing in the cross-linking tank 50, an extension treatment may be applied as required.
在浸漬在染色槽40之步驟中「實質上未進行延伸處理」係意指使該步驟中的延伸倍率相對於被提供至該步驟之延伸膜10的原長度而在1.5倍以下,較佳為1倍(未延伸)。 The "substantially no stretching treatment" in the step of immersing in the dyeing tank 40 means that the stretching ratio in this step is 1.5 times or less with respect to the original length of the stretching film 10 provided to this step, preferably 1 Times (not extended).
為了充分地提高施加於膜之張力,並且實質上未進行延伸處理而實施染色步驟,基材膜較佳為聚烯烴系樹脂、聚酯系樹脂、(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、以及聚醯亞胺系樹脂。 In order to sufficiently increase the tension applied to the film and to perform the dyeing step without substantially performing the stretching treatment, the base film is preferably a polyolefin-based resin, a polyester-based resin, a (meth) acrylic resin, or a cellulose ester-based resin. Resins, polycarbonate resins, polyvinyl acetate resins, polyarylate resins, polystyrene resins, polyether fluorene resins, polyfluorene resins, polyamine resins, and polyimide resins Resin.
接著,參考第3圖及第4圖而說明染色步驟S30的步驟[b]中形成第1膜的終端部100與第2膜的起端部200之接合部15之方法。接合部15的形成方法,只要藉由浸漬在染色槽40或交聯槽50,膜亦不易剝離之方法即可,並無特別限制,例如可藉由使用雙面膠帶(於基材雙面具有黏接層之膜)之接合或使用熱封之接合來形成接合 部15。從不須使用特殊機器之觀點來看,以雙面膠帶之接合較簡便且較佳。於熱封係可使用以往公知之裝置(熱封機)。 Next, a method of forming the joint portion 15 between the terminal portion 100 of the first film and the start portion 200 of the second film in step [b] of the dyeing step S30 will be described with reference to FIGS. 3 and 4. The method for forming the joint portion 15 is not particularly limited as long as the film is not easily peeled by dipping in the dyeing tank 40 or the cross-linking tank 50. For example, a double-sided tape (Adhesive layer film) bonding or using heat-sealed bonding to form the bonding Department 15. From the standpoint of not having to use a special machine, joining with double-sided tape is simpler and better. For the heat sealing system, a conventionally known device (heat sealing machine) can be used.
本發明之方法中,由於在染色步驟S30中不須實施延伸處理,故即使不使用特別強力的接合方法,亦不易產生膜的斷裂或剝離、皺褶的發生之缺失。 In the method of the present invention, since the stretching treatment is not required in the dyeing step S30, even if a particularly strong bonding method is not used, it is not easy to cause the film to be broken or peeled, and the occurrence of wrinkles is not easy to occur.
第1膜的終端部100與第2膜的起端部200之接合部15中的膜接合形態亦無特別限制,例如為第3圖所示,可藉由以雙面膠帶或熱封所形成之1條的帶狀黏接區15a上的黏接來進行接合,或是如第4圖所示,設置複數個黏接區15a。 There is no particular limitation on the film bonding form in the bonding portion 15 of the terminal portion 100 of the first film and the starting end portion 200 of the second film. For example, as shown in FIG. 3, it can be formed by double-sided tape or heat sealing. One of the strip-shaped adhesive regions 15a is adhered for bonding, or as shown in FIG. 4, a plurality of adhesive regions 15a are provided.
步驟[b]中的膜捲切換,例如可使用轉塔方式般之以往所知的自動接紙裝置。此外,市面上亦販售有自動接紙裝置與熱封機呈一體之裝置,該裝置亦可適合地使用。 For the film roll switching in step [b], a conventionally known automatic paper receiving device such as a turret system can be used. In addition, there are also devices on the market that integrate the automatic paper receiving device and the heat sealer, and the device can also be used appropriately.
此處,於染色步驟S30中使用之第1膜及第2膜,如上述般,至少任一者為於延伸步驟S20中所得之延伸膜10。使用第2圖之上述說明中,係說明第1膜及第2膜均為延伸膜10之情形,但並不限定於此,第1膜及第2膜的任一者為延伸膜10,另一者為導引膜。 Here, as described above, at least one of the first film and the second film used in the dyeing step S30 is the stretched film 10 obtained in the stretching step S20. In the above description using FIG. 2, the case where the first film and the second film are both the stretched film 10 is explained, but it is not limited to this. Any one of the first film and the second film is the stretched film 10. One is a guide membrane.
導引膜為運送路徑(產線路徑)保持用的膜,且係在開始染色步驟S30前或是中斷染色步驟S30時通過運送路徑(暫置於運送路徑上)之膜。於染色步驟S30中斷時使導引膜通過運送路徑,可在中斷後的染色步驟 S30被重新開始時,不須再次進行使延伸膜10重新通過運送路徑之作業。 The guide film is a film for holding a transport path (line of production path), and is a film that passes through the transport path (temporarily placed on the transport path) before the dyeing step S30 is started or when the dyeing step S30 is interrupted. When the dyeing step S30 is interrupted, the guide film is passed through the conveying path, and the dyeing step after the interruption can be performed. When S30 is restarted, it is not necessary to perform the operation of re-transmitting the stretched film 10 through the transport path again.
如上述般,於染色步驟S30的運送路徑上,由於配置有染色槽40、交聯槽50般的藥液槽(有時亦有加溫狀態的藥液槽),或是高溫的乾燥爐等,所以在染色步驟S30的中斷後,由於再次從頭開始實施使延伸膜10重新通過之作業,必須進行從藥液槽排出藥劑,或使形成運送路徑之導引輥動作,或是開啟乾燥爐的門等之繁瑣的作業。若實施此作業,除了使膜重新通過之時間之外,使藥液槽的溫度或乾燥爐的溫度再次回到穩定狀態需要耗費極長時間,使製造效率顯著降低。 As described above, on the conveying path of the dyeing step S30, a chemical tank (such as a heated chemical tank) may be provided, such as a dyeing tank 40, a crosslinking tank 50, or a high-temperature drying furnace. Therefore, after the interruption of the dyeing step S30, since the operation of re-passing the stretched film 10 is performed again from the beginning, the medicine must be discharged from the liquid tank, the guide roller forming the transport path must be operated, or the drying furnace must be turned on. Tedious homework and so on. If this operation is carried out, in addition to the time for the membrane to pass again, it will take an extremely long time to return the temperature of the chemical tank or the temperature of the drying furnace to a stable state again, which will significantly reduce the manufacturing efficiency.
以在使導引膜通過運送路徑之狀態下停止產線運送,可直接長時間保持染色步驟S30時的運送路徑,所以於染色步驟S30的再次啟動時,不須排出藥劑,或使導引輥動作,或是開啟乾燥槽的門。因此,於染色步驟S30的重新開始時可顯著地縮短使其運送路徑成為穩定狀態之時間,而順利地重新開始。 In order to stop the line transportation while the guide film is passing through the conveying path, the conveying path in the dyeing step S30 can be directly maintained for a long time, so when the dyeing step S30 is restarted, it is not necessary to discharge the medicine or make the guide roller Action, or open the door of the drying tank. Therefore, when the dyeing step S30 is restarted, the time for making the transport path to a stable state can be significantly shortened, and the process can be restarted smoothly.
導引膜較佳係使用便宜且不易斷裂、不易產生皺褶、即使長時間浸漬在藥液中亦不易被腐蝕等特性之膜。具體而言,較佳可使用延伸聚對苯二甲酸乙二酯、延伸聚丙烯膜等。導引膜並不一定須為被延伸處理後之膜,但藉由施以延伸處理,可提升膜的耐撕裂強度或耐熱性等,而容易得到適合於導引膜之特性。此外,若施以延伸處理,膜面積會增加,所以被延伸處理後之膜,大致上 較未延伸者便宜。 The guide film is preferably a film which is inexpensive, is not easily broken, does not easily generate wrinkles, and is not easily corroded even when immersed in a chemical solution for a long time. Specifically, it is preferable to use stretched polyethylene terephthalate, stretched polypropylene film, or the like. The guiding film does not necessarily have to be a stretched film, but by applying the stretching treatment, the tear resistance or heat resistance of the film can be improved, and characteristics suitable for the guiding film can be easily obtained. In addition, if the stretching process is performed, the film area will increase, so the film after the stretching process is roughly Cheaper than unextended.
使用延伸步驟S20中所得之延伸膜10作為導引膜者並不佳。使用延伸膜10作為導引膜者,使延伸膜10的損耗增大,就製造成本的方面來看並不利。此外,若在使延伸膜10通過運送路徑之狀態下長時間停止膜運送,聚乙烯醇系樹脂層會逐漸溶解於染色槽等之藥劑槽,而污染藥劑槽。 It is not good to use the stretched film 10 obtained in the stretching step S20 as a guide film. If the stretched film 10 is used as the guide film, the loss of the stretched film 10 is increased, which is disadvantageous in terms of manufacturing cost. In addition, if the film conveyance is stopped for a long time while the stretched film 10 is passed through the conveyance path, the polyvinyl alcohol-based resin layer will gradually dissolve in a medicine tank such as a dyeing tank and contaminate the medicine tank.
因此,染色步驟S30中使用之第1膜及第2膜均為延伸膜10時,並非任一者之膜被使用來作為導引膜,而是意指被接合之雙方的延伸膜10經過染色步驟S30而成為偏光性積層膜20。 Therefore, when the first film and the second film used in the dyeing step S30 are both the stretched film 10, not one of the films is used as a guide film, but the stretched film 10 of both sides that are joined is dyed. In step S30, the polarizing laminated film 20 is obtained.
另一方面,第1膜為延伸膜10,且第2膜為導引膜時,例如,為了中斷染色步驟S30,而在中斷之前之延伸膜10的終端部接合導引膜,並直接沿著運送路徑運送接合部,而使導引膜通過運送路徑之情形。第1膜為導引膜,第2膜為延伸膜10時,係例如從使導引膜通過運送路徑之中斷狀態,將延伸膜10接合於導引膜的終端部而以重新開始染色步驟S30之情形。此時,沿著運送路徑而運送接合部進一步第2膜並進行第2膜的染色處理,而得到偏光性積層膜20。 On the other hand, when the first film is the stretch film 10 and the second film is the guide film, for example, in order to interrupt the dyeing step S30, the terminal portion of the stretch film 10 before the interruption is joined to the guide film and directly follows The transport path transports the joint and passes the guide film through the transport path. When the first film is the guide film and the second film is the stretch film 10, for example, the stretch film 10 is bonded to the terminal portion of the guide film from the interrupted state of the guide film through the transport path to restart the dyeing step S30 Situation. At this time, the second portion is further transported along the transport path and the second film is dyed to obtain a polarizing laminated film 20.
於染色步驟S30後,較佳係設置使所得之濕潤的偏光性積層膜乾燥之乾燥步驟。乾燥步驟係可採用自然乾燥、送風乾燥、加熱乾燥等之任意的適當方法。例如於加熱乾燥時,乾燥溫度一般為20至95℃,乾燥時間一 般為1至15分鐘。如以上做法所得到之偏光性積層膜20,可直接使用來作為偏光要素(偏光板),且亦有可用於作為用以製作出包含偏光器層與保護膜之後述偏光板之製造中間體。 After the dyeing step S30, it is preferable to provide a drying step for drying the obtained wet polarized laminated film. The drying step can be performed by any appropriate method such as natural drying, air drying, and heating drying. For example, when heating and drying, the drying temperature is generally 20 to 95 ° C, and the drying time is It usually takes 1 to 15 minutes. The polarizing laminated film 20 obtained as described above can be directly used as a polarizing element (polarizing plate), and also can be used as a manufacturing intermediate for manufacturing the polarizing plate described later including a polarizer layer and a protective film.
偏光性積層膜20具有之偏光器層的厚度為10μm以下,較佳為7μm以下。藉由將偏光器層的厚度設為10μm以下,可構成薄型的偏光性積層膜20。 The thickness of the polarizer layer included in the polarizing laminated film 20 is 10 μm or less, and preferably 7 μm or less. By setting the thickness of the polarizer layer to 10 μm or less, a thin polarizing laminated film 20 can be configured.
(偏光板的製造方法〉 (Manufacturing method of polarizing plate>
藉由以上所說明之製造方法所得之偏光性積層膜,依據第5圖所示之流程圖,經由將保護膜貼合於偏光性積層膜的偏光器層上而得到貼合膜之貼合步驟S40;以及從貼合膜剝離並去除基材膜之剝離步驟S50;可形成在偏光器層上貼合有保護膜之偏光板。亦可不實施剝離步驟S50而藉由貼合步驟S40所得之含有基材膜、偏光器層及保護膜之積層體,以作為偏光板。 According to the polarizing laminated film obtained by the manufacturing method described above, according to the flowchart shown in FIG. 5, a protective film is attached to the polarizer layer of the polarizing laminated film to obtain a laminating step. S40; and a peeling step S50 of peeling and removing the base film from the bonding film; forming a polarizing plate with a protective film bonded on the polarizer layer. The laminated body containing the base film, the polarizer layer, and the protective film obtained by laminating step S40 without performing the peeling step S50 may be used as a polarizing plate.
[4]貼合步驟S40 [4] Laminating step S40
本步驟係將保護膜貼合於偏光性積層膜的偏光器層上,亦即貼合於偏光器層之與基材膜側相反側的面而得到貼合膜之步驟。保護膜係可使用黏接劑或黏著劑貼合於偏光器層。當偏光性積層膜於基材膜的雙面具有偏光器層時,一般於雙面的偏光器層上分別貼合有保護膜。此時,此等保護膜可為同種類的保護膜或是可為不同種類的保護膜。 This step is a step of attaching the protective film to the polarizer layer of the polarizing laminated film, that is, attaching the protective film to the surface of the polarizer layer opposite to the substrate film side to obtain a laminating film. The protective film can be bonded to the polarizer layer using an adhesive or an adhesive. When the polarizing laminated film has polarizer layers on both sides of the base film, a protective film is generally attached to each of the double-sided polarizer layers. In this case, the protective films may be the same type of protective films or may be different types of protective films.
(保護膜) (Protective film)
保護膜係例如可為由鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)般之聚烯烴系樹脂;纖維素三乙酸酯、纖維素二乙酸酯般之纖維素酯系樹脂;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般之聚酯系樹脂;聚碳酸酯系樹脂;(甲基)丙烯酸系樹脂;或此等之混合物、共聚物等所構成之膜。環狀聚烯烴系樹脂及該膜、以及纖維素三乙酸酯等之可使用之市售品的例子如上所述。 The protective film may be, for example, a polyolefin resin such as a chain polyolefin resin (such as a polypropylene resin) or a cyclic polyolefin resin (such as a norbornene resin); a cellulose triacetate; or a fiber. Cellulose diacetate-like resin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate-based polyester resin; polycarbonate resin ; (Meth) acrylic resin; or a film made of such mixtures, copolymers, and the like. Examples of commercially available products such as cyclic polyolefin resin and the film, and cellulose triacetate are as described above.
保護膜亦可為兼具相位差膜、亮度提升膜等之光學功能之保護膜。例如可將由上述材料所構成之樹脂膜進行延伸(單軸延伸或雙軸延伸等),或是於該膜上形成液晶層等,藉此,構成為賦予任意的相位差值之相位差膜。 The protective film may also be a protective film having optical functions such as a retardation film and a brightness enhancement film. For example, a resin film composed of the above-mentioned materials may be stretched (uniaxially stretched or biaxially stretched), or a liquid crystal layer may be formed on the film, thereby constituting a retardation film that gives an arbitrary retardation value.
於保護膜之與偏光器層相反側的表面上,可形成硬塗層、防眩層、抗反射層等之光學層。於保護膜表面形成此等光學層之方法並無特別限定,可使用一般所知的方法。光學層可在實施貼合步驟S40之前,預先形成於保護膜上,或是在實施貼合步驟S40後或是實施後述剝離步驟S50後形成。 An optical layer such as a hard coat layer, an anti-glare layer, or an anti-reflection layer may be formed on the surface of the protective film on the side opposite to the polarizer layer. The method for forming these optical layers on the surface of the protective film is not particularly limited, and a generally known method can be used. The optical layer may be formed on the protective film in advance before the bonding step S40 is performed, or may be formed after the bonding step S40 is performed or after the peeling step S50 described later is performed.
將保護膜貼合於偏光器層上時,於保護膜之偏光器層側表面,為了提升與偏光器層之黏接性,可進行電漿處理、電暈處理、紫外線照射處理、火焰(火炎)處理、皂化處理等之表面處理(易黏著處理),當中,較佳為進行電漿處理、電暈處理或皂化處理。例如當保護膜由環 狀聚烯烴系樹脂所構成時,一般進行電漿處理或電暈處理。此外,當由纖維素酯系樹脂所構成時,一般進行皂化處理。皂化處理可列舉出浸漬在氫氧化鈉或氫氧化鉀般之鹼水溶液之方法。 When the protective film is bonded to the polarizer layer, on the side surface of the polarizer layer of the protective film, in order to improve the adhesion with the polarizer layer, plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) ) Treatment, saponification treatment, and other surface treatments (easy-adhesion treatment), it is preferable to perform plasma treatment, corona treatment, or saponification treatment. For example when the protective film consists of a ring When the resin composition is formed into a polyolefin resin, a plasma treatment or a corona treatment is generally performed. In addition, when composed of a cellulose ester resin, a saponification treatment is generally performed. Examples of the saponification treatment include a method of immersing in an alkali aqueous solution such as sodium hydroxide or potassium hydroxide.
保護膜的厚度較薄者為佳,但若過薄,強度會降低,使加工性變差。另一方面,若過厚,會產生透明性降低,或是貼合後所需的熟化時間增長等問題。因此,保護膜的厚度較佳為90μm以下,尤佳為5至60μm,更佳為5至50μm。此外,從偏光板的薄膜化之觀點來看,偏光器層與保護膜之合計厚度較佳為100μm以下,尤佳為90μm以下,更佳為80μm以下。 The thickness of the protective film is preferably thin, but if it is too thin, the strength is reduced and the workability is deteriorated. On the other hand, if it is too thick, problems such as a decrease in transparency or an increase in the curing time required after bonding may occur. Therefore, the thickness of the protective film is preferably 90 μm or less, more preferably 5 to 60 μm, and even more preferably 5 to 50 μm. From the viewpoint of thinning the polarizing plate, the total thickness of the polarizer layer and the protective film is preferably 100 μm or less, particularly preferably 90 μm or less, and more preferably 80 μm or less.
(黏接劑) (Adhesive)
黏接劑可使用水系黏接劑或光硬化性黏接劑。水系黏接劑可列舉出由聚乙烯醇系樹脂水溶液所構成之黏接劑、水系雙液型胺甲酸乙酯系乳化黏接劑等。尤其當使用以皂化處理等進行表面處理(親水化處理)後之纖維素酯系樹脂膜作為保護膜時,較佳係使用由聚乙烯醇系樹脂水溶液所構成之水系黏接劑。 As the adhesive, a water-based adhesive or a photocurable adhesive can be used. Examples of the water-based adhesive include an adhesive composed of an aqueous solution of a polyvinyl alcohol resin, an aqueous two-liquid urethane-based emulsified adhesive, and the like. In particular, when a cellulose ester-based resin film subjected to a surface treatment (hydrophilization treatment) by a saponification treatment or the like is used as a protective film, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is preferably used.
聚乙烯醇系樹脂除了使乙酸乙烯酯的單聚物之聚乙酸乙烯酯進行皂化處理所得之乙烯醇均聚物之外,亦可使用對乙酸乙烯酯及可與此共聚合之其他單體之共聚物進行皂化處理所得之聚乙烯醇系共聚物、或將此等的羥基予以部分地改質之改質聚乙烯醇系共聚物等。水系黏接劑可含有多元醛、水溶性環氧化合物、三聚氰胺系化 合物、鋯化合物、鋅化合物等之添加劑。使用水系黏接劑時,由此所得之黏接劑層的厚度,一般為1μm以下。 In addition to the polyvinyl alcohol homopolymer obtained by saponifying the polyvinyl acetate monopolymer of polyvinyl acetate, the polyvinyl alcohol resin can also be used for vinyl acetate and other monomers copolymerizable therewith. A polyvinyl alcohol-based copolymer obtained by saponifying the copolymer, or a modified polyvinyl alcohol-based copolymer in which the hydroxyl groups are partially modified. Water-based adhesives may contain polyaldehydes, water-soluble epoxy compounds, and melamine-based compounds Compounds, zirconium compounds, zinc compounds and other additives. When a water-based adhesive is used, the thickness of the adhesive layer thus obtained is generally 1 μm or less.
將水系黏接劑塗佈於偏光性積層膜的偏光器層上及/或保護膜上,並介由黏接劑層貼合此等膜,較佳為使用貼合輥等而進行加壓並使其密著以實施貼合步驟。水系黏接劑(對於光硬化性黏接劑亦同)的塗佈方法並無特別限制,可使用垂流法、繞線棒塗佈法、凹版塗佈法、缺角輪塗佈法、刮刀式塗佈法、模頭塗佈法、浸漬塗佈法、噴霧法等之以往一般所知的方法。 The water-based adhesive is coated on the polarizer layer and / or the protective film of the polarizing laminated film, and these films are bonded via the adhesive layer. It is preferable to press and use a bonding roller and the like. It is made tight to perform the bonding step. The coating method of the water-based adhesive (the same applies to the photocurable adhesive) is not particularly limited, and a vertical flow method, a wire rod coating method, a gravure coating method, a notch wheel coating method, and a doctor blade can be used. Conventionally known methods such as a die coating method, a die coating method, a dip coating method, and a spray method.
當使用水系黏接劑時,在實施上述貼合後,較佳係實施用以去除水系黏接劑中所含有之水而使膜乾燥之乾燥步驟。乾燥係例如可藉由將膜導入於乾燥爐來進行。乾燥溫度(乾燥爐的溫度)較佳為30至90℃。未達30℃時,會有保護膜容易從偏光器層剝離之傾向。此外,當乾燥溫度超過90℃時,會有因熱而導致偏光器層的偏光性能變差之疑慮。乾燥時間可設為10至1000秒,從生產性的觀點來看,較佳為60至750秒,尤佳為150至600秒。 When a water-based adhesive is used, it is preferable to perform a drying step for removing the water contained in the water-based adhesive and drying the film after the above-mentioned bonding is performed. The drying system can be performed, for example, by introducing the film into a drying furnace. The drying temperature (temperature of the drying furnace) is preferably 30 to 90 ° C. When it does not reach 30 degreeC, there exists a tendency for a protective film to peel easily from a polarizer layer. In addition, when the drying temperature exceeds 90 ° C., there is a concern that the polarization performance of the polarizer layer is deteriorated due to heat. The drying time can be set to 10 to 1000 seconds, and from the viewpoint of productivity, it is preferably 60 to 750 seconds, and particularly preferably 150 to 600 seconds.
乾燥步驟後,可設置在室溫或較其略高之溫度例如約20至45℃的溫度進行約12至600小時熟化之熟化步驟。熟化溫度一般係設定較乾燥溫度低。 After the drying step, the curing step may be performed at room temperature or a slightly higher temperature, for example, a temperature of about 20 to 45 ° C., for about 12 to 600 hours. The curing temperature is generally set lower than the drying temperature.
上述光硬化性黏接劑是指以照射紫外線等之活化能射線而硬化之黏接劑,例如可列舉出含有聚合性化合物與光聚合起始劑者、含有光反應性樹脂者、含有黏合劑樹脂及光反應性交聯劑者等。聚合性化合物可列舉出 光硬化性環氧系單體、光硬化性丙烯酸系單體、光硬化性胺甲酸乙酯系單體等之光聚合性單體,或是來自光聚合性單體之低聚物等。光聚合起始劑可列舉出含有藉由照射紫外線等之活性能量線射線以產生中性自由基、陰離子自由基、陽離子自由基之活化物質之物質。含有聚合性化合物及光聚合起始劑之光硬化性黏接劑,較佳可使用含有光硬化性環氧系單體及光陽離子聚合起始劑者。 The photocurable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays, and examples thereof include those containing a polymerizable compound and a photopolymerization initiator, those containing a photoreactive resin, and those containing a binder. Resin and photoreactive crosslinker. Examples of polymerizable compounds A photopolymerizable monomer such as a photocurable epoxy-based monomer, a photocurable acrylic-based monomer, a photocurable urethane-based monomer, or an oligomer derived from the photopolymerizable monomer. Examples of the photopolymerization initiator include those containing an active energy ray irradiated with an ultraviolet ray or the like to generate an activated substance such as a neutral radical, an anionic radical, or a cationic radical. As the photocurable adhesive containing a polymerizable compound and a photopolymerization initiator, a photocurable epoxy-based monomer and a photocationic polymerization initiator are preferably used.
當使用光硬化性黏接劑時,在實施上述貼合後,可依需要而進行乾燥步驟(當光硬化性黏接劑包含溶劑時等),接著進行藉由照射活性能量線射線而使光硬化性黏接劑硬化之硬化步驟。活性能量線的光源並無特別限定,較佳為在波長400nm以下具有發光分布之活性能量線,具體而言,較佳可使用低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、化學燈、黑燈、微波激發汞燈、金屬鹵化物燈等。 When a photocurable adhesive is used, after the above-mentioned bonding is performed, a drying step (when the photocurable adhesive contains a solvent, etc.) may be performed as necessary, and then light is irradiated with active energy rays. Hardening step of hardening adhesive. The light source of the active energy ray is not particularly limited, and preferably an active energy ray having a luminous distribution below a wavelength of 400 nm. Specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high-pressure mercury lamp are preferably used , Chemical lamp, black lamp, microwave excited mercury lamp, metal halide lamp, etc.
對光硬化性黏接劑之光照射強度,可依據光硬化性黏接劑的組成而適當地決定,較佳為以使對於聚合起始劑的活性化有效之波長區的照射強度成為0.1至6000mW/cm2之方式來設定。當照射強度為0.1mW/cm2以上時,反應時間不會過長,為6000mW/cm2以下時,因從光源所輻射出的熱以及光硬化性黏接劑於硬化時的放熱所造成之光硬化性黏接劑的黃變或偏光器層的劣化之疑慮低。 The light irradiation intensity of the photocurable adhesive can be appropriately determined depending on the composition of the photocurable adhesive, and it is preferable that the irradiation intensity in the wavelength region effective for activation of the polymerization initiator is 0.1 to 6000mW / cm 2 of the embodiment is set. When the irradiation intensity of 0.1mW / cm 2 or more, the reaction time is not too long, when 6000mW / cm 2 or less, because when the heat radiated from the heat source and a light-curing bonding agent in the curing caused by There is little doubt about yellowing of the photocurable adhesive or deterioration of the polarizer layer.
關於對光硬化性黏接劑之光照射時間,亦可依光硬化性黏接劑的組成而適當地決定,較佳以使以上 述照射強度與照射時間之積所表示之積算光量成為10至10000mJ/cm2之方式來設定。當積算光量為10mJ/cm2以上時,可充分地產生來自光聚合起始劑的活性物質,而更確實地進行硬化反應,為10000mJ/cm2以下時,照射時間不會過長,可維持良好的生產性。 The light irradiation time to the photocurable adhesive may be appropriately determined depending on the composition of the photocurable adhesive, and it is preferable that the total light amount expressed by the product of the above-mentioned irradiation intensity and irradiation time is 10 to 10000mJ / cm 2 of the embodiment is set. When the accumulated light quantity is 10mJ / cm 2 or more, can be sufficiently generated from the active material of the photopolymerization initiator, the curing reaction more reliably performed, when 10000mJ / cm 2 or less, the irradiation time is not too long, can be maintained Good productivity.
活性能量線照射後之黏接劑層的厚度,一般為0.001至5μm,較佳為0.01至2μm以下,更佳為0.01至1μm。 The thickness of the adhesive layer after active energy ray irradiation is generally 0.001 to 5 μm, preferably 0.01 to 2 μm or less, and more preferably 0.01 to 1 μm.
(黏著劑) (Adhesive)
可使用於保護膜的貼合之黏著劑,一般是由以丙烯酸系樹脂、苯乙烯系樹脂、聚矽氧系樹脂等為基質,於其中加入異氰酸酯化合物、環氧化合物、氮丙啶化合物般之交聯劑之黏著劑組成物所構成。亦可構成為進一步含有微粒以顯現光散射性之黏著劑層。 Adhesives that can be used for the adhesion of protective films generally consist of an acrylic resin, a styrene resin, a polysiloxane resin, or the like as a matrix, and an isocyanate compound, an epoxy compound, or an aziridine compound is added thereto. It is composed of an adhesive composition of a crosslinking agent. It may be configured as an adhesive layer further containing fine particles to express light scattering properties.
黏著劑層的厚度可為1至40μm,在不損及加工性、耐久性的特性之範圍內,較佳係薄塗,具體而言,較佳為3至25μm。3至25μm的厚度,具有良好的加工性,且就抑制偏光器層的尺寸變化上亦適宜。當黏著劑層未達1μm時,黏著性降低,超過40μm時,容易產生黏著劑滲出等缺失。於使用黏著劑而將保護膜貼合於偏光器層之方法中,可在將黏著劑層設置在保護膜面後,貼合於偏光器層,或是在將黏著劑層設置在偏光器層後,再貼合保護膜。 The thickness of the adhesive layer may be 1 to 40 μm, and as long as the processability and durability are not impaired, thin coating is preferable, and specifically, 3 to 25 μm is preferable. It has a thickness of 3 to 25 μm, has good processability, and is also suitable for suppressing the dimensional change of the polarizer layer. When the adhesive layer is less than 1 μm, the adhesiveness is reduced, and when it exceeds 40 μm, it is easy to cause the loss of the adhesive such as bleeding. In the method of bonding the protective film to the polarizer layer using an adhesive, the adhesive layer may be mounted on the protective film surface and then bonded to the polarizer layer, or the adhesive layer may be mounted on the polarizer layer. Then, attach the protective film.
形成黏著劑層之方法並無特別限定,可將 含有以上述基質聚合物為首之各成分之黏著劑組成物(黏著劑溶液)塗佈於保護膜面或偏光器層面,並進行乾燥而形成黏著劑層後,貼合保護膜與偏光器層,或是在將黏著劑層形成於分隔片(剝離膜)後,將該黏著劑層轉印至保護膜面或偏光膜面,接著貼合保護膜與偏光器層。將黏著劑層形成於保護膜面或偏光器層面時,可依需要而對保護膜面或偏光器層面,或是黏著劑層的單面或雙面施以表面處理,例如電暈處理等。 The method for forming the adhesive layer is not particularly limited. An adhesive composition (adhesive solution) containing each component including the above matrix polymer is coated on a protective film surface or a polarizer layer, and dried to form an adhesive layer, and then the protective film and the polarizer layer are bonded, Alternatively, after the adhesive layer is formed on the separator (release film), the adhesive layer is transferred to the protective film surface or the polarizing film surface, and then the protective film and the polarizer layer are bonded together. When the adhesive layer is formed on the surface of the protective film or the polarizer, the surface of the protective film or the surface of the polarizer or one or both sides of the adhesive layer may be subjected to surface treatment, such as corona treatment, as required.
[5]剝離步驟S50 [5] Stripping step S50
本步驟係從貼合保護膜所得之貼合膜,將基材膜剝離並去除之步驟。經過此步驟,可得到於偏光器層上積層有保護膜且不具有基材膜之偏光板。當偏光性積層膜於基材膜的雙面具有偏光器層,並將保護膜貼合於此等兩者的偏光器層時,藉由此剝離步驟S50,可從1片偏光性積層膜得到2片偏光板。 This step is a step of peeling and removing the base film from the bonding film obtained by bonding the protective film. After this step, a polarizing plate with a protective film and no base film laminated on the polarizer layer can be obtained. When the polarizing laminated film has polarizer layers on both sides of the base film, and a protective film is attached to the polarizer layers of these two, by peeling off step S50, one polarizing laminated film can be obtained. 2 polarizing plates.
將基材膜剝離並去除之方法並無特別限定,可以與一般附有黏著劑的偏光板所進行之分隔片(剝離膜)的剝離步驟相同之方法來剝離。基材膜係可於貼合步驟S40後,直接立即剝離,或是於貼合步驟S40後,先捲取為捲狀,並在之後的步驟一邊捲出一邊剝離。 The method for peeling and removing the base film is not particularly limited, and it can be peeled in the same manner as the peeling step of a separator (release film) performed by a polarizing plate with an adhesive generally attached. The base film can be peeled off immediately after the bonding step S40, or after the bonding step S40, it can be rolled up into a roll shape and peeled off after being rolled out in the subsequent steps.
以如上述做法所製造之偏光板,於實際使用時亦可使用作為積層有其他光學層之光學膜。此外,保護膜亦可具有如此光學層之功能。其他光學層可列舉出:可使某種偏光光穿透並且使顯現出與其相反性質之偏光光 反射之反射型偏光膜;於表面具有凹凸形狀之附防眩功能的膜;附表面抗反射功能的膜;於表面具有反射功能之反射膜;兼具反射功能及穿透功能之半穿透反射膜;視角補償膜等。 The polarizing plate manufactured as described above can also be used as an optical film laminated with other optical layers in actual use. In addition, the protective film may also function as such an optical layer. Examples of other optical layers include: a type of polarized light that can penetrate and exhibits the opposite property Reflective reflective polarizing film; film with anti-glare function on the surface with concave and convex shape; film with anti-reflection function on the surface; reflective film with reflective function on the surface; semi-transparent reflection with both reflection function and transmission function Film; viewing angle compensation film, etc.
相當於可使某種偏光光穿透並且使顯現出與其相反性質之偏光光反射之反射型偏光膜之市售品,例如可列舉出「DBEF」(3M公司製,於日本可從Sumitomo 3M股份有限公司取得)、「APF」(3M公司製,於日本可從Sumitomo 3M股份有限公司取得)。 It is equivalent to a commercially available reflective polarizing film that can penetrate a certain type of polarized light and reflect the polarized light of the opposite property. For example, "DBEF" (manufactured by 3M Corporation, available from Sumitomo 3M in Japan) Co., Ltd.), "APF" (manufactured by 3M, available in Japan from Sumitomo 3M Co., Ltd.).
視角補償膜係可列舉出在基材表面塗佈液晶性化合物並進行配向及固定之光學補償膜、由聚碳酸酯系樹脂所構成之相位差膜、以及由環狀聚烯烴系樹脂所構成之相位差膜等。 Examples of the viewing angle compensation film include an optical compensation film coated with a liquid crystal compound on the surface of the substrate, aligned and fixed, a retardation film made of a polycarbonate resin, and a cyclic polyolefin resin. Retardation film, etc.
相當於在基材表面塗佈液晶性化合物並進行配向及固定之光學補償膜之市售品,可列舉出「WV Film」(Fuji Film股份有限公司製)、「NH Film」(JX Nippon Oil and Energy股份有限公司製)、「NR Film」(JX Nippon Oil and Energy股份有限公司製)等。 Commercial products equivalent to optical compensation films that are coated with a liquid crystal compound on the substrate surface and aligned and fixed include "WV Film" (manufactured by Fuji Film Co., Ltd.) and "NH Film" (JX Nippon Oil and Energy Co., Ltd.), "NR Film" (JX Nippon Oil and Energy Co., Ltd.), etc.
相當於由環狀聚烯烴系樹脂所構成之相位差膜之市售品,可列舉出「ARTON Film」(JSR股份有限公司製)、「S-SINA」(積水化學工業股份有限公司製)、「ZEONOR Film」(Zeon股份有限公司製)等。 Examples of commercially available products equivalent to a retardation film made of a cyclic polyolefin resin include "ARTON Film" (made by JSR Corporation), "S-SINA" (made by Sekisui Chemical Industry Co., Ltd.), "ZEONOR Film" (manufactured by Zeon Corporation).
以下,係顯示實施例而更具體地說明本發 明,但本發明並不限定於此等實施例。 Hereinafter, the present invention will be described more specifically by showing examples. The invention is not limited to these examples.
〈實施例1〉 <Example 1>
(1)基材膜的製作 (1) Production of substrate film
藉由使用多層擠壓成形機之共擠壓成形,來製作出3層構造之長條的基材膜;而該3層構造之長條的基材膜係將由丙烯的單聚物「Sumitomo Nobrene FLX80E4」、熔點Tm=163℃)所構成之樹脂層,配置在由含有乙烯單元約5重量%之乙烯/丙烯隨機共聚物(住友化學股份有限公司製的「Sumitomo Nobrene W151」、熔點Tm=138℃)所構成之樹脂層的雙面上。所得之基材膜的厚度為90μm,各層的厚度比(FLX80E4/W151/ FLX80E4)為3/4/3。 A three-layer structured long base film is produced by co-extrusion molding using a multilayer extrusion molding machine; and the three-layer structure long base film is made of a propylene monomer "Sumitomo Nobrene" FLX80E4 ", melting point Tm = 163 ° C) resin layer composed of an ethylene / propylene random copolymer (" Sumitomo Nobrene W151 "manufactured by Sumitomo Chemical Co., Ltd., containing about 5 wt% of ethylene units, melting point Tm = 138 ° C) on both sides of the resin layer. The thickness of the obtained base film was 90 μm, and the thickness ratio (FLX80E4 / W151 / FLX80E4) of each layer was 3/4/3.
(2)底漆層形成步驟 (2) Primer layer forming step
將聚乙烯醇粉末(日本合成化學工業股份有限公司製的「Z-200」、平均聚合度1100、平均皂化度99.5莫耳%)溶解於95℃的熱水中,調製出濃度3重量%的聚乙烯醇水溶液。以相對於聚乙烯醇粉末6重量份為5重量份之比率,將交聯劑(田岡化學工業股份有限公司製的「Sumirez Resin 650」)混合於所得之水溶液,而得到底漆層形成用塗佈液。 Polyvinyl alcohol powder ("Z-200" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average degree of polymerization 1100, average degree of saponification 99.5 mole%) was dissolved in hot water at 95 ° C to prepare a 3% by weight Polyvinyl alcohol aqueous solution. A cross-linking agent ("Sumirez Resin 650" made by Taoka Chemical Industry Co., Ltd.) was mixed with the obtained aqueous solution at a ratio of 5 parts by weight to 6 parts by weight of the polyvinyl alcohol powder to obtain a primer layer-forming coating. Cloth fluid.
一邊連續地運送上述(1)中所製作之基材膜一邊對該單面施以電暈處理,使用微凹版塗佈機將上述底漆層形成用塗佈液連續地塗佈於該電暈處理面,於80℃乾燥10分鐘而藉此形成厚度0.2μm的底漆層。此外,對基材膜之另一面亦施予電暈處理,並與上述相同地於該電暈處理面形成厚度0.2μm的底漆層,以得到於雙面具有底漆 層之基材膜。 Corona treatment was applied to the one side while the base film produced in (1) was continuously conveyed, and the coating solution for forming the primer layer was continuously applied to the corona using a microgravure coater. The treated surface was dried at 80 ° C. for 10 minutes to form a primer layer having a thickness of 0.2 μm. In addition, the other side of the substrate film was also subjected to a corona treatment, and a primer layer having a thickness of 0.2 μm was formed on the corona treated surface in the same manner as described above to obtain a primer on both sides. Layer of substrate film.
(3)積層膜的製作(樹脂層形成步驟) (3) Production of laminated film (resin layer forming step)
將聚乙烯醇粉末(Kuraray股份有限公司製的「PVA124」、平均聚合度2400、平均皂化度98.0至99.0莫耳%)溶解於95℃的熱水,調製出濃度8重量%的聚乙烯醇水溶液,並以此作為聚乙烯醇系樹脂層形成用塗佈液。 Polyvinyl alcohol powder ("PVA124" manufactured by Kuraray Co., Ltd., average degree of polymerization 2400, average degree of saponification 98.0 to 99.0 mole%) was dissolved in hot water at 95 ° C to prepare an 8% by weight aqueous solution of polyvinyl alcohol This was used as a coating liquid for forming a polyvinyl alcohol-based resin layer.
一邊連續地運送上述(2)中所製作之於雙面具有底漆層之基材膜,一邊使用模唇塗佈機將上述聚乙烯醇系樹脂層形成用塗佈液連續地塗佈於一者的底漆層表面,於80℃乾燥2分鐘、於70℃乾燥2分鐘、接著於60℃乾燥4分鐘,藉此於底漆層上形成聚乙烯醇系樹脂層。此外,於另一底漆層表面,亦與上述相同地形成聚乙烯醇系樹脂層,藉此得到積層膜。積層膜之聚乙烯醇系樹脂層的厚度,分別為10.5μm、10.2μm。 While continuously conveying the base film having the primer layer on both sides produced in the above (2), the coating liquid for forming a polyvinyl alcohol-based resin layer was continuously applied to a substrate using a die lip coater. The surface of the primer layer was dried at 80 ° C for 2 minutes, then at 70 ° C for 2 minutes, and then at 60 ° C for 4 minutes, thereby forming a polyvinyl alcohol-based resin layer on the primer layer. In addition, a polyvinyl alcohol-based resin layer was formed on the surface of the other primer layer in the same manner as described above, thereby obtaining a laminated film. The thickness of the polyvinyl alcohol-based resin layer of the laminated film was 10.5 μm and 10.2 μm, respectively.
(4)延伸膜的製作(延伸步驟) (4) Production of stretch film (stretching step)
一邊連續地運送上述(3)中所製作之積層膜,一邊使用輥間延伸裝置,在160℃的延伸溫度(加熱爐內的環境溫度),以5.8倍的倍率朝縱方向施予自由端單軸延伸,並連續地製作延伸膜,然後依序捲取而得到延伸膜的膜捲。延伸膜之2層聚乙烯醇系樹脂層的厚度,分別為5.1μm、4.9μm。 While continuously transporting the laminated film produced in the above (3), using a roll-to-roll stretching device, a free end sheet was applied in a longitudinal direction at a stretching temperature of 160 ° C (ambient temperature in a heating furnace) at a magnification of 5.8 times. The shaft is stretched, a stretched film is continuously produced, and then sequentially wound up to obtain a film roll of the stretched film. The thickness of the two polyvinyl alcohol-based resin layers of the stretched film was 5.1 μm and 4.9 μm, respectively.
重複進行上述(1)至(4)的步驟,而製作出合計2捲的延伸膜捲。 The steps (1) to (4) described above are repeated to produce a total of 2 rolls of stretched film rolls.
(5)偏光性積層膜的製作(染色步驟) (5) Production of polarizing laminated film (dyeing step)
用以實施染色步驟之運送路徑(產線路徑),於染色槽40及交聯槽50之間包含第1洗淨槽,並且於交聯槽50之後包含第2洗淨槽,除此之外,其他使用與第2圖相同之裝置而實施染色步驟,製作出偏光性積層膜。於第2洗淨槽的下游側設置乾燥爐。因此,沿著此運送路徑而被運送之延伸膜,係依序通過染色槽40、第1洗淨槽、交聯槽、第2洗淨槽、乾燥爐而成為偏光性積層膜。 The conveying path (production line path) for performing the dyeing step includes a first washing tank between the dyeing tank 40 and the cross-linking tank 50, and a second washing tank after the cross-linking tank 50. In other cases, the same device as in FIG. 2 was used to perform the dyeing step to produce a polarizing laminated film. A drying furnace is installed on the downstream side of the second washing tank. Therefore, the stretched film transported along this transport path passes through the dyeing tank 40, the first cleaning tank, the cross-linking tank, the second cleaning tank, and the drying furnace in this order to become a polarizing laminated film.
於染色槽40中,容納有相對於水每100重量份為0.35重量份的碘、以及10重量份的碘化鉀之30℃的染色溶液41。於交聯槽50中,容納有相對於水每100重量份為9.5重量份的硼酸、以及5重量份的碘化鉀之75℃的交聯溶液51。於第1洗淨槽及第2洗淨槽中,分別容納有10℃的純水。乾燥爐係其爐內溫度被調整至80℃。 The dyeing tank 40 contains a dyeing solution 41 at 30 ° C. of 0.35 parts by weight of iodine per 100 parts by weight of water and 10 parts by weight of potassium iodide. In the cross-linking tank 50, a cross-linking solution 51 at 75 ° C. containing 9.5 parts by weight of boric acid per 5 parts by weight of water and 5 parts by weight of potassium iodide was contained. In the first and second washing tanks, pure water at 10 ° C was stored. In the drying furnace, the temperature in the furnace was adjusted to 80 ° C.
具體而言,係以下列方式實施染色步驟以製作偏光性積層膜。首先從上述(4)所製作之延伸膜捲的1個中,連續地捲出作為第1膜之延伸膜,並沿著上述運送路徑而連續地運送,藉此對第1膜連續地依序實施:以浸漬(滯留時間:150秒)在染色槽40中之聚乙烯醇系樹脂層的染色處理、以浸漬(滯留時間:4秒)在第1洗淨槽中進行多餘染色溶液洗去之第1洗淨處理、以浸漬(滯留時間:600秒)在交聯槽50中之交聯處理、以浸漬(滯留時間:4秒)在第2洗淨槽中進行多餘交聯溶液洗去之第2洗淨處理、以通過乾燥爐內(滯留時間:300秒)之乾燥處理。 Specifically, the dyeing step is performed in the following manner to produce a polarizing laminated film. First, from one of the stretched film rolls produced in the above (4), the stretched film as the first film is continuously rolled out and continuously conveyed along the conveying path, so that the first film is sequentially sequentially Implementation: Dyeing treatment of the polyvinyl alcohol-based resin layer in the dyeing tank 40 by immersion (retention time: 150 seconds), washing with excess dyeing solution in the first washing tank by immersion (retention time: 4 seconds) The first washing treatment is performed by dipping (retention time: 600 seconds) in the crosslinking tank 50, and the dipping (retention time: 4 seconds) is performed by removing excess crosslinking solution in the second washing tank. The second washing treatment is a drying treatment that passes through a drying furnace (residence time: 300 seconds).
以上述(4)所製作之另1個延伸膜捲之延伸 膜作為第2膜。 Extending with another stretch film roll made in (4) above The film was used as the second film.
當來自膜捲之第1膜的捲出接近於結束時,在暫時停止第1膜的運送之狀態下,使用雙面膠帶,如第3圖般以具有1處的帶狀黏接區15a之方式將第1膜的終端部與第2膜的起端部接合後,再次啟動膜的運送,並接下來沿著上述運送路徑連續地運送第1膜與第2膜之接合部、以及第2膜,藉此實施染色處理、第1洗淨處理、交聯處理、第2洗淨處理、乾燥處理至第2膜的終端部為止。在染色槽40附近測定出對沿著上述運送路徑被運送之膜施加的張力,結果為125N/m。 When the unwinding of the first film from the film roll is nearing the end, in a state in which the transport of the first film is temporarily stopped, a double-sided tape is used, as shown in FIG. After the terminal portion of the first film and the start portion of the second film are joined, the transport of the film is restarted, and then the joint portion of the first film and the second film is continuously transported along the transport path, and the second The film is thereby subjected to a dyeing treatment, a first washing treatment, a crosslinking treatment, a second washing treatment, and a drying treatment up to the terminal portion of the second film. The tension applied to the film conveyed along the conveyance path was measured near the dyeing tank 40, and it was 125 N / m.
〈實施例2〉 <Example 2>
除了將對沿著運送路徑被運送之膜施加的張力變更為500N/m之外,其他與實施例1相同而製作出偏光性積層膜。 A polarizing laminated film was produced in the same manner as in Example 1 except that the tension applied to the film transported along the transport path was changed to 500 N / m.
〈實施例3〉 <Example 3>
除了將對沿著運送路徑被運送之膜施加的張力變更為1000N/m之外,其他與實施例1相同而製作出偏光性積層膜。 A polarizing laminated film was produced in the same manner as in Example 1 except that the tension applied to the film transported along the transport path was changed to 1000 N / m.
〈實施例4〉 <Example 4>
除了使用由從膜捲被捲出之被雙軸延伸的聚丙烯膜所構成之導引膜作為第1膜之外,其他與實施例3相同而製作出偏光性積層膜。 A polarizing laminated film was produced in the same manner as in Example 3 except that a guide film composed of a biaxially stretched polypropylene film rolled out from a film roll was used as the first film.
〈實施例5〉 <Example 5>
除了使用由從膜捲被捲出之被雙軸延伸的聚丙烯膜所構成之導引膜作為第2膜之外,其他與實施例3相同而製 作出偏光性積層膜。 Except for using a guide film composed of a biaxially stretched polypropylene film rolled out from a film roll as the second film, it was produced in the same manner as in Example 3. Make a polarizing laminated film.
〈實施例6〉 <Example 6>
除了以具有2處的帶狀黏接區15a之方式藉由熱封接合第1膜的終端部與第2膜的起端部之外,其他與實施例3相同而製作出偏光性積層膜。 A polarizing laminated film was produced in the same manner as in Example 3, except that the terminal portion of the first film and the starting portion of the second film were joined by heat sealing so as to have two band-shaped adhesive regions 15a.
〈實施例7〉 <Example 7>
除了使用由從膜捲被捲出之被雙軸延伸的聚丙烯膜所構成之導引膜作為第1膜之外,其他與實施例6相同而製作出偏光性積層膜。 A polarizing laminated film was produced in the same manner as in Example 6 except that a guide film composed of a biaxially stretched polypropylene film rolled out from a film roll was used as the first film.
〈實施例8〉 <Example 8>
除了使用由從膜捲被捲出之被雙軸延伸的聚丙烯膜所構成之導引膜作為第2膜之外,其他與實施例6相同而製作出偏光性積層膜。 A polarizing laminated film was produced in the same manner as in Example 6 except that a guide film composed of a biaxially stretched polypropylene film rolled out from a film roll was used as the second film.
〈比較例1〉 <Comparative Example 1>
除了使用由聚乙烯醇所構成之單層膜(Kuraray股份有限公司製的「VF-PS 7500」)的膜捲取代經過實施例1的(1)至(4)所製作之延伸膜的膜捲以作為第1及第2膜的膜捲、以在染色槽40及交聯槽50內使總延伸倍率成為5.0倍之方式進行縱向單軸延伸、以具有1處的帶狀黏接區15a之方式藉由熱封接合第1膜的終端部與第2膜的起端部、以及將對沿著運送路徑而被運送之膜施加的張力變更為400N/m之外,其他與實施例1相同而製作出偏光性積層膜。 In addition to using a film roll of a single-layer film ("VF-PS 7500" made by Kuraray Co., Ltd.) made of polyvinyl alcohol instead of the roll of the stretched film produced in (1) to (4) of Example 1 The film rolls as the first and second films are longitudinally uniaxially stretched so that the total stretching ratio becomes 5.0 times in the dyeing tank 40 and the cross-linking tank 50, and have a single tape-shaped adhesive region 15a. The method is the same as in Example 1 except that the terminal portion of the first film and the start portion of the second film are joined by heat sealing, and the tension applied to the film to be transported along the transport path is changed to 400 N / m. A polarizing laminated film was produced.
〈比較例2〉 <Comparative Example 2>
除了以具有2處的帶狀黏接區15a之方式接合第1膜 的終端部與第2膜的起端部之外,其他與比較例1相同而製作出偏光性積層膜。 Except for joining the first film with two band-shaped adhesive regions 15a A polarizing laminated film was produced in the same manner as in Comparative Example 1 except for the terminal portion of the second film and the starting portion of the second film.
[連續製造性的評估及偏光性積層膜之偏光性能的評估] [Evaluation of continuous manufacturability and evaluation of polarizing performance of polarizing laminated film]
(連續製造性的評估) (Evaluation of continuous manufacturing)
對各實施例及比較例,根據下列評估基準而評估偏光性積層膜的連續製造性。結果如第1表所示。 For each Example and Comparative Example, the continuous manufacturability of the polarizing laminated film was evaluated according to the following evaluation criteria. The results are shown in Table 1.
A:於染色步驟之間,於第1膜與第2膜之接合部未觀察到斷裂、剝離、皺褶等缺失,而能夠無問題地沿著染色步驟的運送路徑連續地運送第1膜及接合於此之第2膜,可連續地製造偏光性積層膜。 A: Between the dyeing step, no breaks, peeling, or wrinkles were observed at the joint between the first film and the second film, and the first film and the film can be continuously transported along the transport path of the dyeing step without problems. The second film bonded to this makes it possible to continuously manufacture a polarizing laminated film.
B:於染色步驟實施中,於膜上觀察到斷裂、接合部之剝離、接合部之皺褶等缺失,難謂可無問題地連續製造偏光性積層膜。 B: In the implementation of the dyeing step, cracks, peeling of the joint portion, and wrinkles of the joint portion were observed on the film. It is difficult to say that the polarizing laminated film can be continuously manufactured without problems.
(偏光性積層膜之偏光性能的評估) (Evaluation of polarizing performance of polarizing laminated film)
對各實施例中所得之偏光性積層膜,測定第1膜與第2膜之接合部附近之膜部分的偏光性能(發光因子修正單體穿透率及發光因子修正偏光度),且與遠離接合部之膜部分的偏光性能比較,並根據下列評估基準來評估。結果如第1表所示。接合部附近之膜部分,對於使用導引膜作為第1膜之實施例4及7,為接合部後之膜部分,對於使用導引膜作為第2膜之實施例5及8,為接合部前之膜部分,對於其他實施例,為接合部前及後之膜部分。 For the polarized laminated films obtained in each example, the polarization performance (light-emitting factor-corrected monomer transmittance and light-factor-corrected polarization) of the film portion near the junction between the first film and the second film was measured, The polarization performance of the film portion of the joint was compared and evaluated based on the following evaluation criteria. The results are shown in Table 1. The film portions near the joint portion are the portions after the joint portion in Examples 4 and 7 using the guide film as the first film, and the embodiments 5 and 8 using the guide film as the second film are the joint portion. The front film portion, for other embodiments, is the film portion before and after the joint.
A:接合部附近之膜部分的偏光性能,與遠離接合部之膜部分的偏光性能為同等。 A: The polarization performance of the film portion near the junction is equivalent to the polarization performance of the film portion far from the junction.
B:接合部附近之膜部分的偏光性能,與遠離接合部之膜部分的偏光性能相比顯著地降低。 B: The polarization performance of the film portion in the vicinity of the bonding portion is significantly lower than that of the film portion away from the bonding portion.
偏光性積層膜的發光因子修正單體穿透率及發光因子修正偏光度,係以使用黏著膠帶將位於基材膜的雙面之偏光器層中之一者的偏光器層予以剝離並去除者作為測定樣本,使用日本分光股份有限公司製的分光光度儀「V7100」,藉由使光從偏光器層入射而測定。 The luminous factor correction monomer transmittance and the luminous factor correction polarization of the polarizing laminated film are obtained by using an adhesive tape to peel off and remove one of the polarizer layers on one of the two polarizer layers on the base film. As a measurement sample, a spectrophotometer "V7100" manufactured by Japan Spectroscopy Co., Ltd. was used, and the measurement was performed by making light incident from a polarizer layer.
如第1表所示,實施例1至8中,即使沿著用以實施染色步驟之運送路徑而運送第1膜與第2膜之接合部,於接合部上亦不會產生膜的斷裂、剝離、皺褶等缺失,而可連續地製造偏光性積層膜。實施例1至8中,除了染色溶液41之外,亦將接合部浸漬在76℃高溫的交聯溶液51,但即使將接合部浸漬在如此之容易產生變形的藥液中,亦不會產生斷裂、剝離。此外,實施例2至8中,與實施例1相比,係在增大施加於膜的張力且更容易產生膜的斷裂之條件下進行染色步驟,但亦未產生膜的斷裂或剝離。再者,於實施例1至8中,偏光性積層膜之接合部附近的偏光性能,與遠離接合部之部分的偏光性能為同等,並未觀察到因接合導致偏光性能的降低,所以可使膜損耗抑制在未達1m。 As shown in Table 1, in Examples 1 to 8, even if the joint portion of the first film and the second film is transported along the transport path for performing the dyeing step, no film breakage, Delamination, wrinkles, etc. are missing, and a polarizing laminated film can be continuously manufactured. In Examples 1 to 8, in addition to the dyeing solution 41, the joint portion was immersed in the cross-linking solution 51 at a high temperature of 76 ° C. However, even if the joint portion was immersed in such a chemical solution that easily deformed, it did not occur Break and peel. In addition, in Examples 2 to 8, as compared with Example 1, the dyeing step was performed under the condition that the tension applied to the film was increased and film breakage was more likely to occur, but film breakage or peeling did not occur. Furthermore, in Examples 1 to 8, the polarization performance in the vicinity of the bonding portion of the polarizing laminated film was equivalent to the polarization performance in the portion far from the bonding portion, and no reduction in polarization performance due to bonding was observed. The film loss is suppressed to less than 1m.
相對於此,在將未延伸的聚乙烯醇單層膜提供至染色步驟,並在染色步驟內進行延伸處理之比較例1及2中,在染色槽40內的延伸處理中,於接合部產生膜的斷裂。 On the other hand, in Comparative Examples 1 and 2 in which an unstretched polyvinyl alcohol monolayer film is provided to the dyeing step and the stretching process is performed in the dyeing step, the stretching process in the dyeing tank 40 is generated at the joint portion. Rupture of the membrane.
實施例2至8中,與比較例1及2相比,施加於膜的張力大,但由於使用聚丙烯系樹脂作為基材膜,所以在上述條件的染色槽40內未被延伸。 In Examples 2 to 8, the tension applied to the film was larger than that of Comparative Examples 1 and 2. However, since polypropylene-based resin was used as the base film, it did not extend in the dyeing tank 40 under the above conditions.
〈參考實施例:偏光板的製作〉 <Reference Example: Production of Polarizing Plate>
將聚乙烯醇粉末(Kuraray股份有限公司製的「KL-318」、平均聚合度1800)溶解於95℃的熱水,調製出濃度3重量%的聚乙烯醇水溶液。以相對於聚乙烯醇粉末2 重量份為1重量份之比率,將交聯劑(田岡化學工業股份有限公司製的「Sumirez Resin 650」)混合於所得之水溶液,而形成黏接劑水溶液。 Polyvinyl alcohol powder ("KL-318" manufactured by Kuraray Co., Ltd., average polymerization degree: 1800) was dissolved in hot water at 95 ° C to prepare a 3% by weight aqueous polyvinyl alcohol solution. Take relative to polyvinyl alcohol powder 2 The weight part is a ratio of 1 weight part, and the crosslinking agent ("Sumirez Resin 650" made by Taoka Chemical Industry Co., Ltd.) was mixed with the obtained aqueous solution, and the adhesive aqueous solution was formed.
一邊連續地運送實施例1中所製作之偏光性積層膜,一邊將上述黏接劑水溶液塗佈於雙面的偏光器層上後,將於貼合面施以皂化處理之保護膜[由三乙醯基纖維素(TAC)所構成之透明保護膜(Konica Minolta Opto股份有限公司製的「KC4UY」、厚度40μm)]貼合於偏光器層上,並通過一對貼合輥之間而藉此壓合,而製作出由TAC/偏光器層/底漆層/基材膜/底漆層/偏光器層/TAC的層構成所形成之貼合膜(貼合步驟)。 While continuously transporting the polarizing laminated film produced in Example 1, the above-mentioned aqueous adhesive solution was applied to the polarizer layer on both sides, and then a protective film of saponification treatment was applied to the bonding surface [from three A transparent protective film ("KC4UY" made by Konica Minolta Opto Co., Ltd., thickness 40 μm) made of acetyl cellulose (TAC) is laminated on the polarizer layer and borrowed between a pair of laminating rollers. This lamination is performed to produce a bonding film composed of a layer structure of TAC / polarizer layer / primer layer / base film / primer layer / polarizer layer / TAC (bonding step).
接著,在基材膜與底漆層之界面上將貼合膜剝離並分割,得到由TAC/偏光器層/底漆層/基材膜所構成之膜、以及由底漆層/偏光器層/TAC所構成之偏光板後,再從前者的膜將基材膜剝離並去除,而得到另1片偏光板。在將基材膜剝離之步驟中,未產生斷裂等缺失。 Next, the bonding film is peeled off and separated at the interface between the base film and the primer layer to obtain a film composed of TAC / polarizer layer / primer layer / base film, and a primer layer / polarizer layer After the polarizing plate composed of / TAC, the base film was peeled off from the former film and removed to obtain another polarizing plate. In the step of peeling the base film, no defects such as breakage occurred.
根據本發明之方法,被提供至染色步驟之偏光膜,為對每個基材膜施以延伸處理之延伸薄膜,且預先進行充分的延伸,故即使將第1膜與第2膜之接合部浸漬在染色槽或交聯槽,亦可抑制該接合部的變形,並且可有效地抑制該接合部上之膜的斷裂或剝離。 According to the method of the present invention, the polarizing film provided to the dyeing step is a stretched film that is subjected to a stretching treatment for each base film and is fully stretched in advance. The immersion in the dyeing tank or the cross-linking tank can also suppress the deformation of the joint portion, and can effectively suppress the cracking or peeling of the film on the joint portion.
若構成為在浸漬在染色槽之步驟中實質上未對膜進行延伸處理,可更有效地抑制以上述浸漬處理所造成之接合 部的變形,並且可防止因將該接合部延伸所產生之皺褶的發生。 If it is comprised so that the film may not be substantially stretched in the step of immersing in a dyeing tank, the joining by the said immersion treatment can be suppressed more effectively The deformation of the portion can be prevented, and the occurrence of wrinkles caused by extending the joint portion can be prevented.
偏光性積層膜的連續製造,必然會伴隨著膜捲的切換,伴隨此,必然會產生先行的膜與接續的膜之接合部,但若根據本發明之方法,對於該接合部,亦不會產生膜的斷裂或剝離,可直接通過用以進行染色步驟之一般的運送路徑(通過染色槽等之運送路徑)。因此可穩定且有效率地連續製造偏光性積層膜。 The continuous production of polarized laminated film will inevitably be accompanied by the switching of the film roll. With this, the joint between the preceding film and the succeeding film will inevitably be produced. However, according to the method of the present invention, the joint will not If the film is broken or peeled off, it can be directly passed through a general conveyance path (through a conveyance path such as a dyeing tank) for performing the dyeing step. Therefore, it is possible to continuously and efficiently manufacture a polarizing laminated film.
此外,若根據本發明之方法,由於可藉由塗佈液的塗佈而形成偏光器層,所以可製造具備薄膜的偏光器層之偏光性積層膜及偏光板。 In addition, according to the method of the present invention, since a polarizer layer can be formed by application of a coating liquid, a polarizing laminated film and a polarizing plate including a thin film polarizer layer can be manufactured.
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