TWI843960B - Polarizing plate set and liquid crystal panel - Google Patents
Polarizing plate set and liquid crystal panel Download PDFInfo
- Publication number
- TWI843960B TWI843960B TW110132088A TW110132088A TWI843960B TW I843960 B TWI843960 B TW I843960B TW 110132088 A TW110132088 A TW 110132088A TW 110132088 A TW110132088 A TW 110132088A TW I843960 B TWI843960 B TW I843960B
- Authority
- TW
- Taiwan
- Prior art keywords
- polarizing plate
- polarizer
- film
- liquid crystal
- back side
- Prior art date
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Images
Abstract
Description
本發明係有關偏光板之套組及液晶面板。 The present invention relates to a set of polarizing plates and a liquid crystal panel.
液晶顯示裝置具有電力消耗低、以低電壓動作、輕量且薄型等特徵，可使用於各種的顯示用元件。構成液晶顯示裝置的液晶面板係具有一對偏光板積層在液晶單元的兩面之構成。 Liquid crystal display devices have the characteristics of low power consumption, low voltage operation, light weight and thinness, and can be used in various display components. The liquid crystal panel that constitutes the liquid crystal display device has a pair of polarizing plates stacked on both sides of the liquid crystal unit.
日本特開2013-37115號公報(參考文獻1)中提出的方式，係使光學積層物前面側所含之偏光膜，較配置在與前面側的相反面之光學積層物中含有的偏光膜更厚5μm以上，並且使配置在與前面側為相反側之光學積層物中含有的偏光膜與反射偏光膜積層，而防止高溫環境下液晶面板之翹曲。此等方式，在使用厚度大的(例如0.5mm以上，再者0.7mm以上)液晶單元、厚度大的(例如50μm以上)反射偏光膜時可發揮效果。不過，如今構成偏光板的各構件除了變得越來越薄、剛度變弱，對於薄質液晶單元而言要防止高溫環境下的液晶面板之翹曲是不夠充分的。 The method proposed in Japanese Patent Publication No. 2013-37115 (reference document 1) is to make the polarizing film contained in the front side of the optical laminate thicker than the polarizing film contained in the optical laminate arranged on the opposite side of the front side by more than 5 μm, and to make the polarizing film contained in the optical laminate arranged on the opposite side of the front side and the reflective polarizing film laminated to prevent the warping of the liquid crystal panel in a high temperature environment. Such methods can be effective when using a thick liquid crystal unit (for example, more than 0.5 mm, more than 0.7 mm) and a thick reflective polarizing film (for example, more than 50 μm). However, the components that make up the polarizer are becoming thinner and weaker, and the thin liquid crystal unit is not sufficient to prevent the warping of the liquid crystal panel in a high temperature environment.
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2013-37115號公報 [Patent Document 1] Japanese Patent Publication No. 2013-37115
本發明的目的是提供一種偏光板之套組，其可減少高溫環境下的液晶面板之翹曲。 The purpose of the present invention is to provide a set of polarizing plates that can reduce the warping of liquid crystal panels in high temperature environments.
[1]一種偏光板之套組，其具有配置在液晶單元的觀察側之前面側偏光板與配置在前述液晶單元的背面之背面側偏光板， [1] A set of polarizing plates, comprising a front-side polarizing plate disposed on the observation side of a liquid crystal cell and a back-side polarizing plate disposed on the back side of the liquid crystal cell,
且以前述前面側偏光板的吸收軸與前述背面側偏光板的吸收軸呈正交方式使前述前面側偏光板與前述背面側偏光板黏合在玻璃板所得之積層體，在85℃加熱250小時時，將85℃的偏光板穿透軸方向之拉伸彈性率及在85℃的偏光板吸收軸方向之拉伸彈性率分別設為Et、Ea時，積層體翹曲成凹狀之側的偏光板之保護膜係滿足下述(1)。 When the laminate obtained by bonding the front polarizer and the back polarizer to a glass plate in such a way that the absorption axis of the front polarizer and the absorption axis of the back polarizer are orthogonal, is heated at 85°C for 250 hours, and the tensile elasticity in the direction of the polarizer's transmission axis at 85°C and the tensile elasticity in the direction of the polarizer's absorption axis at 85°C are set to Et and Ea respectively, the protective film of the polarizer on the side of the laminate that is warped into a concave shape satisfies the following (1).
Et/Ea≧1.1 (1) Et/Ea≧1.1 (1)
[2]如[1]項所述之偏光板之套組，其中，前述前面側偏光板及前述背面側偏光板均具有由聚乙烯醇系樹脂膜形成的偏光片，前述偏光片的厚度均是15μm以下。 [2] The set of polarizing plates as described in item [1], wherein the front polarizing plate and the back polarizing plate both have polarizers formed of polyvinyl alcohol resin films, and the thickness of the polarizers is less than 15 μm.
[3]如[2]項所述之偏光板之套組，其中，前述前面側偏光板係在前述偏光片的至少一面具備活性能量線硬化型樹脂 組成物之硬化層。 [3] A set of polarizing plates as described in item [2], wherein the front polarizing plate is provided with a hardening layer of an active energy ray-hardening resin composition on at least one side of the polarizing plate.
[4]如[2]或[3]項所述之偏光板之套組，其中，前述前面側偏光板係在前述偏光片的一面具備保護膜，而在另一面具備活性能量線硬化型樹脂組成物之硬化層。 [4] A set of polarizing plates as described in [2] or [3], wherein the front polarizing plate is provided with a protective film on one side of the polarizing plate and a hardening layer of an active energy ray-hardening resin composition on the other side.
[5]如[2]至[4]項中任一項所述之偏光板之套組，其中，前述前面側偏光板所具備的偏光片之厚度與前述背面側偏光板所具備的偏光片之厚度之差的大小係5μm以下。 [5] A set of polarizing plates as described in any one of items [2] to [4], wherein the difference between the thickness of the polarizer provided on the front polarizing plate and the thickness of the polarizer provided on the back polarizing plate is less than 5 μm.
[6]一種液晶面板，其具備[1]至[5]項中任一項所述之偏光板之套組，以及液晶單元，前述液晶面板的厚度是0.4mm以下。 [6] A liquid crystal panel comprising a set of polarizing plates as described in any one of items [1] to [5], and a liquid crystal unit, wherein the thickness of the liquid crystal panel is less than 0.4 mm.
若藉由本發明的偏光板之套組即可減少在高溫環境下的液晶面板之翹曲。 The polarizing plate set of the present invention can reduce the warping of liquid crystal panels in high temperature environments.
1:硬化層 1: Hardening layer
2:偏光片 2: Polarizer
10、11:保護膜 10, 11: Protective film
20、21:黏著劑層 20, 21: Adhesive layer
30、31:接著劑層 30, 31: Next is the agent layer
40:亮度改善膜 40: Brightness improvement film
70:玻璃板 70: Glass Plate
80:測定點 80: Measurement point
402:偏光板 402: Polarizing plate
100、101、400:前面側偏光板 100, 101, 400: Front side polarizer
200、201、401:背面側偏光板 200, 201, 401: back side polarizer
300:液晶單元 300: Liquid crystal unit
第1圖係表示本發明的偏光板之套組的一例之剖面圖。 Figure 1 is a cross-sectional view showing an example of a set of polarizing plates of the present invention.
第2圖係表示本發明的液晶面板之一例的剖面圖。 Figure 2 is a cross-sectional view showing an example of a liquid crystal panel of the present invention.
第3圖係將評估用試樣加熱處理之後的示意剖面。 Figure 3 is a schematic cross-section of the evaluation sample after heat treatment.
第4圖係表示測定評估用試樣的翹曲量後之位置的平面圖。 Figure 4 is a plan view showing the position after measuring the warp amount of the evaluation sample.
一邊適宜地參照圖，一邊說明本發明的偏光板之套組及液晶面板。本發明的偏光板之套組係具有配 置在液晶單元的觀察側之前面側偏光板與配置在液晶單元的背面側之背面側偏光板。 The polarizing plate set and liquid crystal panel of the present invention are described while appropriately referring to the figures. The polarizing plate set of the present invention comprises a front side polarizing plate arranged on the observation side of the liquid crystal unit and a back side polarizing plate arranged on the back side of the liquid crystal unit.
一實施形態中，本發明的偏光板是具有第1圖表示的構件。第1圖(a)表示的偏光板之套組，係具有前面側偏光板100與背面側偏光板200。前面側偏光板100係在偏光片2的一面透過接著劑層30而積層保護膜10，在偏光片2的另一面積層活性能量線硬化型接著劑的硬化層1。並且在前述硬化層1上積層黏著劑層20。 In one embodiment, the polarizing plate of the present invention is a component shown in FIG. 1. The polarizing plate set shown in FIG. 1 (a) has a front polarizing plate 100 and a back polarizing plate 200. The front polarizing plate 100 is formed by laminating a protective film 10 on one side of the polarizer 2 through an adhesive layer 30, and laminating a hardening layer 1 of an active energy ray hardening adhesive on the other side of the polarizer 2. An adhesive layer 20 is laminated on the aforementioned hardening layer 1.
背面側偏光板200係在偏光片2的一面透過接著劑層31而積層保護膜11，並在保護膜11上透過黏著劑層21而積層亮度改善膜40。並且在前述偏光片2的另一面積層黏著劑層20。 The back side polarizing plate 200 is formed by laminating a protective film 11 on one side of the polarizer 2 through an adhesive layer 31, and laminating a brightness improvement film 40 on the protective film 11 through an adhesive layer 21. An adhesive layer 20 is also laminated on the other side of the aforementioned polarizer 2.
又，第1圖(b)表示的偏光板之套組係具有前面側偏光板101與背面側偏光板201。前面側偏光板101係在偏光片2的一面透過接著劑層30而積層保護膜10，在偏光片2的另一面積層活性能量線硬化型接著劑的硬化層1。並且在前述硬化層1上積層黏著劑層20。 In addition, the polarizing plate set shown in FIG. 1 (b) has a front polarizing plate 101 and a back polarizing plate 201. The front polarizing plate 101 is formed by laminating a protective film 10 on one side of the polarizer 2 through an adhesive layer 30, and laminating a curing layer 1 of an active energy ray curing adhesive on the other side of the polarizer 2. An adhesive layer 20 is laminated on the aforementioned curing layer 1.
背面側偏光板201係在偏光片2的一面透過接著劑層31而積層保護膜11，在偏光片2的另一面透過黏著劑層21而積層亮度改善膜40。並且在前述保護膜11上積層黏著劑層20。 The back side polarizing plate 201 is formed by laminating a protective film 11 on one side of the polarizer 2 through an adhesive layer 31, and laminating a brightness improvement film 40 on the other side of the polarizer 2 through an adhesive layer 21. An adhesive layer 20 is also laminated on the protective film 11.
第1圖表示的偏光板之套組中，黏著劑層20例如也可以是在液晶單元積層偏光板用之黏著劑層。 In the polarizing plate set shown in FIG. 1, the adhesive layer 20 may be, for example, an adhesive layer for a liquid crystal unit laminated polarizing plate.
本發明的偏光板之套組中，前面側偏光板、 背面側偏光板是以僅在偏光片的一面具備保護膜為佳。 In the polarizing plate set of the present invention, the front polarizing plate and the back polarizing plate are preferably provided with a protective film only on one side of the polarizing plate.
本發明的偏光板之套組中，前面側偏光板及背面側偏光板的形狀並無特別的限制，也可以是矩形。偏光板的形狀為矩形時，前面側偏光板的吸收軸以平行於短邊為佳，背面側偏光板的吸收軸以平行於長邊為佳。 In the polarizing plate set of the present invention, the shapes of the front polarizing plate and the back polarizing plate are not particularly limited and can also be rectangular. When the shape of the polarizing plate is rectangular, the absorption axis of the front polarizing plate is preferably parallel to the short side, and the absorption axis of the back polarizing plate is preferably parallel to the long side.
本發明的偏光板之套組中，在將具備前面側偏光板與背面側偏光板的積層體加熱時，將於85℃的該偏光板之穿透軸方向的拉伸彈性率及於85℃的該偏光板之吸收軸方向的拉伸彈性率分別設為Et、Ea時，具有翹曲成凹狀之側的偏光板所具有之保護膜，係滿足下述(1)。拉伸彈性率可藉由後述的實施例所述之方法測定。 In the polarizing plate set of the present invention, when a laminate having a front polarizing plate and a back polarizing plate is heated, the tensile elasticity of the polarizing plate in the transmission axis direction at 85°C and the tensile elasticity of the polarizing plate in the absorption axis direction at 85°C are set to Et and Ea respectively, and the protective film of the polarizing plate having a side curved into a concave shape satisfies the following (1). The tensile elasticity can be measured by the method described in the embodiment described later.
Et/Ea≧1.1 (1) Et/Ea≧1.1 (1)
Et/Ea是以1.15以上更佳，並以1.20以上又更佳。Et/Ea也可以是2.8以下。 Et/Ea is preferably 1.15 or more, and even more preferably 1.20 or more. Et/Ea may also be 2.8 or less.
積層體的邊緣朝前面側偏光板側翹曲時，翹曲成凹狀之側的偏光板是前面側偏光板，積層體的邊緣朝背面側偏光板側翹曲時，翹曲成凹狀之側的偏光板是背面側偏光板。具體上可參照第3圖加以說明。第3圖係表示將前面側偏光板400及背面側偏光板401分別黏合在玻璃板70而得的積層體經加熱處理之後的示意剖面。第3圖(a)中，翹曲成凹狀之側的偏光板係指背面側偏光板401，第3圖(b)中，翹曲成凹狀之側的偏光板係指前面側偏光板400。翹曲成凹狀之側的偏光板可以是前面側偏光板也可以是背面側偏光板。背面側偏光板由於除了已施予延伸處理
的偏光片之外，大多具備同樣已施予延伸處理的亮度改善膜，故使背面側偏光板的吸收軸方向成為長邊方向時，背面側偏光板加熱時的收縮力大多會大於前面側偏光板。
When the edge of the laminate is curved toward the front side polarizer, the side of the polarizer that is curved into a concave shape is the front side polarizer, and when the edge of the laminate is curved toward the back side polarizer, the side of the polarizer that is curved into a concave shape is the back side polarizer. For details, please refer to FIG. 3 for further explanation. FIG. 3 is a schematic cross-section of a laminate obtained by bonding the front side polarizer 400 and the back side polarizer 401 to the
黏合在玻璃板時偏光板的形狀及玻璃板的形狀雖然無特別的限制，但以矩形為佳，此時可將前面側偏光板及背面側偏光板作成相同的大小。將偏光板黏合在玻璃板時，前面側偏光板的吸收軸與背面側偏光板的吸收軸是以呈正交方式黏合。此時，偏光板為矩形時，前面側偏光板的吸收軸係以平行於短邊為佳，背面側偏光板的吸收軸係以平行於長邊為佳。 When the polarizing plate is bonded to the glass plate, the shape of the polarizing plate and the shape of the glass plate are not particularly limited, but a rectangular shape is preferred. In this case, the front polarizing plate and the back polarizing plate can be made the same size. When the polarizing plate is bonded to the glass plate, the absorption axis of the front polarizing plate and the absorption axis of the back polarizing plate are bonded in an orthogonal manner. In this case, when the polarizing plate is rectangular, the absorption axis of the front polarizing plate is preferably parallel to the short side, and the absorption axis of the back polarizing plate is preferably parallel to the long side.
玻璃板的厚度可作成例如100μm以上400μm以下。在此範圍的厚度時，容易判別前面側偏光板與背面側偏光板何者是翹曲成凹狀之側的偏光板。 The thickness of the glass plate can be made, for example, from 100 μm to 400 μm. When the thickness is within this range, it is easy to distinguish which of the front polarizing plate and the back polarizing plate is the polarizing plate that is curved into a concave shape.
翹曲成凹狀之側的偏光板也可在偏光片的兩面具有保護膜，此時是以至少一方的保護膜滿足式(1)為佳，並以積層在距離偏光片中的液晶單元較遠之側的保護膜滿足式(1)更佳，而以任一保護膜均滿足式(1)又更佳。 The polarizing plate with the curved concave side may also have protective films on both sides of the polarizing plate. In this case, it is preferred that at least one of the protective films satisfies formula (1), and it is more preferred that the protective film laminated on the side farther from the liquid crystal unit in the polarizing plate satisfies formula (1). It is even more preferred that any of the protective films satisfies formula (1).
在85℃的穿透軸方向之拉伸彈性率Et係以500MPa以上10,000MPa以下為佳，也可以是1,000MPa以上8,000MPa以下。在85℃的吸收軸方向之拉伸彈性率Ea係以500MPa以上10,000MPa以下為佳，也可以是1,000MPa以上8,000MPa以下。 The tensile modulus Et in the penetration axis direction at 85°C is preferably 500MPa to 10,000MPa, and can also be 1,000MPa to 8,000MPa. The tensile modulus Ea in the absorption axis direction at 85°C is preferably 500MPa to 10,000MPa, and can also be 1,000MPa to 8,000MPa.
說明構成本發明的偏光板之套組的各構件。 The components of the polarizing plate set of the present invention are described.
(偏光片) (Polarizer)
本發明中使用的偏光片通常是經過以下的步驟製得者：將聚乙烯醇系樹脂膜單軸延伸的步驟、藉由二色性色素將聚乙烯醇系樹脂膜染色使其吸附二色性色素的步驟、以硼酸水溶液處理已吸附二色性色素的聚乙烯醇系樹脂膜之步驟、及硼酸水溶液處理後的水洗步驟。 The polarizer used in the present invention is usually prepared through the following steps: a step of uniaxially stretching a polyvinyl alcohol resin film, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye, a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with a boric acid aqueous solution, and a step of washing with water after the boric acid aqueous solution treatment.
聚乙烯醇系樹脂膜可使用將聚乙酸乙烯酯系樹脂皂化者。聚乙酸乙烯酯系樹脂除了乙酸乙烯酯的均聚物之聚乙酸乙烯酯以外，可舉出乙酸乙烯酯與可共聚合的其他單體之共聚合物等。可與乙酸乙烯酯共聚合的其他單體例如可列舉：不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類及具有銨基的丙烯醯胺類等。 Polyvinyl alcohol resin films can use saponified polyvinyl acetate resins. Polyvinyl acetate resins include copolymers of vinyl acetate and other copolymerizable monomers, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. 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.
聚乙烯醇系樹脂的皂化度，通常是85至100莫耳%左右，並以98莫耳%以上為佳。此聚乙烯醇系樹脂也可改質，可使用：例如經醛類改質的聚乙烯甲醛或聚乙烯乙醛等。且聚乙烯醇系樹脂的聚合度通常是1,000至10,000左右，並以1,500至5,000左右為佳。 The saponification degree of polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. This polyvinyl alcohol resin can also be modified, such as polyvinyl formaldehyde or polyvinyl acetaldehyde modified with aldehydes. The polymerization degree of polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.
將聚乙烯醇系樹脂製膜而得之物可使用作為偏光片的原料膜。將聚乙烯醇系樹脂製膜的方法可用已知的方法進行製膜。聚乙烯醇系原料膜的膜厚，在考量使所獲得的偏光片之厚度成為15μm以下時，係以5至35μm左右為佳，並以5至20μm者更佳。原料膜的膜厚為35μm以上時，必須提高製造偏光片時的延伸倍率，且有使所得的偏光片之尺寸收縮變大之傾向。 The film obtained by filming the polyvinyl alcohol resin can be used as a raw material film for a polarizer. The method of filming the polyvinyl alcohol resin can be carried out by a known method. The film thickness of the polyvinyl alcohol raw material film is preferably about 5 to 35 μm, and more preferably 5 to 20 μm, when considering that the thickness of the obtained polarizer is less than 15 μm. When the film thickness of the raw material film is more than 35 μm, the stretching ratio during the manufacture of the polarizer must be increased, and there is a tendency to shrink the size of the obtained polarizer.
另一方面，原料膜的膜厚為5μm以下時，有施加延伸時的處理性降低，於製造中容易發生切斷等問題之傾向。 On the other hand, when the thickness of the raw material film is less than 5μm, the handling properties during stretching are reduced, and problems such as cutting tend to occur during manufacturing.
聚乙烯醇系樹脂膜的單軸延伸可在二色性色素的染色前、與染色同時或染色之後進行。在染色之後進行單軸延伸時，此單軸延伸可在硼酸處理之前或硼酸處理中進行。又，也可在此等處理的數個階段進行單軸延伸。 The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, during or after dyeing with the dichroic dye. When the uniaxial stretching is performed after dyeing, the uniaxial stretching can be performed before or during the boric acid treatment. In addition, the uniaxial stretching can be performed at several stages of the treatment.
單軸延伸時可在不同周速的輥間進行單軸延伸，也可使用熱輥進行單軸延伸。又，單軸延伸可以是在大氣中進行延伸的乾式延伸，也可以是使用溶劑使聚乙烯醇系樹脂膜在膨脹狀態進行延伸的濕式延伸。延伸倍率通常是3至8倍左右。 During uniaxial stretching, the film can be stretched between rollers of different circumferential speeds or using hot rollers. In addition, uniaxial stretching can be dry stretching in the atmosphere or wet stretching using a solvent to stretch the polyvinyl alcohol resin film in an expanded state. The stretching ratio is usually around 3 to 8 times.
以二色性色素將聚乙烯醇系樹脂膜染色的方法可採用：例如將聚乙烯醇系樹脂膜浸泡在含有二色性色素的水溶液中之方法。二色性色素具體上可使用碘或二色性染料。又，聚乙烯醇系樹脂膜係以在染色處理之前施予水中的浸泡處理為佳。 The method of dyeing the polyvinyl alcohol resin film with a dichroic pigment can be adopted, for example, a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing a dichroic pigment. Specifically, iodine or a dichroic dye can be used as the dichroic pigment. In addition, the polyvinyl alcohol resin film is preferably immersed in water before the dyeing treatment.
使用碘作為二色性色素時，通常可採用將聚乙烯醇系樹脂膜浸泡在含有碘及碘化鉀的水溶液中而染色的方法。此水溶液中的碘之含量通常每100重量份的水係0.01至1重量份左右。又，通常每100重量份的水碘化鉀的含量係0.5至20重量份左右。染色中使用的水溶液之溫度通常是20至40℃左右。 When iodine is used as a dichroic pigment, a method of dyeing a polyvinyl alcohol resin film by immersing it in an aqueous solution containing iodine and potassium iodide is usually adopted. The iodine content in this aqueous solution is usually about 0.01 to 1 weight part per 100 weight parts of water. In addition, the potassium iodide content is usually about 0.5 to 20 weight parts per 100 weight parts of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40°C.
再者，浸泡在該水溶液的時間(染色時間)通常是20至1,800秒左右。 Furthermore, the soaking time in the aqueous solution (dyeing time) is usually around 20 to 1,800 seconds.
另一方面，使用二色性染料作為二色性色素時，通常可採用將聚乙烯醇系樹脂膜浸泡在含有水溶性二色性染料的水溶液中而染色的方法。該水溶液中的二色性染料之含量，通常每100重量份的水，係1×10-4至10重量份左右，並以1×10-3至1重量份左右為佳。該水溶液也可含有硫酸鈉等無機鹽作為染色助劑。染色中使用的二色性染料水溶液之溫度通常是20至80℃左右。又，在該水溶液的浸泡時間(染色時間)通常是10至1,800秒左右。 On the other hand, when using a dichroic dye as a dichroic pigment, a method of dyeing a polyvinyl alcohol resin film by immersing it in an aqueous solution containing a water-soluble dichroic dye can usually be adopted. The content of the dichroic dye in the aqueous solution is usually about 1× 10-4 to 10 parts by weight per 100 parts by weight of water, and preferably about 1× 10-3 to 1 part by weight. The aqueous solution may also contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used in dyeing is usually about 20 to 80°C. In addition, the immersion time in the aqueous solution (dyeing time) is usually about 10 to 1,800 seconds.
經二色性色素染色後的硼酸處理通常可藉由將已染色的聚乙烯醇系樹脂膜浸泡在含有硼酸的水溶液中進行。 Boric acid treatment after dichroic dyeing can usually be performed by soaking the dyed polyvinyl alcohol resin film in an aqueous solution containing boric acid.
含有硼酸的水溶液中之硼酸的量，通常每100重量份的水，係2至15重量份左右，並以5至12重量份為佳。在使用碘作為二色性色素時，該含有硼酸的水溶液以含有碘化鉀為佳。含有硼酸的水溶液中碘化鉀之量，通常每100重量份的之水，係0.1至15重量份左右，並以5至12重量份為佳。浸泡在含有硼酸的水溶液之時間通常是60至1,200秒左右，並以150至600秒左右為佳，而以200至400秒左右更佳。含有硼酸的水溶液之溫度通常是50℃以上，並以50至85℃為佳，而以60至80℃更佳。 The amount of boric acid in the aqueous solution containing boric acid is usually about 2 to 15 parts by weight per 100 parts by weight of water, preferably 5 to 12 parts by weight. When iodine is used as a dichroic pigment, the aqueous solution containing boric acid preferably contains potassium iodide. The amount of potassium iodide in the aqueous solution containing boric acid is usually about 0.1 to 15 parts by weight per 100 parts by weight of water, preferably 5 to 12 parts by weight. The time of immersion in the aqueous solution containing boric acid is usually about 60 to 1,200 seconds, preferably about 150 to 600 seconds, and more preferably about 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually above 50°C, preferably 50 to 85°C, and more preferably 60 to 80°C.
硼酸處理後的聚乙烯系樹脂膜通常進行水洗處理。水洗處理可藉由：例如將硼酸處理後的聚乙烯系樹脂膜浸泡在水中而進行。水洗處理中的水之溫度，通常是5至40℃左右。又，浸泡時間通常是1至120秒左右。 The polyethylene resin film after the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment can be performed by, for example, immersing the polyethylene resin film after the boric acid treatment in water. The temperature of the water in the water washing treatment is usually about 5 to 40°C. In addition, the immersion time is usually about 1 to 120 seconds.
水洗後施予乾燥處理即得偏光片。乾燥處理可利用熱風乾燥機或遠紅外線加熱器進行。乾燥處理的溫度通常是30至100℃左右，並以50至80℃為佳。乾燥處理的時間通常是60至600秒左右，並以120至600秒為佳。 After washing, the polarizer is dried. The drying process can be performed using a hot air dryer or a far infrared heater. The drying temperature is usually around 30 to 100°C, preferably 50 to 80°C. The drying time is usually around 60 to 600 seconds, preferably 120 to 600 seconds.
經乾燥處理可使偏光片的水分率減少至實用程度。該水分率通常是5至20重量%，並以8至15重量%為佳。水分率低於5重量%時，有可能使偏光片失去可撓性，偏光片在其乾燥後受損傷、破裂。 The drying process can reduce the moisture content of the polarizer to a practical level. The moisture content is usually 5 to 20% by weight, and preferably 8 to 15% by weight. When the moisture content is lower than 5% by weight, the polarizer may lose its flexibility, and the polarizer may be damaged or cracked after drying.
又，水分率高於20重量%時，有可能使偏光片的熱安定性惡化。 In addition, when the moisture content is higher than 20% by weight, the thermal stability of the polarizer may deteriorate.
又，偏光片的製程中之聚乙烯醇系樹脂膜的延伸、染色、硼酸處理、水洗步驟、乾燥步驟，可依照：例如日本特開2012-159778號所述之方法進行。在該文獻所述之方法中，係藉由將聚乙烯醇系樹脂塗布在基材膜形成作為偏光片的聚乙烯醇系樹脂層。 In addition, the stretching, dyeing, boric acid treatment, water washing and drying steps of the polyvinyl alcohol resin film in the process of manufacturing the polarizer can be carried out according to, for example, the method described in Japanese Patent Application Laid-Open No. 2012-159778. In the method described in the document, the polyvinyl alcohol resin layer as the polarizer is formed by coating the polyvinyl alcohol resin on the substrate film.
降低偏光片自體的收縮力亦對減少高溫環境下的翹曲有效，具備前面側偏光板及背面側偏光板的偏光片之厚度任一者均以15μm以下為佳，並以4至13μm更佳，而以5至10μm又更佳。 Reducing the shrinkage force of the polarizer itself is also effective in reducing warping in high temperature environments. The thickness of the polarizer with the front side polarizer and the back side polarizer is preferably less than 15μm, more preferably 4 to 13μm, and even more preferably 5 to 10μm.
前述前面側偏光板所具備的偏光片之厚度與前述背面側偏光板所具備的偏光片之厚度之差的大小係以5μm以下為佳，也可為3μm以下。翹曲成凹狀之側的偏光板之保護膜係滿足式(1)時，可藉由如上述將偏光片之厚 度差變小，而於高溫環境下對液晶面板之翹曲的影響變得更小。 The difference between the thickness of the polarizer provided by the front polarizer and the thickness of the polarizer provided by the back polarizer is preferably less than 5μm, and may be less than 3μm. When the protective film of the polarizer on the side that is warped into a concave shape satisfies formula (1), the difference in thickness of the polarizer can be reduced as described above, thereby reducing the effect of the warping of the liquid crystal panel in a high temperature environment.
(保護膜) (Protective film)
保護膜係由樹脂膜構成，並且可由透明的樹脂膜構成。尤其是以透明性、機械強度、熱安定性、水分遮蔽性等優異的材料構成為佳。本說明書中透明的樹脂膜係指可見光域中單體穿透率為80%以上的樹脂膜。 The protective film is made of a resin film, and can be made of a transparent resin film. In particular, it is preferably made of a material with excellent transparency, mechanical strength, thermal stability, moisture shielding, etc. The transparent resin film in this specification refers to a resin film with a single body transmittance of more than 80% in the visible light range.
在偏光片的兩面積層保護膜時，保護膜可使用互為相同者，也可使用互不相同者。又，前面側偏光板中的保護膜與背面側偏光板中的保護膜，可使用互為相同者，也可使用互不相同者。 When protective films are laminated on both sides of the polarizer, the protective films can be the same or different. Also, the protective film in the front polarizer and the protective film in the back polarizer can be the same or different.
形成保護膜的樹脂並無特別的限制，例如可列舉：由甲基丙烯酸甲酯系樹脂、聚烯烴系樹脂、環狀烯烴系樹脂、聚氯乙烯系樹脂、纖維素系樹脂、苯乙烯系樹脂、丙烯腈/丁二烯/苯乙烯系樹脂、丙烯腈/苯乙烯系樹脂、聚乙酸乙烯酯系樹脂、聚偏二氯乙烯系樹脂、聚醯胺系樹脂、聚縮醛系樹脂、聚碳酸酯系樹脂、改質聚苯醚系樹脂、聚對苯二甲酸丁二酯系樹脂、聚對苯二甲酸乙二酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚芳酯系樹脂、聚醯胺醯亞胺系樹脂及聚醯亞胺系樹脂等形成之膜。 The resin forming the protective film is not particularly limited, and examples thereof include: methyl methacrylate resins, polyolefin resins, cycloolefin resins, polyvinyl chloride resins, cellulose resins, styrene resins, acrylonitrile/butadiene/styrene resins, acrylonitrile/styrene resins, polyvinyl acetate resins, polyvinylidene terephthalate resins, and polyvinyl chloride resins. Films formed from vinylidene chloride resins, polyamide resins, polyacetal resins, polycarbonate resins, modified polyphenylene ether resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyamide imide resins and polyimide resins.
此等樹脂可單獨使用或將2種以上組合而使用。又，此等樹脂也可經任何適當的聚合物改質後使用，此聚合物改質例如可列舉：共聚合、交聯、分子末端改質、立體規則性控制及包含隨異質聚合物彼此反應時之混合等 之改質。 These resins can be used alone or in combination of two or more. In addition, these resins can also be used after any appropriate polymer modification, such as copolymerization, crosslinking, molecular end modification, stereoregularity control, and modification including mixing when heterogeneous polymers react with each other.
此等之中，保護膜的材料係以使用甲基丙烯酸甲酯系樹脂、聚對苯二甲酸乙二酯系樹脂、聚烯烴系樹脂，或纖維素系樹脂為佳。此處所稱的聚烯烴系樹脂，係包含鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂。 Among these, the material of the protective film is preferably methyl methacrylate resin, polyethylene terephthalate resin, polyolefin resin, or cellulose resin. The polyolefin resin referred to here includes chain polyolefin resin and cyclic polyolefin resin.
甲基丙烯酸甲酯系樹脂係指含有甲基丙烯酸甲酯單元50重量%以上的聚合物。甲基丙烯酸甲酯單元的含量係以70重量%以上為佳，也可以是100重量%。甲基丙烯酸甲酯單元為100重量%的聚合物係以甲基丙烯酸甲酯單獨聚合而得的甲基丙烯酸甲酯均聚物。 Methyl methacrylate resin refers to a polymer containing 50% by weight or more of methyl methacrylate units. The content of methyl methacrylate units is preferably 70% by weight or more, and can also be 100% by weight. A polymer containing 100% by weight of methyl methacrylate units is a methyl methacrylate homopolymer obtained by polymerizing methyl methacrylate alone.
此甲基丙烯酸甲酯系樹脂通常可使以甲基丙烯酸甲酯作為主成分的單官能單體在自由基聚合起始劑的存在下進行聚合而得。在聚合時也可視需要而與多官能單體或鏈轉移劑共存。 This methyl methacrylate resin is usually obtained by polymerizing a monofunctional monomer with methyl methacrylate as the main component in the presence of a free radical polymerization initiator. During the polymerization, it can also coexist with a multifunctional monomer or a chain transfer agent as needed.
可與甲基丙烯酸甲酯共聚合的單官能單體並無特別限制，例如可列舉：甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸2-乙酯己酯及甲基丙烯酸2-羥酯乙酯等甲基丙烯酸甲酯以外的甲基丙烯酸酯類；丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸2-乙酯己酯及丙烯酸2-羥基乙酯等丙烯酸酯類；2-(羥基甲基)丙烯酸甲酯、3-(羥基乙基)丙烯酸甲酯、2-(羥基甲基)丙烯酸乙酯及2-(羥基甲基)丙烯酸丁酯等羥基烷基丙烯酸酯類；甲基丙烯酸及丙烯酸等不飽和 酸類；氯苯乙烯及溴苯乙烯等鹵化苯乙烯類；乙烯甲苯及α-甲基苯乙烯等取代苯乙烯類；丙烯腈及甲基丙烯腈等不飽和腈類；順丁烯二酸酐及檸康酸酐等不飽和酸酐類；以及苯基順丁烯二醯亞胺及環己基順丁烯二醯亞胺等不飽和醯亞胺類等。此等單體可分別單獨使用，也可將2種以上組合使用。 The monofunctional monomer copolymerizable with methyl methacrylate is not particularly limited, and examples thereof include: methacrylates other than methyl methacrylate such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; 2-(hydroxy) Hydroxyl alkyl acrylates such as methyl methacrylate, methyl 3-(hydroxyethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate, and butyl 2-(hydroxymethyl)acrylate; unsaturated acids such as methacrylic acid and acrylic acid; halogenated styrenes such as chlorostyrene and bromostyrene; substituted styrenes such as vinyltoluene and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated anhydrides such as maleic anhydride and conic anhydride; and unsaturated imides such as phenylmaleimide and cyclohexylmaleimide. These monomers can be used alone or in combination of two or more.
可與甲基丙烯酸甲酯共聚合的多官能單體並無特別的限制，例如可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、九乙二醇二(甲基)丙烯酸酯及十四乙二醇二(甲基)丙烯酸酯等乙二醇或其寡聚物的兩末端羥基經丙烯酸或甲基丙烯酸酯化者；丙二醇或其寡聚物的兩末端羥基經丙烯酸或甲基丙烯酸酯化者；新戊二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯及丁二醇二(甲基)丙烯酸酯等二元醇之羥基經丙烯酸或甲基丙烯酸酯化者；雙酚A、雙酚A的環氧烷加成物，或此等的鹵素取代物之兩末端羥基經丙烯酸或甲基丙烯酸酯化者；三羥甲基丙烷及異戊四醇等多元醇經丙烯酸或甲基丙烯酸酯化者，以及此等多元醇的末端羥基經丙烯酸去水甘油酯或甲基丙烯酸去水甘油酯酯的環氧基開環而加成者；琥珀酸、己二酸、對苯二甲酸、鄰苯二甲酸、此等的鹵素取代物等二元酸及此等的環氧烷加成物等經丙烯酸去水甘油酯或甲基丙烯酸去水甘油酯的環氧基開環而加成者；(甲基)丙烯酸烯丙酯；及二乙烯苯等芳香族二乙烯化合物等。其中，並以 較佳使用乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯及新戊二醇二甲基丙烯酸酯。 The multifunctional monomers copolymerizable with methyl methacrylate are not particularly limited, and examples thereof include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, tetradecaethylene glycol di(meth)acrylate, etc., wherein both terminal hydroxyl groups of ethylene glycol or its oligomers are esterified with acrylic acid or methacrylic acid; propylene glycol or its oligomers are esterified with acrylic acid or methacrylic acid; hydroxyl groups of diols such as neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, and butanediol di(meth)acrylate are esterified with acrylic acid or methacrylic acid; Acrylic acid esterified; bisphenol A, bisphenol A alkylene oxide adducts, or halogen substituted products thereof, wherein both terminal hydroxyl groups are esterified with acrylic acid or methacrylic acid; trihydroxymethylpropane and pentaerythritol and other polyols esterified with acrylic acid or methacrylic acid, and the terminal hydroxyl groups of these polyols are added through the epoxide ring-opening of dehydrated glyceryl acrylate or dehydrated glyceryl methacrylate; succinic acid, adipic acid, terephthalic acid, phthalic acid, halogen substituted dibasic acids such as these, and alkylene oxide adducts thereof are added through the epoxide ring-opening of dehydrated glyceryl acrylate or dehydrated glyceryl methacrylate; allyl (meth)acrylate; and aromatic divinyl compounds such as divinylbenzene, etc. Among them, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and neopentyl glycol dimethacrylate are preferably used.
甲基丙烯酸甲酯系樹脂進一步也可使用對樹脂進行已共聚合的官能基間之反應而改質者。該反應例如可列舉：丙烯酸甲酯的甲酯基與2-(羥基甲基)丙烯酸甲酯的羥基之高分子鏈內脫甲醇縮合反應、或丙烯酸的羧基與2-(羥基甲基)丙烯酸甲酯的羥基之高分子鏈內脫氫縮合反應等。 Methyl methacrylate resins can also be modified by reacting the copolymerized functional groups. Examples of such reactions include: intramolecular demethylation condensation reaction of the methyl group of methyl acrylate with the hydroxyl group of methyl 2-(hydroxymethyl)acrylate, or intramolecular dehydrogenation condensation reaction of the carboxyl group of acrylic acid with the hydroxyl group of methyl 2-(hydroxymethyl)acrylate.
聚對苯二甲酸乙二酯系樹脂係指重複單元的80莫耳(mol)%以上係以對苯二甲酸乙二酯構成的樹脂之意，也可含有其他的二羧酸成分與二醇成分。其他的二羧酸成分並無特別的限制，例如可列舉：間苯二甲酸、4,4’-二羧基二苯基、4,4’-二羧基二苯甲酮、雙(4-羧基苯基)乙烷、己二酸、癸二酸及1,4-二羧基環己烷等。 Polyethylene terephthalate resin refers to a resin in which 80 mol% or more of the repeating units are composed of ethylene terephthalate, and may also contain other dicarboxylic acid components and diol components. There is no particular restriction on other dicarboxylic acid components, for example, isophthalic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis(4-carboxyphenyl)ethane, adipic acid, sebacic acid and 1,4-dicarboxycyclohexane, etc.
其他的二醇成分並無特別的限定，可舉出丙二醇、丁二醇、新戊二醇、二乙二醇、環己二醇、雙酚A的環氧乙烷加成物、聚乙二醇、聚丙二醇及聚丁二醇等。 There is no particular limitation on other glycol components, and examples thereof include propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutylene glycol.
此等的二羧酸成分或二醇成分，可視需要將2種以上組合使用。又，也可併用對-羥基苯甲酸、對-β-羥基乙氧基苯甲酸等羥基羧酸。又，其他的共聚合成分可使用含有少量的醯胺鍵、胺酯鍵、醚鍵或碳酸酯鍵等的二羧酸成分或二醇成分。 These dicarboxylic acid components or diol components can be used in combination of two or more types as needed. In addition, hydroxycarboxylic acids such as p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid can also be used in combination. In addition, other copolymer components can use dicarboxylic acid components or diol components containing a small amount of amide bonds, amine ester bonds, ether bonds or carbonate bonds.
聚對苯二甲酸乙二酯系樹脂的製造方法，可採用使對苯二甲酸及乙二醇(以及視需要的其他之二羧 酸或其他的二醇)直接聚縮合的方法、使對苯二甲酸的二烷酯及乙二醇(以及視需要的其他之二羧酸的二烷酯或其他的二醇)進行酯交換反應後聚縮合的方法、及使對苯二甲酸(及視需要的其他二羧酸)的乙二醇酯(及視需要的其他二醇酯)在觸媒的存在下進行聚縮合之方法等。此外，也可視需要進行固相聚合使分子量提高或使低分子量成分減少。 The method for producing polyethylene terephthalate resins may include direct polycondensation of terephthalic acid and ethylene glycol (and other dicarboxylic acids or other glycols as needed), polycondensation of dialkyl esters of terephthalic acid and ethylene glycol (and other dialkyl esters of dicarboxylic acids or other glycols as needed) after ester exchange reaction, and polycondensation of ethylene glycol esters of terephthalic acid (and other dicarboxylic acids as needed) (and other glycol esters as needed) in the presence of a catalyst. In addition, solid phase polymerization may be performed as needed to increase the molecular weight or reduce the low molecular weight components.
環狀聚烯烴系樹脂例如係使如降冰片烯及其他的環戊二烯衍生物的環狀烯烴單體在觸媒的存在下聚合而得者。使用此種環狀聚烯烴系樹脂一事，因容易獲得具有後述的規定之延遲值的保護膜而佳。 Cyclic polyolefin resins are obtained by polymerizing cyclic olefin monomers such as norbornene and other cyclopentadiene derivatives in the presence of a catalyst. The use of such cyclic polyolefin resins is preferred because it is easy to obtain a protective film having a predetermined delay value described below.
環狀聚烯烴系樹脂例如可列舉：將由環戊二烯與烯烴類或(甲基)丙烯酸或其酯類經Diels-Alder反應而得之降冰片烯或其衍生物作為單體進行開環易位(metathesis)聚合，接著氫化而得的樹脂；將由二環戊二烯與烯烴類或(甲基)丙烯酸或其酯類經Diels-Alder反應而得之四環十二烯或其衍生物作為單體進行開環易位聚合，接著氫化而得的樹脂；將選自降冰片烯、四環十二烯、該等的衍生物及其他的環狀烯烴單體的至少2種單體同樣進行開環易位共聚合，接著氫化而得的樹脂；如降冰片烯、四環十二烯或該等的衍生物之環狀烯烴與鏈狀烯烴及/或具有乙烯基的芳香族化合物進行加成共聚合而得的樹脂等。 Examples of cyclic polyolefin resins include: a resin obtained by ring-opening metathesis polymerization of norbornene or its derivatives obtained by Diels-Alder reaction of cyclopentadiene with olefins or (meth) acrylic acid or its esters, followed by hydrogenation; a resin obtained by Diels-Alder reaction of dicyclopentadiene with olefins or (meth) acrylic acid or its esters, followed by hydrogenation; a resin obtained by ring-opening metathesis polymerization of tetracyclododecene or tetracyclohexene obtained by Diels-Alder reaction of dicyclopentadiene with olefins or (meth) acrylic acid or its esters, followed by hydrogenation; A resin obtained by ring-opening metathesis polymerization of its derivatives as monomers, followed by hydrogenation; a resin obtained by similarly ring-opening metathesis copolymerization of at least two monomers selected from norbornene, tetracyclododecene, their derivatives and other cyclic olefin monomers, followed by hydrogenation; a resin obtained by addition copolymerization of cyclic olefins such as norbornene, tetracyclododecene or their derivatives with chain olefins and/or aromatic compounds having a vinyl group, etc.
鏈狀聚烯烴系樹脂的典型例為聚乙烯系樹脂及聚丙烯系樹脂。其中並以丙烯的均聚物，或以丙烯作為主體並與可與其共聚合的共單體，例如乙烯，以1至20 重量%，較佳為3至10重量%的比例進行共聚合而得的共聚合物為適用。 Typical examples of chain polyolefin resins are polyethylene resins and polypropylene resins. Among them, a homopolymer of propylene, or a copolymer obtained by copolymerizing propylene as the main component with a comonomer that can be copolymerized with it, such as ethylene, at a ratio of 1 to 20% by weight, preferably 3 to 10% by weight, is suitable.
聚烯烴系樹脂也可含有脂環族飽和烴樹脂。藉由含有脂環族飽和烴樹脂，可使延遲值容易控制。脂環族飽和烴樹脂的含量係以相對於聚烯烴系樹脂成為0.1至30重量%為有利，較佳的含量是3至20重量%。如脂環族飽和烴樹脂的含量不到0.1重量%，則不能充分獲得控制延遲值的效果，另一方面如該含量超過30重量%，則有隨時間變化產生從保護膜滲出脂環族飽和烴樹脂之虞慮。 The polyolefin resin may also contain a cycloaliphatic saturated hydrocarbon resin. By containing a cycloaliphatic saturated hydrocarbon resin, the delay value can be easily controlled. The content of the cycloaliphatic saturated hydrocarbon resin is preferably 0.1 to 30% by weight relative to the polyolefin resin, and the preferred content is 3 to 20% by weight. If the content of the cycloaliphatic saturated hydrocarbon resin is less than 0.1% by weight, the effect of controlling the delay value cannot be fully obtained. On the other hand, if the content exceeds 30% by weight, there is a concern that the cycloaliphatic saturated hydrocarbon resin may seep out of the protective film over time.
纖維素系樹脂係指可從棉絨或木漿(闊葉樹漿、針葉樹漿)等原料纖維素獲得的纖維素之羥基中的部份或全部氫原子經乙醯基、丙醯基及/或丁醯基取代的纖維素有機酸酯或纖維素混合有機酸酯。例如可列舉：由纖維素的乙酸酯、丙酸酯、丁酸酯、及該等的混合酯等形成者。其中，並以三乙醯基纖維素膜、二乙醯基纖維素膜、纖維素乙酸酯丙酸酯膜及纖維素乙酸酯丁酸酯膜等為佳。 Cellulose resin refers to cellulose organic acid ester or cellulose mixed organic acid ester in which part or all of the hydrogen atoms in the hydroxyl group of cellulose obtained from raw cellulose such as cotton wool or wood pulp (broad-leaf tree pulp, softwood tree pulp) are replaced by acetyl, propionyl and/or butyryl groups. For example, it can be listed as: cellulose acetate, propionate, butyrate, and mixed esters thereof. Among them, triacetyl cellulose membrane, diacetyl cellulose membrane, cellulose acetate propionate membrane and cellulose acetate butyrate membrane are preferred.
將甲基丙烯酸甲酯系樹脂、聚對苯二甲酸乙二酯系樹脂、聚烯烴系樹脂及纖維素系樹脂作成接著在偏光片用之第2保護膜的方法，只要適宜選擇配合各別的樹脂之方法即可，並無特別的限制。例如可採用：將已溶解在溶劑中的樹脂朝金屬製帶或鼓流鑄，將溶劑乾燥去除而獲得膜之溶劑鑄造法，及將樹脂加熱至其熔融溫度以上混練之，由模頭押出並冷卻而獲得膜之熔融押出法。在此 熔融押出法中，可以是單層膜的押出也可以是多層膜的同時押出。 The method of making methyl methacrylate resin, polyethylene terephthalate resin, polyolefin resin and cellulose resin into the second protective film for polarizer is not particularly limited as long as the method of matching each resin is appropriately selected. For example, the solvent casting method can be adopted, in which the resin dissolved in the solvent is cast toward a metal strip or a drum flow casting, and the solvent is dried and removed to obtain a film, and the melt extrusion method can be adopted, in which the resin is heated to above its melting temperature, kneaded, extruded from a die head and cooled to obtain a film. In this melt extrusion method, a single-layer film can be extruded or multiple layers of film can be extruded simultaneously.
使用作為保護膜之膜可容易購得市售品，若為甲基丙烯酸甲酯系樹脂膜者可舉出之商品名分別為Sumipex(住友化學股份有限公司製)、Acrylite(註冊商標)、ACRYPREN(註冊商標)(以上，三菱嫘縈股份有限公司(Mitsubishi Rayon Co.Ltd)製)、Delaglas(註冊商標)(旭化成股份有限公司製)、Paraglas(註冊商標)、Comograss(註冊商標)(以上，股份有限公司Kuraray製)及Acryviewa(註冊商標)(股份有限公司日本觸媒製)等。若為聚烯烴系樹脂膜可舉出之商品名分別為Zeonor(註冊商標)(日本Zeon股份有限公司)、Arton(註冊商標)(JSR股份有限公司)等。若為聚對苯二甲酸乙二酯系樹脂，可舉出之商品名分別為Nova Clear(註冊商標)(三菱化學股份有限公司製)及帝人A-PET板(帝人化成股份有限公司製)等。若為聚丙烯系樹脂膜，可舉出之商品名分別為FILMAX CPP膜(FILMAX公司製)、SUNTOX(註冊商標)(SUN/TOX股份有限公司製)、Tohcello(註冊商標)(Tocello股份有限公司製)、東洋紡Piren Film(註冊商標)(東洋紡績股份有限公司製)、Torayfan(註冊商標)(Toray膜加工股份有限公司製)、Japan Poriesu(日本Poriesu股份有限公司製)及太閤(註冊商標)FC(二村(Futamura)化學股份有限公司製)等。又，若為纖維素系樹脂膜，可舉出之商品名分別為Fujitac(註冊商標)TD(富士軟片股份有限公司製)，以及KC2UA及Konica Minolta TAC Film KC(Konica Minolta股份有限公司製)等。 Films used as protective films are readily available commercially. In the case of methyl methacrylate resin films, trade names that can be cited include Sumipex (manufactured by Sumitomo Chemical Co., Ltd.), Acrylite (registered trademark), ACRYPREN (registered trademark) (manufactured by Mitsubishi Rayon Co., Ltd.), Delaglas (registered trademark) (manufactured by Asahi Kasei Co., Ltd.), Paraglas (registered trademark), Comograss (registered trademark) (manufactured by Kuraray Co., Ltd.), and Acryviewa (registered trademark) (manufactured by Nippon Catalyst Co., Ltd.). In the case of polyolefin resin films, trade names that can be cited include Zeonor (registered trademark) (Zeon Co., Ltd., Japan), Arton (registered trademark) (JSR Co., Ltd.), etc. In the case of polyethylene terephthalate resins, trade names that can be cited include Nova Clear (registered trademark) (manufactured by Mitsubishi Chemical Co., Ltd.) and Teijin A-PET Sheet (manufactured by Teijin Chemicals Co., Ltd.), etc. In the case of a polypropylene resin film, trade names that can be cited include FILMAX CPP film (manufactured by FILMAX Corporation), SUNTOX (registered trademark) (manufactured by SUN/TOX Co., Ltd.), Tohcello (registered trademark) (manufactured by Tocello Co., Ltd.), Toyobo Piren Film (registered trademark) (manufactured by Toyobo Co., Ltd.), Torayfan (registered trademark) (manufactured by Toray Film Processing Co., Ltd.), Japan Poriesu (manufactured by Japan Poriesu Co., Ltd.), and Taiko (registered trademark) FC (manufactured by Futamura Chemical Co., Ltd.). In addition, if it is a cellulose resin film, the trade names that can be cited are Fujitac (registered trademark) TD (manufactured by Fuji Film Co., Ltd.), KC2UA and Konica Minolta TAC Film KC (manufactured by Konica Minolta Co., Ltd.), etc.
本發明中使用的保護膜及保護膜係可賦予防眩性(Haze，霧度)。賦與防眩性的方法，並無特別的限制，例如可採用：在前述的原料樹脂中混合無機微粒子或有機微粒子並使膜化的方法、採用前述的多層押出，由一方已混合微粒子的樹脂與另一方未混合微粒子的樹脂形成二層膜化之方法、或將已混合粒子的樹脂作為外側而形成三層膜化之方法、及將無機微粒子或有機微粒子在硬化性黏合劑樹脂中混合而成的塗布液塗布在膜的一面，並使黏合劑樹脂硬化而設置防眩層的方法等。 The protective film and protective film used in the present invention can be given anti-glare properties (Haze). There is no particular limitation on the method of giving anti-glare properties, for example, the method of mixing inorganic microparticles or organic microparticles in the aforementioned raw resin and forming a film, the method of using the aforementioned multi-layer extrusion to form a two-layer film with a resin mixed with microparticles on one side and a resin not mixed with microparticles on the other side, or the method of forming a three-layer film with the resin mixed with particles as the outer side, and the method of applying a coating liquid mixed with inorganic microparticles or organic microparticles in a curable adhesive resin on one side of the film, and hardening the adhesive resin to set an anti-glare layer, etc.
又，保護膜可視需要而含有添加劑。添加劑例如可列舉：滑劑、防結塊劑、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝撃性改良劑等。 Furthermore, the protective film may contain additives as needed. Examples of additives include lubricants, anti-caking agents, heat stabilizers, antioxidants, antistatic agents, light-resistant agents, impact resistance improvers, etc.
通常就強度或使用性等而言，保護膜的厚度係1至50μm左右，並以10至40μm為佳。 Generally speaking, in terms of strength and usability, the thickness of the protective film is about 1 to 50μm, and 10 to 40μm is preferred.
保護膜係以在與偏光片黏合之前施予皂化處理、電暈處理或電漿處理等為佳。 It is best to apply saponification treatment, corona treatment or plasma treatment to the protective film before bonding it to the polarizer.
在前面側偏光板的保護膜，另可設置導電層、硬質塗層及低反射層等功能層。又，構成前述防眩層的黏合劑樹脂亦可選擇具有此等功能的樹脂組成物。 Functional layers such as a conductive layer, a hard coating layer, and a low-reflection layer can be provided on the protective film of the front polarizing plate. In addition, the adhesive resin constituting the aforementioned anti-glare layer can also be selected from resin compositions having such functions.
滿足式(1)的保護膜例如也可將樹脂膜延伸而製造。延伸方法並無特別的限制，可以是製膜後横延伸而得的單軸延伸膜，製膜後縱延伸接著横延伸而得的二軸延伸膜等。延伸倍率係例如可作成1.01以上5.00以下， 也可作成1.01以上3.00以下。 The protective film satisfying formula (1) can also be produced by stretching a resin film, for example. There is no particular limitation on the stretching method, and it can be a uniaxially stretched film obtained by stretching the film laterally after film formation, a biaxially stretched film obtained by stretching the film longitudinally and then stretching the film laterally after film formation, etc. The stretching ratio can be, for example, 1.01 or more and 5.00 or less, or 1.01 or more and 3.00 or less.
(亮度改善膜) (Brightness improvement film)
背面側偏光板係以距離偏光片中的液晶單元較遠之側具有亮度改善膜為佳。亮度改善膜的厚度是以35μm以下為佳，並以30μm以下更佳。 The back side polarizing plate preferably has a brightness improvement film on the side farther from the liquid crystal unit in the polarizing film. The thickness of the brightness improvement film is preferably less than 35μm, and more preferably less than 30μm.
亮度改善膜係用作為具有將自光源(背光)射出的光分離成為穿透偏光與反射偏光或散射偏光之功能的偏光轉換元件。此種亮度改善膜可利用來自反射偏光或散射偏光的背光之再回歸光，改善直線偏光的射出效率。 The brightness improvement film is used as a polarization conversion element that has the function of separating the light emitted from the light source (backlight) into penetrating polarized light and reflected polarized light or scattered polarized light. This brightness improvement film can improve the emission efficiency of linear polarized light by utilizing the re-returned light from the backlight of reflected polarized light or scattered polarized light.
亮度改善膜例如可列舉：異方性反射偏光片。異方性反射偏光片可舉出使一方的振動方向之直線偏光穿透，另一方的振動方向之直線偏光反射的異方性多重薄膜。異方性多重薄膜例如可列舉：3M公司製的商品名“APF”。又，異方性反射偏光片，可舉出膽固醇液晶層與λ/4板的複合物。此種複合物可舉出日東電工股份有限公司製的商品名“PCF”。又，異方性反射偏光片可舉出反射光柵偏光片。反射光柵偏光片可舉出對金屬施予微細加工而即使在可見光域亦可放出反射偏光的金屬格子反射偏光片。其中，並以由異方性多重薄膜形成的亮度改善膜為佳。 Examples of brightness improvement films include anisotropic reflective polarizers. Anisotropic reflective polarizers include anisotropic multi-layer films that transmit linear polarized light in one vibration direction and reflect linear polarized light in the other vibration direction. Examples of anisotropic multi-layer films include the product name "APF" manufactured by 3M. Another example of anisotropic reflective polarizers include a composite of a cholesterol liquid crystal layer and a λ/4 plate. An example of such a composite is the product name "PCF" manufactured by Nitto Denko Co., Ltd. Another example of anisotropic reflective polarizers include reflective grating polarizers. The reflective grating polarizers include metal lattice reflective polarizers that are made by finely processing the metal and can emit reflected polarized light even in the visible light range. Among them, the brightness improvement film formed by anisotropic multi-film is preferred.
也可在與亮度改善膜的偏光板之黏合面相反側之面，形成功能性層。功能性層例如可列舉：硬質塗層、防眩層、光擴散層、具有1/4波長的相位差值之相位差層等，據此即可改善與背光帶之間的密合性或顯示影像的均勻性。 A functional layer can also be formed on the surface opposite to the bonding surface of the polarizing plate of the brightness improvement film. Examples of functional layers include: hard coating, anti-glare layer, light diffusion layer, phase difference layer with a phase difference value of 1/4 wavelength, etc., which can improve the adhesion with the backlight belt or the uniformity of the displayed image.
(黏著劑層) (Adhesive layer)
於偏光板的表面亦可積層黏著劑層。透過該黏著劑層可使偏光板黏合在液晶單元。第1圖中之黏著劑層20即相當於此層。 An adhesive layer can also be stacked on the surface of the polarizing plate. The polarizing plate can be bonded to the liquid crystal unit through the adhesive layer. The adhesive layer 20 in Figure 1 is equivalent to this layer.
由黏著劑形成的黏著劑層之厚度係以成為5至25μm為佳，並以成為10至25μm更佳。 The thickness of the adhesive layer formed by the adhesive is preferably 5 to 25 μm, and more preferably 10 to 25 μm.
將前面側偏光板黏合在液晶單元用之黏著劑層與將背面側偏光板黏合在液晶單元用之黏著劑層，可使用互為相同者，也可使用互不相同者。 The adhesive layer used to bond the front polarizing plate to the liquid crystal unit and the adhesive layer used to bond the back polarizing plate to the liquid crystal unit may be the same or different.
又，亮度改善膜與保護膜或偏光片也可藉由黏著劑層而積層。第1圖中之黏著劑層21即相當於此層。由黏著劑形成的黏著劑層之厚度係以成為1至20μm為佳，並以成為1至10μm更佳。 In addition, the brightness improvement film and the protective film or polarizer can also be laminated by means of an adhesive layer. The adhesive layer 21 in FIG. 1 corresponds to this layer. The thickness of the adhesive layer formed by the adhesive is preferably 1 to 20 μm, and more preferably 1 to 10 μm.
形成黏著劑層的黏著劑可適宜的選擇使用：例如以丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺酯、聚醯胺、聚乙烯醚、乙酸乙烯酯/氯乙烯共聚合物、改質聚烯烴、環氧系、氟系、天然橡膠、合成橡膠等橡膠系等聚合物作為基質聚合物者。黏著劑尤其是以光學透明性優異、顯示適度的濕潤性、凝聚性、接著性的黏著特性、耐候性或耐熱性等優異者為佳。 The adhesive forming the adhesive layer can be appropriately selected and used: for example, an adhesive having a base polymer such as acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, vinyl acetate/vinyl chloride copolymer, modified polyolefin, epoxy, fluorine, natural rubber, synthetic rubber, and other rubber-based polymers. The adhesive is preferably one having excellent optical transparency, exhibiting appropriate wettability, cohesion, adhesive properties, weather resistance, or heat resistance.
黏著劑中也可調配其他的各種添加劑。添加劑可舉出矽烷耦合劑或抗靜電劑。 Various other additives can also be mixed into the adhesive. Examples of additives include silane coupling agents or antistatic agents.
(接著劑層) (followed by the agent layer)
保護膜與偏光片之積層或亮度改善膜與偏光片的積 層，例如可藉由使用接著劑使其一體化的方法進行。由接著劑形成的接著劑層之厚度是以0.01至35μm為佳，並以0.01至10μm更佳，而以0.01至5μm又更佳。只要在此範圍中即可使保護膜或亮度改善膜與偏光片之間不發生浮起或剝離，可得到實用上無問題的接着力。 The lamination of the protective film and the polarizer or the lamination of the brightness improvement film and the polarizer can be performed, for example, by integrating them using an adhesive. The thickness of the adhesive layer formed by the adhesive is preferably 0.01 to 35 μm, more preferably 0.01 to 10 μm, and even more preferably 0.01 to 5 μm. As long as it is within this range, the protective film or the brightness improvement film and the polarizer will not float or peel off, and a practically problem-free adhesion can be obtained.
接著劑例如有溶劑型接著劑、乳液型接著劑、感壓性接著劑、再濕性接著劑、聚縮合型接著劑、無溶劑型接著劑、膜狀接著劑及熱熔型接著劑等。又，視需要亦可透過錨塗層設置接著層。 Adhesives include solvent adhesives, emulsion adhesives, pressure-sensitive adhesives, rewetting adhesives, condensation adhesives, solvent-free adhesives, film adhesives, and hot-melt adhesives. In addition, an adhesive layer may be provided through an anchor coating as needed.
較佳的接著劑可舉出水溶性接著劑。此水溶性接著劑例如有以聚乙烯醇系樹脂成為主成分者。水溶性接著劑可使用市售者，也可使用在市售的接著劑中已混合溶劑或添加劑者。水溶性接著劑的市售之聚乙烯醇系樹脂例如有股份有限公司Kuraray製的KL-318等。 Preferable adhesives include water-soluble adhesives. For example, water-soluble adhesives have polyvinyl alcohol resins as the main component. Commercially available water-soluble adhesives can be used, or commercially available adhesives mixed with solvents or additives can be used. Commercially available polyvinyl alcohol resins of water-soluble adhesives include KL-318 manufactured by Kuraray Co., Ltd.
水溶性接著劑可含有交聯劑。交聯劑的種類係以胺化合物、醛化合物、三羥甲基化合物、環氧化合物、異氰酸酯化合物及多價金屬鹽等為佳，並以環氧化合物尤佳。交聯劑的市售品例如有乙二醛或田岡化學工業股份有限公司製的Sumirez樹脂650(30)等。 The water-soluble adhesive may contain a crosslinking agent. The types of crosslinking agents are preferably amine compounds, aldehyde compounds, trihydroxymethyl compounds, epoxy compounds, isocyanate compounds and polyvalent metal salts, and epoxy compounds are particularly preferred. Commercially available crosslinking agents include glyoxal or Sumirez resin 650 (30) manufactured by TAOKA Chemical Industry Co., Ltd.
又，另一較佳的接著劑可舉出由經活性能量線的照射而硬化的樹脂組成物所形成之活性能量線硬化型接著劑。活性能量線硬化型接著劑可舉出含有聚合性化合物及光聚合起始劑者、含有光反應性樹脂者、含有黏合劑樹脂及光反應***聯劑者等。聚合性化合物可舉出如同 光硬化性環氧系單體、光硬化性丙烯酸系單體、光硬化性胺酯系單體的光聚合性單體，或來自光聚合性單體的寡聚物。光聚合起始劑可舉出含有藉由如紫外線的活性能量線之照射而產生如自由基、陽離子或陰離子的活性種之物質。含有聚合性化合物及光聚合起始劑的活性能量線硬化性接著劑，係以使用含有光硬化性環氧系單體及光陽離子聚合起始劑者為佳。 Another preferred adhesive may be an active energy ray-curing adhesive formed by a resin composition that is cured by irradiation with active energy rays. Examples of active energy ray-curing adhesives include those containing a polymerizable compound and a photopolymerization initiator, those containing a photoreactive resin, those containing an adhesive resin and a photoreactive crosslinking agent, etc. Examples of polymerizable compounds include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable amine monomers, or oligomers derived from photopolymerizable monomers. Examples of photopolymerization initiators include substances containing active species such as free radicals, cations, or anions generated by irradiation with active energy rays such as ultraviolet rays. The active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator is preferably one containing a photocurable epoxy monomer and a photocationic polymerization initiator.
使用活性能量線硬化性接著劑時，將偏光片與保護膜黏合之後，可視需要而進行乾燥步驟，接著進行藉由活性能量線照射而使活性能量線硬化性接著劑硬化的步驟。活性能量線的光源雖然無特別的限制，但以在波長400nm以下具有發光分布的紫外線為佳，具體上可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈等。 When using an active energy ray-curable adhesive, after bonding the polarizer and the protective film, a drying step can be performed as needed, and then a step of curing the active energy ray-curable adhesive by irradiating the active energy ray can be performed. Although there is no particular restriction on the light source of the active energy ray, ultraviolet light with a luminescence distribution below a wavelength of 400nm is preferred. Specifically, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc. can be used.
上述接著劑也可含有添加劑。添加劑可舉出離子補捉劑、抗氧化劑、鏈轉移劑、增敏劑、黏著賦與劑、熱可塑性樹脂、充填劑、流動調節劑、塑化劑、消泡劑等。 The above-mentioned adhesives may also contain additives. Examples of additives include ion scavengers, antioxidants, chain transfer agents, sensitizers, adhesives, thermoplastic resins, fillers, flow regulators, plasticizers, defoamers, etc.
(活性能量線硬化型樹脂組成物的硬化層) (Hard layer of active energy ray-hardening resin composition)
活性能量線硬化型樹脂組成物的硬化層可供使用作為保護偏光片的表面之保護層。活性能量線硬化型樹脂組成物的硬化層與一般保護膜相比較，由於可變薄，故對於偏光板的薄型化有效。第1圖中的活性能量線硬化型樹脂組成物之硬化層1即相當於此。 The hardened layer of the active energy ray hardening resin composition can be used as a protective layer to protect the surface of the polarizer. Compared with the general protective film, the hardened layer of the active energy ray hardening resin composition can be thinner, so it is effective for thinning the polarizer. The hardened layer 1 of the active energy ray hardening resin composition in Figure 1 is equivalent to this.
本發明的偏光板之套組中，偏光板(尤其是前面側偏光板)係以偏光片的至少一面具備活性能量線硬化型樹脂組成物之硬化層為佳，並以在偏光片之接近液晶單元之側具備活性能量線硬化型樹脂組成物的硬化層更佳。此情況，由於可使偏光片與液晶單元的距離變小，故伴隨偏光片收縮而使液晶單元變形之力變小，對高溫環境中的液晶面板之翹曲的影響更小。就此點而言，由前面側偏光板的偏光片之接近液晶單元之側的面至液晶單元之接近前面側偏光板的偏光片之側的面之距離，係以例如30μm以下為佳，並以25μm以下更佳。 In the polarizing plate set of the present invention, the polarizing plate (especially the front side polarizing plate) is preferably provided with a hardening layer of an active energy ray hardening resin composition on at least one side of the polarizing plate, and more preferably provided with a hardening layer of an active energy ray hardening resin composition on the side of the polarizing plate close to the liquid crystal unit. In this case, since the distance between the polarizing plate and the liquid crystal unit can be reduced, the force of deformation of the liquid crystal unit accompanying the contraction of the polarizing plate is reduced, and the effect on the warping of the liquid crystal panel in a high temperature environment is smaller. In this regard, the distance from the side of the polarizing plate of the front side polarizing plate close to the liquid crystal unit to the side of the liquid crystal unit close to the polarizing plate of the front side polarizing plate is preferably, for example, less than 30μm, and more preferably less than 25μm.
活性能量線硬化型樹脂組成物的硬化層之厚度係以0.01至20μm為佳，並以0.01至10μm更佳，而以0.01至5μm又更佳。 The thickness of the hardened layer of the active energy ray-hardening resin composition is preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, and even more preferably 0.01 to 5 μm.
形成活性能量線硬化型樹脂組成物的硬化層之活性能量線硬化型樹脂組成物，可使用與上述活性能量線硬化性接著劑相同者。活性能量線硬化型樹脂組成物與活性能量線硬化性接著劑，可以使用互為相同者，也可使用互不相同者。 The active energy ray-curing resin composition forming the hardened layer of the active energy ray-curing resin composition may be the same as the above-mentioned active energy ray-curing adhesive. The active energy ray-curing resin composition and the active energy ray-curing adhesive may be the same or different.
(偏光板的製造方法) (Polarizing plate manufacturing method)
上述說明的構件，例如可透過接著劑層或黏著劑層使其積層而相互黏合。又，也可採用使用剝離膜而製造偏光板的方法。 The components described above can be laminated and bonded to each other, for example, through a bonding agent layer or an adhesive layer. Alternatively, a method of manufacturing a polarizing plate using a release film can be adopted.
以下，以第1圖(a)表示的偏光板之套組為例說明構成本發明的偏光板之前面側偏光板及背面側偏光 板的製造方法。 The following describes the manufacturing method of the front side polarizing plate and the back side polarizing plate constituting the polarizing plate of the present invention, taking the set of polarizing plates shown in FIG. 1 (a) as an example.
(前面側偏光板的製造方法) (Manufacturing method of front side polarizing plate)
準備剝離膜、偏光片2及保護膜10，在偏光片的一面透過接著劑而黏合保護膜，且在偏光片的另一面透過揮發性液體而積層剝離膜。當然，保護膜與偏光片的黏合及剝離膜與偏光片之積層也可分別依序進行。 Prepare a release film, a polarizer 2, and a protective film 10, adhere the protective film to one side of the polarizer through an adhesive, and layer the release film on the other side of the polarizer through a volatile liquid. Of course, the bonding of the protective film and the polarizer and the layering of the release film and the polarizer can also be performed separately and in sequence.
揮發性液體例如有水或水與親水性液體的混合物等。親水性液體係以在第2步驟的加熱處理後不殘留者為佳例如可列舉：甲醇、乙醇、1-丁醇、四氫呋喃、丙酮、乙腈、N,N-二甲基甲醯胺、二甲基亞碸、甲酸、乙酸等。揮發性液體中也可添加抗靜電劑等添加劑。 Volatile liquids include water or a mixture of water and a hydrophilic liquid. The hydrophilic liquid is preferably one that does not remain after the heat treatment in step 2, for example: methanol, ethanol, 1-butanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, formic acid, acetic acid, etc. Antistatic agents and other additives may also be added to the volatile liquid.
形成剝離膜的樹脂並非特別的限制者，例如可列舉：由甲基丙烯酸甲酯系樹脂、聚烯烴系樹脂、環狀烯烴系樹脂、聚氯乙烯系樹脂、纖維素系樹脂、苯乙烯系樹脂、丙烯腈/丁二烯/苯乙烯系樹脂、丙烯腈/苯乙烯系樹脂、聚乙酸乙烯酯系樹脂、聚偏二氯乙烯系樹脂、聚醯胺系樹脂、聚縮醛系樹脂、聚碳酸酯系樹脂、改質聚苯醚系樹脂、聚對苯二甲酸丁二酯系樹脂、聚對苯二甲酸乙二酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚芳酯系樹脂、聚醯胺醯亞胺系樹脂及聚醯亞胺系樹脂等形成之膜。 The resin forming the peeling film is not particularly limited, and examples thereof include methyl methacrylate resins, polyolefin resins, cycloolefin resins, polyvinyl chloride resins, cellulose resins, styrene resins, acrylonitrile/butadiene/styrene resins, acrylonitrile/styrene resins, polyvinyl acetate resins, and polyvinyl acetate resins. Films formed from vinylidene chloride resins, polyamide resins, polyacetal resins, polycarbonate resins, modified polyphenylene ether resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyamide imide resins and polyimide resins.
當將保護膜黏合在偏光片時，為提高接著性，可在偏光片及/或保護膜的黏合面進行如電漿處理、電暈處理、紫外線照射處理、火焰(flame)處理、皂化處理的易接著處理。又，對剝離膜也進行與保護膜相同的處理 可用於改善揮發性液體的濕潤性。 When the protective film is bonded to the polarizer, in order to improve the adhesion, the bonding surface of the polarizer and/or the protective film can be subjected to an easy-to-bond treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, or saponification treatment. In addition, the release film is also subjected to the same treatment as the protective film. It can be used to improve the wettability of volatile liquids.
使用活性能量線硬化型接著劑作為接著劑時係藉由照射活性能量線而使接著劑硬化，接著進行加熱處理，將揮發性液體揮發去除。使用水性接著劑作為接著劑時係藉由進行加熱處理，一面使偏光片與保護膜接著，一面使揮發性液體揮發去除。就簡化步驟而言，係以使用水性接著劑為佳。 When using an active energy ray-curing adhesive as an adhesive, the adhesive is cured by irradiating active energy rays, and then heat treatment is performed to evaporate and remove the volatile liquid. When using a water-based adhesive as an adhesive, the polarizer and the protective film are bonded by heat treatment while the volatile liquid is evaporated and removed. In terms of simplifying the steps, it is better to use a water-based adhesive.
乾燥溫度係以30至90℃為佳。如低於30℃時，可能有乾燥時間變長、產生外觀不良之疑慮。又，如乾燥溫度超過90℃時，可能有因熱而致偏光片的偏光性能劣化之疑慮。乾燥時間可設成10至1,000秒左右，就生產性之觀點而言，係以60至750秒為佳，並以150至600秒更佳。 The drying temperature is preferably between 30 and 90°C. If it is lower than 30°C, the drying time may be prolonged, resulting in poor appearance. Also, if the drying temperature exceeds 90°C, the polarization performance of the polarizer may be deteriorated due to heat. The drying time can be set to about 10 to 1,000 seconds. From the perspective of productivity, 60 to 750 seconds is preferred, and 150 to 600 seconds is more preferred.
藉由在偏光片透過由揮發性液體形成之層將剝離膜積層，於本步驟的加熱溫度可提高至例如超過60℃而90℃以下左右。亦即，將加熱溫度設定成較高溫，除了可防止偏光片的破裂，也可因該高溫加熱而使偏光片的收縮率變小，從而獲得尺寸安定性高的單面保護偏光板。藉由使單面保護偏光板的收縮率變小，在使用此偏光板製作液晶面板時，可更減少該液晶面板的翹曲。 By laminating the exfoliation film through a layer formed by a volatile liquid on the polarizer, the heating temperature in this step can be increased to, for example, above 60°C and below 90°C. That is, setting the heating temperature to a higher temperature can not only prevent the polarizer from breaking, but also reduce the shrinkage rate of the polarizer due to the high temperature heating, thereby obtaining a single-sided protected polarizer with high dimensional stability. By reducing the shrinkage rate of the single-sided protected polarizer, when the liquid crystal panel is made using the polarizer, the warp of the liquid crystal panel can be further reduced.
為了藉由加熱使偏光片與剝離膜積層中使用的揮發性液體揮發，保護膜及剝離膜的至少一方的膜之透濕度係以400g/m2‧24小時以上為佳，並以420g/m2‧24小時以上更佳。透濕度在此範圍中時，由於在之後的 第2步驟可使揮發性液體有效率的揮發去除，故可更提高生產性。 In order to volatilize the volatile liquid used in the lamination of the polarizer and the release film by heating, the moisture permeability of at least one of the protective film and the release film is preferably 400g/ m2 ‧24 hours or more, and more preferably 420g/ m2 ‧24 hours or more. When the moisture permeability is within this range, the volatile liquid can be efficiently evaporated and removed in the subsequent second step, thereby further improving productivity.
在基材膜上塗布活性能量線硬化型樹脂組成物，以使活性能量線硬化型樹脂組成物的硬化層1積層在偏光片2上。接著，自前述單面保護偏光板將剝離膜剝離去除，將單面保護偏光板中的偏光片2與基材膜上的活性能量線硬化型樹脂組成物積層。藉由照射活性能量線使活性能量線硬化型樹脂組成物硬化而形成硬化層1。將基材膜剝離去除，在硬化層1上形成黏著劑層20，即可獲得由黏著劑層20/活性能量線硬化型樹脂組成物的硬化層1/偏光片2/接著劑層30/保護膜10所形成之前面側偏光板。 An active energy ray curing resin composition is applied to a substrate film so that a curing layer 1 of the active energy ray curing resin composition is laminated on the polarizer 2. Next, the release film is peeled off from the aforementioned single-sided protective polarizer, and the polarizer 2 in the single-sided protective polarizer is laminated with the active energy ray curing resin composition on the substrate film. The active energy ray curing resin composition is cured by irradiating active energy rays to form a curing layer 1. The substrate film is peeled off and removed, and an adhesive layer 20 is formed on the curing layer 1, so that the front side polarizer formed by the adhesive layer 20/the curing layer 1 of the active energy ray curing resin composition/the polarizer 2/the adhesive layer 30/the protective film 10 can be obtained.
(背面側偏光板的製造方法) (Manufacturing method of back side polarizing plate)
藉由與前面側偏光板的製造方法相同之方法，準備剝離膜、偏光片2及保護膜11，將保護膜透過接著劑而黏合在偏光片2的一面，同時將剝離膜透過揮發性液體而積層在偏光片2的另一面。使偏光片2與保護膜11接著並去除揮發性液體之後，將剝離膜剝離而獲得單面保護偏光板。 By the same method as the manufacturing method of the front side polarizing plate, a release film, a polarizer 2 and a protective film 11 are prepared, and the protective film is bonded to one side of the polarizer 2 through an adhesive, and the release film is deposited on the other side of the polarizer 2 through a volatile liquid. After the polarizer 2 and the protective film 11 are bonded and the volatile liquid is removed, the release film is peeled off to obtain a single-sided protected polarizing plate.
藉由使亮度改善膜透過黏著劑層而積層在單面保護偏光板中的保護膜上，並將黏著劑層20積層在偏光片2上，可獲得由黏著劑層20/偏光片2/接著劑層31/保護膜11/黏著劑層21/亮度改善膜40所形成的背面側偏光板。 By allowing the brightness improvement film to pass through the adhesive layer and be laminated on the protective film in the single-sided protected polarizing plate, and laminating the adhesive layer 20 on the polarizer 2, a back-side polarizing plate formed by the adhesive layer 20/polarizer 2/adhesive layer 31/protective film 11/adhesive layer 21/brightness improvement film 40 can be obtained.
本發明的偏光板之形狀並無特別的限制， 可以是矩形。以卷至卷(roll to roll)方式製成偏光板時，可將其裁斷成預定形狀。本發明的偏光板可以是對角線15吋以下的矩形狀，也可以是對角線3吋以上的矩形狀，也可以是對角線7吋以上的矩形狀。 The shape of the polarizing plate of the present invention is not particularly limited, and can be rectangular. When the polarizing plate is made by roll-to-roll method, it can be cut into a predetermined shape. The polarizing plate of the present invention can be a rectangle with a diagonal of less than 15 inches, a rectangle with a diagonal of more than 3 inches, or a rectangle with a diagonal of more than 7 inches.
(液晶面板的製造方法) (Manufacturing method of liquid crystal panel)
藉由將本發明的偏光板之套組分別黏合在液晶單元的兩面即可獲得液晶面板。黏合係以透過前面側偏光板的黏著劑層、透過背面側偏光板的黏著劑層分別進行為佳。又，係以前面側偏光板係積層在液晶單元的觀察側，背面側偏光板係積層在液晶單元的背面為佳。本發明的液晶面板可適用於液晶顯示裝置。前面側偏光板係以使其吸收軸與液晶單元的短邊方向成為大約平行的方式黏合為佳，背面側偏光板係以使其吸收軸與液晶單元的長邊方向成為大約平行的方式黏合為佳。本說明書中「大約平行」係表示例如形成之角度為0±5°，並以0±1°為佳。 A liquid crystal panel can be obtained by bonding the set of polarizing plates of the present invention to the two sides of a liquid crystal unit respectively. The bonding is preferably performed through the adhesive layer of the front side polarizing plate and through the adhesive layer of the back side polarizing plate respectively. In addition, it is preferred that the front side polarizing plate is laminated on the observation side of the liquid crystal unit and the back side polarizing plate is laminated on the back side of the liquid crystal unit. The liquid crystal panel of the present invention can be applied to liquid crystal display devices. The front side polarizing plate is preferably bonded in a manner that its absorption axis is approximately parallel to the short side direction of the liquid crystal unit, and the back side polarizing plate is preferably bonded in a manner that its absorption axis is approximately parallel to the long side direction of the liquid crystal unit. In this manual, "approximately parallel" means, for example, that the angle formed is 0±5°, and preferably 0±1°.
液晶單元係具有2片單元基板與挾持在該等基板間之液晶層。單元基板通常大多是以玻璃構成，但也可以是塑膠基板。其他，本發明的液晶面板中使用的液晶單元自身，也可用此領域中採用的各種材質構成。若藉由本發明的偏光板之套組，即使該液晶單元的厚度為0.4mm以下，也可明顯的減少翹曲。本發明中之液晶單元的厚度係包含液晶層與挾持液晶層的一對基板之厚度者。 The liquid crystal unit has two unit substrates and a liquid crystal layer clamped between the substrates. The unit substrate is usually mostly made of glass, but it can also be a plastic substrate. In addition, the liquid crystal unit itself used in the liquid crystal panel of the present invention can also be made of various materials used in this field. If the polarizing plate set of the present invention is used, the warp can be significantly reduced even if the thickness of the liquid crystal unit is less than 0.4mm. The thickness of the liquid crystal unit in the present invention includes the thickness of the liquid crystal layer and a pair of substrates clamping the liquid crystal layer.
[實施例] [Implementation example]
以下，藉由實施例更詳細的說明本發明，但 本發明並非侷限於此等例之範圍者。例中，表示含量或使用量的%及份，如無特別的說明即係重量基準。又，實施例中使用的評估方法係如下述。 The present invention is described in more detail below by way of examples, but the present invention is not limited to the scope of these examples. In the examples, the percentage and part of the content or usage amount are based on weight unless otherwise specified. In addition, the evaluation method used in the examples is as follows.
(1)厚度： (1)Thickness:
使用股份有限公司Nikon製的數位微米計MH-15M測定。 Measured using a digital micrometer MH-15M manufactured by Nikon Corporation.
(2)拉伸彈性率 (2) Tensile elasticity
從膜切出寬度15mm×長度150mm的試驗片。接著，以配備恆溫槽的拉伸試驗機〔股份有限公司島津製作所製AUTOGRAPH(註冊商標)AG-1S試驗機〕的上下鉗具，以使鉗具的間隔成為100mm的方式挾住上述試驗片長邊方向的兩末端，在85℃的環境下以50mm/分鐘的拉伸速度拉伸，作成應力-應變曲線，計算出85℃的拉伸彈性率。 A test piece with a width of 15 mm and a length of 150 mm was cut from the film. Then, the upper and lower clamps of a tensile testing machine equipped with a constant temperature bath (Autograph (registered trademark) AG-1S testing machine manufactured by Shimadzu Corporation) were used to clamp the two ends of the long side of the test piece so that the interval between the clamps was 100 mm. The test piece was stretched at a tensile speed of 50 mm/min in an environment of 85°C, and a stress-strain curve was drawn to calculate the tensile elasticity at 85°C.
(3)透濕度 (3) Moisture permeability
依據JIS Z 0208測定透濕度。溫、濕度條件係設成40度、90% RH。 Moisture permeability was measured according to JIS Z 0208. The temperature and humidity conditions were set to 40 degrees and 90% RH.
(4)翹曲成凹狀之側的偏光板之判斷及高溫環境下的翹曲量之測定 (4) Determination of the concave side of the polarizing plate and measurement of the amount of warping in a high temperature environment
將具有背面側偏光板/玻璃板/前面側偏光板之構成的評估用試樣，靜置於85℃的環境下250小時之後，將前面側偏光板作為上側，置於二元測定器的測定台上。二元測定器係使用股份有限公司Nikon製的“NEXIV(註冊商標)VMR-12072”。接著，在測定台的表面對準焦點，將此作為基準，在評估用試樣面上的25處分別對準焦點，自作為基 準的焦點測定其高度。將25處的測定點之高度的最大值與最小值之差作為翹曲量，將前面側偏光板側評估用試樣的邊緣翹曲之翹曲設為正翹曲，背面側偏光板側評估用試樣的邊緣翹曲之翹曲設為負翹曲。正翹曲之情況，翹曲成凹狀之側的偏光板是前面側偏光板，負翹曲之情況，翹曲成凹狀之側的偏光板是背面側偏光板。 The evaluation sample with the structure of back polarizing plate/glass plate/front polarizing plate was placed in an environment of 85°C for 250 hours, and then placed on the measuring table of a binary measuring machine with the front polarizing plate as the upper side. The binary measuring machine used was "NEXIV (registered trademark) VMR-12072" manufactured by Nikon Corporation. Then, the focus was aligned on the surface of the measuring table, and the focus was aligned at 25 points on the evaluation sample surface using this as a reference, and the height was measured from the focus point used as the reference. The difference between the maximum and minimum values of the height of the 25 measurement points is taken as the amount of warp, and the edge warp of the sample for evaluation on the front polarizer side is set as positive warp, and the edge warp of the sample for evaluation on the back polarizer side is set as negative warp. In the case of positive warp, the polarizer on the side that is warped into a concave shape is the front polarizer, and in the case of negative warp, the polarizer on the side that is warped into a concave shape is the back polarizer.
具體上，將第4圖表示的點80作為測定點。第4圖表示的25個點係距離偏光板的邊緣7mm內側的領域中之點，短邊方向是以大約間隔20mm設置，長邊方向是以大約間隔35mm設置。又，第4圖中之符號402是表示偏光板，70是表示玻璃板。
Specifically, point 80 shown in Figure 4 is used as the measurement point. The 25 points shown in Figure 4 are points in the area 7mm inside the edge of the polarizing plate, and are set at intervals of approximately 20mm in the short side direction and approximately 35mm in the long side direction. In addition, the
[製造例1]偏光片的製作 [Manufacturing Example 1] Manufacturing of polarizer
藉由乾式延伸將厚度20μm的聚乙烯醇膜(平均聚合度約2,400，皂化度99.9莫耳%以上)單軸延伸至約4倍，並且在保持緊繃狀態之下，將其浸泡在40℃的純水中40秒之後，在碘/碘化鉀/水的重量比為0.052/5.7/100的水溶液中以28℃浸泡30秒進行染色處理。然後，在碘化鉀/硼酸/水的重量比為11.0/6.2/100的水溶液中於70℃浸泡120秒。接著，以8℃的純水洗淨15秒之後，以保持在300N的張力之狀態，以60℃乾燥50秒，接著以75℃乾燥20秒，獲得於聚乙烯醇膜中已吸附定向碘之厚度7μm的偏光片。 A 20 μm thick polyvinyl alcohol film (average degree of polymerization of about 2,400, saponification degree of 99.9 mol% or more) was uniaxially stretched to about 4 times by dry stretching, and then soaked in pure water at 40°C for 40 seconds while being tautly stretched, and then dyed by soaking in an aqueous solution of iodine/potassium iodide/water at a weight ratio of 0.052/5.7/100 at 28°C for 30 seconds. Then, it was soaked in an aqueous solution of potassium iodide/boric acid/water at a weight ratio of 11.0/6.2/100 at 70°C for 120 seconds. Then, after washing with pure water at 8°C for 15 seconds, it was dried at 60°C for 50 seconds while maintaining a tension of 300N, and then dried at 75°C for 20 seconds to obtain a 7μm thick polarizer with oriented iodine adsorbed in the polyvinyl alcohol film.
[製造例2]水系接著劑的製作 [Production Example 2] Production of water-based adhesives
相對於水100重量份，溶解3重量份的羧基改質聚乙 烯醇〔購自股份有限公司Kuraray的商品名「KL-318」〕，在此水溶液中添加為水溶性環氧樹脂的聚醯胺環氧系添加劑〔購自田岡化學工業股份有限公司的商品名「Sumirez Resin樹脂(註冊商標)650(30)」，固形份濃度30重量%的水溶液〕1.5重量份，調製成水系接著劑。 3 parts by weight of carboxyl-modified polyvinyl alcohol (trade name "KL-318" purchased from Kuraray Co., Ltd.) was dissolved in 100 parts by weight of water, and 1.5 parts by weight of polyamide epoxy additive (trade name "Sumirez Resin Resin (Registered Trademark) 650 (30)" purchased from TAOKA Chemical Industry Co., Ltd., solid content concentration 30% by weight aqueous solution) was added to the aqueous solution to prepare a water-based adhesive.
[製造例3]活性能量線硬化型樹脂組成物 [Production Example 3] Active energy ray-curing resin composition
將作為聚合化合物的氧雜環丁烷化合物(2官能)(OXT221)50質量份、脂環式環氧化合物(2官能)(CEL2021P)35質量份、芳香族環氧化合物(3官能)(TECHMORE VG3101L 15質量份及作為光陽離子聚合起始劑的三芳基硫鎓六氟磷酸鹽2.25質量份混合，獲得活性能量線硬化型樹脂組成物。 An active energy ray-curable resin composition was obtained by mixing 50 parts by mass of an oxycyclobutane compound (difunctional) (OXT221) as a polymerizing compound, 35 parts by mass of an alicyclic epoxy compound (difunctional) (CEL2021P), 15 parts by mass of an aromatic epoxy compound (trifunctional) (TECHMORE VG3101L) and 2.25 parts by mass of triarylsulfonium hexafluorophosphate as a photopolymerization initiator.
[保護膜A、B、C、D、E及剝離膜F、G] [Protective films A, B, C, D, E and peeling films F, G]
準備以下5種保護膜及2種剝離膜。 Prepare the following 5 types of protective films and 2 types of peeling films.
保護膜A：25KCHCN-TC。凸版印刷股份有限公司製的附硬質塗層之三乙醯基纖維素膜經皂化處理之膜。厚度是32μm，透濕度是450g/m2‧24小時。 Protective film A: 25KCHCN-TC. A saponified triacetyl cellulose film with a hard coating manufactured by Toppan Printing Co., Ltd. The thickness is 32μm and the moisture permeability is 450g/ m2 ‧24 hours.
保護膜B：ZT12。日本ZEON股份有限公司製的環狀聚烯烴系樹脂膜。厚度是20μm，藉由横一軸延伸而製得者。 Protective film B: ZT12. Ring-shaped polyolefin resin film made by ZEON Co., Ltd., Japan. Thickness is 20μm, made by horizontal uniaxial stretching.
保護膜C：Zero Tack(註冊商標)。KONICA MINOLTA股份有限公司製的三乙醯基纖維素膜經皂化處理之膜。厚度是20μm。 Protective film C: Zero Tack (registered trademark). A saponified triacetyl cellulose film manufactured by KONICA MINOLTA Co., Ltd. The thickness is 20μm.
保護膜D：KC2UAW。KONICA MINOLTA股份有限公 司製的三乙醯基纖維素膜經皂化處理之膜。厚度是25μm。 Protective film D: KC2UAW. A saponified triacetyl cellulose film made by KONICA MINOLTA Co., Ltd. The thickness is 25μm.
保護膜E：ZEONOR(註冊商標)。日本ZEON股份有限公司製的環狀聚烯烴系樹脂膜。厚度是20μm。 Protective film E: ZEONOR (registered trademark). Ring-shaped polyolefin resin film manufactured by ZEON Co., Ltd., Japan. Thickness is 20μm.
剝離膜F：TD80UL。富士軟片股份有限公司製的三乙醯基纖維素膜。厚度是80μm，透濕度是502g/m2‧24小時。 Peeling film F: TD80UL. Triacetyl cellulose film manufactured by Fuji Film Co., Ltd. Thickness is 80μm, moisture permeability is 502g/ m2 ‧24 hours.
剝離膜G：住友化學股份有限公司製的聚甲基丙烯酸甲酯膜。厚度是80μm，透濕度是50g/m2‧24小時。 Peeling film G: Polymethyl methacrylate film manufactured by Sumitomo Chemical Co., Ltd. Thickness: 80 μm, moisture permeability: 50 g/m 2 ‧24 hours.
[實施例1] [Implementation Example 1]
[前面側偏光板A的製作] [Production of front polarizing plate A]
將製造例1中獲得的偏光片連續運送的同時亦將保護膜A從保護膜A的卷連續解開，並由剝離膜G的卷將剝離膜G連續捲起。接著，將水性接著劑注入偏光片與保護膜A之間並且亦將純水注入偏光片與剝離膜G之間，通過黏合輥而作成由保護膜A/水性接著劑/偏光片/純水/剝離膜G所形成的積層膜。接著運送積層膜，藉由在乾燥爐中進行80℃、300秒的加熱處理，使水性接著劑乾燥並且使介在偏光片與剝離膜G之間的純水揮發去除，獲得附剝離膜之單面保護偏光板。從附剝離膜之單面保護偏光板將剝離膜G剝離，獲得單面保護偏光板。 The polarizer obtained in Manufacturing Example 1 is continuously transported while the protective film A is continuously unwound from the roll of the protective film A, and the peeling film G is continuously rolled up from the roll of the peeling film G. Then, a water-based adhesive is injected between the polarizer and the protective film A and pure water is also injected between the polarizer and the peeling film G, and a laminated film formed of protective film A/water-based adhesive/polarizer/pure water/peeling film G is formed by a bonding roll. The laminated film is then transported and heated in a drying oven at 80°C for 300 seconds to dry the aqueous adhesive and evaporate the pure water between the polarizer and the release film G to obtain a single-sided protective polarizing plate with a release film. The release film G is peeled off from the single-sided protective polarizing plate with a release film to obtain a single-sided protective polarizing plate.
另一方面，在厚度50μm的環狀聚烯烴系樹脂膜〔ZEONOR(註冊商標)，日本ZEON股份有限公司製〕之單面，塗布製造例3中調製的活性能量線硬化型樹脂組成物，使其硬化後的膜厚大約成為3μm。在該塗布面黏合 上述單面保護偏光板的偏光片，利用紫外線照射裝置〔照射燈是使用Fusion UV Systems公司社製的「D VALVE」〕以280至320nm的累計光量成為200mJ/cm2之方式從環狀聚烯烴系樹脂膜側照射紫外線，使活性能量線硬化型樹脂組成物硬化。將環狀聚烯烴系樹脂膜剝離，在活性能量線硬化型樹脂組成物的硬化層施予電暈處理。將黏著劑層〔Lintec股份有限公司製的商品名“# KT”。厚度是20μm。〕黏合在硬化物層上。如此，製作成由保護膜A/水性接著劑層/偏光片/活性能量線硬化型樹脂組成物的硬化層/黏著劑層所構成之前面側偏光板A。 On the other hand, the active energy ray-curable resin composition prepared in Production Example 3 was applied to one side of a 50 μm thick cyclic polyolefin resin film [ZEONOR (registered trademark), manufactured by ZEON Co., Ltd., Japan] so that the film thickness after curing was about 3 μm. The polarizer of the above-mentioned single-sided protective polarizing plate was adhered to the coated surface, and ultraviolet rays were irradiated from the cyclic polyolefin resin film side using an ultraviolet irradiation device [the irradiation lamp was "D VALVE" manufactured by Fusion UV Systems Co., Ltd.] in such a manner that the accumulated light amount at 280 to 320 nm was 200 mJ/ cm2 , thereby curing the active energy ray-curable resin composition. The cyclic polyolefin resin film is peeled off, and the curing layer of the active energy ray curing resin composition is subjected to a corona treatment. An adhesive layer [trade name "#KT" manufactured by Lintec Co., Ltd., thickness 20μm.] is adhered to the curing layer. In this way, a front-side polarizing plate A composed of a protective film A/aqueous adhesive layer/polarizer/curing layer of the active energy ray curing resin composition/adhesive layer is produced.
[背面側偏光板B的製作] [Production of back side polarizing plate B]
將製造例1中獲得的偏光片連續運送並將保護膜B從保護膜B的卷連續解開，而且由剝離膜F的卷將剝離膜F連續捲起。接著，將水性接著劑注入偏光片與經電暈處理的保護膜B之間並將純水注入偏光片與剝離膜F之間，通過黏合輥而作成由保護膜B/水性接著劑/偏光片/純水/剝離膜F所形成的積層膜。接著運送積層膜，藉由在乾燥爐中進行80℃、300秒的加熱處理，使水性接著劑乾燥並使介在偏光片與剝離膜F之間的純水揮發去除，獲得附剝離膜之單面保護偏光板。從附剝離膜之單面保護偏光板中將剝離膜F剝離，獲得單面保護偏光板。 The polarizer obtained in Manufacturing Example 1 is continuously transported and the protective film B is continuously unwound from the roll of the protective film B, and the peeling film F is continuously rolled up from the roll of the peeling film F. Then, a water-based adhesive is injected between the polarizer and the protective film B treated with corona, and pure water is injected between the polarizer and the peeling film F, and a laminated film formed of the protective film B/water-based adhesive/polarizer/pure water/peeling film F is formed by a bonding roll. The laminated film is then transported and heated in a drying oven at 80°C for 300 seconds to dry the aqueous adhesive and evaporate the pure water between the polarizer and the release film F to obtain a single-sided protective polarizing plate with a release film. The release film F is peeled off from the single-sided protective polarizing plate with a release film to obtain a single-sided protective polarizing plate.
將黏著劑層〔Lintec股份有限公司製的商品名“# L2”。厚度是5μm。〕黏合在前述單面保護偏光板的保護膜B上，並且在該黏著劑層上黏合亮度改善膜〔3M公 司製的商品名”Advanced Polarized Film，第三代(Version 3)。厚度是26μm。〕)。然後，將黏著劑層〔Lintec股份有限公司製的商品名“# KT”。厚度是20μm。〕黏合在偏光片上。如此，製作成由亮度改善膜/黏著劑層/保護膜B/水性接著劑層/偏光片/黏著劑層所構成的背面側偏光板B。 The adhesive layer [Lintec Co., Ltd., trade name "#L2". Thickness is 5μm.] is bonded to the protective film B of the aforementioned single-sided protective polarizing plate, and the brightness improvement film [3M Co., Ltd., trade name "Advanced Polarized Film, third generation (Version 3). Thickness is 26μm.] is bonded to the adhesive layer. Then, the adhesive layer [Lintec Co., Ltd., trade name "#KT". Thickness is 20μm.] is bonded to the polarizer. In this way, the back side polarizing plate B composed of brightness improvement film/adhesive layer/protective film B/water-based adhesive layer/polarizer/adhesive layer is produced.
[評估用試樣的製作] [Preparation of samples for evaluation]
將前面側偏光板A裁斷成穿透軸方向155.25mm、吸收軸方向95.90mm的矩形狀，將背面側偏光板B裁斷成吸收軸方向155.25μm、穿透軸方向95.90mm的矩形狀。接著，準備厚度為0.4mm的玻璃板(康寧(Corning)公司製，型號：EAGLE XG(註冊商標))，以前面側偏光板的吸收軸與背面側偏光板的吸收軸呈正交的方式，透過各別的黏著劑層將前面側偏光板及背面側偏光板黏合在玻璃板。 Cut the front polarizing plate A into a rectangular shape with a transmission axis of 155.25 mm and an absorption axis of 95.90 mm, and cut the back polarizing plate B into a rectangular shape with an absorption axis of 155.25 μm and a transmission axis of 95.90 mm. Then, prepare a glass plate with a thickness of 0.4 mm (Corning, model: EAGLE XG (registered trademark)), and bond the front polarizing plate and the back polarizing plate to the glass plate through respective adhesive layers in such a way that the absorption axis of the front polarizing plate is orthogonal to the absorption axis of the back polarizing plate.
對於獲得的評估用試樣進行高溫環境下的翹曲量之測定，將結果表示於表1中。翹曲成凹狀之側的偏光板係背面側偏光板，保護膜B係85℃的背面側偏光板的穿透軸方向之拉伸彈性率為2,190MPa，背面側偏光板的吸收軸方向之拉伸彈性率為1,786MPa。 The obtained evaluation samples were measured for warping in a high temperature environment, and the results are shown in Table 1. The side of the polarizing plate that is warped into a concave shape is the back side polarizing plate, and the protective film B is the back side polarizing plate at 85°C. The tensile elasticity in the transmission axis direction is 2,190 MPa, and the tensile elasticity in the absorption axis direction of the back side polarizing plate is 1,786 MPa.
[實施例2] [Example 2]
前面側偏光板係使用實施例1中使用的前面側偏光板A。背面側偏光板則係於背面側偏光板B的製作中，除了將保護膜B變更成保護膜C，將剝離膜F變更成剝離膜G以外，其餘與背面側偏光板B同樣製作，製作成由亮度改 善膜/黏著劑層/保護膜C/水性接著劑層/偏光片/黏著劑層所構成之背面側偏光板C。然後，除了將背面側偏光板B變更成本實施例的背面側偏光板C以外，與實施例1相同的操作，製作成評估用試樣。 The front polarizing plate is the front polarizing plate A used in Example 1. The back polarizing plate is made in the same way as the back polarizing plate B except that the protective film B is changed to the protective film C and the release film F is changed to the release film G in the production of the back polarizing plate B. The back polarizing plate C is made of a brightness improvement film/adhesive layer/protective film C/water-based adhesive layer/polarizer/adhesive layer. Then, the evaluation sample is made in the same operation as in Example 1 except that the back polarizing plate B is changed to the back polarizing plate C of this example.
對於獲得的評估用試樣進行高溫環境下的翹曲量之測定，將結果表示於表1中。翹曲成凹狀之側的偏光板係背面側偏光板，保護膜C係85℃的背面側偏光板的穿透軸方向之拉伸彈性率為3,260MPa，背面側偏光板的吸收軸方向之拉伸彈性率為2,890MPa。 The obtained evaluation samples were measured for warping in a high temperature environment, and the results are shown in Table 1. The side of the polarizing plate that is warped into a concave shape is the back side polarizing plate, and the protective film C is the back side polarizing plate at 85°C. The tensile elasticity in the transmission axis direction is 3,260 MPa, and the tensile elasticity in the absorption axis direction of the back side polarizing plate is 2,890 MPa.
[實施例3] [Implementation Example 3]
前面側偏光板係使用實施例1中使用的前面側偏光板A。背面側偏光板則係於背面側偏光板C的製作中，除了將保護膜C變更成保護膜D以外，其餘與背面側偏光板C同樣的製作，製作成由亮度改善膜/黏著劑層/保護膜D/水性接著劑層/偏光片/黏著劑層所構成之背面側偏光板D。然後，除了將背面側偏光板B變更成本實施例的背面側偏光板D以外，與實施例1相同的操作，製作成評估用試樣。 The front polarizing plate is the front polarizing plate A used in Example 1. The back polarizing plate is made in the same way as the back polarizing plate C except that the protective film C is changed to the protective film D, and the back polarizing plate D is made of the brightness improvement film/adhesive layer/protective film D/water-based adhesive layer/polarizer/adhesive layer. Then, the evaluation sample is made in the same way as Example 1 except that the back polarizing plate B is changed to the back polarizing plate D of this example.
對於獲得的評估用試樣進行高溫環境下的翹曲量之測定，將結果表示於表1中。翹曲成凹狀之側的偏光板係背面側偏光板，保護膜D係85℃的背面側偏光板的穿透軸方向之拉伸彈性率為3,460MPa，背面側偏光板的吸收軸方向之拉伸彈性率為3,031MPa。 The obtained evaluation samples were measured for warping in a high temperature environment, and the results are shown in Table 1. The side of the polarizing plate that is warped into a concave shape is the back side polarizing plate, and the protective film D is 85°C. The tensile elasticity of the back side polarizing plate in the transmission axis direction is 3,460MPa, and the tensile elasticity of the back side polarizing plate in the absorption axis direction is 3,031MPa.
[比較例1] [Comparison Example 1]
前面側偏光板係使用實施例1中使用的前面側偏光板A。背面側偏光板則係於背面側偏光板B的製作中，除了將保護膜B變更成保護膜E以外，其餘與背面側偏光板B同樣製作，製作成由亮度改善膜/黏著劑層/保護膜E/水性接著劑層/偏光片/黏著劑層所構成之背面側偏光板E。然後，除了將背面側偏光板B變更成本實施例的背面側偏光板E以外，與實施例1相同的操作，製作成評估用試樣。 The front polarizing plate is the front polarizing plate A used in Example 1. The back polarizing plate is made in the same way as the back polarizing plate B except that the protective film B is replaced by the protective film E, and the back polarizing plate E is made of the brightness improvement film/adhesive layer/protective film E/water-based adhesive layer/polarizer/adhesive layer. Then, the evaluation sample is made in the same way as in Example 1 except that the back polarizing plate B is replaced by the back polarizing plate E of this example.
對於獲得的評估用試樣進行高溫環境下的翹曲量之測定，將結果表示於表1中。翹曲成凹狀之側的偏光板係背面側偏光板，保護膜E係85℃的背面側偏光板的穿透軸方向之拉伸彈性率為1,767MPa，背面側偏光板的吸收軸方向之拉伸彈性率為1,813MPa。 The obtained evaluation samples were measured for warping in a high temperature environment, and the results are shown in Table 1. The side of the polarizing plate that is warped into a concave shape is the back side polarizing plate, and the protective film E is 85°C. The tensile elasticity in the transmission axis direction of the back side polarizing plate is 1,767MPa, and the tensile elasticity in the absorption axis direction of the back side polarizing plate is 1,813MPa.
[表1]
如表1表示，翹曲成凹狀之側的偏光板中之保護膜的拉伸彈性率Et、Ea滿足Et/Ea≧1.1時，可使高溫環境下的翹曲量變小。 As shown in Table 1, when the tensile modulus Et and Ea of the protective film in the polarizing plate on the side that is warped into a concave shape satisfies Et/Ea≧1.1, the warping amount in a high temperature environment can be reduced.
[產業上應用的可能性] [Possibility of industrial application]
若藉由本發明的偏光板之套組，因可減少高溫環境下的液晶面板之翹曲而有用。 The polarizing plate set of the present invention is useful because it can reduce the warping of liquid crystal panels in high temperature environments.
1:硬化層 1: Hardening layer
2:偏光片 2: Polarizer
10、11:保護膜 10, 11: Protective film
20、21:黏著劑層 20, 21: Adhesive layer
30、31:接著劑層 30, 31: Next is the agent layer
40:亮度改善膜 40: Brightness improvement film
100、101:前面側偏光板 100, 101: Front side polarizer
200、201:背面側偏光板 200, 201: Back side polarizing plate
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016211367A JP2018072533A (en) | 2016-10-28 | 2016-10-28 | Polarizing plate set and liquid crystal panel |
| JP2016-211367 | 2016-10-28 |
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| US8351000B2 (en) | 2009-09-30 | 2013-01-08 | Fujifilm Corporation | Optical film and method for producing same, polarizer, and liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8351000B2 (en) | 2009-09-30 | 2013-01-08 | Fujifilm Corporation | Optical film and method for producing same, polarizer, and liquid crystal display device |
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