TWI435124B - Adhesive type polarizing plate and image display device - Google Patents
Adhesive type polarizing plate and image display device Download PDFInfo
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- TWI435124B TWI435124B TW100118354A TW100118354A TWI435124B TW I435124 B TWI435124 B TW I435124B TW 100118354 A TW100118354 A TW 100118354A TW 100118354 A TW100118354 A TW 100118354A TW I435124 B TWI435124 B TW I435124B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
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Description
本發明係關於一種於偏光板之至少單面積層有黏著劑層之黏著型偏光板、以及使用其之圖像顯示裝置。The present invention relates to an adhesive polarizing plate having an adhesive layer on at least a single-layer layer of a polarizing plate, and an image display device using the same.
液晶顯示裝置具有將液晶單元之至少單側配置有偏光板之液晶面板與背光源等光源組合之構成,通常,液晶單元與偏光板係經由黏著劑層而積層。又,於有機EL(Electro-Luminescence,電致發光)顯示裝置中,為了遮蔽外光之鏡面反射,採用於單元之視認側經由黏著劑層而貼合圓偏光板之構成。於將上述使用偏光板之圖像顯示裝置供於實際使用時,尤其是於高溫、高濕之環境下使用時,有時會於畫面之端部產生漏光。The liquid crystal display device has a configuration in which a liquid crystal panel in which at least one side of a liquid crystal cell is disposed with a polarizing plate and a light source such as a backlight are combined. Usually, the liquid crystal cell and the polarizing plate are laminated via an adhesive layer. Further, in an organic EL (Electro-Luminescence) display device, in order to shield the specular reflection of external light, a circular polarizing plate is bonded to the viewing side of the unit via an adhesive layer. When the image display device using the polarizing plate described above is used for practical use, especially when used in an environment of high temperature and high humidity, light leakage may occur at the end portion of the screen.
可認為上述伴隨環境變化之漏光係由以下原因引起,即由於溫度、濕度等之變化,而使各構件發生尺寸變化,由於其界面之應力,而使構成偏光板之各構件之相位差發生變化。即,可認為其原因在於:偏光板通常具有於偏光元件上經由接著劑層積層透明保護膜而成之構成,但隨著環境變化,於該透明保護膜與偏光元件之界面、及該透明保護膜與貼合於透明保護膜上之其它構件之間之界面產生應力,因該應力引起之光彈性雙折射而使透明保護膜之相位差特性發生變化。尤其是於畫面之端部,由於與畫面之中央部相比,各構件之尺寸變化增大,故存在端部之漏光變得明顯之傾向。It is considered that the light leakage accompanying the environmental change is caused by a change in the size of each member due to a change in temperature, humidity, etc., and the phase difference of each member constituting the polarizing plate changes due to the stress at the interface. . That is, the reason for this is considered to be that the polarizing plate usually has a configuration in which a transparent protective film is laminated on the polarizing element via an adhesive, but the interface between the transparent protective film and the polarizing element and the transparent protection as the environment changes. The interface between the film and other members bonded to the transparent protective film generates stress, and the phase difference characteristic of the transparent protective film changes due to the photoelastic birefringence caused by the stress. In particular, at the end portion of the screen, since the dimensional change of each member is larger than the central portion of the screen, light leakage at the end portion tends to be conspicuous.
又,隨著近年來之圖像顯示裝置之大型化、高亮度化之潮流,而存在由於光源之發熱容易導致圖像顯示裝置內部之溫度上升之傾向。又,存在液晶顯示裝置、有機EL顯示裝置之類之薄型之圖像顯示裝置之用途多樣化,於高溫高濕等嚴酷環境下使用之機會增加之傾向。因此,伴隨環境變化之畫面端部之漏光更容易被視認。In addition, with the trend of increasing the size and brightness of image display devices in recent years, there is a tendency that the temperature inside the image display device rises due to heat generation of the light source. Further, there are various applications in which a thin image display device such as a liquid crystal display device or an organic EL display device is used, and the chance of being used in a severe environment such as high temperature and high humidity tends to increase. Therefore, light leakage at the end of the screen accompanying environmental changes is more easily recognized.
就抑制上述畫面端部之漏光之觀點而言,提出了使用光彈性係數之絕對值較小之透明保護膜,而減小透明保護膜之相位差變化的方法(例如專利文獻1)。又,提出了藉由減小透明保護膜之製造時之機械方向與垂直於機械方向之方向的拉伸彈性模數之差(例如專利文獻2)、或將透明保護膜之線膨脹係數與黏著劑層之彈性模數之積設為特定之範圍(例如專利文獻3、4),而減小透明保護膜之相位差變化的方法等。In order to suppress the light leakage at the end of the screen, a method of reducing the phase difference of the transparent protective film by using a transparent protective film having a small absolute value of the photoelastic coefficient has been proposed (for example, Patent Document 1). Further, it has been proposed to reduce the difference in tensile elastic modulus between the mechanical direction and the direction perpendicular to the mechanical direction in the production of the transparent protective film (for example, Patent Document 2), or to increase the coefficient of linear expansion and adhesion of the transparent protective film. The method of reducing the phase difference of the transparent protective film by setting the product of the elastic modulus of the agent layer to a specific range (for example, Patent Documents 3 and 4).
[專利文獻1]日本專利特開2000-352619號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-352619
[專利文獻2]日本專利特開2008-217021號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-217021
[專利文獻3]日本專利特開2002-122739號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-122739
[專利文獻4]日本專利特開2002-122740號公報[Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-122740
如專利文獻1等所記載般,就減小由環境引起之透明保護膜之相位差變化而抑制畫面之端部之漏光之觀點而言,透 明保護膜之光彈性係數之絕對值較小為宜,理論上亦認為藉由使用光彈性係數大致為零之透明保護膜可消除漏光之問題。然而,根據本發明者等人之研究,可明確即便於使用光彈性係數之絕對值較小之透明保護膜之情形時,亦會產生伴隨使用環境變化之畫面端部之漏光。As described in Patent Document 1, etc., the viewpoint of suppressing the change in the phase difference of the transparent protective film caused by the environment and suppressing the light leakage at the end portion of the screen is It is preferable that the absolute value of the photoelastic coefficient of the protective film is small, and it is theoretically considered that the problem of light leakage can be eliminated by using a transparent protective film having a photoelastic coefficient of substantially zero. However, according to the study by the inventors of the present invention, it is clarified that even when a transparent protective film having a small absolute value of the photoelastic coefficient is used, light leakage at the end of the screen accompanying the change in the use environment occurs.
鑒於上述問題,本發明之目的在於提供一種即便使用環境發生變化亦難以產生圖像顯示裝置之漏光之黏著型偏光板、及使用其之圖像顯示裝置。In view of the above problems, an object of the present invention is to provide an adhesive polarizing plate which is less likely to cause light leakage of an image display device even when the use environment changes, and an image display device using the same.
本發明者等人對即便使用光彈性係數較小之透明保護膜之情形時亦產生漏光之原因進行了研究,結果發現如下新見解:藉由變更貼合偏光板與液晶單元之黏著劑層之種類,可使漏光之狀況發生變化。並且,由該見解出發,基於如下推定原理進行銳意研究,即圖像顯示裝置之使用環境下之漏光不僅由透明保護膜之相位差變化引起,而且還由於黏著劑層亦產生相位差,結果發現,藉由特定之透明保護膜與接著劑層之組合可抑制漏光,從而完成本發明。The present inventors have studied the cause of light leakage even in the case of using a transparent protective film having a small photoelastic coefficient, and as a result, found a new finding by changing the adhesive layer of the laminated polarizing plate and the liquid crystal cell. The type can change the condition of light leakage. In addition, based on this finding, the research is based on the following estimation principle, that is, the light leakage in the use environment of the image display device is not only caused by the phase difference change of the transparent protective film, but also due to the phase difference of the adhesive layer, and it is found that The present invention can be completed by suppressing light leakage by a combination of a specific transparent protective film and an adhesive layer.
本發明係關於一種於偏光元件之至少單面積層有透明保護膜,且於該透明保護膜之未與偏光元件積層之側之面上積層有黏著劑層的黏著型偏光板。上述黏著劑層係由含有包含(甲基)丙烯酸烷基酯及具有芳香環結構之(甲基)丙烯酸酯作為單體單元之丙烯酸系聚合物的黏著劑所形成。The present invention relates to an adhesive polarizing plate in which at least a single-layer layer of a polarizing element has a transparent protective film, and an adhesive layer is laminated on a side of the transparent protective film which is not laminated with the polarizing element. The above adhesive layer is formed of an adhesive containing an acrylic polymer containing an alkyl (meth)acrylate and a (meth) acrylate having an aromatic ring structure as a monomer unit.
上述透明保護膜之光彈性係數X(m2 /N)之絕對值為50×10-12 以下。又,當將構成上述黏著劑層之丙烯酸系聚合 物中的具有芳香環結構之(甲基)丙烯酸酯單體單元之含量設為Y%時,X與Y滿足下式。The absolute value of the photoelastic coefficient X (m 2 /N) of the transparent protective film is 50 × 10 -12 or less. In addition, when the content of the (meth) acrylate monomer unit having an aromatic ring structure in the acrylic polymer constituting the pressure-sensitive adhesive layer is Y%, X and Y satisfy the following formula.
-1×1011 X+3≦Y≦-1×1011 X+23-1×10 11 X+3≦Y≦-1×10 11 X+23
於本發明之黏著型偏光板中,上述透明保護膜較佳為含有選自由丙烯酸系樹脂、環狀烯烴系樹脂、苯基順丁烯二醯亞胺系樹脂、纖維素系樹脂、及改性聚碳酸酯樹脂所組成之群中之至少1種樹脂。In the adhesive polarizing plate of the present invention, the transparent protective film preferably contains an acrylic resin, a cyclic olefin resin, a phenyl maleimide resin, a cellulose resin, and a modification. At least one resin selected from the group consisting of polycarbonate resins.
進而,本發明係關於一種使用上述黏著型偏光板之圖像顯示裝置。Further, the present invention relates to an image display device using the above-described adhesive polarizing plate.
於本發明之黏著型偏光板中,構成黏著劑層之丙烯酸系聚合物含有特定量之具有芳香環結構之(甲基)丙烯酸酯單體單元(B成分)。B成分之含量Y可根據透明保護膜之光彈性係數X之值來決定,在由於加熱等環境變化而使透明保護膜之相位差值發生變化之情形時,可以使黏著劑層產生與透明保護膜相反符號之相位差變化之方式進行調整。In the adhesive polarizing plate of the present invention, the acrylic polymer constituting the adhesive layer contains a specific amount of a (meth) acrylate monomer unit (component B) having an aromatic ring structure. The content Y of the component B can be determined according to the value of the photoelastic coefficient X of the transparent protective film. When the phase difference of the transparent protective film is changed due to environmental changes such as heating, the adhesive layer can be produced and transparently protected. The phase difference of the opposite sign of the film is changed in such a manner as to change.
根據上述構成,於透明保護膜之相位差變化較大之畫面端部附近,黏著劑層之相位差變化亦變大(其中,黏著劑層之相位差變化之符號與透明保護膜之相位差變化之符號相反),於黏著型偏光板之整個面內,透明保護膜之相位差變化與黏著劑層之相位差變化彼此抵消。因此,貼合有本發明之黏著型偏光板之圖像顯示裝置即便於曝露於加熱環境等之情形時,亦可實現漏光較少之圖像顯示。According to the above configuration, the phase difference of the adhesive layer is also changed in the vicinity of the end portion of the screen where the phase difference of the transparent protective film is largely changed (wherein the phase difference of the adhesive layer changes with the phase difference of the transparent protective film) In contrast, in the entire surface of the adhesive polarizing plate, the phase difference change of the transparent protective film and the phase difference change of the adhesive layer cancel each other. Therefore, the image display device to which the adhesive polarizing plate of the present invention is bonded can realize image display with less light leakage even when exposed to a heating environment or the like.
以下,一面參照圖式,一面對本發明進行說明。如圖1所示,本發明之黏著型偏光板10於偏光元件1之單面包含第1透明保護膜2,於透明保護膜2上設置有黏著劑層5。偏光元件1與第1透明保護膜2經由未圖示之接著劑層而積層。又,較佳為於偏光元件1之積層有第1透明保護膜2之側的相反側之面上經由未圖示之接著劑層而積層第2透明保護膜3。Hereinafter, the present invention will be described with reference to the drawings. As shown in FIG. 1, the adhesive polarizing plate 10 of the present invention includes a first transparent protective film 2 on one surface of a polarizing element 1, and an adhesive layer 5 on the transparent protective film 2. The polarizing element 1 and the first transparent protective film 2 are laminated via an adhesive layer (not shown). Moreover, it is preferable that the second transparent protective film 3 is laminated on the surface of the polarizing element 1 on the side opposite to the side on which the first transparent protective film 2 is laminated via an adhesive layer (not shown).
於使用本發明之黏著型偏光板10而形成圖像顯示裝置100之情形時,如圖2所示,配置有第1透明保護膜2之側之面經由黏著劑層5貼合於圖像顯示單元20上。即,第1透明保護膜及黏著劑層5配置於圖像顯示單元20與偏光元件1之間。再者,於圖2中,圖像顯示單元20之兩面貼合有黏著型偏光板10,亦可僅於圖像顯示單元20之單面貼合黏著型偏光板。When the image display device 100 is formed by using the adhesive polarizing plate 10 of the present invention, as shown in FIG. 2, the surface on the side where the first transparent protective film 2 is disposed is bonded to the image display via the adhesive layer 5. On unit 20. That is, the first transparent protective film and the adhesive layer 5 are disposed between the image display unit 20 and the polarizing element 1. Further, in FIG. 2, the adhesive display type polarizer 10 is bonded to both surfaces of the image display unit 20, and the adhesive polarizing plate may be attached to only one side of the image display unit 20.
偏光元件1並無特別限定,可使用各種者。作為偏光元件,例如可列舉於聚乙烯醇系膜、部分縮甲醛化聚乙烯醇系膜、乙烯/乙酸乙烯酯共聚物系部分皂化膜等親水性高分子膜上吸附碘、二色性染料等二色性物質並進行單軸延伸而成者、聚乙烯醇之脫水處理物、聚氯乙烯之脫鹽酸處理物等多烯系配向膜等。其中,較佳為包含聚乙烯醇系膜與碘等二色性物質之偏光元件。該等偏光元件之厚度並無特別限制,通常為5~80μm左右。The polarizing element 1 is not particularly limited, and various types can be used. Examples of the polarizing element include adsorption of iodine, dichroic dye, and the like on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene/vinyl acetate copolymer partial saponified film. The dichroic substance is uniaxially stretched, a dehydration treatment of polyvinyl alcohol, a polyene-based alignment film such as a dechlorination treatment of polyvinyl chloride, or the like. Among them, a polarizing element comprising a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable. The thickness of the polarizing elements is not particularly limited, but is usually about 5 to 80 μm.
以碘對聚乙烯醇系膜進行染色並進行單軸延伸而成之偏 光元件例如可利用以下方式製成:藉由將聚乙烯醇浸漬於碘之水溶液中而進行染色,並延伸至原長之3~7倍。視需要亦可浸漬於硼酸、或可含有硫酸鋅、氯化鋅等之碘化鉀等之水溶液中。進而視需要亦可於染色前將聚乙烯醇系膜浸漬於水中進行水洗。藉由水洗聚乙烯醇系膜,可清洗聚乙烯醇系膜表面之污垢或抗結塊劑,此外亦具有使聚乙烯醇系膜膨潤而防止染色不均等不均勻之效果。延伸可於以碘染色後進行,亦可一面染色一面延伸,並且還可於延伸之後以碘進行染色。亦可於硼酸或碘化鉀等之水溶液或水浴中進行延伸。Dyeing of polyvinyl alcohol film with iodine and uniaxial stretching The optical element can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine to carry out dyeing and extending to 3 to 7 times the original length. If necessary, it may be immersed in boric acid or an aqueous solution containing potassium iodide such as zinc sulfate or zinc chloride. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the surface of the polyvinyl alcohol-based film can be washed with dirt or an anti-caking agent, and the polyvinyl alcohol-based film can be swollen to prevent unevenness in dyeing unevenness. The extension may be carried out after dyeing with iodine, or may be extended on one side of the dyeing, and may also be dyed with iodine after stretching. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide.
作為配置於偏光元件之一主面之第1透明保護膜2,可使用光彈性係數之絕對值為50×10-12 m2 /N以下者。若光彈性係數過大,則於對第1保護膜施加應力之情形時,存在容易於圖像顯示中產生不均之傾向。再者,光彈性係數可測定對膜賦予特定張力之情形時之相位差值,並由對應力與相位差值作圖而成之斜率求出。關於光彈性係數之符號,將賦予拉伸應力之情形時相位差增加者定義為正,相位差減少者定義為負。As the first transparent protective film 2 disposed on one main surface of the polarizing element, the absolute value of the photoelastic coefficient can be 50×10 -12 m 2 /N or less. When the photoelastic coefficient is too large, when stress is applied to the first protective film, there is a tendency that unevenness is likely to occur in image display. Further, the photoelastic coefficient can be used to determine the phase difference value in the case where a specific tension is applied to the film, and is obtained from the slope obtained by plotting the stress and the phase difference. Regarding the sign of the photoelastic coefficient, when the tensile stress is given, the phase difference increase is defined as positive, and the phase difference decrease is defined as negative.
作為形成第1透明保護膜之材料,只要光彈性係數為上述範圍,則並無特別限制,較佳為透明性、機械強度、熱穩定性、隔水性、各向同性等優異者。作為形成第1透明保護膜之材料,可較佳地使用環狀聚烯烴系樹脂、丙烯酸系樹 脂、苯基順丁烯二醯亞胺系樹脂、纖維素系樹脂、改性聚碳酸酯樹脂等。The material for forming the first transparent protective film is not particularly limited as long as the photoelastic coefficient is in the above range, and is preferably excellent in transparency, mechanical strength, thermal stability, water barrier properties, isotropy, and the like. As a material for forming the first transparent protective film, a cyclic polyolefin resin or an acrylic tree can be preferably used. A fat, a phenyl maleimide-based resin, a cellulose resin, a modified polycarbonate resin, or the like.
上述環狀聚烯烴系樹脂為以環狀烯烴作為聚合單元進行聚合而成之樹脂之總稱,例如可列舉日本專利特開平1-240517號公報、日本專利特開平3-14882號公報、日本專利特開平3-122137號公報等中記載之樹脂。作為具體例,可列舉:環狀烯烴之開環(共)聚合物、環狀烯烴之加成聚合物、環狀烯烴與乙烯、丙烯等α-烯烴之共聚物(具有代表性的是無規共聚物)、及以不飽和羧酸或其衍生物對該等進行改性而成之接枝改性物、以及該等之氫化物。作為環狀烯烴之具體例,可列舉降冰片烯系單體。The above-mentioned cyclic polyolefin-based resin is a general term for a resin obtained by polymerizing a cyclic olefin as a polymerization unit, and examples thereof include Japanese Patent Laid-Open No. Hei No. 1-240517, Japanese Patent Laid-Open No. Hei No. Hei No. 3-148882, and Japanese Patent No. The resin described in Kaikai No. 3-122137 or the like. Specific examples thereof include a ring-opening (co)polymer of a cyclic olefin, an addition polymer of a cyclic olefin, and a copolymer of a cyclic olefin and an α-olefin such as ethylene or propylene (typically random). a copolymer) and a graft modified product obtained by modifying the unsaturated carboxylic acid or a derivative thereof, and the like. Specific examples of the cyclic olefin include a norbornene-based monomer.
作為降冰片烯系單體,例如可列舉降冰片烯、及其烷基及/或亞烷基取代物等。又,作為環狀聚烯烴系樹脂,可於不損害本發明之目的之範圍內併用上述以外之可開環聚合之其它環狀烯烴類。Examples of the norbornene-based monomer include norbornene, an alkyl group thereof, and/or an alkylene substituent. Further, as the cyclic polyolefin-based resin, other cyclic olefins which can be subjected to ring-opening polymerization other than the above can be used in combination within the range not impairing the object of the present invention.
作為上述環狀聚烯烴系樹脂,市售有各種製品。作為具體例,可列舉:JAPAN ZEON製之商品名「Zeonex」、「Zeonor」,JSR製之商品名「Arton」,TICONA製之商品名「Topas」,三井化學製之商品名「Apel」。Various products are commercially available as the above cyclic polyolefin resin. Specific examples include the product names "Zeonex" and "Zeonor" manufactured by JAPAN ZEON, the product name "Arton" manufactured by JSR, the product name "Topas" manufactured by TICONA, and the product name "Apel" manufactured by Mitsui Chemicals.
作為上述丙烯酸系樹脂,可列舉:聚甲基丙烯酸甲酯等聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、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)、具有脂環族烴基之聚合物(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)丙烯酸降冰片酯共聚物等)。較佳為列舉聚(甲基)丙烯酸甲酯等聚(甲基)丙烯酸C1-6烷基酯。更佳為列舉以(甲基)丙烯酸甲酯為主成分(50~100重量%、較佳為70~100重量%)之(甲基)丙烯酸甲酯系樹脂。Examples of the acrylic resin include poly(meth)acrylate such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymer, and methyl methacrylate-(meth)acrylate. Copolymer, methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example) Methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth)acrylate copolymer, etc.). Preferably, a poly(meth)acrylic acid C1-6 alkyl ester such as poly(methyl) acrylate is used. More preferably, the methyl (meth) acrylate resin containing methyl (meth) acrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is used.
作為丙烯酸系樹脂之具體例,例如可列舉:三菱麗陽(Mitsubishi Rayon)製之ACRYPET VH或ACRYPET VRL20A、日本專利特開2004-70296號公報中記載之分子內具有環結構之丙烯酸系樹脂、藉由分子內交聯或分子內環化反應所得之高Tg丙烯酸系樹脂。Specific examples of the acrylic resin include, for example, an acrylic resin having a ring structure in the molecule described in the Japanese Patent Publication No. 2004-70296, the ACRYPET VH or the ACRYPET VRL20A manufactured by Mitsubishi Rayon. A high Tg acrylic resin obtained by intramolecular crosslinking or intramolecular cyclization.
又,作為丙烯酸系樹脂,亦可較佳地使用具有內酯環結構之(甲基)丙烯酸系樹脂。具有內酯環結構之(甲基)丙烯酸系樹脂於較高之耐熱性、較高之透明性、及藉由雙軸延伸而具有較高之機械強度之方面較佳。Further, as the acrylic resin, a (meth)acrylic resin having a lactone ring structure can also be preferably used. The (meth)acrylic resin having a lactone ring structure is preferred in terms of high heat resistance, high transparency, and high mechanical strength by biaxial stretching.
作為具有內酯環結構之(甲基)丙烯酸系樹脂,可列舉:日本專利特開2000-230016號公報、日本專利特開2001-151814號公報、日本專利特開2002-120326號公報、日本專利特開2002-254544號公報、日本專利特開2005-146084號公報等中記載之具有內酯環結構之(甲基)丙烯酸系樹脂。Examples of the (meth)acrylic resin having a lactone ring structure include JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, and JP-A. A (meth)acrylic resin having a lactone ring structure described in JP-A-2005-146084, and the like.
作為苯基順丁烯二醯亞胺系樹脂,可列舉使順丁烯二醯亞胺之氮原子上鍵結有經取代或未經取代之苯基的單體進行聚合所得之物質。作為苯基順丁烯二醯亞胺系樹脂之原料單體,例如可列舉:N-苯基順丁烯二醯亞胺、N-(2-甲基苯基)順丁烯二醯亞胺、N-(2-乙基苯基)順丁烯二醯亞胺、 N-(2-丙基苯基)順丁烯二醯亞胺、N-(2-異丙基苯基)順丁烯二醯亞胺、N-(2,6-二甲基苯基)順丁烯二醯亞胺、N-(2,6-二丙基苯基)順丁烯二醯亞胺、N-(2,6-二異丙基苯基)順丁烯二醯亞胺、N-(2-甲基-6-乙基苯基)順丁烯二醯亞胺、N-(2-氯苯基)順丁烯二醯亞胺、N-(2,6-二氯苯基)順丁烯二醯亞胺、N-(2-溴苯基)順丁烯二醯亞胺、N-(2,6-二溴苯基)順丁烯二醯亞胺、N-(2-聯苯基)順丁烯二醯亞胺、N-(2-氰基苯基)順丁烯二醯亞胺等。上述順丁烯二醯亞胺系單體例如可自東京化成工業(股份有限公司)等獲得。The phenyl maleimide-based resin may be one obtained by polymerizing a monomer having a substituted or unsubstituted phenyl group bonded to a nitrogen atom of maleimide. Examples of the raw material monomer of the phenyl maleic acid imide resin include N-phenyl maleimide and N-(2-methylphenyl) maleimide. , N-(2-ethylphenyl) maleimide, N-(2-propylphenyl)maleimide, N-(2-isopropylphenyl)maleimide, N-(2,6-dimethylphenyl) Maleimide, N-(2,6-dipropylphenyl)maleimide, N-(2,6-diisopropylphenyl)maleimide , N-(2-methyl-6-ethylphenyl) maleimide, N-(2-chlorophenyl) maleimide, N-(2,6-dichloride Phenyl) maleimide, N-(2-bromophenyl)maleimide, N-(2,6-dibromophenyl)maleimide, N- (2-biphenyl) maleimide, N-(2-cyanophenyl) maleimide, and the like. The above maleimide-based monomer can be obtained, for example, from Tokyo Chemical Industry Co., Ltd. or the like.
又,為了改善脆性或成形加工性、耐熱性等,苯基順丁烯二醯亞胺系樹脂亦可為與苯基順丁烯二醯亞胺系單體以外之單體進行共聚所得之物質,作為以上述目的使用之其他單體成分,例如可列舉:乙烯、丙烯、1-丁烯、1,3-丁二烯、2-甲基-1-丁烯、2-甲基-1-戊烯、1-己烯等烯烴,丙烯腈、丙烯酸甲酯、甲基丙烯酸甲酯、順丁烯二酸酐、乙酸乙烯酯等。上述苯基順丁烯二醯亞胺-烯烴共聚物例如可自東曹(Tosoh)股份有限公司獲得。Further, in order to improve brittleness, moldability, heat resistance and the like, the phenyl maleimide-based resin may be a material obtained by copolymerizing a monomer other than the phenyl maleimide-based monomer. Examples of other monomer components used for the above purpose include ethylene, propylene, 1-butene, 1,3-butadiene, 2-methyl-1-butene, and 2-methyl-1- An olefin such as pentene or 1-hexene, acrylonitrile, methyl acrylate, methyl methacrylate, maleic anhydride, vinyl acetate or the like. The above phenyl maleimide-olefin copolymer is available, for example, from Tosoh Corporation.
作為上述纖維素系樹脂,較佳為纖維素與脂肪酸之酯。作為上述纖維素酯之具體例,可列舉:三乙醯基纖維素、二乙醯基纖維素、三丙醯基纖維素、二丙醯基纖維素等。其中,尤佳為三乙醯基纖維素。The cellulose resin is preferably an ester of cellulose and a fatty acid. Specific examples of the cellulose ester include triethyl fluorenyl cellulose, diethyl fluorenyl cellulose, tripropyl fluorenyl cellulose, and dipropyl fluorenyl cellulose. Among them, it is especially preferred to be triethylsulfonyl cellulose.
又,作為含有纖維素系樹脂之膜,亦可使用市售品。作為三乙醯基纖維素膜之市售品之例,可列舉:富士膠片(Fuji Film)製之商品名「UV-50」、「UV-80」、「SH-80」、「TD-80U」、 「TD-TAC」、「UZ-TAC」、或柯尼卡美能達(Konica Minolta)製之「KC系列」等。Moreover, as a film containing a cellulose resin, a commercial item can also be used. Examples of the commercially available product of the triethylenesulfonated cellulose film include Fujifilm (product name "UV-50", "UV-80", "SH-80", and "TD-80U" manufactured by Fujifilm. , "TD-TAC", "UZ-TAC", or "KC Series" made by Konica Minolta.
作為上述改性聚碳酸酯樹脂,雙酚成分除了4,4'-(丙烷-2,2-二基)二苯酚(雙酚A)以外,亦可列舉含有表現負之雙折射之雙酚成分作為單體單元而減小光彈性係數者。作為此種構成改性聚碳酸酯之表現負之雙折射的雙酚成分,例如可列舉具有芴結構之雙酚。As the modified polycarbonate resin, in addition to 4,4'-(propane-2,2-diyl)diphenol (bisphenol A), the bisphenol component may contain a bisphenol component which exhibits negative birefringence. The photoelastic coefficient is reduced as a monomer unit. As such a bisphenol component which exhibits a negative birefringence of the modified polycarbonate, for example, a bisphenol having a fluorene structure can be mentioned.
作為上述改性聚碳酸酯樹脂,例如可較佳地使用日本專利特開2001-194530號公報、日本專利特開2001-139676號公報、WO 01/081959號國際公開說明書、WO 2006/041190號國際公開說明書等中記載之聚碳酸酯樹脂。As the above-mentioned modified polycarbonate resin, for example, Japanese Patent Laid-Open Publication No. 2001-194530, Japanese Patent Laid-Open No. 2001-139676, No. WO 01/081959 International Publication No. WO WO 01/041190 The polycarbonate resin described in the specification and the like.
作為含有改性聚碳酸酯樹脂之膜,亦可使用市售品。作為此種改性聚碳酸酯膜,例如可列舉帝人化成製之商品名「PURE-ACE WR系列」等。As a film containing a modified polycarbonate resin, a commercial item can also be used. As such a modified polycarbonate film, for example, the product name "PURE-ACE WR series" manufactured by Teijin Chemical Co., Ltd., and the like can be mentioned.
第1透明保護膜2可為實質上不具有相位差之光學各向同性膜,亦可為具有相位差之光學各向異性膜,但由於配置於圖像顯示單元20與偏光元件1之間,故較佳為相位差不均較小且光學均一性較高。於使用光學各向異性膜作為第1透明保護膜之情形時,第1透明保護膜可兼有作為偏光元件之保護膜之作用、及作為相位差板之作用。例如,當於液晶顯示裝置中使用本發明之黏著型偏光板時,第1保護膜兼有作為光學補償膜之作用。又,當於有機EL顯示裝置中使用本發明之黏著型偏光板時,可藉由使用1/4波長板作為第1保護膜而製成圓偏光板。The first transparent protective film 2 may be an optically isotropic film having substantially no phase difference, or may be an optically anisotropic film having a phase difference. However, since it is disposed between the image display unit 20 and the polarizing element 1, Therefore, it is preferable that the phase difference is small and the optical uniformity is high. When the optically anisotropic film is used as the first transparent protective film, the first transparent protective film functions as a protective film for the polarizing element and functions as a phase difference plate. For example, when the adhesive polarizing plate of the present invention is used in a liquid crystal display device, the first protective film functions as an optical compensation film. Further, when the adhesive polarizing plate of the present invention is used in an organic EL display device, a circular polarizing plate can be produced by using a quarter-wave plate as the first protective film.
第1透明保護膜之厚度可適當決定,通常就強度、操作性等作業性、薄膜性等方面而言,為1~500μm左右。尤佳為5~200μm。The thickness of the first transparent protective film can be appropriately determined, and it is usually about 1 to 500 μm in terms of workability such as strength and workability, and film properties. Especially good is 5~200μm.
於黏著型偏光板包含第2透明保護膜3之情形時,第2保護膜並無特別限制,但較佳為使用透明性、機械強度、熱穩定性、隔水性等優異之透明膜。作為形成第2保護膜之材料,可較佳地使用作為形成第1保護膜之材料而例示者等。When the second transparent protective film 3 is included in the adhesive polarizing plate, the second protective film is not particularly limited, but a transparent film excellent in transparency, mechanical strength, thermal stability, water barrier, and the like is preferably used. As a material for forming the second protective film, those exemplified as the material for forming the first protective film can be preferably used.
於第2透明保護膜之未接著偏光元件之面上亦可實施硬塗層或抗反射處理、防黏附、以擴散或防眩為目的之處理。抗反射層、防黏附層、擴散層、防眩層等可設成透明保護膜自身,除此之外,亦可作為另外之光學層而設置與透明保護膜不同者。The surface of the second transparent protective film that is not attached to the polarizing element may be subjected to a treatment such as hard coating or anti-reflection treatment, anti-adhesion, diffusion or anti-glare. The antireflection layer, the anti-adhesion layer, the diffusion layer, the antiglare layer, and the like may be provided as the transparent protective film itself, or may be provided as a separate optical layer different from the transparent protective film.
偏光元件1與透明保護膜2、3較佳為使用接著劑進行積層。作為接著劑,可較佳地使用水系接著劑等。作為水系接著劑,可例示:異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯系乳膠系、水系聚胺基甲酸酯、水系聚酯等。再者,於貼合偏光元件與透明保護膜時,可對透明保護膜實施活化處理。活化處理可採用各種方法,例如可採用皂化處理、電暈處理、低壓UV處理、電漿處理等。It is preferable that the polarizing element 1 and the transparent protective films 2 and 3 are laminated using an adhesive. As the adhesive, a water-based adhesive or the like can be preferably used. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, an ethylene-based latex, an aqueous polyurethane, and an aqueous polyester. Further, when the polarizing element and the transparent protective film are bonded, the transparent protective film can be subjected to an activation treatment. The activation treatment may be carried out by various methods such as saponification treatment, corona treatment, low pressure UV treatment, plasma treatment, and the like.
黏著劑層5係由黏著劑所形成。作為該黏著劑之基質聚合物,可使用含有(甲基)丙烯酸烷基酯單體單元(A成分)、及具有芳香環結構之(甲基)丙烯酸酯單體單元(B成分)之丙烯酸系聚合物。再者,於本說明書及申請專利範圍中,「(甲 基)丙烯酸酯」之記載係指「丙烯酸酯及/或甲基丙烯酸酯」。The adhesive layer 5 is formed of an adhesive. As the matrix polymer of the adhesive, an acrylic system containing a (meth)acrylic acid alkyl ester monomer unit (component A) and a (meth) acrylate monomer unit (component B) having an aromatic ring structure can be used. polymer. Furthermore, in the scope of this specification and the patent application, "(A The term "acrylic ester" means "acrylate and/or methacrylate".
作為上述基質聚合物之丙烯酸系聚合物中具有芳香環結構之(甲基)丙烯酸酯(B成分)之含量Y(%)相對於第1透明保護膜之光彈性係數X(m2 /N),滿足-1×1011 X+3≦Y≦-1×1011 X+23。The content Y (%) of the (meth) acrylate (component B) having an aromatic ring structure in the acrylic polymer as the matrix polymer is relative to the photoelastic coefficient X (m 2 /N) of the first transparent protective film. , satisfying -1 × 10 11 X + 3 ≦ Y ≦ - 1 × 10 11 X + 23.
於本發明中,以曝露於加熱環境下之情形時的黏著型偏光板之相位差變化之絕對值減小之方式,將B成分之含量Y設為上述範圍。黏著型偏光板之相位差變化之絕對值越小越佳。具體而言,相位差變化較佳為±2nm以內,更佳為±1nm以內。In the present invention, the content Y of the component B is set to the above range so that the absolute value of the change in the phase difference of the adhesive polarizing plate when exposed to a heating environment is reduced. The smaller the absolute value of the phase difference change of the adhesive polarizing plate, the better. Specifically, the phase difference change is preferably within ±2 nm, and more preferably within ±1 nm.
如此般,就減小黏著型偏光板之相位差變化,抑制圖像顯示裝置之畫面端部之漏光之觀點而言,丙烯酸系聚合物中具有芳香環結構之(甲基)丙烯酸酯(B成分)之含量Y(%)較佳為-1×1011 X+4以上,更佳為-1×1011 X+5以上,進而較佳為-1×1011 X+6以上。又,Y較佳為-1×1011 X+21以下,更佳為-1×1011 X+20以下,進而較佳為-1×1011 X+19以下。如此般,藉由對應第1透明保護膜之光彈性係數X之值而調整丙烯酸系聚合物中之B成分之含量Y,可藉由黏著劑層之雙折射抵消透明保護膜之光彈性雙折射,而減小黏著型偏光板整體之相位差變化。進而,第1透明保護膜之光彈性係數X(m2 /N)之絕對值較佳為30×10-12 以下,更佳為20×10-12 以下,進而較佳為10×10-12 以下。In this way, the (meth) acrylate having an aromatic ring structure in the acrylic polymer is reduced in terms of reducing the phase difference change of the adhesive polarizing plate and suppressing light leakage at the end of the screen of the image display device. The content Y (%) is preferably -1 × 10 11 X + 4 or more, more preferably -1 × 10 11 X + 5 or more, still more preferably -1 × 10 11 X + 6 or more. Further, Y is preferably -1 × 10 11 X + 21 or less, more preferably -1 × 10 11 X + 20 or less, still more preferably - 1 × 10 11 X + 19 or less. In this manner, by adjusting the content Y of the B component in the acrylic polymer corresponding to the value of the photoelastic coefficient X of the first transparent protective film, the photoelastic birefringence of the transparent protective film can be offset by the birefringence of the adhesive layer. And the phase difference of the entire adhesive polarizing plate is reduced. Further, the absolute value of the photoelastic coefficient X (m 2 /N) of the first transparent protective film is preferably 30 × 10 -12 or less, more preferably 20 × 10 -12 or less, still more preferably 10 × 10 -12 the following.
形成黏著劑層之丙烯酸系聚合物中的(甲基)丙烯酸烷基酯(A成分)之烷基之碳數為1~18左右,較佳為碳數1~9,烷基可為直鏈、支鏈之任一者。作為(甲基)丙烯酸烷基酯之具 體例,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯等。該等可單獨或組合使用。該等烷基之平均碳數較佳為4~12。The alkyl group of the (meth)acrylic acid alkyl ester (component A) in the acrylic polymer forming the adhesive layer has a carbon number of about 1 to 18, preferably a carbon number of 1 to 9, and the alkyl group may be a linear chain. Any of the branches. As a (meth)acrylic acid alkyl ester Examples of the method include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate Octyl ester, decyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and the like. These may be used singly or in combination. The average carbon number of the alkyl groups is preferably from 4 to 12.
作為形成黏著劑層之丙烯酸系聚合物中的具有芳香環結構之(甲基)丙烯酸酯(B成分)之芳香環結構,可列舉:苯環、萘環、噻吩環、吡啶環、吡咯環、呋喃環等。作為具有芳香環結構之(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基-2-羥基丙酯、苯酚環氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸2-萘氧基乙酯、(甲基)丙烯酸2-(4-甲氧基-1-萘氧基)乙酯、(甲基)丙烯酸苯氧基丙酯、苯氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸噻吩酯、(甲基)丙烯酸吡啶酯、(甲基)丙烯酸吡咯酯、(甲基)丙烯酸苯酯、聚(甲基)丙烯酸苯乙烯酯等。Examples of the aromatic ring structure of the (meth) acrylate (component B) having an aromatic ring structure in the acrylic polymer forming the pressure-sensitive adhesive layer include a benzene ring, a naphthalene ring, a thiophene ring, a pyridine ring, and a pyrrole ring. Furan ring and the like. Examples of the (meth) acrylate having an aromatic ring structure include phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, and phenoxy-2-hydroxypropyl (meth)acrylate. , phenol ethylene oxide modified (meth) acrylate, 2-naphthyloxyethyl (meth) acrylate, 2-(4-methoxy-1-naphthalenyloxy) (meth) acrylate , phenoxypropyl (meth)acrylate, phenoxyethylene (meth) acrylate, thiophene (meth) acrylate, pyridyl (meth) acrylate, pyrrolyl (meth) acrylate, ( Phenyl methacrylate, styrene poly(meth)acrylate, and the like.
如此般,雖然藉由使丙烯酸系聚合物含有特定量之具有芳香環結構之(甲基)丙烯酸酯成分(B成分)可使相位差變化減小之理由並不確定,但可推定其原因在於,B成分於側鏈具有極化率較高之芳香環結構,故雙折射之表現傾向與(甲基)丙烯酸烷基酯成分(A成分)大不相同。In this manner, the reason why the change in phase difference can be reduced by causing the acrylic polymer to contain a specific amount of the (meth) acrylate component (component B) having an aromatic ring structure is not determined, but it is presumed that Since the B component has an aromatic ring structure having a high polarizability in the side chain, the birefringence tends to be significantly different from the alkyl (meth)acrylate component (component A).
又,構成黏著劑之丙烯酸系聚合物除了上述A成分及B成 分之外亦可含有其他單體單元(C成分)作為單體單元。Further, the acrylic polymer constituting the adhesive is composed of the above A component and B. In addition to the fraction, other monomer units (component C) may be contained as a monomer unit.
作為上述C成分,例如可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或(4-羥基甲基環己基)-甲基(丙烯酸酯)等含有羥基之單體;(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、順丁烯二酸、反丁烯二酸、巴豆酸等含有羧基之單體;順丁烯二酸酐、衣康酸酐等含有酸酐基之單體;丙烯酸之己內酯加成物;烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯等含有磺酸基之單體;2-羥基乙基丙烯醯基磷酸酯等含有磷酸基之單體等。Examples of the C component include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyl (meth)acrylate. Hexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)-methyl (acrylic acid) a monomer containing a hydroxyl group such as an ester; (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, croton a monomer having a carboxyl group such as an acid; an acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; a caprolactone adduct of acrylic acid; allylsulfonic acid and 2-(meth)acrylamide- a monomer containing a sulfonic acid group such as 2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid or sulfopropyl (meth)acrylate; and a phosphate group such as 2-hydroxyethylpropenyl phosphate Monomers, etc.
又,作為上述C成分,可列舉含氮之乙烯基單體。例如亦可列舉如下單體作為改性目的之單體例:順丁烯二醯亞胺;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺或N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸烷基胺基烷基酯系單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;N-(甲基) 丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體等。Further, examples of the C component include a nitrogen-containing vinyl monomer. For example, the following monomer may be cited as a monomer for modification purposes: maleimide, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N - diethyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-butyl (N-substituted) guanamine monomer such as (meth) acrylamide or N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; (methyl Aminoethyl acrylate, aminopropyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, etc. Alkylaminoalkyl acrylate monomer; methoxyethyl (meth) acrylate, alkoxyalkyl (meth) acrylate, etc. ;N-(methyl) Propylene methoxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl-8-oxy VIII An amber quinone imine monomer such as methylene amber imine.
進而,作為上述C成分,亦可使用乙酸乙烯酯、丙酸乙烯酯、N-乙烯基羧酸醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯基系單體;丙烯腈、甲基丙烯腈等腈系單體;(甲基)丙烯酸縮水甘油酯等含有環氧基之丙烯酸系單體;聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系丙烯酸酯單體;氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯、丙烯酸2-甲氧基乙酯等(甲基)丙烯酸酯系單體等。Further, as the component C, vinyl such as vinyl acetate, vinyl propionate, N-vinylcarboxylic acid decylamine, styrene, α-methylstyrene or N-vinyl caprolactam may be used. Monomer; nitrile monomer such as acrylonitrile or methacrylonitrile; epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; polyethylene glycol (meth) acrylate or polypropylene glycol ( a diol-based acrylate monomer such as methyl acrylate, methoxyethylene glycol (meth) acrylate or methoxy polypropylene glycol (meth) acrylate; fluorine (meth) acrylate, polyoxyl A (meth) acrylate monomer such as (meth) acrylate or 2-methoxyethyl acrylate.
為將基質聚合物改性,上述C成分可任意使用。上述C成分可使用1種或2種以上。C成分之比例較佳為作為丙烯酸系聚合物中之單體單元,設為10重量%以下,進而較佳設為6重量%以下。若C成分之比例超過10重量%,則存在有損作為黏著劑之柔軟性之情形。In order to modify the matrix polymer, the above C component can be used arbitrarily. One or two or more kinds of the above C components can be used. The ratio of the component C is preferably 10% by weight or less, and more preferably 6% by weight or less, as the monomer unit in the acrylic polymer. When the ratio of the component C exceeds 10% by weight, the flexibility as an adhesive may be impaired.
作為上述C成分,就接著性良好之方面而言,可較佳地使用含有羧基之單體,尤其是丙烯酸。於使用含有羧基之單體之情形時,其比例為0.1~10重量%左右,較佳為0.5~8重量%,進而較佳為1~6重量%。又,由於可成為與異氰酸酯交聯劑之交聯點,故可較佳地使用含有羥基之單體。於使用含有羥基之單體之情形時,其比例為0.1~10重量%左右,較佳為0.5~8重量%,進而較佳為1~6重量%。As the above-mentioned component C, a monomer having a carboxyl group, particularly acrylic acid, can be preferably used in terms of good adhesion. In the case of using a monomer having a carboxyl group, the ratio thereof is about 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 6% by weight. Further, since it can be a crosslinking point with an isocyanate crosslinking agent, a monomer having a hydroxyl group can be preferably used. In the case of using a monomer having a hydroxyl group, the ratio thereof is about 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 6% by weight.
上述丙烯酸系聚合物可藉由各種公知之方法來製造。例如可適當選擇塊體聚合法、溶液聚合法、懸浮聚合法等自由基聚合法。作為自由基聚合起始劑,可使用偶氮系、過氧化物系之各種公知者。反應溫度通常設為50~80℃左右,反應時間設為1~8小時。又,上述製造法中較佳為溶液聚合法,作為丙烯酸系聚合物之溶劑,通常可使用乙酸乙酯、甲苯等。溶液濃度通常設為20~80重量%左右。又,丙烯酸系聚合物可以水系之乳劑之形式而獲得。The above acrylic polymer can be produced by various known methods. For example, a radical polymerization method such as a bulk polymerization method, a solution polymerization method, or a suspension polymerization method can be appropriately selected. As the radical polymerization initiator, various known azo-based or peroxide-based compounds can be used. The reaction temperature is usually set to about 50 to 80 ° C, and the reaction time is set to 1 to 8 hours. Further, in the above production method, a solution polymerization method is preferred, and as the solvent of the acrylic polymer, ethyl acetate, toluene or the like can be usually used. The solution concentration is usually set to about 20 to 80% by weight. Further, the acrylic polymer can be obtained in the form of an aqueous emulsion.
丙烯酸系聚合物之重量平均分子量較佳為100萬~300萬。丙烯酸系聚合物之重量平均分子量更佳為超過200萬~300萬,進而較佳為210萬~270萬。若重量平均分子量過小,則有時無法於黏著劑層上產生抵消透明保護膜之雙折射之程度之雙折射,漏光之抑制變得不充分。另一方面,若重量平均分子量超過300萬,則存在接著性降低之傾向。The weight average molecular weight of the acrylic polymer is preferably from 1,000,000 to 3,000,000. The weight average molecular weight of the acrylic polymer is more preferably from 2,000,000 to 3,000,000, and further preferably from 2.1 million to 2.7 million. When the weight average molecular weight is too small, birefringence which cancels the degree of birefringence of the transparent protective film on the adhesive layer may not occur, and the suppression of light leakage may be insufficient. On the other hand, when the weight average molecular weight exceeds 3,000,000, the adhesiveness tends to decrease.
形成本發明之黏著劑層之黏著劑除了作為基質聚合物之上述丙烯酸系聚合物外,亦可含有交聯劑。藉由交聯劑可提高與光學膜之密著性及耐久性,並且可實現高溫下之可靠性及黏著劑本身之形狀保持。作為交聯劑,可適當使用異氰酸酯系、環氧系、過氧化物系、金屬螯合物系、唑啉系等。該等交聯劑可使用1種或組合2種以上使用。作為交聯劑,較佳為含有與羥基顯示反應性之官能基之交聯劑,尤佳為異氰酸酯系交聯劑。The adhesive forming the adhesive layer of the present invention may contain a crosslinking agent in addition to the above acrylic polymer as a matrix polymer. The adhesion and durability to the optical film can be improved by the crosslinking agent, and the reliability at high temperatures and the shape retention of the adhesive itself can be achieved. As the crosslinking agent, an isocyanate type, an epoxy type, a peroxide type, a metal chelate type, or the like can be suitably used. Oxazoline and the like. These crosslinking agents can be used alone or in combination of two or more. The crosslinking agent is preferably a crosslinking agent containing a functional group reactive with a hydroxyl group, and particularly preferably an isocyanate crosslinking agent.
交聯劑之使用量相對於基質聚合物100重量份,為10重量份以下,較佳為0.01~5重量份,進而較佳為0.02~3重量份。 若交聯劑之使用比例超過10重量份,則存在交聯過度進行而接著性降低之傾向。The amount of the crosslinking agent used is 10 parts by weight or less, preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, per 100 parts by weight of the base polymer. When the ratio of use of the crosslinking agent exceeds 10 parts by weight, the crosslinking tends to proceed excessively and the adhesion tends to decrease.
於黏著劑中,視需要亦可於不脫離本發明之目的之範圍內適當使用黏著賦予劑、塑化劑、玻璃纖維、玻璃珠、金屬粉、包含其他無機粉末等之填充劑、顏料、著色劑、填充劑、抗氧化劑、紫外線吸收劑、矽烷偶聯劑等各種添加劑。又,亦可形成含有微粒且顯示光擴散性之黏著劑層等。In the adhesive, if necessary, an adhesive imparting agent, a plasticizer, a glass fiber, a glass bead, a metal powder, a filler containing other inorganic powder, a pigment, and a coloring can be suitably used without departing from the object of the present invention. Various additives such as a agent, a filler, an antioxidant, a UV absorber, and a decane coupling agent. Further, an adhesive layer containing fine particles and exhibiting light diffusibility may be formed.
作為上述添加劑,較佳為矽烷偶聯劑。作為矽烷偶聯劑,可列舉:3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等具有環氧結構之矽烷偶聯劑;3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基甲基二甲氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙基胺等含有胺基之矽烷偶聯劑;3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等含有(甲基)丙烯醯基之矽烷偶聯劑;3-異氰酸酯丙基三乙氧基矽烷等含有異氰酸酯基之矽烷偶聯劑;3-氯丙基三甲氧基矽烷;含有乙醯乙醯基之三甲氧基矽烷等。矽烷偶聯劑可單獨使用1種,另外亦可混合2種以上使用,矽烷偶聯劑之調配量相對於丙烯酸系聚合物100重量份,為0.01~2重量份,較佳為0.02~1重量份。As the above additive, a decane coupling agent is preferred. Examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 2-(3,4-epoxycyclohexyl). a decane coupling agent having an epoxy structure such as ethyltrimethoxydecane; 3-aminopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropyltrimethoxydecane, N -(2-Aminoethyl) 3-aminopropylmethyldimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, etc. Alkylene-based decane coupling agent; 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. 3-octane cyanide-containing decane coupling agent such as 3-isocyanate propyl triethoxy decane; 3-chloropropyltrimethoxydecane; trimethoxydecane containing acetamidine. The decane coupling agent may be used singly or in combination of two or more. The amount of the decane coupling agent is 0.01 to 2 parts by weight, preferably 0.02 to 1 by weight based on 100 parts by weight of the acrylic polymer. Share.
本發明之黏著型偏光板10可藉由在第1透明保護膜2上利用上述黏著劑形成黏著劑層而製造。黏著劑層之形成法並 無特別限制,可列舉:於透明保護膜上,以流延方式、塗敷方式等適宜之展開方式塗佈黏著劑溶液並加以乾燥之方法;藉由設有黏著劑層之脫模片進行轉印之方法等。塗佈法可採用反向塗佈、凹版印刷塗佈等輥塗法、旋塗法、絲網塗佈法、噴注式塗佈法、浸塗法、噴塗法等。於塗佈黏著劑溶液後,在乾燥步驟中使溶劑或水揮發,藉此獲得特定厚度之黏著劑層。The adhesive polarizing plate 10 of the present invention can be produced by forming an adhesive layer on the first transparent protective film 2 with the above-mentioned adhesive. The formation of the adhesive layer and There is no particular limitation, and a method of applying an adhesive solution by a suitable spreading method such as a casting method or a coating method on a transparent protective film and drying it; and transferring it by a release sheet provided with an adhesive layer The method of printing, etc. The coating method may be a roll coating method such as reverse coating or gravure coating, a spin coating method, a screen coating method, a spray coating method, a dip coating method, a spray coating method, or the like. After the application of the adhesive solution, the solvent or water is volatilized in the drying step, thereby obtaining an adhesive layer of a specific thickness.
黏著劑層之厚度可根據使用目的或接著力等適當決定,通常為1~500μm,較佳為1~50μm。更佳為1~40μm,進而較佳為5~30μm,尤佳為10~25μm。若薄於1μm,則耐久性變差,而若變厚,則容易產生由發泡等引起之隆起或剝離,容易導致外觀不良。The thickness of the adhesive layer can be appropriately determined depending on the purpose of use or the adhesion, and is usually 1 to 500 μm, preferably 1 to 50 μm. More preferably, it is 1 to 40 μm, further preferably 5 to 30 μm, and particularly preferably 10 to 25 μm. When it is thinner than 1 μm, durability is deteriorated, and if it is thick, it is likely to be swelled or peeled off by foaming or the like, and it is likely to cause poor appearance.
又,就黏著劑層之形成而言,可藉由在脫模膜上塗佈UV硬化性之黏著劑漿料(syrup)並照射電子束、UV等放射線,而形成含有上述丙烯酸系聚合物之黏著劑層。此時,由於黏著劑中含有交聯劑,故可實現高溫下之可靠性及黏著劑本身之形狀保持。Further, in the formation of the adhesive layer, the UV-curable adhesive syrup can be applied to the release film and irradiated with radiation such as an electron beam or UV to form the acrylic polymer. Adhesive layer. At this time, since the adhesive contains a crosslinking agent, the reliability at a high temperature and the shape retention of the adhesive itself can be achieved.
再者,黏著劑層之交聯除了可以上述乾燥步驟、UV照射步驟進行以外,亦可選擇於乾燥後,藉由加熱狀態或室溫放置狀態下之老化來促進交聯之類之交聯形態。Further, in addition to the drying step and the UV irradiation step, the crosslinking of the adhesive layer may be selected to promote cross-linking such as crosslinking by drying in a heated state or at room temperature after drying. .
於本發明之黏著型偏光板之黏著劑層5之露出面貼合圖像顯示單元等而供於實際應用之前,較佳為以防止黏著劑層之污染等為目的而臨時黏著分隔件進行覆蓋。藉此,可防止於通常之操作狀態下與黏著劑層接觸。作為分隔件, 例如可使用塑膠膜、橡膠片、紙、布、不織布、網狀物、發泡片材或金屬箔、及該等之積層體等適當之薄片體,視需要可使用以聚矽氧系或長鏈烷基系、氟系或硫化鉬等適當之剝離劑進行塗佈處理而成者等基於先前之適合之材料。Before the exposed surface of the adhesive layer 5 of the adhesive polarizing plate of the present invention is attached to an image display unit or the like for practical use, it is preferable to temporarily cover the separator for the purpose of preventing contamination of the adhesive layer or the like. . Thereby, contact with the adhesive layer in a normal operation state can be prevented. As a partition, For example, a plastic film, a rubber sheet, a paper, a cloth, a non-woven fabric, a mesh, a foamed sheet or a metal foil, and a laminate such as the laminate may be used, and if necessary, it may be used in the form of polyfluorene or long. A suitable release agent such as an alkyl group, a fluorine type or a molybdenum sulfide is coated and treated, and the like is based on a material suitable for the prior art.
本發明之黏著型偏光板可較佳地用於液晶顯示裝置或有機EL顯示裝置等各種圖像顯示裝置中。本發明之圖像顯示裝置除了使用本發明之黏著型偏光板以外,可設為與先前之圖像顯示裝置同樣之結構。The adhesive polarizing plate of the present invention can be preferably used in various image display devices such as a liquid crystal display device or an organic EL display device. The image display device of the present invention can be configured similarly to the conventional image display device except that the adhesive polarizing plate of the present invention is used.
液晶顯示裝置例如可藉由適當組裝液晶單元、本發明之偏光板等光學構件、以及視需要之照明系統(背光源等)等各構成零件並組入驅動電路中等而製造。關於液晶顯示裝置之構成,只要可於液晶單元之單側或兩側使用本發明之黏著型偏光板,則其他構成並無特別限制。The liquid crystal display device can be manufactured by, for example, assembling an optical member such as a liquid crystal cell, an optical member such as a polarizing plate of the present invention, and an optional illumination system (such as a backlight) into a driving circuit. The configuration of the liquid crystal display device is not particularly limited as long as the adhesive polarizing plate of the present invention can be used on one side or both sides of the liquid crystal cell.
如穿透型液晶顯示裝置般形成於液晶單元之視認側及光源側之兩側配置有偏光板之液晶顯示裝置時,就抑制漏光之觀點而言,適宜採用於液晶單元之兩側配置有本發明之黏著型偏光板之構成。When a liquid crystal display device in which a polarizing plate is disposed on both the viewing side and the light source side of the liquid crystal cell as in the case of a transmissive liquid crystal display device, it is preferable to use a substrate disposed on both sides of the liquid crystal cell from the viewpoint of suppressing light leakage. The composition of the adhesive polarizing plate of the invention.
有機EL顯示裝置例如可藉由在有機EL單元(有機發光層)之視認側配置本發明之黏著型偏光板而製造。尤其是如上所述,藉由使用1/4波長板作為第1透明保護膜,可抑制由外光之反射引起之視認性下降。再者,亦可不使用1/4波長板作為透明保護膜,而將於本發明之偏光板上另外積層1/4 波長板而形成圓偏光板者配置於有機EL單元之視認側。The organic EL display device can be produced, for example, by disposing the adhesive polarizing plate of the present invention on the viewing side of the organic EL unit (organic light-emitting layer). In particular, as described above, by using a quarter-wave plate as the first transparent protective film, deterioration in visibility due to reflection of external light can be suppressed. Furthermore, it is also possible to use no 1/4 wavelength plate as a transparent protective film, and to additionally deposit 1/4 of the polarizing plate of the present invention. A polarizing plate is formed on the wavelength plate to be disposed on the viewing side of the organic EL unit.
本發明之圖像顯示裝置可用於任意適當之用途中。其用途例如可列舉:台式電腦、筆記本電腦、影印機等OA設備;行動電話、鐘錶、數位相機、個人數位助理(PDA)、便攜遊戲機等行動裝置;攝像機、電視、電子爐等家用電器設備;後方監控器、汽車導航系統用監控器、汽車音響裝置等車載設備;商業店鋪用資訊用監控器等展示設備;監視用監控器等警備設備;護理用監控器、醫療用監控器等護理/醫療設備等。The image display device of the present invention can be used in any suitable application. Examples of the use thereof include OA equipment such as desktop computers, notebook computers, and photocopiers; mobile phones, clocks, digital cameras, personal digital assistants (PDAs), portable game machines, and the like; and home appliances such as cameras, televisions, and electronic stoves. ; rear monitors, car navigation system monitors, car audio equipment and other in-vehicle equipment; commercial shop information monitors and other display equipment; surveillance monitors and other security equipment; nursing monitors, medical monitors and other care / Medical equipment, etc.
以下,列舉實施例及比較例進一步進行說明,但本發明並不限於該等實施例。Hereinafter, the examples and comparative examples will be further described, but the present invention is not limited to the examples.
於附有冷凝管、攪拌翼、溫度計之4口燒瓶中連同乙酸乙酯140重量份一併加入丙烯酸丁酯97重量份、丙烯酸苄酯5重量份及2,2'-偶氮雙異丁腈0.1重量份,充分進行氮氣置換後,一面於氮氣流下攪拌,一面於55℃下反應8小時,獲得重量平均分子量200萬之丙烯酸系聚合物之溶液。相對於該丙烯酸系聚合物之溶液之固形物成份100重量份,以固形物成份計添加交聯劑(Nippon Polyurethane(股份有限公司)製,商品名「Coronate L」)0.45重量份,並添加矽烷偶聯劑(Shin-Etsu Silicones製,商品名「KBM 403」)0.1重量份,製成黏著劑溶液。97 parts by weight of butyl acrylate, 5 parts by weight of benzyl acrylate and 2,2'-azobisisobutyronitrile were added together with 140 parts by weight of ethyl acetate in a 4-neck flask equipped with a condenser tube, a stirring blade and a thermometer. After 0.1 part by weight, the mixture was purged with nitrogen gas, and the mixture was reacted at 55 ° C for 8 hours while stirring under a nitrogen stream to obtain a solution of an acrylic polymer having a weight average molecular weight of 2,000,000. 0.45 parts by weight of a crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L") was added to the solid content of 100 parts by weight of the solution of the acrylic polymer, and decane was added thereto. 0.1 parts by weight of a coupling agent (manufactured by Shin-Etsu Silicones, trade name "KBM 403") was used to prepare an adhesive solution.
利用反向輥塗法,以乾燥後之黏著劑層之厚度成為20μm之方式,於已實施脫模處理之包含聚酯膜(厚度38μm)之分隔件上塗佈所得之黏著劑溶液,於155℃下加熱處理3分鐘,使溶劑揮發而獲得黏著劑層。The obtained adhesive solution was applied to the separator including the polyester film (thickness: 38 μm) which had been subjected to the release treatment by a reverse roll coating method so that the thickness of the adhesive layer after drying became 20 μm. The mixture was heat-treated at ° C for 3 minutes to volatilize the solvent to obtain an adhesive layer.
於不同周速之輥間,將以平均聚合度2400、皂化度99.9莫耳%之聚乙烯醇作為主成分之高分子膜一面染色一面延伸輸送,獲得聚乙烯醇系偏光元件。首先,於30℃之水浴中浸漬1分鐘使聚乙烯醇膜膨潤,同時沿輸送方向延伸至1.2倍後,於30℃之碘化鉀濃度0.03重量%、碘濃度0.3重量%之水溶液中浸漬1分鐘,藉此一面染色,一面沿輸送方向,以完全未延伸之膜(原長)為基準延伸至3倍。接著,一面於60℃之硼酸濃度4重量%、碘化鉀濃度5重量%之水溶液中浸漬30秒鐘,一面沿輸送方向,以原長為基準延伸至6倍。繼而,將所得之延伸膜於70℃下乾燥2分鐘,藉此獲得偏光元件。再者,偏光元件之厚度為30μm。A polymer film having a polymerization degree of 2400 and a saponification degree of 99.9 mol% as a main component was stretched and conveyed while being dyed at different peripheral speeds to obtain a polyvinyl alcohol-based polarizing element. First, the polyvinyl alcohol film was immersed in a water bath at 30 ° C for 1 minute to swell, and was extended to 1.2 times in the transport direction, and then immersed in an aqueous solution having a potassium iodide concentration of 0.03 wt% and an iodine concentration of 0.3 wt% at 30 ° C for 1 minute. By this, one side of the dyeing is extended to three times in the conveying direction with respect to the film which is completely unstretched (original length). Subsequently, it was immersed in an aqueous solution having a boric acid concentration of 4% by weight and a potassium iodide concentration of 5% by weight at 60 ° C for 30 seconds, and was extended to 6 times in the transport direction with respect to the original length. Then, the obtained stretched film was dried at 70 ° C for 2 minutes, whereby a polarizing element was obtained. Further, the thickness of the polarizing element was 30 μm.
於以該方式獲得之偏光元件之兩面上,經由聚乙烯醇系接著劑貼合改性甲基丙烯酸甲酯系樹脂膜(東洋鋼板製,商品名「Fine Cast Film RZ-30NA-S」,光彈性係數:1.5×10-12 m2 /N),製作於偏光元件上積層有透明保護膜之偏光板。A modified methyl methacrylate-based resin film (manufactured by Toyo Steel Co., Ltd., trade name "Fine Cast Film RZ-30NA-S", light was bonded to both surfaces of the polarizing element obtained in this manner via a polyvinyl alcohol-based adhesive. Elastic coefficient: 1.5 × 10 -12 m 2 /N), a polarizing plate in which a transparent protective film is laminated on a polarizing element.
於上述偏光板之透明保護膜之表面以線棒塗佈底塗劑,形成底塗層(厚度100nm)。底塗劑係使用聚乙烯亞胺系(日 本觸媒製,EPOMIN P-1000)。繼而,於底塗層上貼合形成有上述黏著劑層之脫模片,製成黏著型偏光板。The primer was applied to the surface of the transparent protective film of the above polarizing plate by a bar to form an undercoat layer (thickness: 100 nm). The primer is made of polyethyleneimine (day) This catalyst system, EPOMIN P-1000). Then, a release sheet in which the above-mentioned adhesive layer was formed was bonded to the undercoat layer to form an adhesive polarizing plate.
於實施例1之黏著劑之製備中,改變丙烯酸丁酯與丙烯酸苄酯之添加比,除此以外,與實施例1同樣地製作黏著劑溶液。An adhesive solution was prepared in the same manner as in Example 1 except that the addition ratio of butyl acrylate to benzyl acrylate was changed in the preparation of the adhesive of Example 1.
於實施例1之黏著劑之製備中,改變丙烯酸丁酯與丙烯酸苄酯之添加比,除此以外,與實施例1同樣地製作黏著劑溶液。又,於實施例1之偏光板之製作中,使用環狀烯烴系樹脂膜(JAPAN ZEON製,商品名「Zeonor Film ZB14-55124」,光彈性係數:4.0×10-12 m2 /N)替代甲基丙烯酸甲酯系樹脂膜作為透明保護膜。除此以外,與實施例1同樣地製作黏著型偏光板。An adhesive solution was prepared in the same manner as in Example 1 except that the addition ratio of butyl acrylate to benzyl acrylate was changed in the preparation of the adhesive of Example 1. Further, in the production of the polarizing plate of the first embodiment, a cyclic olefin resin film (manufactured by JAPAN ZEON, trade name "Zeonor Film ZB14-55124", photoelastic coefficient: 4.0 × 10 -12 m 2 /N) was used instead. A methyl methacrylate resin film is used as a transparent protective film. An adhesive polarizing plate was produced in the same manner as in Example 1 except the above.
於實施例1之黏著劑之製備中,改變丙烯酸丁酯與丙烯酸苄酯之添加比,除此以外,與實施例1同樣地製作黏著劑溶液。又,於實施例1之偏光板之製作中,使用三乙醯基纖維素膜(富士膠片製,商品名「FUJITAC TD80UL」,光彈性係數:16×10-12 m2 /N)替代改性甲基丙烯酸甲酯系樹脂膜作為透明保護膜。除此以外,與實施例1同樣地製作黏著型偏光板。An adhesive solution was prepared in the same manner as in Example 1 except that the addition ratio of butyl acrylate to benzyl acrylate was changed in the preparation of the adhesive of Example 1. Further, in the production of the polarizing plate of Example 1, a triethylenesulfonated cellulose film (manufactured by Fujifilm, trade name "FUJITAC TD80UL", photoelastic coefficient: 16 × 10 -12 m 2 /N) was used instead of the modification. A methyl methacrylate resin film is used as a transparent protective film. An adhesive polarizing plate was produced in the same manner as in Example 1 except the above.
於實施例1之黏著劑之製備中,改變丙烯酸丁酯與丙烯酸 苄酯之添加比,除此以外,與實施例1同樣地製作黏著劑溶液。又,於實施例1之偏光板之製作中,使用三乙醯基纖維素膜(柯尼卡美能達製,商品名「KC4KR-1」,光彈性係數:21.8×10-12 m2 /N)替代改性甲基丙烯酸甲酯系樹脂膜作為透明保護膜。除此以外,與實施例1同樣地製作黏著型偏光板。An adhesive solution was prepared in the same manner as in Example 1 except that the addition ratio of butyl acrylate to benzyl acrylate was changed in the preparation of the adhesive of Example 1. Further, in the production of the polarizing plate of Example 1, a triethylenesulfonated cellulose film (manufactured by Konica Minolta, trade name "KC4KR-1", photoelastic coefficient: 21.8 × 10 -12 m 2 /N was used. An alternative modified methyl methacrylate resin film is used as the transparent protective film. An adhesive polarizing plate was produced in the same manner as in Example 1 except the above.
於實施例1之黏著劑之製備中,改變丙烯酸丁酯與丙烯酸苄酯之添加比,除此以外,與實施例1同樣地製作黏著劑溶液。又,於實施例1之偏光板之製作中,使用苯基順丁烯二醯亞胺系樹脂膜(東曹(股份有限公司)製,商品名「TI-160α」,光彈性係數:-14×10-12 m2 /N)替代改性甲基丙烯酸甲酯系樹脂膜作為透明保護膜。除此以外,與實施例1同樣地製作黏著型偏光板。An adhesive solution was prepared in the same manner as in Example 1 except that the addition ratio of butyl acrylate to benzyl acrylate was changed in the preparation of the adhesive of Example 1. Further, in the production of the polarizing plate of Example 1, a phenyl maleimide-based resin film (manufactured by Tosoh Corporation, trade name "TI-160α", and a photoelastic coefficient: -14 was used. ×10 -12 m 2 /N) Instead of the modified methyl methacrylate resin film as a transparent protective film. An adhesive polarizing plate was produced in the same manner as in Example 1 except the above.
於實施例1之黏著劑之製備中,改變丙烯酸丁酯與丙烯酸苄酯之添加比,除此以外,與實施例1同樣地製作黏著劑溶液。又,於實施例1之偏光板之製作中,使用改性聚碳酸酯膜(帝人化成製,商品名「PURE-ACE WR」,光彈性係數:-30×10-12 m2 /N)替代改性甲基丙烯酸甲酯系樹脂膜作為透明保護膜。除此以外,與實施例1同樣地製作黏著型偏光板。An adhesive solution was prepared in the same manner as in Example 1 except that the addition ratio of butyl acrylate to benzyl acrylate was changed in the preparation of the adhesive of Example 1. Further, in the production of the polarizing plate of Example 1, a modified polycarbonate film (manufactured by Teijin Chemical Co., Ltd., trade name "PURE-ACE WR", photoelastic coefficient: -30 × 10 -12 m 2 /N) was used instead. The modified methyl methacrylate resin film was used as a transparent protective film. An adhesive polarizing plate was produced in the same manner as in Example 1 except the above.
自包含VA(Vertical Alignment)及IPS(In-Plane Switching)模式之液晶單元之液晶電視(索尼製,商品名「BRAVIA」)取下液晶面板,除去液晶單元之上下所配置之偏光板,清 洗該液晶單元之玻璃面(表面及背面)。繼而,於上述液晶單元之兩面貼合上述各實施例及比較例中所製作之黏著型偏光板。A liquid crystal panel (manufactured by Sony, trade name "BRAVIA") containing a liquid crystal cell of VA (Vertical Alignment) and IPS (In-Plane Switching) mode is used to remove the liquid crystal panel, and the polarizing plate disposed above and below the liquid crystal cell is removed. Wash the glass surface (surface and back) of the liquid crystal cell. Then, the adhesive polarizing plates produced in the above respective Examples and Comparative Examples were bonded to both surfaces of the liquid crystal cell.
將貼合有各實施例及比較例之黏著型偏光板之液晶面板投入95℃之空氣循環式恆溫槽內24小時後,取出液晶面板,放置於亮度10000cd/m2 之背光源上,使其顯示黑色,藉由亮度測定裝置(TOPCON製,商品名「BM-5A」),測定畫面中央部及畫面角部(4角)之正面方向之亮度。The liquid crystal panel to which the adhesive polarizing plates of the respective examples and comparative examples were bonded was placed in an air circulating type thermostatic chamber at 95 ° C for 24 hours, and then the liquid crystal panel was taken out and placed on a backlight having a brightness of 10000 cd/m 2 to be placed thereon. The black color is displayed, and the luminance in the front direction of the center portion of the screen and the corner portion (four corners) of the screen is measured by a luminance measuring device (manufactured by TOPCON, trade name "BM-5A").
又,將投入95℃之空氣循環式恆溫槽內24小時前後之液晶面板放置於亮度10000cd/m2 之背光上,使其顯示黑色,藉由面內亮度測定裝置(I-SYSTEM製,商品名「Eye Scale-4W」)測定畫面之面內亮度。Further, the liquid crystal panel placed in an air circulating type thermostatic chamber at 95 ° C for 24 hours was placed on a backlight having a brightness of 10000 cd/m 2 to display black, and the in-plane luminance measuring device (product name: I-SYSTEM) "Eye Scale-4W") measures the in-plane brightness of the screen.
將亮度之測定結果與各實施例及比較例之黏著型偏光板之黏著劑組成及透明保護膜之光彈性係數之值一併示於表1中。再者,表1中,X表示透明保護膜之光彈性係數,Y表示構成黏著劑之丙烯酸系聚合物中的具有芳香族環結構之(甲基)丙烯酸酯單體單元之含量(重量%)。又,角部之亮度為畫面4角之平均值,「亮度差」表示畫面中央部與角部之差。表1中之△σ表示高溫試驗投入前之面內亮度之偏差σ0h 與高溫試驗投入後之面內亮度之偏差σ24h 的差△σ=σ24h -σ0h 。The measurement results of the brightness are shown in Table 1 together with the adhesive composition of the adhesive polarizing plate of each of the examples and the comparative examples and the photoelastic coefficient of the transparent protective film. In addition, in Table 1, X represents the photoelastic coefficient of the transparent protective film, and Y represents the content (% by weight) of the (meth) acrylate monomer unit having an aromatic ring structure in the acrylic polymer constituting the adhesive. . Further, the brightness of the corner portion is the average value of the corners of the screen, and the "brightness difference" indicates the difference between the center portion and the corner portion of the screen. Table 1 represents the variation of △ σ inner surface of the front of the high temperature test input luminance deviation σ 0h inner surface of the rear of the high-temperature test [sigma] input luminance difference △ 24h of σ = σ 24h -σ 0h.
如表1所示,可知於使用實施例之黏著型偏光板之液晶顯示裝置中,畫面中央與角部之亮度差較小,加熱試驗前後之面內亮度之偏差變化亦得到抑制。如此般,使用本發明 之黏著型偏光板之液晶顯示裝置難以產生由使用環境之變化引起之漏光及亮度變化。As shown in Table 1, it is understood that in the liquid crystal display device using the adhesive polarizing plate of the embodiment, the difference in luminance between the center and the corner of the screen is small, and variations in the in-plane luminance before and after the heating test are also suppressed. So, using the present invention The liquid crystal display device of the adhesive type polarizing plate is less likely to cause light leakage and brightness change caused by changes in the use environment.
1‧‧‧偏光元件1‧‧‧Polarized elements
2、3‧‧‧透明保護膜2, 3‧‧‧ transparent protective film
5‧‧‧黏著劑層5‧‧‧Adhesive layer
10‧‧‧黏著型偏光板10‧‧‧Adhesive polarizer
20‧‧‧圖像顯示單元20‧‧‧Image display unit
100‧‧‧圖像顯示裝置100‧‧‧Image display device
圖1係本發明之一實施形態之黏著型偏光板之概略剖面圖;及圖2係本發明之一實施形態之圖像顯示裝置之概略剖面圖。1 is a schematic cross-sectional view showing an adhesive polarizing plate according to an embodiment of the present invention; and FIG. 2 is a schematic cross-sectional view showing an image display device according to an embodiment of the present invention.
1‧‧‧偏光元件1‧‧‧Polarized elements
2、3‧‧‧透明保護膜2, 3‧‧‧ transparent protective film
5‧‧‧黏著劑層5‧‧‧Adhesive layer
10‧‧‧黏著型偏光板10‧‧‧Adhesive polarizer
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JP2010235655A JP5280421B2 (en) | 2010-01-14 | 2010-10-20 | Adhesive polarizing plate and image display device |
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TWI568582B (en) * | 2016-07-05 | 2017-02-01 | 住華科技股份有限公司 | Polarizer |
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KR20190027022A (en) | 2017-09-04 | 2019-03-14 | 효성화학 주식회사 | Polarizing plate |
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KR100812507B1 (en) * | 2005-08-19 | 2008-03-11 | 주식회사 엘지화학 | Acrylic Pressure Sensitive Adhesive Composition |
JP4751312B2 (en) * | 2006-12-22 | 2011-08-17 | 日東電工株式会社 | Optical film, polarizing plate, and image display device |
JP2011526647A (en) * | 2008-07-01 | 2011-10-13 | エルジー・ケム・リミテッド | Adhesive composition, protective film for polarizing plate, polarizing plate and liquid crystal display device |
CN201583678U (en) * | 2009-07-07 | 2010-09-15 | 天马微电子股份有限公司 | Polaroid and LCD module |
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