TWI686629B - Polarizing plate and method for producing the same - Google Patents
Polarizing plate and method for producing the same Download PDFInfo
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Description
本發明係關於包含偏光片以及積層於其上的增亮膜之偏光板及其製造方法。 The present invention relates to a polarizing plate including a polarizing plate and a brightness enhancement film laminated thereon and a manufacturing method thereof.
近年伴隨智慧型手機為代表的液晶行動終端的大型化,在受限的電池容量,為了實現長時間驅動,使用增亮膜,可提高背光的利用效率。另一方面,從設計、攜帶性的面,對液晶行動終端的薄型化的要求日益提高,即使於其所使用的偏光板,進一步要求薄型輕量化。 In recent years, with the increase in the size of LCD mobile terminals represented by smartphones, in order to achieve long-term driving with limited battery capacity, the use of brightening films can improve the efficiency of backlight utilization. On the other hand, from the aspect of design and portability, the demand for thinning of liquid crystal mobile terminals is increasing, and even for the polarizing plates used therefor, further thinning and lightening are required.
增亮膜,係液晶顯示裝置的背光、其反射光入射時,具有反射指定偏光軸的直線偏光或指定方向的圓偏光而透過其他的光之性質的膜。例如,於配置於液晶單元的背光側之偏光片(吸收型直線偏光片)的背光側,藉由配置增亮膜,背光入射增亮膜時,只有透過指定偏光狀態(可透過偏光片之偏光狀態)的光,供應予偏光片,另一方面不讓指定偏光狀態以外的光透過,使其反射。設置於比增亮膜更背光側之反射層等,在該增亮膜面反射的光,藉由反射層而逆轉行進方向,可再入射增亮膜,此時再入 射的光之一部分或全部,以指定偏光狀態的光,透過增亮膜,可供應予偏光片。 The brightness enhancement film is a backlight of a liquid crystal display device, and when reflected light is incident, it has a property of reflecting linear polarized light of a specified polarizing axis or circular polarized light of a specified direction and transmitting other light. For example, on the backlight side of the polarizer (absorption linear polarizer) arranged on the backlight side of the liquid crystal cell, by configuring the brightness enhancement film, when the backlight enters the brightness enhancement film, only the specified polarization state (the polarized light that can pass through the polarizer) is transmitted State) light is supplied to the polarizer, and on the other hand, it does not transmit light other than the specified polarization state and reflects it. A reflective layer, etc., which is arranged on the back side of the brightness enhancement film. The light reflected on the surface of the brightness enhancement film is reversed by the reflective layer and can enter the brightness enhancement film again. Part or all of the emitted light can be supplied to the polarizer through the brightness enhancement film through the light in the specified polarization state.
如此,若使用增亮膜,被偏光片吸收之偏光的光不透過偏光片側而被反射,藉由重複在增亮膜-反射層之間反射及逆轉,該偏光的光轉換為可透過偏光片的偏光的光,可將其供應予偏光片。藉此,因可提高背光的利用效率,可能減少消耗電力,而且,以相同的消耗電力(背光光量)比較的情況,與不使用增亮膜時比較,畫面可變明亮(例如日本特開平11-248941號公報、日本特開平11-248942號公報、日本特開平11-64840號公報及日本特開平11-64841號公報)。 As such, if a brightness enhancement film is used, the polarized light absorbed by the polarizer is reflected without passing through the polarizer side, and by repeatedly reflecting and reversing between the brightness enhancement film and the reflective layer, the polarized light is converted into a transparent polarizer The polarized light can be supplied to the polarizer. As a result, the use efficiency of the backlight can be improved, and power consumption may be reduced. In addition, when the same power consumption (backlight light amount) is compared, the screen may become brighter than when the brightness enhancement film is not used (for example, Japanese Patent Laid-Open No. 11) -248941, JP 11-248942, JP 11-64840 and JP 11-64841).
於日本專利第5332599號說明書中揭露偏光片上隔著黏著劑層(感壓式接著劑層)之厚度40至100μm的增亮膜之偏光板。 In the specification of Japanese Patent No. 5332599, a polarizing plate with a brightness enhancement film with a thickness of 40 to 100 μm interposed by an adhesive layer (pressure-sensitive adhesive layer) on a polarizer is disclosed.
於偏光片上隔著黏著劑層貼合增亮膜的偏光板,要求可承受濕熱環境之耐久性,傳統的偏光板,實施例如60℃、90%RH的濕熱耐久性測試時,於偏光板的端部,在增亮膜與黏著劑層的界面,有產生剝離的問題。該問題,在增亮膜的厚度越小越顯著。 A polarizer with a brightness enhancement film attached to the polarizer through an adhesive layer is required to withstand the durability of a humid and hot environment. Traditional polarizers, such as 60°C and 90% RH, are used in the polarizer’s durability test. At the end, there is a problem of peeling at the interface of the brightness enhancement film and the adhesive layer. This problem is more pronounced as the thickness of the brightness enhancement film is smaller.
本發明的目的,在於提供一種依序包含偏光片、黏著劑層及增亮膜,於濕熱環境下不易產生黏著劑層與增亮膜之間的剝離,且濕熱耐久性佳的偏光板,以及其製造方法。 The object of the present invention is to provide a polarizing plate comprising a polarizer, an adhesive layer and a brightness enhancement film in sequence, which is not likely to cause peeling between the adhesive layer and the brightness enhancement film in a hot and humid environment, and has a high humidity and heat durability, and Its manufacturing method.
本發明,係提供以下所示的偏光板及其製造方法,以及液晶顯示裝置。 The present invention provides the following polarizing plate, its manufacturing method, and liquid crystal display device.
[1]一種偏光板,依序包含偏光片、黏著劑層及增亮膜;其中於前述增亮膜之前述黏著劑層側的表面,係實施有表面活性化處理。 [1] A polarizing plate comprising a polarizer, an adhesive layer and a brightness enhancement film in sequence; wherein the surface on the adhesive layer side of the brightness enhancement film is subjected to surface activation treatment.
[2]如[1]記載之偏光板,其中前述黏著劑層與前述增亮膜相接。 [2] The polarizing plate according to [1], wherein the adhesive layer is in contact with the brightness enhancement film.
[3]如[1]或[2]記載之偏光板,其中前述偏光片與前述黏著劑層相接。 [3] The polarizing plate according to [1] or [2], wherein the polarizer is in contact with the adhesive layer.
[4]如[1]至[3]中任一項記載之偏光板,其中前述表面活性化處理為電暈處理。 [4] The polarizing plate according to any one of [1] to [3], wherein the surface activation treatment is corona treatment.
[5]如[1]至[4]中任一項記載之偏光板,其中前述增亮膜的厚度為10至30μm。 [5] The polarizing plate according to any one of [1] to [4], wherein the thickness of the brightness enhancement film is 10 to 30 μm.
[6]如[1]至[5]中任一項記載之偏光板,其中前述偏光片的厚度為15μm以下。 [6] The polarizing plate according to any one of [1] to [5], wherein the thickness of the polarizer is 15 μm or less.
[7]如[1]至[6]中任一項記載之偏光板,其中前述黏著劑層之23至80℃的溫度範圍之儲存彈性模數為0.15至1MPa,其厚度為3至20μm。 [7] The polarizing plate according to any one of [1] to [6], wherein the storage elastic modulus of the adhesive layer in the temperature range of 23 to 80° C. is 0.15 to 1 MPa, and the thickness thereof is 3 to 20 μm.
[8]如[1]至[7]中任一項記載之偏光板,更包含積層於前述偏光片之與前述黏著劑層相反側的面上之保護膜。 [8] The polarizing plate according to any one of [1] to [7], further comprising a protective film laminated on the surface of the polarizer opposite to the adhesive layer.
[9]如[8]記載之偏光板,其中前述保護膜係由聚烯烴系樹脂或纖維素系樹脂所構成。 [9] The polarizing plate according to [8], wherein the protective film is made of polyolefin resin or cellulose resin.
[10]一種液晶顯示裝置,包含:液晶單元以 及如[1]至[9]中任一項記載之偏光板。 [10] A liquid crystal display device comprising: a liquid crystal cell And the polarizing plate as described in any one of [1] to [9].
[11]一種偏光板的製造方法,其係依序包含偏光片、黏著劑層及增亮膜之偏光板的製造方法,包括:於前述增亮膜之前述黏著劑層側的表面,實施表面活性化處理的步驟;以及於實施前述表面活性化處理後的前述表面上,積層前述黏著劑層的步驟。 [11] A method of manufacturing a polarizing plate, which is a method of manufacturing a polarizing plate sequentially including a polarizer, an adhesive layer, and a brightness enhancement film, including: implementing a surface on the surface of the brightness enhancement film on the side of the adhesive layer The step of activation treatment; and the step of depositing the adhesive layer on the surface after the surface activation treatment.
根據本發明,可提供一種即使增亮膜的厚度小,於濕熱環境下不易產生黏著劑層與增亮膜之間的剝離,濕熱耐久性佳的偏光板。關於本發明的偏光板,可適合應用於液晶顯示裝置為代表的圖像顯示裝置,特別是中小型行動終端(平板電腦、智慧型手機等)用的液晶顯示裝置。 According to the present invention, even if the thickness of the brightness enhancement film is small, it is not easy to cause peeling between the adhesive layer and the brightness enhancement film in a humid and hot environment, and the polarizing plate with excellent humid and heat durability. The polarizing plate of the present invention can be suitably applied to image display devices typified by liquid crystal display devices, particularly liquid crystal display devices for small and medium-sized mobile terminals (tablet computers, smart phones, etc.).
1‧‧‧偏光板 1‧‧‧ Polarizer
10‧‧‧偏光片 10‧‧‧ Polarizer
20‧‧‧第1黏著劑層 20‧‧‧1st adhesive layer
30‧‧‧增亮膜 30‧‧‧Brightening film
40‧‧‧保護膜 40‧‧‧Protection film
50‧‧‧第2黏著劑層 50‧‧‧ 2nd adhesive layer
60‧‧‧分隔構件 60‧‧‧Partition
70、80‧‧‧分隔構件 70、80‧‧‧Partition
90‧‧‧表面保護膜 90‧‧‧Surface protective film
100、200、300‧‧‧積層體 100, 200, 300 ‧‧‧ laminate
第1圖係表示本發明的偏光板的層構成之一例的剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing an example of the layer configuration of the polarizing plate of the present invention.
第2圖(a)及(b)係表示本發明的偏光板的製造方法之一例的剖面示意圖。 2 (a) and (b) are schematic cross-sectional views showing an example of a method of manufacturing a polarizing plate of the present invention.
第3圖(a)及(b)係表示本發明的偏光板的製造方法之其他一例的剖面示意圖。 Figs. 3 (a) and (b) are schematic cross-sectional views showing another example of the method of manufacturing the polarizing plate of the present invention.
以下,一邊顯示實施態樣,一邊詳細地說明本發明。 Hereinafter, the present invention will be described in detail while showing an embodiment.
(1)偏光板的構成 (1) Structure of polarizing plate
第1圖係表示本發明的偏光板的層構成之一例的剖面示意圖。如第1圖所示的偏光板1之本發明的偏光板,依序包含偏光片10、第1黏著劑層20及增亮膜30。本發明的偏光板,可更包含其他膜、層,例如第1圖所示的偏光板1,包含:積層於偏光片10之與第1黏著劑層20相反側的面上之保護膜40;積層於保護膜40的外表面之第2黏著劑層50;積層於第2黏著劑層50的外表面之分隔構件60。第2黏著劑層50係用以將偏光板貼附於其他構件(例如液晶單元、其他光學膜)。分隔構件60,係在第2黏著劑層50貼合於其他構件前為了保護其表面而暫時貼附的膜。
Fig. 1 is a schematic cross-sectional view showing an example of the layer configuration of the polarizing plate of the present invention. The polarizing plate of the present invention as the polarizing plate 1 shown in FIG. 1 includes a
增亮膜30之第1黏著劑層20側的表面,實施表面活性化處理。藉此,於濕熱環境下不易產生第1黏著劑層20與增亮膜30之間的剝離,可成為濕熱耐久性佳的偏光板。表面活性化處理以電暈處理較理想。
The surface of the
(2)偏光片 (2) Polarizer
偏光片10係具備吸收具有平行於其吸收軸的振動面之直線偏光而穿透具有垂直於吸收軸(與穿透軸平行)的振動面之直線偏光的性質之吸收型偏光片,可適合使用二色性色素吸附配向於聚乙烯醇系樹脂膜的偏光膜。偏光片10,例如可藉由包含下述步驟製造:將聚乙烯醇系樹脂膜
進行一軸延伸的步驟;聚乙烯醇系樹脂膜用二色性色素染色而使二色性色素吸附的步驟;吸附有二色性色素的聚乙烯醇系樹脂膜用硼酸水溶液處理的步驟;以及藉由硼酸水溶液處理後的水洗步驟。
The
作為聚乙烯醇系樹脂,可使用聚乙酸乙烯酯系樹脂經皂化者。作為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之外,可使用乙酸乙烯酯及可與其共聚合的其他單體的共聚物。作為可與乙酸乙烯酯共聚合的其他單體之例,包括不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基的(甲基)丙烯醯胺類等。於本說明書,所謂「(甲基)丙烯酸」係指選自丙烯酸及甲基丙烯酸中之至少一者。 As the polyvinyl alcohol-based resin, a saponified polyvinyl acetate-based resin can be used. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith can be used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth)acrylamides having ammonium groups, and the like. In this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid.
聚乙烯醇系樹脂的皂化度通常為85至100莫耳%左右,較理想為98莫耳%以上。聚乙烯醇系樹脂,可經改性,可使用例如經醛類改性的聚乙烯甲醛或聚乙烯縮醛等。聚乙烯醇系樹脂的平均聚合度,通常為1000至10000左右,較理想為1500至5000左右。聚乙烯醇系樹脂的平均聚合度,可根據JIS K 6726求得。 The saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, and more preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formaldehyde or polyvinyl acetal modified with aldehydes may be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, and more preferably about 1,500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.
如此的聚乙烯醇系樹脂製膜者,可使用作為偏光片10(偏光膜)的原料膜。聚乙烯醇系樹脂製膜的方法,無特別限制,可採用習知的方法。聚乙烯醇系原料膜的厚度,無特別限制,為了使偏光片10的厚度為15μm以下,以使用5至35μm左右者較理想。更理想為20μm以下。延伸厚度超過35μm之聚乙烯醇系原料膜,為了得
到厚度為15μm以下的偏光片10,必須提高延伸倍率,即使於偏光片10的厚度為15μm以下的情況,高溫環境下的尺寸收縮變大。而且,於厚度未達5μm的情況,延伸時的操作性低,偏光片製造時,變得容易產生切斷的缺陷。
Such a polyvinyl alcohol-based resin film maker can use a raw material film as the polarizer 10 (polarizing film). The method of forming a polyvinyl alcohol-based resin film is not particularly limited, and a conventional method can be used. The thickness of the polyvinyl alcohol-based raw material film is not particularly limited. In order to make the thickness of the
聚乙烯醇系樹脂膜的一軸延伸,可在二色性色素的染色前、與染色同時或染色後進行。一軸延伸在染色後進行時,該一軸延伸,可在硼酸處理前或硼酸處理中進行。而且,可在該等複數階段進行一軸延伸。 The uniaxial extension of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after the dyeing of the dichroic pigment. When the uniaxial stretching is performed after dyeing, the uniaxial stretching can be performed before or during boric acid treatment. Moreover, one-axis extension can be performed in these plural stages.
一軸延伸時,可在轉速相異的滾輪間進行一軸延伸,亦可使用熱滾輪進行一軸延伸。而且,一軸延伸,可為在大氣中進行延伸的乾式延伸,亦可為使用溶劑,使聚乙烯醇系樹脂膜在溶脹(swelling)的狀態下進行延伸之濕式延伸。延伸倍率,通常為3至8倍左右。 When one axis is extended, one axis can be extended between rollers with different rotation speeds, or one axis can be extended using hot rollers. The uniaxial stretching may be dry stretching in the atmosphere, or wet stretching using a solvent to stretch the polyvinyl alcohol-based resin film in a swollen state. The stretch magnification is usually about 3 to 8 times.
作為聚乙烯醇系樹脂膜以二色性色素染色的方法,例如採用該膜浸漬於含有二色性色素的水溶液的方法。作為二色性色素係使用碘、二色性有機染料。再者,聚乙烯醇系樹脂膜以在染色處理前實施對水的浸漬處理較理想。 As a method of dyeing the polyvinyl alcohol-based resin film with a dichroic dye, for example, a method of immersing the film in an aqueous solution containing a dichroic dye is used. As a dichroic dye system, iodine or a dichroic organic dye is used. Furthermore, the polyvinyl alcohol-based resin film is preferably subjected to water immersion treatment before dyeing treatment.
作為藉由碘的染色處理,通常採用聚乙烯醇系樹脂膜浸漬於含有碘及碘化鉀的水溶液之方法。該水溶液之碘的含量,對水每100重量份而言為0.01至1重量份左右。碘化鉀的含量,對水每100重量份可為0.5至20重量份左右。而且,該水溶液的溫度,可為20至40℃左右。另一方面,作為藉由二色性有機染料的染色處理,通 常採用聚乙烯醇系樹脂膜浸漬於含有二色性有機染料的水溶液的方法。含有二色性有機染料的水溶液,可含有硫酸鈉等的無機鹽作為染色助劑。該水溶液之二色性有機染料的含量,對水每100重量份可為1×10-4至10重量份左右。該水溶液的溫度可為20至80℃左右。 As a dyeing treatment by iodine, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is generally used. The content of iodine in the aqueous solution is about 0.01 to 1 part by weight per 100 parts by weight of water. The content of potassium iodide may be about 0.5 to 20 parts by weight per 100 parts by weight of water. Moreover, the temperature of the aqueous solution may be about 20 to 40°C. On the other hand, as a dyeing treatment by a dichroic organic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic organic dye is generally used. Aqueous solutions containing dichroic organic dyes may contain inorganic salts such as sodium sulfate as dyeing aids. The content of the dichroic organic dye in the aqueous solution may be about 1×10 -4 to 10 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution may be around 20 to 80°C.
作為藉由二色性色素染色後的硼酸處理,通常採用染色的聚乙烯醇系樹脂膜浸漬於含有硼酸的水溶液之方法。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較理想。含有硼酸的水溶液之硼酸的量,對水每100重量份而言,可為2至15重量份左右。該水溶液之碘化鉀的量,對水每100重量份而言,可為0.1至15重量份左右。該水溶液的溫度,可為50℃以上,例如50至85℃。 As a boric acid treatment after being dyed with a dichroic dye, a method of immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid is generally used. When iodine is used as the dichroic dye, the aqueous solution containing boric acid preferably contains potassium iodide. The amount of boric acid in the aqueous solution containing boric acid may be about 2 to 15 parts by weight per 100 parts by weight of water. The amount of potassium iodide in the aqueous solution may be about 0.1 to 15 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution may be above 50°C, for example from 50 to 85°C.
硼酸處理後的聚乙烯醇系樹脂膜,通常進行水洗處理。水洗處理,例如可藉由將硼酸處理過的聚乙烯醇系樹脂膜浸漬於水而進行。水洗處理之水的溫度,通常為5至40℃左右。 The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water for washing treatment is usually about 5 to 40°C.
水洗後,實施乾燥處理,得到偏光片10。乾燥處理,可使用熱風乾燥機、遠紅外線加熱器進行。偏光片10的厚度以15μm以下較理想,以10μm以下更理想。偏光片10的厚度為15μm以下,在偏光板,進而液晶顯示裝置的薄膜化上有利。偏光片10的厚度通常為4μm以上。
After washing with water, a drying process is performed to obtain
(3)第1黏著劑層 (3) The first adhesive layer
第1黏著劑層20,係存在於偏光片10與增亮膜30之間的層。第1黏著劑層20,典型地係使偏光片10與第1黏著劑層20相接地直接積層於偏光片10。例如,偏光片10上貼合保護膜,並於其上積層第1黏著劑層20時,得知即使於濕熱環境下亦不易產生在黏著劑層與增亮膜之間的剝離。第1黏著劑層20,可由如(甲基)丙烯酸系、橡膠系、胺酯(urethane)系、酯系、聚矽氧系、聚乙烯醚系的樹脂為主成分的黏著劑組成物所構成。其中,以透明性、耐候性、耐熱性佳的(甲基)丙烯酸系樹脂作為基質聚合物之黏著劑組成物為適合。黏著劑組成物可為活性能量線硬化型或熱硬化型。
The first
作為上述(甲基)丙烯酸系基質聚合物,適合使用例如(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯之(甲基)丙烯酸酯系基質聚合物、以及使用2種以上該等的(甲基)丙烯酸酯的共聚合系基質聚合物。於基質聚合物,較理想為極性單體共聚合。作為極性單體,例如(甲基)丙烯酸、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯醯胺、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸環氧丙酯之具有羧基、羥基、醯胺基、胺基、環氧基等的單體。 As the (meth)acrylic matrix polymer, for example, butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate are suitably used (Meth)acrylate-based matrix polymers of esters, and copolymerized matrix polymers using two or more of these (meth)acrylates. For matrix polymers, it is more desirable to copolymerize polar monomers. As polar monomers, for example, (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, (meth)acrylic acid N,N-di A monomer having a carboxyl group, a hydroxyl group, an amide group, an amine group, an epoxy group, etc. of methylaminoethyl ester and glycidyl (meth)acrylate.
黏著劑組成物,通常更含有交聯劑。作為交聯劑,例如2價以上的金屬離子,與羧基之間形成羧酸金屬鹽者;多胺化合物,與羧基之間形成醯胺鍵者;聚環 氧化合物或多元醇,與羧基之間形成酯鍵者;多異氰酸酯化合物,與羧基之間形成醯胺鍵者。其中,較理想為多異氰酸酯化合物。 The adhesive composition usually contains a crosslinking agent. As a cross-linking agent, for example, a metal ion having a valence of 2 or more forms a metal salt of a carboxylic acid with a carboxyl group; a polyamine compound forms an amide bond with a carboxyl group; polycyclic Oxygen compounds or polyols form ester bonds with carboxyl groups; polyisocyanate compounds form amide bonds with carboxyl groups. Among them, polyisocyanate compounds are more desirable.
所謂活性能量線硬化型黏著劑組成物,係指具有接受如紫外線、電子束之活性能量線的照射而硬化的性質,照射活性能量線之前也有黏著性,可與膜等的被附著體密合,藉由活性能量線的照射而硬化,具有可調整密合力的性質之黏著劑組成物。活性能量線硬化型黏著劑組成物以紫外線硬化型較理想。活性能量線硬化型黏著劑組成物,除了基質聚合物、交聯劑之外,可更含有活性能量線聚合性化合物。再者,依據需要,可含有光聚合引發劑、光敏劑等。 The so-called active energy ray-curable adhesive composition refers to the property that it is hardened by being irradiated with active energy rays such as ultraviolet rays and electron beams. It is also adhesive before being irradiated with active energy rays, and can adhere to adherends such as films It is hardened by the irradiation of active energy rays and has an adhesive composition with properties that can adjust the adhesive force. The active energy ray-curable adhesive composition is preferably ultraviolet-curable. The active energy ray-curable adhesive composition may contain an active energy ray polymerizable compound in addition to the matrix polymer and the cross-linking agent. Furthermore, if necessary, it may contain a photopolymerization initiator, a photosensitizer, and the like.
黏著劑組成物,可包含:賦予光散射性用的微粒子;珠粒;基質聚合物以外的樹脂;黏著性賦予劑;填充劑;抗氧化劑;紫外線吸收劑;顏料;著色劑等的添加劑。 The adhesive composition may include fine particles for imparting light scattering properties; beads; resins other than the matrix polymer; adhesive imparting agents; fillers; antioxidants; ultraviolet absorbers; pigments; and additives such as colorants.
第1黏著劑層20,可藉由將上述黏著劑組成物的有機溶劑稀釋液塗布於基材上,使其乾燥而形成。基材,可為偏光片10、增亮膜30、分隔構件等。於使用活性能量線硬化型黏著劑組成物時,於所形成的黏著劑層,藉由照射活性能量線即可成為所期望的硬化物。
The first
第1黏著劑層20係以23至80℃的溫度範圍下顯示0.15至1MPa的儲存彈性模數者較理想。藉此,於濕熱環境下,抑制伴隨偏光片10的收縮而容易產生的尺
寸變化,可提高偏光板的耐久性。而且,搭載偏光板的液晶顯示裝置(例如中小型行動終端用的液晶顯示裝置)放置於濕熱環境下時,因偏光板的移動受到抑制,可提高液晶顯示裝置的信賴性。
The first
所謂「23至80℃的溫度範圍下顯示0.15至1MPa的儲存彈性模數」,係指在該範圍的任一溫度,儲存彈性模數為上述範圍內的值。儲存彈性模數通常係隨溫度上升而遞減,因此23℃及80℃之儲存彈性模數只要是皆在上述範圍內,於該範圍的溫度,可顯示上述範圍內的儲存彈性模數。第1黏著劑層20的儲存彈性模數,可使用市售的黏彈性測定裝置,例如後述的實施例所示的REOMETRIC公司製的黏彈性測定裝置「DYNAMIC ANALYZER RDA 11」進行測定。
The so-called "storage elastic modulus showing 0.15 to 1 MPa in a temperature range of 23 to 80°C" refers to any temperature in this range, and the storage elastic modulus is a value within the above range. The storage elastic modulus usually decreases with increasing temperature. Therefore, as long as the storage elastic modulus at 23°C and 80°C is within the above range, the temperature within this range can display the storage elastic modulus within the above range. The storage elastic modulus of the first
作為調整儲存彈性模數為上述範圍的方法,例如於包含基質聚合物及交聯劑的黏著劑組成物中,再添加寡聚物,具體為胺酯(甲基)丙烯酸酯系寡聚物,成為活性能量線硬化型黏著劑組成物(較理想為紫外線硬化型黏著劑組成物)。更理想為照射活性能量線,使黏著劑層適度地硬化。 As a method of adjusting the storage elastic modulus to the above range, for example, an adhesive composition containing a matrix polymer and a crosslinking agent is further added with an oligomer, specifically an amine (meth)acrylate oligomer, Becomes an active energy ray-curable adhesive composition (ideally an ultraviolet-curable adhesive composition). It is more desirable to irradiate active energy rays to harden the adhesive layer moderately.
第1黏著劑層20的厚度可為1至40μm,從一邊保持良好的加工性一邊抑制偏光板的尺寸變化的觀點,較理想為3至25μm(例如3至20μm)。
The thickness of the first
(4)增亮膜 (4) Brightening film
增亮膜30,也稱為反射型偏光膜,可使用具有從光源(背光)的射出光分離為透過偏光與反射偏光或散射偏光的功能之偏光轉換元件。如上述,藉由配置增亮膜30於偏光片10上,利用反射偏光或散射偏光之遞迴光,可提高從偏光片10射出的直線偏光的射出效率。增亮膜30,通常與第1黏著劑層20相接地積層。
The
增亮膜30,例如可為各向異性反射偏光片。各向異性反射偏光片之一例為透過一振動方向的直線偏光而反射另一振動方向的直線偏光之各向異性多重薄膜,其具體例為3M製的DBEF(日本特開平4-268505號公報等)。各向異性反射偏光片的其他之一例為膽固醇型液晶層與λ/4板的複合體,其具體例為日東電工製的PCF(日本特開平11-231130號公報等)。各向異性反射偏光片的另一其他例為反射柵偏光片,其具體例為對金屬實施細微加工,在可見光區域亦射出反射偏光之金屬格子反射偏光片(美國專利第6288840號說明書等)、於高分子基質中添加金屬微粒子而延伸的膜(日本特開平8-184701號公報)。
The
增亮膜30之與第1黏著劑層20相反側的面,可設置如硬塗層、抗眩層、光擴散層、具有1/4波長的相位差值的相位差層之光學層。藉由光學層的形成,可提高與背光膠帶的密合性、顯示圖像的均勻性。增亮膜30的厚度,可為10至100μm左右,從偏光板的薄膜化的觀點,較理想為10至50μm,更理想為10至30μm。
An optical layer such as a hard coat layer, an anti-glare layer, a light diffusion layer, and a phase difference layer having a phase difference value of 1/4 wavelength may be provided on the surface of the
本發明的偏光板中,於增亮膜30之第1黏
著劑層20側的表面,實施表面活性化處理。該表面活性化處理,係在增亮膜30與第1黏著劑層20的貼合之前進行。藉此,於濕熱環境下不易產生增亮膜30與第1黏著劑層20之間的剝離,可成為濕熱耐久性佳的偏光板1。
In the polarizing plate of the present invention, the first adhesive on the
表面活性化處理,可為表面的親水化處理,可為乾式處理,亦可為濕式處理。作為乾式處理,例如電暈處理、電漿處理、如輝光放電的放電處理;火焰處理;臭氧處理;UV臭氧處理;如紫外線處理、電子束處理的電離活性線處理等。作為濕式處理,例如使用如水、丙酮的溶劑之超音波處理、鹼處理、錨塗(anchor coating)處理等。該等處理,可單獨進行,亦可組合2種以上進行。 The surface activation treatment may be a hydrophilization treatment of the surface, a dry treatment, or a wet treatment. As dry treatment, for example, corona treatment, plasma treatment, discharge treatment such as glow discharge; flame treatment; ozone treatment; UV ozone treatment; ionization active ray treatment such as ultraviolet treatment, electron beam treatment, etc. As the wet treatment, for example, ultrasonic treatment of a solvent such as water or acetone, alkali treatment, anchor coating treatment, etc. are used. These treatments can be performed individually or in combination of two or more.
其中,從濕熱環境下之增亮膜30的剝離抑制效果及偏光板的生產性的觀點,表面活性化處理以電暈處理及/或電漿處理較理想。只要是該等之表面活性化處理,即使於增亮膜30的厚度小至30μm以下在溼熱環境下,亦可有效地抑制第1黏著劑層20與增亮膜30之間的剝離。再者,於第1黏著劑層20之增亮膜30側的表面,亦可合併實施表面活性化處理實施,即使只於增亮膜30的表面實施表面活性化處理,亦可得到充分的效果。意外的是相反地只在第1黏著劑層20之增亮膜30側的表面實施表面活性化處理時,則缺乏效果。
Among them, corona treatment and/or plasma treatment are preferable for the surface activation treatment from the viewpoint of the peeling suppression effect of the
(5)保護膜 (5) Protective film
保護膜40,係任意積層於偏光片10之與第1黏著劑
層20相反側的面之膜。但是,偏光板,從保護偏光片10的觀點,以包含保護膜40較理想。保護膜40為具有透光性(較理想為光學上透明)的熱塑性樹脂,例如鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)之聚烯烴系樹脂;如纖維素三乙酸酯、纖維素二乙酸酯之纖維素酯系樹脂;如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯之聚酯系樹脂;聚碳酸酯系樹脂;(甲基)丙烯酸系樹脂;聚苯乙烯系樹脂;聚氯乙烯系樹脂;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;聚偏氯乙烯系樹脂;聚醯胺系樹脂;聚縮醛系樹脂;改性聚苯醚系樹脂;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;聚醯亞胺系樹脂等所構成的膜。其中,以使用聚烯烴系樹脂、纖維素系樹脂較理想。
The
作為鏈狀聚烯烴系樹脂,除了聚乙烯樹脂、聚丙烯樹脂之鏈狀烯烴的均聚物之外,例如2種以上的鏈狀烯烴所構成的共聚物。 As the chain polyolefin resin, in addition to homopolymers of chain olefins of polyethylene resin and polypropylene resin, for example, copolymers composed of two or more chain olefins.
環狀聚烯烴系樹脂,係環狀烯烴為聚合單元所聚合的樹脂的通稱。列舉環狀聚烯烴系樹脂的具體例時,有環狀烯烴的開環(共)聚合物、環狀烯烴的加成聚合物、環狀烯烴與如乙烯、丙烯的鏈狀烯烴的共聚物(代表為無規共聚物)及該等以不飽和羧酸、其衍生物改性的接枝聚合物以及該等的氫化物等。其中,以使用降莰烯、多環降莰烯系單體等的降莰烯系單體作為環狀烯烴之降莰烯系樹 脂較理想。 Cyclic polyolefin resin is a general term for resins polymerized by polymerization units. Specific examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, and copolymers of cyclic olefins and chain olefins such as ethylene and propylene ( Representatives are random copolymers) and graft polymers modified with unsaturated carboxylic acids and their derivatives, and hydrides of these. Among them, norbornene-based monomers using norbornene-based monomers such as norbornene, polycyclic norbornene-based monomers as cyclic olefins Fat is ideal.
所謂纖維素系樹脂,係指從棉籽絨、木材紙漿(闊葉樹紙漿、針葉樹紙漿)等的原料纖維素所得之纖維素的羥基之氫原子的一部分或全部,經乙醯基、丙醯基及/或丁醯基取代之纖維素有機酸酯或纖維素混合有機酸酯。例如纖維素的乙酸酯、丙酸酯、丁酸酯及該等的混合酯等所構成者。其中,較理想為三乙醯基纖維素、二乙醯基纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯。 The cellulose-based resin refers to a part or all of the hydrogen atoms of the hydroxyl group of cellulose obtained from raw cellulose such as cotton seed velvet, wood pulp (broadleaf pulp, conifer pulp), etc., through acetyl, propyl and/ Or cellulose organic acid ester substituted with butyl acetyl group or cellulose mixed organic acid ester. Examples include cellulose acetate, propionate, butyrate, and mixed esters of these. Among them, triethyl acetyl cellulose, diethyl acetyl cellulose, cellulose acetate propionate and cellulose acetate butyrate are more preferable.
保護膜40的相位差值,控制為適合液晶顯示裝置的值為有用。例如於水平配向(IPS)模式的液晶顯示裝置中,以使用實質上相位差值為0的膜較理想。所謂實質上相位差值為0,係指波長590nm之面內相位差值為10nm以下,波長590nm之厚度方向相位差值的絕對值為10nm以下,波長480至750nm之厚度方向相位差值的絕對值為15nm以下。
It is useful to control the phase difference value of the
依據液晶顯示裝置的模式,對保護膜40進行延伸及/或收縮加工,可賦予適合的相位差值。
Depending on the mode of the liquid crystal display device, the
保護膜40的厚度,可為1至100μm左右,從強度、操作性等的觀點,以5至60μm較理想,5至50μm更理想。只要是該範圍內的厚度,即可機械上保護偏光片10,即使暴露於濕熱環境下,偏光片10亦不收縮,可保持安定的光學特性。
The thickness of the
保護膜40,可隔著接著劑層貼合於偏光片10。作為形成接著劑層的接著劑,可使用水系接著劑或活
性能量線硬化性接著劑。
The
作為水系接著劑,例如聚乙烯醇系樹脂水溶液所構成的接著劑、水系二液型胺酯(urethane)系乳液接著劑等。其中,適合使用聚乙烯醇系樹脂水溶液所構成的接著劑。作為聚乙烯醇系樹脂,除了乙酸乙烯酯的均聚物之聚乙酸乙烯酯經皂化處理所得之乙烯醇均聚物之外,可使用乙酸乙烯酯及可與其共聚合之其他單體的共聚物經皂化處理所得之聚乙烯醇系共聚物或該等的羥基經部分改性的改性聚乙烯醇系聚合物等。水系接著劑,可包括醛化合物、環氧化合物、三聚氰胺系化合物、羥甲基化合物、異氰酸酯化合物、胺化合物、多價金屬鹽等的交聯劑。 As the water-based adhesive, for example, an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane-based emulsion adhesive, or the like. Among them, an adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin is suitably used. As the polyvinyl alcohol-based resin, in addition to the vinyl alcohol homopolymer obtained by saponification of polyvinyl acetate homopolymer polyvinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can be used The polyvinyl alcohol-based copolymer obtained by the saponification treatment or the modified polyvinyl alcohol-based polymer whose hydroxyl groups are partially modified. The water-based adhesive may include crosslinking agents such as aldehyde compounds, epoxy compounds, melamine-based compounds, methylol compounds, isocyanate compounds, amine compounds, and polyvalent metal salts.
於使用水系接著劑時,偏光片10與保護膜40貼合後,為了除去包含於水系接著劑中的水,以實施乾燥步驟較理想。乾燥步驟後,可設置例如於20至45℃左右的溫度下固化的固化步驟。
When the water-based adhesive is used, after the
所謂上述活性能量線硬化性接著劑,係指藉由照射如紫外線等的活性能量線而硬化的接著劑,例如包括聚合性化合物及光聚合引發劑者、包括光反應性樹脂者、包括黏結劑樹脂及光反應性交聯劑者等。作為聚合性化合物,例如光硬化性環氧系單體、光硬化性(甲基)丙烯酸系單體、光硬化性胺酯系單體等的光聚合性單體、源自光聚合性單體的寡聚物等。作為光聚合引發劑,例如包括藉由照射如紫外線等的活性能量線而產生中性自由基、陰離子自由基、陽離子自由基的活性物種之物質。作為包括 聚合性化合物及光聚合引發劑的活性能量線硬化性接著劑,可使用例如包括光硬化性環氧系單體及光陽離子聚合引發劑者較理想。 The above-mentioned active energy ray-curable adhesive refers to an adhesive that is hardened by irradiating active energy rays such as ultraviolet rays, and includes, for example, a polymerizable compound and a photopolymerization initiator, a photoreactive resin, and a binder. Resin and photoreactive crosslinking agent etc. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy-based monomers, photocurable (meth)acrylic monomers, and photocurable amine ester-based monomers, and photopolymerizable monomers. Oligomers, etc. Examples of the photopolymerization initiator include substances that generate active species of neutral radicals, anionic radicals, and cationic radicals by irradiating active energy rays such as ultraviolet rays. As included For the active energy ray-curable adhesive of the polymerizable compound and the photopolymerization initiator, for example, those including a photocurable epoxy-based monomer and a photocationic polymerization initiator are preferably used.
於使用活性能量線硬化性接著劑時,偏光片10與保護膜40在貼合後,依需要進行乾燥步驟,然後,進行藉由照射活性能量線而使活性能量線硬化性接著劑硬化之硬化步驟。活性能量線的光源,無特別限制,較理想為具有波長400nm以下之發光分佈之紫外線,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、金屬鹵素燈等。
When the active energy ray-curable adhesive is used, after the
偏光片10與保護膜40在貼合時,可於該等的至少一者的貼合面實施皂化處理、電暈處理、電漿處理等。
When the
(6)第2黏著劑層及分隔構件 (6) Second adhesive layer and partition member
積層於保護膜40的外表面之第2黏著劑層50,係為了偏光板貼附於其他構件(例如液晶單元、其他光學膜)而設置的任意層。關於構成第2黏著劑層50的黏著劑組成物的組成,係引用關於第1黏著劑層20上的記載。第2黏著劑層50的儲存彈性模數,可與第1黏著劑層20相同,亦可為不同。
The second
分隔構件60,係在第2黏著劑層50貼合於其他構件之前為了保護其表面而暫時貼附的膜,可使用例如於聚對苯二甲酸乙二酯的透明樹脂所構成的膜,實施藉
由聚矽氧系等的離型劑之處理者。於第1黏著劑層20的表面,為了在與增亮膜貼合為止之前保護其表面,可貼附與上述相同的分隔構件。
The
本發明的偏光板的製造方法,係依序包含偏光片、第1黏著劑層及增亮膜之偏光板的製造方法,包括下述步驟:於增亮膜之第1黏著劑層側的表面,實施表面活性化處理的第1步驟;以及於實施表面活性化處理的前述表面上,積層第1黏著劑層的第2步驟。 The method for manufacturing a polarizing plate of the present invention is a method for manufacturing a polarizing plate including a polarizer, a first adhesive layer and a brightness enhancement film in sequence, including the following steps: on the surface of the first adhesive layer side of the brightness enhancement film , The first step of performing the surface activation treatment; and the second step of depositing the first adhesive layer on the aforementioned surface where the surface activation treatment is performed.
參考第2圖,說明如第1圖所示的偏光板1的製造方法的一實施態樣係如下述。首先,於偏光片10的單面,隔著接著劑層,貼合保護膜40,於其上,積層第2黏著劑層50的同時,於偏光片10的另一面,貼合第1黏著劑層20,得到第2圖(a)所示的層構成的積層體100。如圖所示,於第2黏著劑層50的外表面,暫時貼附分隔構件60,於第1黏著劑層20的外表面,暫時貼附分隔構件70。
Referring to FIG. 2, an embodiment of the method for manufacturing the polarizing plate 1 shown in FIG. 1 will be described below. First, on one side of the
然後,從積層體100的第1黏著劑層20,剝離除去分隔構件70,然後於其剝離面,以上述第1步驟,於貼合面(積層面),積層事先實施表面活性化處理的增亮膜30,得到偏光板1(第2圖(b)、第2步驟)。於第1黏著劑層20的與增亮膜30的貼合面,亦可實施表面活性化處
理。
Then, from the first
於積層體100的製作,在可得到依序包含第2黏著劑層50/保護膜40/偏光片10/第1黏著劑層20的層構成下,積層的順序不限於上述的例。例如,可為於偏光片10的單面,積層保護膜40,於其上設置第2黏著劑層50,然後於偏光片10的另一面,積層第1黏著劑層20之順序;亦可為於偏光片10的單面,積層保護膜40,於偏光片10的另一面,積層第1黏著劑層20,然後於保護膜40上設置第2黏著劑層50之順序。
In the production of the
增亮膜30朝積層體100的第1黏著劑層20之貼合方法,可為單片貼合法,亦可為如日本特開2004-262071號公報記載的薄片‧滾輪複合貼合法。而且,可用長條狀生產,且所需的數量大時,滾輪對滾輪的貼合方法亦為有用(關於下述實施態樣也相同)。
The method of attaching the
然後,參考第3圖,說明如第1圖所示的偏光板1的製造方法的其他實施態樣係如下述。首先,於偏光片10的單面,隔著接著劑層,貼合保護膜40,於其上,積層第2黏著劑層50,得到第3圖(a)所示的層構成的積層體200。如圖所示,可於第2黏著劑層50的外表面暫時貼附分隔構件60,亦可於偏光片10的外表面暫時貼附表面保護膜90。於保護膜40的與第2黏著劑層50的貼合面,以及第2黏著劑層50的與保護膜40的貼合面之至少一者,以及偏光片10的與表面保護膜90的貼合面,以及表面保護膜90的與偏光片10的貼合面之至少一者,可進行
電暈處理、電漿處理等的表面活性化處理。
Next, referring to FIG. 3, another embodiment of the method of manufacturing the polarizing plate 1 shown in FIG. 1 will be described as follows. First, on one side of the
另一方面,以上述第1步驟,於增亮膜30的表面實施表面活性化處理後,於該表面積層第1黏著劑層20,得到積層體300。第1黏著劑層20之與增亮膜30的貼合面,亦可進行如電暈處理、電漿處理等的表面活性化處理。如圖所示,可於第1黏著劑層20的外表面暫時貼附分隔構件80。
On the other hand, in the first step described above, after the surface activation treatment is performed on the surface of the
然後,從積層體300的第1黏著劑層20,剝離除去分隔構件80,從積層體200的偏光片10,剝離除去表面保護膜90後,於偏光片10上,貼合第1黏著劑層20,得到偏光板1(第3圖(b)、第2步驟)。
Then, the
於具備表面保護膜90的積層體200的製作,在可得到依序包含第2黏著劑層50/保護膜40/偏光片10/表面保護膜90的層構成下,積層的順序不限於上述的例。例如,可為於偏光片10的單面,積層保護膜40,於其上設置第2黏著劑層50,然後於偏光片10的另一面,積層表面保護膜90之順序;亦可為於偏光片10的單面,積層保護膜40,於偏光片10的另一面,積層表面保護膜90,然後於保護膜40上設置第2黏著劑層50之順序。
In the production of the
關於本發明的偏光板,可應用於液晶顯示裝置。液晶顯示裝置包括液晶單元以及貼合於其表面之本發明的偏光板。偏光板朝液晶單元之貼合,可隔著黏著劑層(第1圖所 示的偏光板1之第2黏著劑層50)進行。本發明的偏光板,通常可使用作為配置於液晶單元的背光側之偏光板。液晶單元的驅動方式,可為傳統習知的任意方式,較理想為IPS模式。使用本發明的偏光板之液晶顯示裝置,濕熱耐久性佳。 The polarizing plate of the present invention can be applied to a liquid crystal display device. The liquid crystal display device includes a liquid crystal cell and the polarizing plate of the present invention attached to the surface thereof. The polarizing plate is attached to the liquid crystal cell with an adhesive layer (Figure 1) The second adhesive layer 50) of the polarizing plate 1 shown is performed. The polarizing plate of the present invention can generally be used as a polarizing plate disposed on the backlight side of a liquid crystal cell. The driving method of the liquid crystal cell can be any conventionally known method, and the IPS mode is more ideal. The liquid crystal display device using the polarizing plate of the present invention has good moisture and heat durability.
以下,顯示實施例及比較例,更具體地說明本發明,但本發明不限於該等例。再者,膜的厚度、相位差值及黏著劑層的儲存彈性模數,係根據下述測定。 Examples and comparative examples are shown below, and the present invention will be described more specifically, but the present invention is not limited to these examples. In addition, the film thickness, the phase difference value, and the storage elastic modulus of the adhesive layer are measured according to the following.
(1)厚度 (1) Thickness
使用尼康公司(Nikon)製數位測微計「MH-15M」測定。 It was measured using a digital micrometer "MH-15M" made by Nikon.
(2)面內相位差值及厚度方向相位差值 (2) In-plane phase difference and thickness direction phase difference
使用平行尼柯爾(Nicol)旋轉法為原理之相位差計之王子計測機器(股)製的「KOBRA-ADH」,於23℃,以波長590nm、483nm或755nm的光進行測定。 Using the "KOBRA-ADH" manufactured by the Prince Measuring Machine (Co) of the phase difference meter based on the parallel Nicol rotation method, the measurement was performed at 23°C with light having a wavelength of 590 nm, 483 nm, or 755 nm.
(3)儲存彈性模數 (3) Storage elastic modulus
黏著劑層的儲存彈性模數G’,係根據以下的(I)至(III)測定。 The storage elastic modulus G'of the adhesive layer is measured according to (I) to (III) below.
(I)從黏著劑層取出2個25±1mg的樣品,分別成形為約球狀。 (I) Two 25±1 mg samples were taken from the adhesive layer and formed into approximately spherical shapes.
(II)所得的約球狀樣品,貼附於I型治具的上下面,上 下面一起用L型治具夾住。測定樣品的構成為L型治具/黏著劑/I型治具/黏著劑/L型治具。 (II) The obtained approximately spherical sample is attached to the upper and lower surfaces of the Type I fixture. Let's use an L-shaped fixture together. The composition of the measurement sample is L-shaped jig/adhesive/I-type jig/adhesive/L-type jig.
(III)如此製作的樣品的儲存彈性模數G’,使用IT計測控制(股)製的動態黏彈性測定裝置「DVA-220」,溫度23℃、頻率1Hz、初期變形1N的條件下測定。 (III) The storage elastic modulus G'of the sample prepared in this way was measured under the conditions of a temperature of 23°C, a frequency of 1 Hz, and an initial deformation of 1 N using a dynamic viscoelasticity measuring device "DVA-220" made by IT Measurement Control (Co).
(厚度7μm的偏光片A的製作) (Production of polarizer A with a thickness of 7 μm)
厚度20μm的聚乙烯醇膜(平均聚合度約為2400、皂化度為99.9莫耳%以上),藉由乾式延伸進行約5倍的一軸延伸,進一步在保持張力的狀態下,浸漬於60℃的純水1分鐘後,於碘/碘化鉀/水的重量比為0.05/5/100的水溶液中,於28℃下浸漬60秒。然後,於碘化鉀/硼酸/水的重量比為8.5/8.5/100的水溶液中,於72℃下浸漬300秒。接著於26℃的純水中洗淨20秒後,於65℃下乾燥,得到碘吸附配向於聚乙烯醇膜的厚度7μm的偏光片A。 Polyvinyl alcohol film with a thickness of 20 μm (average degree of polymerization of about 2400 and saponification degree of 99.9 mol% or more) is uniaxially stretched about 5 times by dry stretching, and further immersed in 60°C while maintaining tension After 1 minute of pure water, it was immersed in an aqueous solution having a weight ratio of iodine/potassium iodide/water of 0.05/5/100 at 28°C for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide/boric acid/water of 8.5/8.5/100 at 72°C for 300 seconds. Next, it was washed in pure water at 26°C for 20 seconds, and then dried at 65°C, to obtain a polarizing plate A having a thickness of 7 μm with iodine adsorbed on the polyvinyl alcohol film.
(厚度12μm的偏光片B的製作) (Production of polarizer B with a thickness of 12 μm)
除了使用厚度30μm的聚乙烯醇膜(平均聚合度約為2400、皂化度為99.9莫耳%以上)之外,與偏光片A同樣地,得到碘吸附配向於聚乙烯醇膜的厚度12μm的偏光片B。 In addition to using a polyvinyl alcohol film with a thickness of 30 μm (average degree of polymerization of about 2400 and a saponification degree of 99.9 mol% or more), as in the case of polarizer A, polarized light with a thickness of 12 μm iodine adsorbed and aligned to the polyvinyl alcohol film Slice B.
(增亮膜C及D的準備) (Preparation of Brightening Films C and D)
以下2種增亮膜: The following 2 kinds of brightening films:
‧厚度26μm的增亮膜C;3M製「Advanced Polarized Film,Version 3」 ‧Brightness Enhancement Film C with a thickness of 26μm; "Advanced Polarized" made by 3M Film, Version 3"
‧厚度17μm的增亮膜D;3M製「Advanced Polarized Film,Version 4」 ‧Brightness enhancing film D with thickness of 17μm; "Advanced Polarized Film, Version 4" made by 3M
(保護膜E及F的準備) (Preparation of protective films E and F)
以下2種保護膜: The following 2 protective films:
‧保護膜E;日本ZEON(股)製的環狀聚烯烴系樹脂膜(厚度23μm、波長590nm的面內相位差值=2.1nm、波長590nm的厚度方向相位差值=2.8nm、波長483nm的厚度方向相位差值=2.5nm、波長755nm的厚度方向相位差值=-4.2nm) ‧Protective film E; cyclic polyolefin resin film made by Japan Zeon Co., Ltd. (thickness 23 μm, in-plane retardation value of wavelength 590 nm = 2.1 nm, thickness direction retardation value of wavelength 590 nm = 2.8 nm, wavelength 483 nm (Phase difference in thickness direction = 2.5nm, 755nm thickness phase difference value = -4.2nm)
‧保護膜F;日本ZEON(股)製的環狀聚烯烴系樹脂膜(厚度13μm、波長590nm的面內相位差值=0.8nm、波長590nm的厚度方向相位差值=3.4nm、波長483nm的厚度方向相位差值=3.5nm、波長755nm的厚度方向相位差值=2.8nm) ‧Protective film F; cyclic polyolefin resin film made by Japan Zeon Co., Ltd. (thickness 13 μm, in-plane retardation value at wavelength 590 nm = 0.8 nm, thickness direction retardation value at wavelength 590 nm = 3.4 nm, wavelength 483 nm (Phase difference in thickness direction = 3.5 nm, phase difference in thickness direction at 755 nm = 2.8 nm)
(黏著劑層的調製或準備) (Preparation or preparation of adhesive layer)
‧以下2種黏著劑層 ‧The following 2 adhesive layers
‧第1黏著劑層;將丙烯酸丁酯與丙烯酸的共聚物添加有胺酯丙烯酸酯寡聚物及異氰酸酯系交聯劑之有機溶劑溶液,用狹縫塗布機,塗布於實施離型處理過的厚度38μm的聚對苯二甲酸乙二酯所構成的分隔構件的離型處理面,使乾燥後的厚度成為15μm,使其乾燥,得到附有分 隔構件的黏著劑層(該黏著劑層的儲存彈性模數,於23℃為0.40MPa,於80℃為0.18MPa) ‧The first adhesive layer; the copolymer of butyl acrylate and acrylic acid is added with an organic solvent solution of urethane acrylate oligomer and isocyanate-based cross-linking agent, and applied to the release-treated with a slit coater The release processing surface of the partition member made of polyethylene terephthalate with a thickness of 38 μm was dried to a thickness of 15 μm, and dried to obtain an attached The adhesive layer of the partition member (the storage elastic modulus of the adhesive layer is 0.40MPa at 23℃ and 0.18MPa at 80℃)
‧第2黏著劑層;於實施離型處理過的厚度38μm的聚對苯二甲酸乙二酯所構成的分隔構件的離型處理面設置有厚度25μm的丙烯酸系黏著劑層之市售的附有分隔構件的黏著劑層(不調配胺酯丙烯酸酯寡聚物。該黏著劑層的儲存彈性模數,於23℃為0.05MPa,於80℃為0.04MPa) ‧Second adhesive layer; a commercially available attachment of acrylic adhesive layer with a thickness of 25 μm is provided on the release processing surface of the partition member made of polyethylene terephthalate with a thickness of 38 μm that has undergone release treatment Adhesive layer with partitioning member (no amine acrylate oligomer. The storage elastic modulus of this adhesive layer is 0.05MPa at 23°C and 0.04MPa at 80°C)
(水系接著劑的調製) (Preparation of water-based adhesive)
對水100重量份,溶解羧基改性的聚乙烯醇[Kuraray(股)製「KL-318」]3重量份,調製聚乙烯醇水溶液。於所得之水溶液,混合水溶性聚醯胺環氧樹脂[田岡化學工業(股)製「SUMIREZ RESIN 650(30)」、固形物濃度30重量%]對水100重量份而言用1.5重量份的比例,得到水系接著劑。
To 100 parts by weight of water, 3 parts by weight of carboxyl-modified polyvinyl alcohol ["KL-318" manufactured by Kuraray Co., Ltd.] was dissolved to prepare a polyvinyl alcohol aqueous solution. To the obtained aqueous solution, mix water-soluble polyamide epoxy resin ["SUMIREZ RESIN 650 (30)" manufactured by Taoka Chemical Industry Co., Ltd.,
以與第2圖所示的順序相同的順序製作偏光板。首先,於偏光片A的單面,使用上述水系接著劑,貼合保護膜E。貼合前,於保護膜E之與偏光片A的貼合面,實施15.9kJ/m2的電暈處理。然後,於80℃,乾燥5分鐘,於40℃固化168小時。然後,於偏光片A之與保護膜E相反側的面,貼合第1黏著劑層。貼合前,於偏光片A的貼合面及第1黏著劑層的貼合面兩者,實施15.9kJ/m2的電暈 處理。 The polarizing plate was produced in the same order as shown in FIG. 2. First, the protective film E was bonded to one side of the polarizer A using the above-mentioned water-based adhesive. Before bonding, a corona treatment of 15.9 kJ/m 2 was performed on the bonding surface of the protective film E and the polarizer A. Then, it was dried at 80°C for 5 minutes and cured at 40°C for 168 hours. Then, the first adhesive layer is bonded to the surface of the polarizer A opposite to the protective film E. Before bonding, a corona treatment of 15.9 kJ/m 2 was performed on both the bonding surface of the polarizer A and the bonding surface of the first adhesive layer.
然後,於保護膜E的外表面貼合第2黏著劑層。貼合前,於保護膜E的貼合面及第2黏著劑層的貼合面兩者,實施15.9kJ/m2的電暈處理。最後,剝離第1黏著劑層的分隔構件,於增亮膜C的單面實施15.9kJ/m2的電暈處理後,增亮膜C以其電暈處理面側貼合於第1黏著劑層的外表面,得到偏光板。 Then, the second adhesive layer is bonded to the outer surface of the protective film E. Before bonding, both the bonding surface of the protective film E and the bonding surface of the second adhesive layer were subjected to a corona treatment of 15.9 kJ/m 2 . Finally, the separation member of the first adhesive layer was peeled off, and after a corona treatment of 15.9 kJ/m 2 was performed on one side of the brightness enhancement film C, the brightness enhancement film C was bonded to the first adhesive with its corona treatment side The outer surface of the layer is polarized.
除了使用保護膜F取代保護膜E之外,與實施例1同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 1, except that the protective film F was used instead of the protective film E.
除了使用增亮膜D取代增亮膜C之外,與實施例1同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 1, except that the brightness enhancement film D was used instead of the brightness enhancement film C.
除了使用偏光片B取代偏光片A之外,與實施例1同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 1, except that polarizing plate B was used instead of polarizing plate A.
除了使用偏光片B取代偏光片A之外,與實施例3同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 3, except that polarizing plate B was used instead of polarizing plate A.
以與第3圖所示的順序相同的順序,製作偏光板。首先,於偏光片A的單面,使用上述水系接著劑貼合保護膜E。貼合前,於保護膜E之與偏光片A的貼合面,實施15.9kJ/m2的電暈處理。然後,於80℃,乾燥5分鐘,於40℃固化168小時。然後,於偏光片A之與保護膜E相反側的面,貼合表面保護膜(Toray加工(股)製「TORETEC 7332」)。貼合前,於偏光片A的貼合面,實施15.9kJ/m2的電暈處理。再者,於保護膜E的外表面貼合第2黏著劑層。貼合前,保護膜E的貼合面及第2黏著劑層的貼合面兩者,實施15.9kJ/m2的電暈處理。 The polarizing plate was produced in the same order as shown in FIG. 3. First, on one side of the polarizer A, the protective film E is bonded using the above-mentioned water-based adhesive. Before bonding, a corona treatment of 15.9 kJ/m 2 was performed on the bonding surface of the protective film E and the polarizer A. Then, it was dried at 80°C for 5 minutes and cured at 40°C for 168 hours. Then, a surface protective film ("TORETEC 7332" manufactured by Toray Processing Co., Ltd.) was bonded to the surface of the polarizer A opposite to the protective film E. Before bonding, the bonding surface of the polarizer A was subjected to a corona treatment of 15.9 kJ/m 2 . Furthermore, the second adhesive layer is attached to the outer surface of the protective film E. Before bonding, both the bonding surface of the protective film E and the bonding surface of the second adhesive layer were subjected to a corona treatment of 15.9 kJ/m 2 .
然後,於增亮膜C的單面貼合第1黏著劑層(附有分隔構件)。貼合前,增亮膜C的貼合面及第1黏著劑層的貼合面兩者,實施15.9kJ/m2的電暈處理。最後,剝離偏光片A的表面保護膜及第1黏著劑層的分隔構件後,對藉由表面保護膜的剝離而露出的偏光片A的露出面(外表面),實施15.9kJ/m2的電暈處理,然後於該電暈處理面,貼合第1黏著劑層,得到偏光板。 Then, the first adhesive layer (with a partition member) was bonded to one side of the brightness enhancement film C. Before bonding, both the bonding surface of the brightness enhancement film C and the bonding surface of the first adhesive layer were subjected to a corona treatment of 15.9 kJ/m 2 . Finally, after peeling the surface protective film of the polarizer A and the partition member of the first adhesive layer, the exposed surface (outer surface) of the polarizer A exposed by the peeling of the surface protective film was subjected to 15.9 kJ/m 2 After corona treatment, the first adhesive layer was bonded to the corona treatment surface to obtain a polarizing plate.
除了使用保護膜F取代保護膜E之外,與實施例6同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 6, except that the protective film F was used instead of the protective film E.
除了使用增亮膜D取代增亮膜C之外,與實施例6同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 6, except that the brightness enhancement film D was used instead of the brightness enhancement film C.
除了使用偏光片B取代偏光片A之外,與實施例6同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 6, except that polarizing plate B was used instead of polarizing plate A.
除了使用偏光片B取代偏光片A之外,與實施例8同樣地製作偏光板。 A polarizing plate was produced in the same manner as in Example 8 except that polarizing plate B was used instead of polarizing plate A.
朝偏光片A的露出面(經表面保護膜的剝離所露出的面)之第1黏著劑層的貼合時,除了對偏光片A的露出面不實施電暈處理之外,與實施例6同樣地製作偏光板。 When bonding the first adhesive layer to the exposed surface of the polarizer A (the surface exposed by peeling of the surface protective film), except that the exposed surface of the polarizer A was not subjected to corona treatment, it was the same as Example 6. The polarizing plate was produced in the same way.
除了增亮膜C或D之與第1黏著劑層的貼合面,不進行電暈處理之外,分別與實施例1至11同樣地製作偏光板。再者,於比較例6至11,增亮膜C或D與第1黏著劑層的貼合前,雖於增亮膜C或D的貼合面不進行電暈處理,但於第1黏著劑層的貼合面,進行電暈處理。 A polarizing plate was produced in the same manner as in Examples 1 to 11, except that the bonding surface of the brightness enhancing film C or D and the first adhesive layer was not subjected to corona treatment. In addition, in Comparative Examples 6 to 11, before the brightening film C or D was bonded to the first adhesive layer, although the corona treatment was not performed on the bonding surface of the brightening film C or D, it was adhered to the first The adhesive surface of the agent layer is corona treated.
從所得之偏光板,切取111mm×65mm大小的樣品,隔著第2黏著劑層,貼合於無鹼玻璃(康寧公司製「Eagle XG」)。對該玻璃貼合樣品,實施投入60℃、90%RH的烤箱500小時的濕熱耐久性測試,根據下述基準,目視評價測試後的樣品的外觀。結果表示於表1。再者,表1之「表面活性化處理」的欄,係表示對增亮膜的貼合面是否進行表面活性化處理。 From the obtained polarizing plate, a sample with a size of 111 mm×65 mm was cut, and it was bonded to an alkali-free glass (“Eagle XG” manufactured by Corning Corporation) via a second adhesive layer. This glass-laminated sample was subjected to a damp heat durability test for 500 hours in an oven at 60° C. and 90% RH, and the appearance of the sample after the test was visually evaluated according to the following criteria. The results are shown in Table 1. In addition, the column of “surface activation treatment” in Table 1 indicates whether the surface of the brightening film is subjected to surface activation treatment.
A:於偏光板的端部,沒有觀察到增亮膜與黏著劑層的界面之剝離,外觀良好 A: At the end of the polarizing plate, no peeling of the interface between the brightness enhancement film and the adhesive layer was observed, and the appearance was good
B:只於偏光板的端部,觀察到上述剝離 B: Only at the end of the polarizing plate, the above peeling was observed
C:不僅是偏光板的端部,直到中央部為止都觀察到上述剝離的進行 C: The progress of the above peeling is observed not only at the end of the polarizing plate but up to the center
1‧‧‧偏光板 1‧‧‧ Polarizer
10‧‧‧偏光片 10‧‧‧ Polarizer
20‧‧‧第1黏著劑層 20‧‧‧1st adhesive layer
30‧‧‧增亮膜 30‧‧‧Brightening film
40‧‧‧保護膜 40‧‧‧Protection film
50‧‧‧第2黏著劑層 50‧‧‧ 2nd adhesive layer
60‧‧‧分隔構件 60‧‧‧Partition
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JP2006062281A (en) * | 2004-08-30 | 2006-03-09 | Teijin Dupont Films Japan Ltd | Optical film laminated body and liquid crystal display device including the same |
TW200900757A (en) * | 2007-02-13 | 2009-01-01 | Sumitomo Chemical Co | Thin type polarizer and a display used thereof |
TW201111176A (en) * | 2009-06-30 | 2011-04-01 | Zeon Corp | Luminance improving film having adhesive layer, polarizing plate, and liquid crystal display device comprising the luminance improving film and the polarizing plate |
TW201142380A (en) * | 2010-02-25 | 2011-12-01 | Sumitomo Chemical Co | Manufacturing method of polarizing plate |
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