TWI784930B - Built-in liquid crystal panel and liquid crystal display device - Google Patents
Built-in liquid crystal panel and liquid crystal display device Download PDFInfo
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- 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
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Abstract
[課題]本發明提供一種抗靜電機能良好且可滿足觸控感測器感度、加濕環境下之導通可靠性及耐久性的內置型液晶面板。 [解決手段]一種內置型液晶面板,其特徵在於具有:內置型液晶單元,其具有液晶層、第1透明基板與第2透明基板、觸控感測器部及驅動電極兼感測器部,該液晶層含有在電場不存在之狀態下呈平行配向之液晶分子,前述第1透明基板與第2透明基板從兩面夾持前述液晶層,前述觸控感測器部設於前述液晶層與第1透明基板之間,前述驅動電極兼感測器部設於前述液晶層與第2透明基板之間;及 附黏著劑層之偏光薄膜,係未夾導電層並透過第1黏著劑層配置於前述內置型液晶單元之視辨側的第1透明基板側; 其中,前述附黏著劑層之偏光薄膜依序具有表面處理層、第1偏光薄膜、第1黏著劑層,或是依序具有表面處理層、第1偏光薄膜、錨定層、第1黏著劑層; 選自前述表面處理層、錨定層、第1黏著劑層中之至少任1層含有抗靜電劑。[Problem] The present invention provides a built-in liquid crystal panel that has good antistatic performance and satisfies touch sensor sensitivity, conduction reliability and durability in a humidified environment. [Solution] A built-in liquid crystal panel, characterized by having: a built-in liquid crystal unit having a liquid crystal layer, a first transparent substrate and a second transparent substrate, a touch sensor unit, and a drive electrode and sensor unit, The liquid crystal layer contains liquid crystal molecules aligned in parallel in the absence of an electric field, the first transparent substrate and the second transparent substrate sandwich the liquid crystal layer from both sides, and the touch sensor unit is provided between the liquid crystal layer and the second transparent substrate. 1 Between the transparent substrates, the aforementioned driving electrodes and sensor parts are arranged between the aforementioned liquid crystal layer and the second transparent substrate; and the polarizing film with the adhesive layer is not sandwiched between the conductive layer and is arranged through the first adhesive layer. The first transparent substrate side of the viewing side of the aforementioned built-in liquid crystal unit; wherein, the aforementioned polarizing film with an adhesive layer has a surface treatment layer, a first polarizing film, and a first adhesive layer in sequence, or has a surface in sequence Treatment layer, first polarizing film, anchor layer, first adhesive layer; at least one layer selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer contains an antistatic agent.
Description
發明領域 本發明關於一種於液晶單元內部納入觸控感測機能之內置型液晶單元,及一種於該內置型液晶單元之視辨側具有附黏著劑層之偏光薄膜的內置型液晶面板。此外,本發明關於一種使用該液晶面板之液晶顯示裝置。使用本發明之內置型液晶面板的附觸控感測機能之液晶顯示裝置可作為行動機器等各種輸入顯示裝置使用。Field of the Invention The present invention relates to a built-in liquid crystal unit incorporating a touch sensing function inside the liquid crystal unit, and a built-in liquid crystal panel having a polarizing film with an adhesive layer on the viewing side of the built-in liquid crystal unit. In addition, the present invention relates to a liquid crystal display device using the liquid crystal panel. The liquid crystal display device with touch sensing function using the built-in liquid crystal panel of the present invention can be used as various input display devices such as mobile devices.
發明背景 液晶顯示裝置一般是依其影像形成方式,於液晶單元兩側隔著黏著劑層而貼合有偏光薄膜。另外,於液晶顯示裝置之顯示畫面搭載觸控面板之產品業已實用化。就觸控面板而言,有電容式、阻抗膜式、光學式、超音波式或電磁感應式等各種格式,近期多採用電容式。近年多使用內嵌有電容感測器作為觸控感測器部之附觸控感測機能之液晶顯示裝置。Background of the Invention In liquid crystal display devices, a polarizing film is generally bonded on both sides of the liquid crystal unit through an adhesive layer according to its image forming method. In addition, products equipped with a touch panel on the display screen of a liquid crystal display device have already been put into practical use. As far as touch panels are concerned, there are various formats such as capacitive, resistive film, optical, ultrasonic, or electromagnetic induction. Recently, capacitive is mostly used. In recent years, a liquid crystal display device with a touch sensing function embedded with a capacitive sensor as a touch sensor portion has been widely used.
就製造液晶顯示裝置方面來看,將前述附黏著劑層之偏光薄膜黏貼至液晶單元時會從附黏著劑層之偏光薄膜之黏著劑層剝離脫模薄膜,並因該脫模薄膜之剝離產生靜電。因而產生的靜電會影響液晶顯示裝置內部的液晶層配向,招致不良後果。所以,例如藉由在偏光薄膜外面形成抗靜電層,可抑制靜電的產生。In terms of manufacturing liquid crystal display devices, when the aforementioned polarizing film with an adhesive layer is attached to a liquid crystal cell, the release film will be peeled off from the adhesive layer of the polarizing film with an adhesive layer, and the peeling of the release film will cause static electricity. The resulting static electricity will affect the alignment of the liquid crystal layer inside the liquid crystal display device, leading to adverse consequences. Therefore, for example, by forming an antistatic layer on the outside of the polarizing film, generation of static electricity can be suppressed.
另一方面,附觸控感測機能之液晶顯示裝置的電容感測器係用以檢測使用者手指接近其表面時透明電極圖案與手指所形成之微弱的電容量。如果於上述透明電極圖案與使用者手指之間具有如抗靜電層之導電層,驅動電極與感測器電極間之電場會紊亂,造成感測器電極容量不穩定,降低觸控面板感度而成為故障之原因。就附觸控感測機能之液晶顯示裝置來說,必須抑制產生靜電以及電容感測器之故障。例如針對前述課題,有文獻提議在附觸控感測機能之液晶顯示裝置中,於液晶層之視辨側配置偏光薄膜以減低顯示不良或故障的發生,該偏光薄膜具有表面電阻值為1.0×109 ~1.0×1011 Ω/□之抗靜電層(專利文獻1)。 先前技術文獻 專利文獻On the other hand, the capacitance sensor of the liquid crystal display device with touch sensing function is used to detect the weak capacitance formed by the transparent electrode pattern and the finger when the user's finger approaches the surface. If there is a conductive layer such as an antistatic layer between the above-mentioned transparent electrode pattern and the user's finger, the electric field between the drive electrode and the sensor electrode will be disturbed, resulting in unstable capacitance of the sensor electrode and reducing the sensitivity of the touch panel. cause of failure. For liquid crystal display devices with touch sensing functions, it is necessary to suppress the generation of static electricity and failure of capacitive sensors. For example, in response to the above-mentioned problems, there are documents suggesting that in a liquid crystal display device with touch sensing function, a polarizing film is arranged on the viewing side of the liquid crystal layer to reduce the occurrence of display defects or failures. The polarizing film has a surface resistance value of 1.0× 10 9 ~1.0×10 11 Ω/□ antistatic layer (Patent Document 1). Prior Art Documents Patent Documents
專利文獻1:日本特開2013-105154號公報Patent Document 1: Japanese Unexamined Patent Publication No. 2013-105154
發明概要 發明欲解決之課題 藉由專利文獻1中記載之具有抗靜電層的偏光薄膜,可某程度抑制靜電產生。但在專利文獻1,抗靜電層之配置場所偏離產生靜電的根本位置,所以效果比不上對黏著劑層賦予抗靜電機能。又已知,在附觸控感測機能之液晶顯示裝置中,藉由於偏光薄膜側面設置導通結構,可賦予來自側面的導通性,不過當抗靜電層很薄時,側面與導通結構的接觸面積小,便無法獲得充分的導電性而發生導通不良。另一方面,抗靜電層一旦變厚,觸控感測器感度就會下降。此外,設在偏光薄膜外面的抗靜電層在加濕或加熱環境下(加濕或加熱可靠性試驗後)會因為與設在側面之導通結構密著性不良而無法獲得充分的導電性,引發導通不良。Summary of the Invention Problems to be Solved by the Invention The polarizing film with an antistatic layer described in Patent Document 1 can suppress the generation of static electricity to a certain extent. However, in Patent Document 1, the arrangement location of the antistatic layer deviates from the fundamental location where static electricity is generated, so the effect is not as good as that of imparting antistatic function to the adhesive layer. It is also known that in a liquid crystal display device with touch sensing function, by providing a conductive structure on the side of the polarizing film, conductivity from the side can be given, but when the antistatic layer is very thin, the contact area between the side and the conductive structure If the temperature is too small, sufficient conductivity cannot be obtained and poor conduction occurs. On the other hand, once the antistatic layer becomes thicker, the sensitivity of the touch sensor will decrease. In addition, the antistatic layer provided on the outside of the polarizing film cannot obtain sufficient conductivity due to poor adhesion to the conductive structure provided on the side under a humidified or heated environment (after the humidified or heated reliability test), causing Poor conduction.
此外,被賦予抗靜電機能的黏著劑層比設置於前述偏光薄膜上之抗靜電層更能抑制靜電產生,可有效防止靜電不均。但已知,一旦因為重視黏著劑層之抗靜電機能而提高黏著劑層之導電機能,會降低觸控感測器感度。特別是在附觸控感測機能之液晶顯示裝置中,觸控感測器感度會下降。此外已知,為提高導電機能而摻混於黏著劑層中之抗靜電劑在加濕環境下(加濕可靠性試驗後)會偏析於與偏光薄膜之界面或移動到液晶單元之視辨側界面,耐久性不足。In addition, the adhesive layer endowed with antistatic function can suppress the generation of static electricity better than the antistatic layer provided on the aforementioned polarizing film, and can effectively prevent uneven static electricity. However, it is known that once the conductive function of the adhesive layer is increased due to the emphasis on the antistatic function of the adhesive layer, the sensitivity of the touch sensor will be reduced. Especially in a liquid crystal display device with a touch sensing function, the sensitivity of the touch sensor will decrease. In addition, it is known that the antistatic agent mixed in the adhesive layer to improve the conductivity will segregate at the interface with the polarizing film or move to the viewing side of the liquid crystal cell in a humidified environment (after the humidification reliability test) Interface, lack of durability.
本發明目的在於提供一種內置型液晶面板,其具有內置型液晶單元及應用在其視辨側之附黏著劑層之偏光薄膜,該內置型液晶面板之抗靜電機能良好,且可滿足觸控感測器感度及加濕環境下之導通可靠性及耐久性。The purpose of the present invention is to provide a built-in liquid crystal panel, which has a built-in liquid crystal unit and a polarizing film with an adhesive layer applied on its viewing side. The built-in liquid crystal panel has good antistatic performance and can satisfy the touch feeling. Sensor sensitivity and conduction reliability and durability in humidified environment.
又,本發明目的在於提供一種使用前述內置型液晶面板之內置型液晶面板,更進一步提供使用該液晶面板之液晶顯示裝置。 用以解決課題之手段Furthermore, the object of the present invention is to provide a built-in liquid crystal panel using the aforementioned built-in liquid crystal panel, and further provide a liquid crystal display device using the liquid crystal panel. means to solve problems
本發明人等為了解決前述課題反覆精闢研討的結果發現藉由下述內置型液晶面板可解決上述課題,而至完成本發明。As a result of intensive studies to solve the above-mentioned problems, the present inventors found that the above-mentioned problems can be solved by the following built-in type liquid crystal panel, and completed the present invention.
即,本發明關於一種內置型液晶面板,其特徵在於具有: 內置型液晶單元,其具有液晶層、第1透明基板與第2透明基板、觸控感測器部及驅動電極兼感測器部,該液晶層含有在電場不存在之狀態下呈平行配向(homogenious alignment)之液晶分子,前述第1透明基板與第2透明基板從兩面夾持前述液晶層,前述觸控感測器部設於前述液晶層與第1透明基板之間,前述驅動電極兼感測器部設於前述液晶層與第2透明基板之間;及 附黏著劑層之偏光薄膜,係未夾導電層並透過第1黏著劑層配置於前述內置型液晶單元之視辨側的第1透明基板側; 其中,前述附黏著劑層之偏光薄膜依序具有表面處理層、第1偏光薄膜、第1黏著劑層,或是依序具有表面處理層、第1偏光薄膜、錨定層、第1黏著劑層; 選自前述表面處理層、錨定層、第1黏著劑層中之至少任1層含有抗靜電劑。That is, the present invention relates to a built-in liquid crystal panel, characterized by comprising: a built-in liquid crystal cell having a liquid crystal layer, a first transparent substrate and a second transparent substrate, a touch sensor unit, and a drive electrode and sensor unit The liquid crystal layer contains liquid crystal molecules in a homogenious alignment in the absence of an electric field, the first transparent substrate and the second transparent substrate sandwich the liquid crystal layer from both sides, and the touch sensor part is disposed on Between the aforementioned liquid crystal layer and the first transparent substrate, the aforementioned driving electrode and sensor part is arranged between the aforementioned liquid crystal layer and the second transparent substrate; The adhesive layer is disposed on the first transparent substrate side of the viewing side of the built-in liquid crystal unit; wherein, the polarizing film attached to the adhesive layer has a surface treatment layer, a first polarizing film, and a first adhesive layer in sequence, or It has a surface treatment layer, a first polarizing film, an anchor layer, and a first adhesive layer in sequence; at least one layer selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer contains an antistatic agent.
前述內置型液晶面板中,可於前述附黏著劑層之偏光薄膜的前述表面處理層、錨定層、第1黏著劑層中之含有抗靜電劑之層的側面具有導通結構。In the aforementioned built-in type liquid crystal panel, a conduction structure may be provided on the side of the surface treatment layer, the anchor layer, and the layer containing the antistatic agent in the first adhesive layer of the polarizing film attached to the adhesive layer.
前述內置型液晶面板中,選自前述表面處理層、錨定層及第1黏著劑層中之至少任1層宜滿足下述表面電阻值: 前述表面處理層之表面電阻值為1×107 ~1×1011 Ω/□, 前述錨定層之表面電阻值為1×108 ~1×1011 Ω/□, 前述第1黏著劑層之表面電阻值為1×108 ~1×1011 Ω/□。In the aforementioned built-in liquid crystal panel, at least one layer selected from the aforementioned surface treatment layer, the anchor layer, and the first adhesive layer should satisfy the following surface resistance value: The surface resistance value of the aforementioned surface treatment layer is 1×10 7 ~1×10 11 Ω/□, the surface resistance value of the anchor layer is 1×10 8 ~1×10 11 Ω/□, the surface resistance value of the first adhesive layer is 1×10 8 ~1×10 11Ω /□.
前述內置型液晶面板中,前述第1黏著劑層可含有抗靜電劑。就抗靜電劑而言,宜為鹼金屬鹽及/或有機陽離子-陰離子鹽。In the built-in liquid crystal panel, the first adhesive layer may contain an antistatic agent. As antistatic agents, alkali metal salts and/or organic cation-anion salts are preferred.
前述內置型液晶面板中,選自前述表面處理層、錨定層、第1黏著劑層中之任2層以上宜含有抗靜電劑。In the aforementioned built-in liquid crystal panel, any two or more layers selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer preferably contain an antistatic agent.
前述內置型液晶面板中,於前述內置型液晶單元之第2透明基板側可具有透過第2黏著劑層配置之第2偏光薄膜。In the aforementioned built-in liquid crystal panel, a second polarizing film disposed through the second adhesive layer may be provided on the side of the second transparent substrate of the aforementioned built-in liquid crystal cell.
又,本發明關於一種具有前述內置型液晶面板之液晶顯示裝置。 發明效果Furthermore, the present invention relates to a liquid crystal display device having the aforementioned built-in liquid crystal panel. Invention effect
本發明之內置型液晶面板之視辨側的附黏著劑層之偏光薄膜於選自表面處理層、錨定層及黏著劑層中之至少任1層賦予了抗靜電機能,故內置型液晶面板中可於側面與導通結構接觸,且可充分確保接觸面積。所以,可確保在附黏著劑層之偏光薄膜中之至少1層側面的導通,藉此可抑制因導通不良而產生的靜電不均,也可滿足加濕環境下之導通可靠性。選自表面處理層、錨定層及黏著劑層中之至少2層被賦予抗靜電機能時,可更有效確保導通,既可抑制因導通不良而產生的靜電不均,亦可滿足加濕環境下的導通可靠性。The polarizing film attached to the adhesive layer on the viewing side of the built-in liquid crystal panel of the present invention has an antistatic function on at least one layer selected from the surface treatment layer, the anchor layer and the adhesive layer, so the built-in liquid crystal panel The side can be in contact with the conduction structure, and the contact area can be sufficiently ensured. Therefore, conduction can be ensured on at least one side of the polarizing film with an adhesive layer, thereby suppressing static unevenness due to poor conduction, and satisfying conduction reliability in a humidified environment. When at least two layers selected from the surface treatment layer, the anchor layer and the adhesive layer are endowed with an antistatic function, the conduction can be ensured more effectively, and the uneven static electricity caused by poor conduction can be suppressed, and it can also meet the humidification environment Under the conduction reliability.
又,本發明之附黏著劑層之偏光薄膜可將選自表面處理層、錨定層及黏著劑層中之至少任1層的表面電阻值控制在預定範圍內。如此一來,本發明之附黏著劑層之偏光薄膜既可控制不使觸控感測器感度降低、加濕環境下之耐久性不惡化,還可降低附黏著劑層之偏光薄膜中之至少1層的表面電阻值而賦予預定的抗靜電機能。所以,本發明之附黏著劑層之偏光薄膜具有良好的抗靜電機能,同時可滿足觸控感測器感度及加濕環境下的耐久性。In addition, the polarizing film with an adhesive layer of the present invention can control the surface resistance value of at least one layer selected from the surface treatment layer, the anchor layer, and the adhesive layer within a predetermined range. In this way, the polarizing film with an adhesive layer of the present invention can control the sensitivity of the touch sensor from being reduced, and the durability in a humid environment is not deteriorated, and can also reduce at least The surface resistance value of the first layer is given a predetermined antistatic function. Therefore, the polarizing film with the adhesive layer of the present invention has good antistatic performance, and can satisfy the sensitivity of the touch sensor and the durability under humidified environment.
用以實施發明之形態 以下參照圖式說明本發明。在本發明之內置型液晶面板之視辨側使用之附黏著劑層之偏光薄膜A依序具有表面處理層4、第1偏光薄膜1、第1黏著劑層2,或是依序具有表面處理層4、第1偏光薄膜1、錨定層3、第1黏著劑層2。圖1係依序具有表面處理層4、第1偏光薄膜1、錨定層3、第1黏著劑層2之情況。如圖2所示,本發明之附黏著劑層之偏光薄膜A可藉由前述黏著劑層2配置在內置型液晶單元B之視辨側的透明基板41側。又,圖1中雖無記載,不過本發明之附黏著劑層之偏光薄膜A可於第1黏著劑層2設置分離件,並可於表面處理層4設置表面保護薄膜。另,前述附內嵌觸控感測機能之液晶單元用黏著劑層之偏光薄膜為了以選自前述表面處理層、錨定層及第1黏著劑層中之至少任1層賦予導電性而控制了表面電阻值。前述至少1層受到表面電阻值之控制即可,不過從確保加濕或加熱環境下與設於側面之導通結構的密著性及接觸面積的觀點來看,至少2層特別是錨定層3及第1黏著劑層2有受到表面電阻值控制為宜。Modes for Carrying Out the Invention The present invention will be described below with reference to the drawings. The polarizing film A attached to the adhesive layer used on the viewing side of the built-in liquid crystal panel of the present invention has a
從表面電阻值之穩定性及與黏著劑層之密著性的觀點來看,前述錨定層3之厚度宜為0.01~0.5μm,0.01~0.2μm較佳,0.01~0.1μm更佳。又,從抗靜電機能及觸控感測器感度的觀點來看,前述錨定層3之表面電阻值宜為1×108
~1×1012
Ω/□,1×108
~1×1011
Ω/□較佳,1×108
~1×1010
Ω/□更佳。From the viewpoint of the stability of the surface resistance value and the adhesion to the adhesive layer, the thickness of the
從確保耐久性及確保與側面導通結構之接觸面積的觀點來看,前述第1黏著劑層2之厚度宜為5~100μm,5~50μm較佳,10~35μm更佳。又,針對前述第1黏著劑層2控制導電性時,從抗靜電機能及觸控感測器感度的觀點來看,前述第1黏著劑層2之表面電阻值宜為1×108
~1×1012
Ω/□,1×108
~1×1011
Ω/□較佳,1×108
~1×1010
Ω/□更佳。From the viewpoint of ensuring durability and ensuring a contact area with the side conduction structure, the thickness of the first
又,針對前述表面處理層4控制導電性時,從抗靜電機能及觸控感測器感度的觀點來看,前述表面處理層4之表面電阻值宜為1×107
~1×1011
Ω/□,1×107
~1×1010
Ω/□較佳,1×107
~1×109
Ω/□更佳。In addition, when controlling the conductivity of the
此外,前述附黏著劑層之偏光薄膜A之黏著劑層2側的表面電阻值宜控制在1×108
~1×1011
Ω/□,以達滿足抗靜電機能且不降低觸控感測器感度或減弱加濕環境下之耐久性。前述表面電阻值可藉由個別控制前述表面處理層4、錨定層3及第1黏著劑層2中之至少1層的表面電阻值來調節。前述表面電阻值宜為1×108
~6×1010
Ω/□,1×108
~4×1010
Ω/□更佳。In addition, the surface resistance of the
以下說明附黏著劑層之偏光薄膜A。如上述,本發明之附黏著劑層之偏光薄膜A依序具有表面處理層4、第1偏光薄膜1、第1黏著劑層2,或是依序具有表面處理層4、第1偏光薄膜1、錨定層3、第1黏著劑層2。The polarizing film A with an adhesive layer will be described below. As mentioned above, the polarizing film A with an adhesive layer of the present invention has the
<第1偏光薄膜> 第1偏光薄膜一般常使用偏光件單面或兩面具有透明保護薄膜者。偏光件並無特別限定,可使用各種物質。偏光件可舉如於聚乙烯醇系薄膜、部分甲醛化聚乙烯醇系薄膜、乙烯・乙酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜吸附碘或二色性染料之二色性物質並予以單軸延伸者,以及聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系配向薄膜等。該等中,又以由聚乙烯醇系薄膜與碘等之二色性物質所構成的偏光件為宜。該等偏光件之厚度無特別限制,一般在80μm左右以下。<First Polarizing Film> As the first polarizing film, one with a transparent protective film on one or both sides of the polarizer is generally used. The polarizer is not particularly limited, and various substances can be used. Polarizers can be dichroic substances that adsorb iodine or dichroic dyes to hydrophilic polymer films such as polyvinyl alcohol films, partially formaldehyde polyvinyl alcohol films, and ethylene-vinyl acetate copolymer-based partially saponified films. And uniaxially stretched, and polyene-based oriented films such as dehydrated polyvinyl alcohol or polyvinyl chloride dehydrochloridized. Among them, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, and is generally below about 80 μm.
又,偏光件可使用厚度10μm以下的薄型偏光件。從薄型化觀點來說,該厚度在1~7μm為宜。這種薄型偏光件少有厚度不均、視辨性佳且少有尺寸變化,所以耐久性佳,再者作為偏光薄膜的厚度也可期許薄型化此點相當適宜。Also, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. This kind of thin polarizer has little thickness unevenness, good visibility, and little dimensional change, so it has good durability, and it is also suitable for thinning the thickness of the polarizing film.
構成透明保護薄膜之材料例如可使用透明性、機械強度、熱穩定性、水分隔絕性、等向性等優異的熱可塑性樹脂。這種熱可塑性樹脂之具體例可列舉三醋酸纖維素等纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂及該等之混合物。另,透明保護薄膜可透過黏著劑層貼合於偏光件之單側,另一單側則可使用(甲基)丙烯酸系、胺甲酸乙酯系、丙烯酸胺甲酸乙酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂作為透明保護薄膜。透明保護薄膜中可含有1種以上任意且適當的添加劑。As a material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, heat stability, water barrier property, isotropy, etc. can be used. Specific examples of such thermoplastic resins include cellulose resins such as cellulose triacetate, polyester resins, polyether resins, polyresins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, etc. Resins, (meth)acrylic resins, cyclic polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. In addition, the transparent protective film can be attached to one side of the polarizer through the adhesive layer, and the other side can use (meth)acrylic, urethane, acrylic urethane, epoxy, A thermosetting resin such as polysiloxane or an ultraviolet curable resin is used as a transparent protective film. The transparent protective film may contain one or more arbitrary and appropriate additives.
用來貼合前述偏光件與透明保護薄膜的黏著劑層只要在光學上呈透明即無特別限制,可使用水系、溶劑系、熱熔系、自由基硬化型、陽離子硬化型等各種形態的物質,以水系黏著劑或自由基硬化型黏著劑為宜。The adhesive layer used to bond the above-mentioned polarizer and transparent protective film is not particularly limited as long as it is optically transparent, and various forms such as water-based, solvent-based, hot-melt, radical-curable, and cation-curable can be used. , it is advisable to use water-based adhesives or free-radical hardening adhesives.
<抗靜電劑> 如前述,為了賦予表面處理層、錨定層及第1黏著劑層之至少1層導電性,可使用抗靜電劑。抗靜電劑可列舉如離子性界面活性劑系、導電性聚合物、導電性微粒子等可賦予抗靜電性之材料。又,可使用離子性化合物作為抗靜電劑。<Antistatic agent> As mentioned above, an antistatic agent can be used in order to impart conductivity to at least one layer of the surface treatment layer, the anchor layer, and the first adhesive layer. Examples of the antistatic agent include materials capable of imparting antistatic properties, such as ionic surfactants, conductive polymers, and conductive fine particles. Also, an ionic compound can be used as an antistatic agent.
離子性界面活性劑可列舉陽離子系(例如,4級銨鹽型、鏻鹽型、鋶鹽型等)、陰離子系(羧酸型、磺酸鹽型、硫酸鹽型、磷酸鹽型、亞磷酸鹽型等)、兩性離子系(磺基甜菜鹼型、烷基甜菜鹼型、烷基咪唑啉鎓甜菜鹼型等)或非離子系(多元醇衍生物、β-環糊精包合物、去水山梨醇脂肪酸單酯・二酯、聚環氧烷衍生物、氧化胺等)各種界面活性劑。Ionic surfactants include cationic (for example, quaternary ammonium salt type, phosphonium salt type, permeic acid type, etc.), anionic (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphorous acid type, etc.) salt type, etc.), zwitterionic (sulfobetaine type, alkyl betaine type, alkylimidazolinium betaine type, etc.) or nonionic (polyol derivatives, β-cyclodextrin inclusion complex, Sorbitan fatty acid monoesters and diesters, polyalkylene oxide derivatives, amine oxides, etc.) various surfactants.
導電性聚合物可列舉聚苯胺系、聚噻吩系、聚吡咯系、聚喹啉系等之聚合物,該等中又宜使用容易成為水溶性導電性聚合物或水分散性導電性聚合物之聚苯胺、聚噻吩等。尤以聚噻吩為宜。Examples of conductive polymers include polyaniline, polythiophene, polypyrrole, and polyquinone Polymers such as phyllolines, and polyaniline, polythiophene, etc., which tend to become water-soluble conductive polymers or water-dispersible conductive polymers, are preferably used among them. Polythiophene is especially preferred.
又,導電性微粒子可列舉氧化錫系、氧化銻系、氧化銦系、氧化鋅系等金屬氧化物。該等中又以氧化錫系為宜。就氧化錫系之物而言,例如除了氧化錫以外,還可列舉銻摻雜氧化錫、銦摻雜氧化錫、鋁摻雜氧化錫、鎢摻雜氧化錫、氧化鈦-氧化鈰-氧化錫之複合體、氧化鈦-氧化錫之複合體等。微粒子之平均粒徑為1~100nm左右,宜為2~50nm。Moreover, metal oxides, such as a tin oxide system, an antimony oxide system, an indium oxide system, and a zinc oxide system, are mentioned as electroconductive fine particle. Among them, the tin oxide system is preferable. For the tin oxide series, for example, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide The composite body, the composite body of titanium oxide-tin oxide, etc. The average particle size of the microparticles is about 1-100 nm, preferably 2-50 nm.
此外,就前述以外的抗靜電劑可列舉:乙炔黑、科琴碳黑(Ketjen black)、天然石墨、人造石墨、鈦黑或是具有陽離子型(4級銨鹽等)、兩性離子型(甜菜鹼化合物等)、陰離子型(磺酸鹽等)或非離子型(甘油等)之離子導電性基之單體均聚合物或該單體與其他單體之共聚物、具4級銨鹽基之具有源自丙烯酸酯或甲基丙烯酸酯部位的聚合物等的具離子導電性聚合物;將聚乙烯甲基丙烯酸酯共聚物等親水性聚合物合金化至丙烯酸系樹脂等類型的永久抗靜電劑。In addition, antistatic agents other than the aforementioned can be cited: acetylene black, Ketjen black (Ketjen black), natural graphite, artificial graphite, titanium black or cationic (4-grade ammonium salt, etc.), zwitterionic (beet Alkali compounds, etc.), anionic (sulfonate, etc.) or non-ionic (glycerin, etc.) ion-conductive monomer homopolymers or copolymers of such monomers and other monomers, with 4-level ammonium base Ionically conductive polymers such as polymers derived from acrylate or methacrylate moieties; alloying of hydrophilic polymers such as polyethylene methacrylate copolymers to permanent antistatic properties such as acrylic resins agent.
≪離子性化合物≫ 又,就離子性化合物而言,可適當使用鹼金屬鹽及/或有機陽離子-陰離子鹽。鹼金屬鹽可使用鹼金屬之有機鹽及無機鹽。另,本發明中所謂的「有機陽離子-陰離子鹽」為有機鹽,意指其陽離子部分係以有機物構成,陰離子部分可為有機物亦可為無機物。「有機陽離子-陰離子鹽」亦稱為離子性液體、離子性固體。≪Ionic compound≫ In addition, as an ionic compound, an alkali metal salt and/or an organic cation-anion salt can be used suitably. As the alkali metal salt, organic salts and inorganic salts of alkali metals can be used. In addition, the so-called "organic cation-anion salt" in the present invention is an organic salt, which means that the cationic part is composed of organic matter, and the anion part can be organic or inorganic. "Organic cation-anion salts" are also called ionic liquids and ionic solids.
<鹼金屬鹽> 構成鹼金屬鹽之陽離子部的鹼金屬離子可列舉鋰、鈉、鉀之各離子。該等鹼金屬離子中又以鋰離子為宜。<Alkali metal salt> Examples of the alkali metal ions constituting the cation portion of the alkali metal salt include lithium, sodium, and potassium ions. Among the alkali metal ions, lithium ions are preferred.
鹼金屬鹽之陰離子部可以有機物構成亦可以無機物構成。構成有機鹽之陰離子部可使用譬如CH3 COO- 、CF3 COO- 、CH3 SO3 - 、CF3 SO3 - 、(CF3 SO2 )3 C- 、C4 F9 SO3 - 、C3 F7 COO- 、(CF3 SO2 )(CF3 CO)N- 、- O3 S(CF2 )3 SO3 - 、PF6 - 、CO3 2- 及下述通式(1)至(4)所示者等; (1):(Cn F2n+1 SO2 )2 N- (惟,n為1~10之整數)、 (2):CF2 (Cm F2m SO2 )2 N- (惟,m為1~10之整數)、 (3):- O3 S(CF2 )l SO3 - (惟,l為1~10之整數)、 (4):(Cp F2p+1 SO2 )N- (Cq F2q+1 SO2 )(惟,p、q為1~10之整數)。尤其,含氟原子之陰離子部可獲得離子解離性良好的離子化合物,故宜使用。構成無機鹽之陰離子部可使用Cl- 、Br- 、I- 、AlCl4 - 、Al2 Cl7 - 、BF4 - 、PF6 - 、ClO4 - 、NO3 - 、AsF6 - 、SbF6 - 、NbF6 - 、TaF6 - 、(CN)2 N- 等。就陰離子部而言,宜為(CF3 SO2 )2 N- 、(C2 F5 SO2 )2 N- 等前述通式(1)所示(全氟烷基磺醯基)醯亞胺,尤宜為(CF3 SO2 )2 N- 所示(三氟甲烷磺醯基)醯亞胺。The anion portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. As the anion part constituting the organic salt, for example, CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , (CF 3 SO 2 ) 3 C - , C 4 F 9 SO 3 - , C 3 F 7 COO - , (CF 3 SO 2 )(CF 3 CO)N - , - O 3 S(CF 2 ) 3 SO 3 - , PF 6 - , CO 3 2- and the following general formulas (1) to (4) as shown; (1): (C n F 2n+1 SO 2 ) 2 N - (however, n is an integer from 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N - (but, m is an integer of 1 to 10), (3): - O 3 S(CF 2 ) l SO 3 - (but, l is an integer of 1 to 10), (4): (C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (provided that p and q are integers from 1 to 10). In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , AsF 6 - , SbF 6 - can be used for the anion part of the inorganic salt , NbF 6 - , TaF 6 - , (CN) 2 N - , etc. As for the anion part, (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , etc. are preferably (perfluoroalkylsulfonyl)imides represented by the aforementioned general formula (1). , especially (CF 3 SO 2 ) 2 N - (trifluoromethanesulfonyl)imide.
鹼金屬之有機鹽具體上宜為醋酸鈉、褐藻酸鈉、木質磺酸鈉、甲苯磺酸鈉、LiCF3 SO3 、Li(CF3 SO2 )2 N、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(C4 F9 SO2 )2 N、Li(CF3 SO2 )3 C、KO3 S(CF2 )3 SO3 K、LiO3 S(CF2 )3 SO3 K等,該等中以LiCF3 SO3 、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(C4 F9 SO2 )2 N、Li(CF3 SO2 )3 C等為宜,較宜為Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(C4 F9 SO2 )2 N等含氟鋰醯亞胺鹽,尤宜為(全氟烷基磺醯基)醯亞胺鋰鹽。The organic salt of alkali metal is preferably sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N , Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, KO 3 S(CF 2 ) 3 SO 3 K, LiO 3 S (CF 2 ) 3 SO 3 K, etc. Among them, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, etc. are suitable, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) are more suitable 2 N and other fluorine-containing lithium imide salts, especially lithium (perfluoroalkylsulfonyl) imide salts.
又,鹼金屬之無機鹽可列舉過氯酸鋰、碘化鋰。Moreover, examples of inorganic salts of alkali metals include lithium perchlorate and lithium iodide.
<有機陽離子-陰離子鹽> 本發明中使用之有機陽離子-陰離子鹽係由陽離子成分及陰離子成分構成,前述陽離子成分係由有機物所構成。陽離子成分具體上可列舉:吡啶鎓陽離子、哌啶鎓(piperidinium)陽離子、吡咯啶鎓(pyrrolidinium)陽離子、具有吡咯啉骨架之陽離子、具有吡咯骨架之陽離子、咪唑啉鎓(imidazolium)陽離子、四氫嘧啶鎓(tetrahydropyrimidinium)陽離子、二氫嘧啶鎓陽離子、吡唑鎓(pyrazolium)陽離子、吡唑啉鎓(pyrazolinium)陽離子、四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子等。<Organic cation-anion salt> The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the above-mentioned cation component is composed of an organic substance. The cation component specifically includes: pyridinium cation, piperidinium (piperidinium) cation, pyrrolidinium (pyrrolidinium) cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium (imidazolium) cation, tetrahydrogen Pyrimidinium (tetrahydropyrimidinium) cation, dihydropyrimidinium cation, pyrazolium (pyrazolium) cation, pyrazolinium (pyrazolinium) cation, tetraalkylammonium cation, trialkylconium cation, tetraalkylphosphonium cation, etc.
陰離子成分例如可使用Cl- 、Br- 、I- 、AlCl4 - 、Al2 Cl7 - 、BF4 - 、PF6 - 、ClO4 - 、NO3 - 、CH3 COO- 、CF3 COO- 、CH3 SO3 - 、CF3 SO3 - 、(CF3 SO2 )3 C- 、AsF6 - 、SbF6 - 、NbF6 - 、TaF6 - 、(CN)2 N- 、C4 F9 SO3 - 、C3 F7 COO- 、((CF3 SO2 )(CF3 CO)N- 、- O3 S(CF2 )3 SO3 - 及下述通式(1)至(4)所示者等; (1):(Cn F2n+1 SO2 )2 N- (惟,n為1~10之整數)、 (2):CF2 (Cm F2m SO2 )2 N- (惟,m為1~10之整數)、 (3):- O3 S(CF2 )l SO3 - (惟,l為1~10之整數)、 (4):(Cp F2p+1 SO2 )N- (Cq F2q+1 SO2 )(惟,p、q為1~10之整數)。其中,尤其是含氟原子之陰離子成分可獲得離子解離性良好的離子化合物,故宜使用。As anion components, for example, Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , (CN) 2 N - , C 4 F 9 SO 3 - , C 3 F 7 COO - , ((CF 3 SO 2 )(CF 3 CO)N - , - O 3 S(CF 2 ) 3 SO 3 - and the following general formulas (1) to (4) (1): (C n F 2n+1 SO 2 ) 2 N - (provided that n is an integer from 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N - (Only, m is an integer of 1~10), (3): - O 3 S(CF 2 ) l SO 3 - (Only, l is an integer of 1~10), (4): (C p F 2p+ 1 SO 2 )N - (C q F 2q+1 SO 2 ) (provided that p and q are integers ranging from 1 to 10). Among them, especially the anionic components containing fluorine atoms can obtain ionic compounds with good ion dissociation properties, Therefore, it should be used.
又,離子性化合物除了前述的鹼金屬鹽、有機陽離子-陰離子鹽以外,還可列舉氯化銨、氯化鋁、氯化銅、氯化亞鐵、氯化鐵、硫酸銨等無機鹽。該等離子性化合物可單獨使用或可將多數種併用。Moreover, examples of ionic compounds include inorganic salts such as ammonium chloride, aluminum chloride, cupric chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the aforementioned alkali metal salts and organic cation-anion salts. These ionic compounds may be used alone or in combination.
<錨定層> 賦予錨定層導電性時,如前述,錨定層宜形成為厚度0.01~0.5μm且表面電阻值為1×108 ~1×1012 Ω/□。導電性之錨定層可由各種抗靜電劑組成物形成。就形成錨定層之抗靜電劑而言,前述示例中又以離子性界面活性劑系、導電性聚合物、導電性微粒子等為宜。<Anchor layer> When imparting conductivity to the anchor layer, as described above, the anchor layer is preferably formed to have a thickness of 0.01 to 0.5 μm and a surface resistance value of 1×10 8 to 1×10 12 Ω/□. The conductive anchor layer can be formed from various antistatic agent compositions. As for the antistatic agent for forming the anchor layer, ionic surfactants, conductive polymers, conductive fine particles, etc. are suitable in the aforementioned examples.
從光學特性、外觀、抗靜電效果及抗靜電效果於加熱時、加濕時之穩定性的觀點來看,該等抗靜電劑中又宜使用導電性聚合物。尤其,宜使用聚苯胺、聚噻吩等水溶性導電性聚合物或水分散性導電性聚合物。因為水溶性導電性聚合物或水分散性導電性聚合物可將形成抗靜電層時之塗佈液調製成水溶液或水分散液,該塗佈液無須使用非水系有機溶劑,能抑制光學薄膜基材因該有機溶劑變質之情況。又,水溶液或水分散液可含有水以外的水系溶劑。譬如,可列舉甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、正戊醇、異戊醇、二級戊醇、三級戊醇、1-乙基-1-丙醇、2-甲基-1-丁醇、正己醇、環己醇等醇類。From the viewpoint of optical characteristics, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, conductive polymers are preferably used among these antistatic agents. In particular, water-soluble conductive polymers such as polyaniline and polythiophene, or water-dispersible conductive polymers are preferably used. Because water-soluble conductive polymers or water-dispersible conductive polymers can prepare the coating solution for forming an antistatic layer into an aqueous solution or a water dispersion, the coating solution does not need to use non-aqueous organic solvents, and can inhibit the formation of optical film substrates. The material is deteriorated by the organic solvent. In addition, the aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-amyl alcohol, isoamyl alcohol, secondary amyl alcohol, tertiary pentanol Alcohols such as alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, etc.
又,前述聚苯胺、聚噻吩等水溶性導電性聚合物或水分散性導電性聚合物宜於分子中具有親水性官能基。親水性官能基可列舉如碸基、胺基、醯胺基、亞胺基、四級銨鹽基、羥基、巰基、肼基、羧基、硫酸酯基、磷酸酯基或該等之鹽等。因為分子內具有親水性官能基,可輕易溶於水或可以微粒狀輕易地分散於水中,而得以輕易地調製出前述水溶性導電性聚合物或水分散性導電性聚合物。In addition, the water-soluble conductive polymer such as polyaniline and polythiophene or the water-dispersible conductive polymer preferably has a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include phenyl group, amine group, amido group, imine group, quaternary ammonium group, hydroxyl group, mercapto group, hydrazine group, carboxyl group, sulfate group, phosphate group, or salts thereof. Because the molecule has a hydrophilic functional group, it can be easily dissolved in water or easily dispersed in water in the form of particles, so that the aforementioned water-soluble conductive polymer or water-dispersible conductive polymer can be easily prepared.
就水溶性導電聚合物之市售物例子來說,可列舉聚苯胺磺酸(Mitsubishi Rayon Co., Ltd.製,聚苯乙烯換算所得重量平均分子量150000)等。就水分散性導電聚合物之市售物例子來說,可列舉聚噻吩系導電性聚合物(Nagase ChemteX Co., Ltd.製、商品名Denatron系列)等。Examples of commercially available water-soluble conductive polymers include polyanilinesulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight in terms of polystyrene: 150,000) and the like. Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (manufactured by Nagase ChemteX Co., Ltd., trade name Denatron series) and the like.
又,就錨定層之形成材料而言,在抗靜電劑之皮膜形成性、提升對於光學薄膜之密著性等目的下,亦可連同前述抗靜電劑一起添加黏結劑成分。抗靜電劑為水溶性導電性聚合物或水分散性導電性聚合物之水系材料時,使用水溶性或水分散性之黏結劑成分。黏結劑之例可列舉含唑啉基聚合物、聚胺甲酸乙酯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚醚系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、環氧樹脂、聚乙烯基吡咯啶酮、聚苯乙烯系樹脂、聚乙二醇、新戊四醇等。尤以聚胺甲酸乙酯系樹脂、聚酯系樹脂、丙烯酸系樹脂為宜。該等黏結劑可依其用途適當使用1種或2種以上。In addition, as for the forming material of the anchor layer, a binder component may be added together with the above-mentioned antistatic agent for the purpose of film-forming property of the antistatic agent and improvement of adhesion to the optical film. When the antistatic agent is a water-based material of a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of binders include Azoline-based polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, Polystyrene-based resins, polyethylene glycol, neopentylthritol, and the like. In particular, polyurethane-based resins, polyester-based resins, and acrylic-based resins are preferred. One or more types of these binders can be used appropriately depending on the application.
抗靜電劑、黏結劑之使用量依該等之種類而定,不過宜以所得錨定層之表面電阻值成為1×108 ~1×1012 Ω/□的方式予以控制。The amount of antistatic agent and binder used depends on the types of these, but should be controlled so that the surface resistance of the obtained anchor layer becomes 1×10 8 ~1×10 12 Ω/□.
<第1黏著劑層> 賦予第1黏著劑層導電性時,如前述,第1黏著劑層宜形成為厚度5~100μm且表面電阻值為1×108 ~1×1012 Ω/□。導電性之第1黏著劑層可由各種黏著劑中摻合有抗靜電劑之組成物形成。<First Adhesive Layer> When imparting conductivity to the first adhesive layer, as described above, the first adhesive layer is preferably formed to have a thickness of 5 to 100 μm and a surface resistance of 1×10 8 to 1×10 12 Ω/□. The conductive first adhesive layer can be formed of a composition in which an antistatic agent is mixed with various adhesives.
形成第1黏著劑層之黏著劑可使用各種黏著劑,譬如可列舉:橡膠系黏著劑、丙烯酸系黏著劑、聚矽氧系黏著劑、胺甲酸乙酯系黏著劑、乙烯基烷基醚系黏著劑、聚乙烯吡咯啶酮系黏著劑、聚丙烯醯胺系黏著劑、纖維素系黏著劑等。可按前述黏著劑之種類選擇黏著性的基底聚合物。從光學透明性佳、顯示適度的濡溼性、凝聚性及黏著性的黏著特性,且耐候性及耐熱性等優異的觀點來看,前述黏著劑中又宜使用丙烯酸系黏著劑。Various adhesives can be used as the adhesive forming the first adhesive layer, for example, rubber-based adhesives, acrylic adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, etc. Adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. The adhesive base polymer can be selected according to the type of the aforementioned adhesive. Among the aforementioned adhesives, an acrylic adhesive is preferably used from the viewpoint of good optical transparency, moderate wettability, cohesiveness, and adhesiveness, and excellent weather resistance and heat resistance.
前述丙烯酸系黏著劑含有(甲基)丙烯酸系聚合物作為基底聚合物。(甲基)丙烯酸系聚合物通常作為單體單元含有(甲基)丙烯酸烷酯為主成分。另外,(甲基)丙烯酸酯意指丙烯酸酯及/或甲基丙烯酸酯,本發明之(甲基)表相同意思。The aforementioned acrylic adhesive contains a (meth)acrylic polymer as a base polymer. A (meth)acrylic polymer usually contains an alkyl (meth)acrylate as a main component as a monomer unit. In addition, (meth)acrylate means acrylate and/or methacrylate, and (meth) in this invention means the same thing.
構成(甲基)丙烯酸系聚合物之主骨架的(甲基)丙烯酸烷酯可列舉直鏈狀或支鏈狀之烷基碳數1~18之物。該等可單獨使用或可組合使用。該等烷基之平均碳數宜為3~9。Examples of the alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer include linear or branched alkyl groups having 1 to 18 carbon atoms. These may be used alone or in combination. The average carbon number of these alkyl groups is preferably 3-9.
又,從黏著特性、耐久性、相位差的調整、折射率之調整等觀點來看,可使用如(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苯甲酯等含有芳香族環的(甲基)丙烯酸烷酯。In addition, from the viewpoints of adhesive properties, durability, phase difference adjustment, and refractive index adjustment, aromatic ring-containing materials such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate can be used. Alkyl (meth)acrylates.
在前述(甲基)丙烯酸系聚合物中,以改善黏著性及耐熱性為目的,可將具有(甲基)丙烯醯基或乙烯基等的不飽和雙鍵之聚合性的官能基之1種以上的共聚單體藉由共聚合來導入。該種共聚單體之具體例可列舉如:(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯及(4-羥甲基環己基)-甲基丙烯酸酯等含羥基單體;(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、伊康酸、馬來酸、延胡索酸、巴豆酸等含羧基單體;馬來酸酐、伊康酸酐等含酐基單體;丙烯酸的己內酯加成物;苯乙烯磺酸或烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸、(甲基)丙烯醯胺丙烷磺酸、磺丙基(甲基)丙烯酸酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。In the aforementioned (meth)acrylic polymers, for the purpose of improving adhesiveness and heat resistance, one of polymerizable functional groups having unsaturated double bonds such as (meth)acryl groups or vinyl groups can be added The above comonomers are introduced by copolymerization. Specific examples of such comonomers include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 6-Hydroxyhexyl, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12-Hydroxylauryl (meth)acrylate and (4-Hydroxymethylcyclohexyl)-methyl Hydroxyl-containing monomers such as acrylate and other hydroxyl groups; (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and other carboxyl-containing monomers Monomers; monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrenesulfonic acid or allylsulfonic acid, 2-(meth)acrylamide-2-methanol Monomers containing sulfonic acid groups such as propanesulfonic acid, (meth)acrylamide propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid; 2-hydroxyethyl Phosphate-containing monomers such as acryl phosphate, etc.
又,亦可列舉下列以改質為目的之單體例:(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺及N-羥甲基(甲基)丙烯醯胺、N-羥甲丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺乙酯、(甲基)丙烯酸N,N-二甲基胺乙酯、(甲基)丙烯酸三級丁基胺乙酯等(甲基)丙烯酸烷基胺烷酯系單體;(甲基)丙烯酸甲氧乙酯、(甲基)丙烯酸乙氧乙酯等(甲基)丙烯酸烷氧基烷酯系單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺及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、N-丙烯醯基嗎福林等琥珀醯亞胺系單體;N-環己基馬來亞醯胺及N-異丙基馬來亞醯胺、N-月桂基馬來亞醯胺及N-苯基馬來亞醯胺等馬來亞醯胺系單體;N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體等。In addition, the following examples of monomers for the purpose of modification can also be cited: (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide And N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide and other (N-substituted) amide monomers; (meth)aminoethyl acrylate, (methyl ) N,N-dimethylaminoethyl acrylate, tertiary butylaminoethyl (meth)acrylate and other alkylaminoalkyl (meth)acrylate monomers; methoxyethyl (meth)acrylate, Alkoxyalkyl (meth)acrylate monomers such as ethoxyethyl (meth)acrylate; N-(meth)acryloxymethylene succinimide and N-(meth)acryl Succinyl-6-oxyhexamethylene succinimide, N-(meth)acryl-8-oxyoctamethylene succinimide, N-acrylylmoephrine and other succinimides Amine monomers; maleimides such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide Amine monomers; N-methyl iconamide, N-ethyl iconamide, N-butyl iconamide, N-octyl iconamide, N-2-ethyl Iconimide-based monomers such as ylhexyl iconimide, N-cyclohexyl iconimide, and N-lauryl iconimide.
此外,亦可使用下述單體作為改質單體:乙酸乙烯酯、丙酸乙烯酯、N-乙烯吡咯啶酮、甲基乙烯吡咯啶酮、乙烯吡啶、乙烯哌啶酮、乙烯嘧啶、乙烯哌、乙烯吡、乙烯吡咯、乙烯咪唑、乙烯唑、乙烯嗎福林、N-乙烯羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯己內醯胺等乙烯基系單體;丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體;(甲基)丙烯酸環氧丙酯等含環氧基丙烯酸系單體;(甲基)丙烯酸聚乙二醇、(甲基)丙烯酸聚丙二醇、(甲基)丙烯酸甲氧基乙二醇、(甲基)丙烯酸甲氧基聚丙二醇等二醇系丙烯酸酯單體;(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯及2-甲氧乙基丙烯酸酯等丙烯酸酯系單體等。此外,可列舉異戊二烯、丁二烯、異丁烯、乙烯基醚等。In addition, the following monomers can also be used as modifying monomers: vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, ethylene Piper , vinylpyridine , vinyl pyrrole, vinyl imidazole, vinyl Vinyl monomers such as azoles, vinylmorphine, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinylcaprolactam, etc.; cyanoacrylic acid such as acrylonitrile and methacrylonitrile Ester-based monomers; epoxy-based acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyl (meth)acrylate Glycol-based acrylate monomers such as ethylene glycol and methoxypolypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane (meth)acrylate And acrylate-based monomers such as 2-methoxyethyl acrylate. In addition, isoprene, butadiene, isobutylene, vinyl ether, etc. are mentioned.
進一步,上述以外之可共聚單體可列舉含矽原子之矽烷系單體等。矽烷系單體可列舉如3-丙烯醯氧基丙基三乙氧矽烷、乙烯基三甲氧矽烷、乙烯基三乙氧矽烷、4-乙烯基丁基三甲氧矽烷、4-乙烯基丁基三乙氧矽烷、8-乙烯基辛基三甲氧矽烷、8-乙烯基辛基三乙氧矽烷、10-甲基丙烯醯氧基癸基三甲氧矽烷、10-丙烯醯氧基癸基三甲氧矽烷、10-甲基丙烯醯氧基癸基三乙氧矽烷、10-丙烯醯氧基癸基三乙氧矽烷等。Furthermore, examples of copolymerizable monomers other than those mentioned above include silicon atom-containing silane-based monomers and the like. Silane-based monomers such as 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltrimethoxysilane, Ethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltrimethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane , 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, etc.
另,共聚單體亦可使用下列單體:三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物等具有2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵之多官能性單體;及在聚酯、環氧、胺甲酸乙酯等骨架上附加2個以上之(甲基)丙烯醯基、乙烯基等不飽和雙鍵作為與單體成分相同之官能基的聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯等。In addition, the following monomers can also be used as comonomers: tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bis Phenol A Diglycidyl Ether Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Neopentylthritol Tri(meth)acrylate Ester, neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, caprolactone modified dipenteoerythritol Polyfunctional monomers such as hexa(meth)acrylate and other esterified products of (meth)acrylic acid and polyols having two or more unsaturated double bonds such as (meth)acryl and vinyl groups; and in polyester , Polyester (meth)acrylate with two or more unsaturated double bonds such as (meth)acryl and vinyl added to the skeleton of epoxy and urethane as the same functional group as the monomer component, Epoxy (meth)acrylate, urethane (meth)acrylate, etc.
(甲基)丙烯酸系聚合物在全構成單體之重量比率中係以(甲基)丙烯酸烷酯作為主成分,且(甲基)丙烯酸系聚合物中之前述共聚單體的比率無特別限制,前述共聚單體的比率在全構成單體之重量比率中佔0~20%左右,以0.1~15%左右為宜,0.1~10%左右更佳。The (meth)acrylic polymer contains alkyl (meth)acrylate as the main component in the weight ratio of the total constituent monomers, and the ratio of the aforementioned comonomers in the (meth)acrylic polymer is not particularly limited. , the ratio of the aforementioned comonomer accounts for about 0-20% in the weight ratio of the total constituent monomers, preferably about 0.1-15%, more preferably about 0.1-10%.
從黏著性、耐久性的觀點來看,該等共聚單體中又宜使用含羥基單體、含羧基單體。含羥基單體及含羧基單體可以併用。當黏著劑組成物含有交聯劑時,該等共聚單體會成為交聯劑的反應點。含羥基單體、含羧基單體等於分子間富有與交聯劑之反應性,所以很適合用來提升所得黏著劑層之凝聚性及耐熱性。在重工性之觀點上以含羥基單體為宜,又在兼具耐久性及重工性的觀點上則以含羧基單體為宜。又,添加抗靜電劑時,從可輕易降低電阻值、加濕環境下也容易穩定的觀點來看,宜使用含醯胺基單體,亦可與前述含羥基單體及含羧基單體併用。Among these comonomers, hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesiveness and durability. A hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used in combination. When the adhesive composition contains a cross-linking agent, these comonomers will become the reaction sites of the cross-linking agent. Hydroxyl-containing monomers and carboxyl-containing monomers are rich in reactivity with crosslinking agents between molecules, so they are very suitable for improving the cohesion and heat resistance of the obtained adhesive layer. In terms of reworkability, hydroxyl-containing monomers are suitable, and in terms of both durability and reworkability, carboxyl-containing monomers are suitable. In addition, when adding an antistatic agent, it is preferable to use an amide group-containing monomer from the viewpoint that the resistance value can be easily lowered and that it is easy to stabilize in a humidified environment, and it can also be used in combination with the aforementioned hydroxyl-containing monomer and carboxyl-containing monomer. .
共聚單體含有含羥基單體時,其比率宜為0.01~15重量%,0.03~10重量%較佳,0.05~7重量%更佳。共聚單體含有含羧基單體時,其比率宜為0.05~10重量%,0.1~8重量%較佳,0.2~6重量%更佳。含有含醯胺基單體時,其比率宜為0.1重量%以上。When the comonomer contains a hydroxyl-containing monomer, the ratio is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, more preferably 0.05 to 7% by weight. When the comonomer contains a carboxyl group-containing monomer, the ratio is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight. When an amide group-containing monomer is contained, the ratio is preferably 0.1% by weight or more.
本發明之(甲基)丙烯酸系聚合物通常係使用重量平均分子量在50萬~300萬範圍之物。若考慮耐久性尤其是耐熱性,宜使用重量平均分子量為70萬~270萬之物。更以80萬~250萬為宜。重量平均分子量若小於50萬,在耐熱性觀點來看不宜。又,重量平均分子量若大於300萬,為了調整用以塗敷之黏度,需要大量的稀釋溶劑而增加成本,故不適宜。另,重量平均分子量係指以GPC(凝膠滲透層析術)測定且經聚苯乙烯換算計算所得之值。The (meth)acrylic polymer of the present invention usually uses a weight average molecular weight in the range of 500,000 to 3,000,000. In consideration of durability, especially heat resistance, it is preferable to use one with a weight average molecular weight of 700,000 to 2,700,000. It is more appropriate to use 800,000 to 2.5 million. If the weight average molecular weight is less than 500,000, it is unfavorable from the viewpoint of heat resistance. Also, if the weight average molecular weight exceeds 3 million, a large amount of diluent solvent is required to increase the cost in order to adjust the viscosity for coating, so it is not suitable. In addition, the weight average molecular weight means the value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
這種(甲基)丙烯酸系聚合物之製造可適宜選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等的公知製造方法。此外,所得(甲基)丙烯酸系聚合物可為無規共聚物、嵌段共聚物、接枝共聚物等中之任一者。For the production of such a (meth)acrylic polymer, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. In addition, the obtained (meth)acrylic polymer may be any of random copolymer, block copolymer, graft copolymer, and the like.
就用來形成第1黏著劑層之抗靜電劑來看,從與基底聚合物之相溶性、黏著劑層之透明性的觀點來看,前述例示中又以離子性化合物為佳。特別是在使用以(甲基)丙烯酸系聚合物作為基底聚合物之丙烯酸系黏著劑的情況下,宜使用離子性化合物。從以較少量之添加即可輕易降低電阻值、加濕環境下也容易穩定的觀點來看,離子性化合物宜為離子性液體。Regarding the antistatic agent used to form the first adhesive layer, ionic compounds are preferred in the above examples from the viewpoints of compatibility with the base polymer and transparency of the adhesive layer. Especially in the case of using an acrylic adhesive using a (meth)acrylic polymer as a base polymer, it is preferable to use an ionic compound. The ionic compound is preferably an ionic liquid from the viewpoint that the resistance value can be easily lowered by adding a small amount, and that it is easy to be stable in a humidified environment.
前述黏著劑、抗靜電劑之使用量依該等種類而定,不過以所得第1黏著劑層之表面電阻值成為1×108 ~1×1012 Ω/□的方式予以控制時,譬如,相對於黏著劑之基底聚合物(如(甲基)丙烯酸系聚合物)100重量份,宜在抗靜電劑(譬如為離子性化合物)為20重量份之範圍內作使用。使用0.05重量份以上之抗靜電劑對於提升抗靜電性能而言相當適宜。此外,抗靜電劑(B)宜為0.1重量份以上,更宜為0.5重量份以上。在滿足耐久性的觀點上,宜在20重量份以下作使用,更宜在10重量份以下作使用。The amount of the aforementioned adhesive and antistatic agent used depends on the type, but when controlled so that the surface resistance value of the obtained first adhesive layer becomes 1×10 8 ~1×10 12 Ω/□, for example, With respect to 100 parts by weight of the base polymer (such as (meth)acrylic polymer) of the adhesive, it is preferable to use the antistatic agent (such as an ionic compound) within the range of 20 parts by weight. It is quite appropriate to use more than 0.05 parts by weight of antistatic agent to improve antistatic performance. In addition, the antistatic agent (B) is preferably at least 0.1 parts by weight, more preferably at least 0.5 parts by weight. From the viewpoint of satisfying durability, it is preferably used in an amount of not more than 20 parts by weight, more preferably not more than 10 parts by weight.
又,於形成第1黏著劑層之黏著劑組成物中可含有與基底聚合物對應的交聯劑。譬如,使用(甲基)丙烯酸系聚合物作為基底聚合物時,可使用有機系交聯劑或多官能性金屬螯合物作為交聯劑。有機系交聯劑可列舉異氰酸酯系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合物係多價金屬與有機化合物呈共價鍵結或配位鍵結者。多價金屬原子可列舉Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。有機化合物中可行共價鍵結或配位鍵結之原子可舉如氧原子等,就有機化合物則可列舉烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。In addition, a crosslinking agent corresponding to the base polymer may be contained in the adhesive composition forming the first adhesive layer. For example, when a (meth)acrylic polymer is used as the base polymer, an organic crosslinking agent or a polyfunctional metal chelate compound can be used as the crosslinking agent. Examples of the organic crosslinking agent include isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, and imine crosslinking agents. Multifunctional metal chelates are those in which polyvalent metals and organic compounds are covalently bonded or coordinately bonded. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Atoms that can be covalently bonded or coordinately bonded in organic compounds include oxygen atoms, and organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.
相對於(甲基)丙烯酸系聚合物100重量份,交聯劑之使用量宜為3重量份以下,較宜為0.01~3重量份,更宜為0.02~2重量份,又以0.03~1重量份更佳。Relative to 100 parts by weight of the (meth)acrylic polymer, the amount of the crosslinking agent used is preferably less than 3 parts by weight, more preferably 0.01~3 parts by weight, more preferably 0.02~2 parts by weight, and 0.03~1 Parts by weight are better.
又,於形成第1黏著劑層之黏著劑組成物中可含有矽烷耦合劑及其他添加劑。譬如,可依使用用途適度添加聚丙二醇等聚伸烷基二醇之聚醚化合物、著色劑、顏料等粉體、染料、界面活性劑、可塑劑、賦黏劑、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機或有機充填劑、金屬粉、粒狀、箔狀物等。另,亦可在可控制之範圍內採用添加還原劑之氧化還原系。相對於(甲基)丙烯酸系聚合物100重量份,該等添加劑宜在5重量份以下、較宜在3重量份以下且更宜在1重量份以下之範圍內作使用。In addition, a silane coupling agent and other additives may be contained in the adhesive composition forming the first adhesive layer. For example, polyether compounds of polyalkylene glycols such as polypropylene glycol, powders such as coloring agents and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, and leveling agents can be appropriately added according to the application. , softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, metal powder, granular, foil, etc. In addition, a redox system in which a reducing agent is added can also be used within a controllable range. With respect to 100 parts by weight of the (meth)acrylic polymer, these additives are preferably used in the range of not more than 5 parts by weight, more preferably not more than 3 parts by weight, and more preferably not more than 1 part by weight.
<表面處理層> 賦予表面處理層導電性時,如前述,表面處理層宜形成為表面電阻值為1×107 ~1×1011 Ω/□。對於前述表面處理層,藉由含有抗靜電劑可賦予導電性。表面處理層除了可設置在用於第1偏光薄膜之透明保護薄膜以外,亦可有別於透明保護薄膜另外設置。就前述表面處理層而言,可設置硬塗層、防眩處理層、抗反射層、抗黏層等。用以賦予前述表面處理層導電性的抗靜電劑可使用前述示例之物,惟宜含有選自離子性界面活性劑、導電性微粒子及導電性聚合物中之至少任1種。從光學特性、外觀、抗靜電效果及抗靜電效果在加熱時、加濕時之穩定性的觀點來看,用於表面處理層之抗靜電劑宜為導電性微粒子。<Surface treatment layer> When imparting conductivity to the surface treatment layer, as described above, the surface treatment layer is preferably formed so that the surface resistance value is 1×10 7 to 1×10 11 Ω/□. Conductivity can be imparted to the said surface treatment layer by containing an antistatic agent. In addition to the transparent protective film used for the first polarizing film, the surface treatment layer may be provided separately from the transparent protective film. As the aforementioned surface treatment layer, a hard coat layer, an antiglare treatment layer, an antireflection layer, an antisticking layer, and the like may be provided. The antistatic agent for imparting conductivity to the surface treatment layer can use the ones exemplified above, but preferably contains at least one selected from the group consisting of ionic surfactants, conductive fine particles, and conductive polymers. From the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, the antistatic agent used in the surface treatment layer is preferably conductive fine particles.
前述表面處理層宜為硬塗層。硬塗層之形成材料例如可使用熱可塑性樹脂、利用熱或放射線而硬化之材料。前述材料可列舉熱硬化型樹脂或紫外線硬化型樹脂、電子束硬化型樹脂等的放射線硬化性樹脂。該等中又以紫外線硬化型樹脂為宜,該紫外線硬化型樹脂可藉由利用紫外線照射的硬化處理,以簡單的加工操作有效率地形成硬化樹脂層。該等硬化型樹脂可列舉聚酯系、丙烯酸系、胺甲酸乙酯系、醯胺系、聚矽氧系、環氧系、三聚氰胺系等各種樹脂,且包含該等之單體、寡聚物、聚合物等。從加工速度的迅速性、對於基材之熱損較少的觀點來看,尤以放射線硬化型樹脂特別是紫外線硬化型樹脂為宜。適合使用的紫外線硬化型樹脂可列舉如具有紫外線聚合性官能基者,其中包含具有2個以上特別是3~6個該官能基之丙烯酸系單體或寡聚物成分者。又,紫外線硬化型樹脂中可摻混有光聚合引發劑。The aforementioned surface treatment layer is preferably a hard coat layer. As a material for forming the hard coat layer, for example, a thermoplastic resin, a material cured by heat or radiation can be used. Examples of the aforementioned material include radiation curable resins such as thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among them, an ultraviolet curable resin is preferable, and the ultraviolet curable resin can efficiently form a cured resin layer with a simple processing operation by hardening treatment by ultraviolet irradiation. Such curable resins include polyester-based, acrylic-based, urethane-based, amide-based, polysiloxane-based, epoxy-based, and melamine-based resins, and include monomers and oligomers thereof. , polymers, etc. From the standpoint of rapid processing speed and less heat loss to the substrate, radiation-curable resins, especially ultraviolet-curable resins, are preferable. Examples of suitably used ultraviolet curable resins include those having ultraviolet polymerizable functional groups, those containing acrylic monomers or oligomer components having 2 or more, especially 3 to 6 functional groups. In addition, a photopolymerization initiator may be blended in the ultraviolet curable resin.
另,就前述表面處理層來說,可設置以提升視辨性為目的之防眩處理層或抗反射層。又,於前述硬塗層上可設置防眩處理層或抗反射層。防眩處理層之構成材料無特別限定,譬如可使用放射線硬化型樹脂、熱硬化型樹脂、熱可塑性樹脂等。抗反射層可使用氧化鈦、氧化鋯、氧化矽、氟化鎂等。抗反射層可設置複數層。其他,表面處理層可列舉抗黏層等。In addition, an anti-glare treatment layer or an anti-reflection layer for the purpose of improving visibility may be provided for the above-mentioned surface treatment layer. In addition, an antiglare treatment layer or an antireflection layer may be provided on the aforementioned hard coat layer. The constituent material of the antiglare treatment layer is not particularly limited, and for example, radiation curable resin, thermosetting resin, thermoplastic resin, etc. can be used. For the antireflection layer, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, etc. can be used. The antireflection layer may be provided in plural layers. In addition, examples of the surface treatment layer include an antisticking layer and the like.
前述表面處理層之厚度可按表面處理層種類適宜設定,一般宜為0.1~100μm。譬如,硬塗層之厚度宜為0.5~20μm。硬塗層厚度並無特別限制,不過,太薄會無法獲得作為硬塗層的充分硬度,另外太厚又容易產生破裂或剝離。硬塗層厚度較宜為1~10μm。The thickness of the above-mentioned surface treatment layer can be appropriately set according to the type of surface treatment layer, and generally it is preferably 0.1-100 μm. For example, the thickness of the hard coat layer is preferably 0.5-20 μm. The thickness of the hard coat layer is not particularly limited, but if it is too thin, sufficient hardness cannot be obtained as a hard coat layer, and if it is too thick, cracking or peeling will easily occur. The thickness of the hard coating is preferably 1-10 μm.
前述表面處理層的抗靜電劑、黏結劑(樹脂材料等)之使用量依該等之種類而定,不過宜以所得表面處理層之表面電阻值成為1×107 ~1×1011 Ω/□的方式予以控制。通常,相對於抗靜電劑100重量份,黏結劑宜為1000重量份以下,更宜為10~200重量份。The amount of antistatic agent and binder (resin material, etc.) used in the above-mentioned surface treatment layer depends on the type of these, but the surface resistance value of the obtained surface treatment layer is preferably 1×10 7 ~1×10 11 Ω/ □ way to control. Usually, relative to 100 parts by weight of the antistatic agent, the binder is preferably less than 1000 parts by weight, more preferably 10-200 parts by weight.
<其他層> 對於本發明之附黏著劑層之偏光薄膜,除了前述各層以外,亦可於第1偏光薄膜之設置錨定層之側表面設置易黏著層或施行電暈處理、電漿處理等各種易黏著處理。<Other layers> For the polarizing film with an adhesive layer of the present invention, in addition to the above-mentioned layers, an easy-adhesive layer may be provided on the side surface of the first polarizing film where the anchor layer is provided, or corona treatment, plasma treatment, etc. may be performed. Various easy-adhesive treatments.
以下說明內置型液晶單元B、內置型液晶面板C。The built-in liquid crystal unit B and the built-in liquid crystal panel C will be described below.
(內置型液晶單元B) 如圖2所示,內置型液晶單元B具有液晶層20、從兩面夾持前述液晶層20之第1透明基板41及第2透明基板42,該液晶層20含有在電場不存在之狀態下呈平行配向之液晶分子。又,前述液晶層20與第1透明基板41之間具有觸控感測器部31,前述液晶層20與第2透明基板42之間具有驅動電極兼感測器部32。(Built-in liquid crystal cell B) As shown in FIG. 2, the built-in liquid crystal cell B has a liquid crystal layer 20, a first
用於內置型液晶單元B之液晶層20可使用含有在電場不存在之狀態下呈平行配向之液晶分子的液晶層。就液晶層20來說,適宜使用譬如IPS方式之液晶層。其他,液晶層20譬如可使用TN型或STN型、π型、VA型等任意類型之液晶層。前述液晶層20之厚度例如為1.5μm~4μm左右。As the liquid crystal layer 20 used in the built-in liquid crystal cell B, a liquid crystal layer containing liquid crystal molecules aligned in parallel in the absence of an electric field can be used. For the liquid crystal layer 20, for example, an IPS type liquid crystal layer is suitably used. In addition, for the liquid crystal layer 20 , for example, any type of liquid crystal layer such as TN type, STN type, π type, or VA type can be used. The thickness of the aforementioned liquid crystal layer 20 is, for example, about 1.5 μm˜4 μm.
如上述,內置型液晶單元B於液晶單元內具有觸控感測器部31及驅動電極兼感測器部32,液晶單元外部則不具觸控感測器部。即,在比內置型液晶單元B之第1透明基板41更靠視辨側(比內置型液晶面板C之第1黏著劑層2更靠液晶單元側)之側未設置導電層(表面電阻值為1×1013
Ω/□以下)。又,在圖2中記載之內置型液晶面板C顯示了各構成之順序,不過於內置型液晶面板C可適度具有其他構成。可於液晶單元上(第1透明基板41)設置彩色濾光片基板。As mentioned above, the built-in liquid crystal unit B has the
形成前述透明基板之材料可列舉如玻璃或聚合物薄膜。前述聚合物薄膜可列舉如聚對苯二甲酸乙二酯、聚環烯烴、聚碳酸酯等。前述透明基板係由玻璃形成時,其厚度例如為0.1mm~1mm左右。前述透明基板係由聚合物薄膜形成時,其厚度例如為10μm~200μm左右。上述透明基板可於其表面具有易黏著層或硬塗層。The material for forming the aforementioned transparent substrate may be, for example, glass or a polymer film. Examples of the aforementioned polymer film include polyethylene terephthalate, polycycloolefin, and polycarbonate. When the aforementioned transparent substrate is formed of glass, its thickness is, for example, about 0.1 mm to 1 mm. When the aforementioned transparent substrate is formed of a polymer film, its thickness is, for example, about 10 μm˜200 μm. The above-mentioned transparent substrate may have an easy-adhesive layer or a hard coat layer on its surface.
形成觸控感測器部31(電容感測器)、驅動電極兼感測器部32作為透明導電層。前述透明導電層之構成材料無特別限定,可列舉如金、銀、銅、鉑、鈀、鋁、鎳、鉻、鈦、鐵、鈷、錫、鎂、鎢等金屬及該等金屬之合金等。又,前述透明導電層之構成材料可列舉銦、錫、鋅、鉀、銻、鋯、鎘之金屬氧化物,具體上可列舉氧化銦、氧化錫、氧化鈦、氧化鎘及由該等之混合物等所構成之金屬氧化物。其他可使用由碘化銅等所構成之其他金屬化合物等。前述金屬氧化物中可視需求進一步含有上述群組所示金屬原子之氧化物。例如,適合使用含有氧化錫之氧化銦(ITO)、含銻之氧化錫等,尤宜使用ITO。ITO宜含有氧化銦80~99重量%及氧化錫1~20重量%。A touch sensor part 31 (capacitive sensor) and a driving electrode and
觸控感測器部31係配置在第1偏光薄膜1與液晶層20之間,通常可以透明電極圖案形成在第1透明基板41上(內置型液晶單元B內之液晶層20側)。關於驅動電極兼感測器部32亦可利用常法形成透明電極圖案。上述透明電極圖案通常係與形成於透明基板端部之繞線(routing wires;未圖示)電連接,上述繞線則與控制器IC(未圖示)連接。透明電極圖案之形狀除了櫛形以外,可視用途採用任意形狀如條紋狀或菱形形狀等。透明電極圖案之高度例如為10nm~100nm,寬為0.1mm~5mm。The
(內置型液晶面板C) 如圖2所示,本發明之內置型液晶面板C可於內置型液晶單元B之視辨側具有附黏著劑層之偏光薄膜A,且於其相反側具有第2偏光薄膜11。前述附黏著劑層之偏光薄膜A係未夾導電層並透過前述第1黏著劑層2配置於前述內置型液晶單元B之第1透明基板41之側。另一方面,於前述內置型液晶單元B之第2透明基板42之側透過第2黏著劑層12配置有第2偏光薄膜11。前述附黏著劑層之偏光薄膜A的第1偏光薄膜1、第2偏光薄膜11係以各偏光件之透射軸(或吸收軸)直交的方式配置在液晶層20兩側。(Built-in liquid crystal panel C) As shown in Figure 2, the built-in liquid crystal panel C of the present invention can have polarizing film A with an adhesive layer on the viewing side of built-in liquid crystal unit B, and has a second polarizing film A on its opposite side. Polarizing
第2偏光薄膜11可使用在第1偏光薄膜1中所說明之物。第2偏光薄膜11可使用與第1偏光薄膜1相同之物,亦可使用不同物。As the second
於第2黏著劑層12之形成可使用第1黏著劑層2中所說明之黏著劑。用來形成第2黏著劑層12之黏著劑可使用與第1黏著劑層2相同之物,亦可使用不同物。第2黏著劑層12之厚度無特別限制,例如為1~100μm左右。宜為2~50μm,較宜為2~40μm,更宜為5~35μm。The adhesive described in the first
又,在內置型液晶面板C中,可在前述附黏著劑層之偏光薄膜A之選自前述表面處理層4、錨定層3及第1黏著劑層2中之至少任1層側面設置導通結構51或50。圖2中例示出在表面處理層4及第1偏光薄膜1之側面設有導通結構51之情況。又,圖2中例示出在錨定層3及第1偏光薄膜2之側面設有導通結構50之情況。另外,圖2中設有導通結構51、50,且導通結構可設在選自含有抗靜電劑之表面處理層4、錨定層3及第1黏著劑層2中之至少任1層的側面。譬如,就算有2層含有抗靜電劑,當錨定層3及第1黏著劑層2之2層已賦予有導電性時,只要有設置導通結構50,可不設導通結構51。導通結構51、50可設於選自前述表面處理層4、錨定層3及第1黏著劑層2中之至少任1層的側面全部,亦可局部設置。局部設置前述導通結構時,為了確保在側面之導通,前述導通結構宜以佔前述側面面積之1面積%以上且理想為3面積%以上之比率來設置。Also, in the built-in liquid crystal panel C, conduction can be provided on the side of at least any one layer selected from the aforementioned
藉由前述導通結構51、50,可從選自前述表面處理層4、錨定層3及第1黏著劑層2中之至少任1層的側面,於其他的適當位置連接電位,藉以抑制靜電發生。形成導通結構51、50之材料可列舉如銀、金或其他金屬糊等導電性糊,其他亦可使用導電性黏著劑及其他任意的適當導電材料。導通結構51、50亦可以由選自前述表面處理層4、錨定層3及第1黏著劑層2中之至少任1層的側面延伸的線狀形成。Through the above-mentioned
其他,配置在液晶層20之視辨側的第1偏光薄膜1及配置在液晶層20之視辨側的相反側之第2偏光薄膜11,可分就各配置位置的適性與其他光學薄膜積層使用。又,前述其他光學薄膜可舉如:反射板或反透射板、相位差板(含1/2或1/4等波長板)、視覺補償薄膜、增亮薄膜等可用於形成液晶顯示裝置等的光學層。該等可使用1層或2層以上。In addition, the first polarizing film 1 arranged on the viewing side of the liquid crystal layer 20 and the second
(液晶顯示裝置) 使用本發明之內置型液晶面板C的內嵌觸控感測機能之液晶顯示裝置可適當使用於照明系統使用背光或反射板等用以形成液晶顯示裝置的構件。 實施例(Liquid Crystal Display Device) A liquid crystal display device with a built-in touch sensor function using the built-in liquid crystal panel C of the present invention can be suitably used in an illumination system using a backlight or a reflector as a member for forming a liquid crystal display device. Example
以下,以製造例、實施例來具體說明本發明,惟本發明不受該等實施例限定。另外,各例中之份及%皆為重量基準。以下,未特別規定之室溫放置條件全部為23℃且65%RH。Hereinafter, the present invention will be described concretely with reference to manufacturing examples and examples, but the present invention is not limited by these examples. In addition, the parts and % in each example are based on weight. Below, all room temperature storage conditions not specified in particular are 23°C and 65%RH.
<測定(甲基)丙烯酸系聚合物之重量平均分子量> 以GPC(凝膠滲透層析術)測定(甲基)丙烯酸系聚合物的重量平均分子量(Mw)。針對Mw/Mn亦同樣進行測定。 ・分析裝置:東曹公司製、HLC-8120GPC ・管柱:東曹公司製、G7000HXL +GMHXL +GMHXL ・管柱尺寸:各7.8mmφ×30cm,計90cm ・管柱溫度:40℃ ・流量:0.8mL/min ・注入量:100μL ・溶析液:四氫呋喃 ・檢測器:示差折射計(RI) ・標準試料:聚苯乙烯<Measurement of the weight average molecular weight of the (meth)acrylic polymer> The weight average molecular weight (Mw) of the (meth)acrylic polymer was measured by GPC (gel permeation chromatography). Mw/Mn was also measured similarly. ・Analyzer: Tosoh Corporation, HLC-8120GPC ・Column: Tosoh Corporation, G7000H XL +GMH XL +GMH XL ・Column size: 7.8mmφ×30cm each, 90cm in total ・Column temperature: 40℃・ Flow rate: 0.8mL/min ・Injection volume: 100μL ・Eluent: THF ・Detector: Differential refractometer (RI) ・Standard sample: Polystyrene
<製作偏光薄膜> 將厚80μm之聚乙烯醇薄膜放置在速度比不同的輥件間,在30℃、0.3%濃度之碘溶液中進行1分鐘染色並同時延伸至3倍。之後,在60℃且含有4%濃度之硼酸及10%濃度之碘化鉀的水溶液中浸漬0.5分鐘的同時進行延伸使總延伸倍率成為6倍。接著,在30℃且含有1.5%濃度之碘化鉀的水溶液中浸漬10秒鐘藉以洗淨後,在50℃下乾燥4分鐘而獲得厚30μm之偏光件。於該偏光件兩面利用聚乙烯醇系黏著劑貼合經皂化處理之厚80μm之三醋酸纖維素薄膜,作成偏光薄膜。<Making Polarizing Film> Place a polyvinyl alcohol film with a thickness of 80 μm between rollers with different speed ratios, dye it in 0.3% iodine solution at 30°C for 1 minute and extend it to 3 times at the same time. Thereafter, it was stretched while being immersed in an aqueous solution containing 4% boric acid and 10% potassium iodide at 60° C. for 0.5 minutes so that the total stretching ratio became 6 times. Next, it was immersed in an aqueous solution containing 1.5% potassium iodide at 30° C. for 10 seconds to clean it, and then dried at 50° C. for 4 minutes to obtain a polarizer with a thickness of 30 μm. A saponified 80 μm thick cellulose triacetate film was bonded to both sides of the polarizer with a polyvinyl alcohol-based adhesive to form a polarizing film.
<形成表面處理層> 在實施例1、2、10中,於上述所得偏光薄膜單面以乾燥後厚度成為表1所示厚度的方式予以調整後,以線棒塗佈含有ATO(銻摻雜氧化錫)粒子之紫外線硬化型樹脂分散液(SUMITOMO OSAKA CEMENT Co.,Ltd.製、ASHC-101)作為抗靜電性硬塗層之形成材,然後在80℃下加熱乾燥1分鐘而形成塗膜。接著,以金屬鹵素燈對塗膜照射300mJ/cm2 之紫外線,使塗膜硬化而形成抗靜電性之硬塗層。<Formation of Surface Treatment Layer> In Examples 1, 2, and 10, one side of the polarizing film obtained above was adjusted so that the thickness after drying became the thickness shown in Table 1, and then ATO (antimony-doped UV-curable resin dispersion of tin oxide) particles (SUMITOMO OSAKA CEMENT Co., Ltd., ASHC-101) is used as a forming material for an antistatic hard coat layer, and then heated and dried at 80°C for 1 minute to form a coating film . Next, the coating film was irradiated with 300mJ/cm 2 of ultraviolet rays by a metal halide lamp to harden the coating film to form an antistatic hard coat layer.
另一方面,在實施例3~9及比較例1、2中形成了不含抗靜電劑之硬塗層。前述不含抗靜電劑之硬塗層用的塗敷液係將紫外線硬化型丙烯酸系樹脂(DIC Co.製,UNIDIC 17-806)100份、光聚合引發劑(Ciba Specialty Chemicals公司製,IRGACURE 184)3份及甲苯100份混合而調製。使用該調製液,以乾燥後厚度成為表1所示厚度的方式予以調整後,以線棒塗佈後在80℃下加熱乾燥1分鐘而形成塗膜。接著,以金屬鹵素燈對塗膜照射300mJ/cm2 之紫外線,使塗膜硬化而形成硬塗層。On the other hand, in Examples 3-9 and Comparative Examples 1 and 2, a hard coat layer not containing an antistatic agent was formed. The aforementioned coating solution for the hard coat layer containing no antistatic agent comprises 100 parts of ultraviolet curable acrylic resin (manufactured by DIC Co., UNIDIC 17-806), photopolymerization initiator (manufactured by Ciba Specialty Chemicals, IRGACURE 184 ) and 100 parts of toluene were mixed and prepared. Using this preparation solution, after drying, it adjusted so that the thickness may become the thickness shown in Table 1, and after coating with a wire bar, it heat-dried at 80 degreeC for 1 minute, and formed the coating film. Next, the coating film was irradiated with 300 mJ/cm 2 of ultraviolet light with a metal halide lamp to harden the coating film to form a hard coat layer.
(調製錨定層形成材) 在實施例9中,將以固體成分計含有10~50重量%之噻吩系聚合物的溶液(商品名:Denatron P-580W、Nagase ChemteX Co., Ltd.製)8.6份、含有含唑啉基丙烯酸聚合物之溶液(商品名:Epocros WS-700、(股)日本觸媒製)1份及水90.4份混合,調製出固體成分濃度為0.5重量%之錨定層形成用塗佈液。所得錨定層形成用塗佈液含有0.04重量%之聚噻吩系聚合物及0.25重量%之含唑啉基丙烯酸聚合物。(Preparation of an anchor layer forming material) In Example 9, a solution containing 10 to 50% by weight of a thiophene polymer in terms of solid content (trade name: Denatron P-580W, manufactured by Nagase ChemteX Co., Ltd.) 8.6 servings, containing Mix 1 part of an oxazoline-based acrylic polymer solution (trade name: Epocros WS-700, manufactured by Nippon Shokubai Co., Ltd.) and 90.4 parts of water to prepare a coating for forming an anchor layer with a solid content concentration of 0.5% by weight. liquid. The obtained coating solution for forming an anchor layer contained 0.04% by weight of a polythiophene-based polymer and 0.25% by weight of a polythiophene-based polymer containing Azoline-based acrylic polymer.
(形成錨定層) 將該錨定層形成用塗佈液以乾燥後厚度成為表1所示厚度的方式塗佈於上述偏光薄膜之單面(未設置硬塗層之側),在80℃下乾燥2分鐘而形成錨定層。所得錨定層中分別含有8重量%之噻吩系聚合物及50重量%之含唑啉基丙烯酸聚合物。(Formation of Anchor Layer) The coating solution for forming an anchor layer was coated on one side of the above-mentioned polarizing film (the side not provided with a hard coat layer) so that the thickness after drying became the thickness shown in Table 1, and heated at 80° C. Dry for 2 minutes to form an anchor layer. The resulting anchor layer contains 8% by weight of thiophene polymer and 50% by weight of Azoline-based acrylic polymer.
(調製丙烯酸系聚合物) 於具備攪拌葉片、溫度計、氮氣導入管、冷卻器之4口燒瓶內饋入單體混合物,該單體混合物含有丙烯酸丁酯74.8份、苯氧基乙基丙烯酸酯23份、N-乙烯基-2-吡咯啶酮(NVP)0.5份、丙烯酸0.3份、丙烯酸4-羥丁酯0.4份。接著,於前述單體混合物(固體成分)100份連同乙酸乙酯100份一同饋入作為聚合引發劑之2,2’-偶氮雙異丁腈0.1份,緩慢攪拌的同時導入氮氣進行氮取代後,將燒瓶內液溫保持在55℃附近進行8小時聚合反應,調製出重量平均分子量(Mw)160萬且Mw/Mn=3.7之丙烯酸系聚合物溶液。(Preparation of acrylic polymer) Feed the monomer mixture into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler. The monomer mixture contains 74.8 parts of butyl acrylate, 23 parts of phenoxyethyl acrylate 0.5 parts of N-vinyl-2-pyrrolidone (NVP), 0.3 parts of acrylic acid, and 0.4 parts of 4-hydroxybutyl acrylate. Next, feed 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator into 100 parts of the aforementioned monomer mixture (solid content) together with 100 parts of ethyl acetate, and introduce nitrogen gas while stirring slowly to carry out nitrogen substitution. Afterwards, the liquid temperature in the flask was kept at around 55° C. to carry out polymerization reaction for 8 hours to prepare an acrylic polymer solution with a weight average molecular weight (Mw) of 1.6 million and Mw/Mn=3.7.
(調製黏著劑組成物) 相對於上述所得丙烯酸系聚合物溶液之固體成分100份,以表1所示使用量摻合表1所示離子性化合物,並進一步摻合異氰酸酯交聯劑(三井化學公司製TAKENATE D160N,三羥甲丙烷六亞甲基二異氰酸酯)0.1份、過氧化苯甲醯(日本油脂公司製NYPER BMT)0.3份及γ-環氧丙氧基丙基甲氧矽烷(信越化學工業公司製:KBM-403)0.2份,調製出丙烯酸系黏著劑組成物溶液。(Preparation of adhesive composition) With respect to 100 parts of the solid content of the acrylic polymer solution obtained above, the ionic compound shown in Table 1 was blended in the amount shown in Table 1, and an isocyanate crosslinking agent (Mitsui Chemicals Takenate D160N manufactured by the company, 0.1 parts of trimethylolpropane hexamethylene diisocyanate), 0.3 parts of benzoyl peroxide (NYPER BMT manufactured by NOF Corporation), and γ-glycidoxypropylmethoxysilane (Shin-Etsu Chemical Co., Ltd. Industrial Co., Ltd.: KBM-403) 0.2 parts to prepare an acrylic adhesive composition solution.
(形成黏著劑層) 接著,將上述丙烯酸系黏著劑組成物溶液以乾燥後之黏著劑層厚度為表1所示厚度的方式塗佈於業經聚矽氧系剝離劑處理之聚對苯二甲酸乙二酯薄膜(分離薄膜:Mitsubishi Chemical Polyester Film Co., Ltd.製,MRF38)的單面上,在155℃下乾燥1分鐘而於分離薄膜表面形成黏著劑層。再將該黏著劑層轉印至形成有錨定層之偏光薄膜或未形成錨定層之偏光薄膜上。(Formation of Adhesive Layer) Next, the above-mentioned acrylic adhesive composition solution was applied to the polyterephthalic acid treated with a silicone release agent so that the thickness of the adhesive layer after drying was as shown in Table 1. One side of an ethylene glycol ester film (separation film: manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) was dried at 155° C. for 1 minute to form an adhesive layer on the surface of the separation film. Then transfer the adhesive layer to the polarized film with the anchor layer or the polarized film without the anchor layer.
實施例1~10及比較例1、2 以表1所示組合於上述所得偏光薄膜單面(未設置硬塗層之側)依序形成錨定層及黏著劑層,製作出附黏著劑層之偏光薄膜。Examples 1-10 and Comparative Examples 1 and 2 were combined as shown in Table 1 on one side of the polarizing film obtained above (the side not provided with a hard coat layer) to sequentially form an anchor layer and an adhesive layer to produce an adhesive layer The polarizing film.
另,在實施例1~8、10及比較例1、2中未形成錨定層。又,在實施例1、2及比較例1中,於黏著劑組成物之調製未摻合離子性化合物。In addition, no anchor layer was formed in Examples 1-8, 10 and Comparative Examples 1, 2. In addition, in Examples 1 and 2 and Comparative Example 1, no ionic compound was blended in the preparation of the adhesive composition.
針對上述實施例及比較例中所得附黏著劑層之偏光薄膜進行以下評估。評估結果顯示於表1。The following evaluations were performed on the polarizing film with the adhesive layer obtained in the above examples and comparative examples. The evaluation results are shown in Table 1.
<表面電阻值(Ω/□):導電性> 分就表面處理層、錨定層、黏著劑層測定表面電阻值。 表面處理層的表面電阻值係針對附粘著劑層之偏光薄膜的表面處理層進行測定。 錨定層之表面電阻值係針對形成黏著劑層前之附錨定層之偏光薄膜的錨定層側表面進行測定。未形成錨定層時係測定偏光薄膜表面的表面電阻值。 黏著劑層之表面電阻值係針對形成於分離薄膜上之黏著劑層表面進行測定。<Surface resistance value (Ω/□): conductivity> The surface resistance value was measured for the surface treatment layer, anchor layer, and adhesive layer. The surface resistance value of the surface treatment layer was measured with respect to the surface treatment layer of the polarizing film to which the adhesive layer was attached. The surface resistance value of the anchor layer is measured on the anchor layer side surface of the polarizing film with the anchor layer before the adhesive layer is formed. When the anchor layer was not formed, the surface resistance value of the surface of the polarizing film was measured. The surface resistance value of the adhesive layer was measured on the surface of the adhesive layer formed on the separation film.
<ESD試驗> 從附黏著劑層之偏光薄膜剝去分離薄膜後,如圖2所示貼合至內置型液晶單元之視辨側。接著,於已貼合之偏光薄膜側面部以覆蓋硬塗層、偏光薄膜、錨定層、黏著劑層之各側面部的方式塗佈寬5mm的銀糊並與外部之接地電極連接。又,將內置型液晶單元內部之透明電極圖案周邊部的繞線配線(未圖示)與控制器IC(未圖示)連接,製作出內嵌觸控感測機能之液晶顯示裝置。在施加電壓10kV下對該液晶顯示裝置之偏光薄膜面發射靜電放電槍(Electrostatic discharge Gun),測定因電氣而出現白斑之部分消失的時間,並以下述基準進行判斷。惟,實施例1中未以銀糊形成導通結構。 (評估基準) ◎:3秒以內。 〇:超過3秒至5秒以內。 △:超過5秒至20秒以內。 ×:超過20秒。<ESD Test> After peeling off the separation film from the polarizing film with the adhesive layer attached, it was attached to the viewing side of the built-in liquid crystal cell as shown in Fig. 2 . Next, a silver paste with a width of 5mm was coated on the sides of the laminated polarizing film to cover the hard coat layer, polarizing film, anchor layer, and adhesive layer, and connected to the external ground electrode. In addition, the wiring (not shown) around the transparent electrode pattern inside the built-in liquid crystal cell is connected to the controller IC (not shown) to manufacture a liquid crystal display device with built-in touch sensing function. An electrostatic discharge gun (Electrostatic discharge Gun) was fired on the polarizing film surface of the liquid crystal display device under an applied voltage of 10 kV, and the time for disappearance of the part with white spots due to electricity was measured, and judged according to the following criteria. However, in Example 1, no conductive structure was formed with silver paste. (Evaluation criteria) ⊚: Within 3 seconds. 〇: More than 3 seconds to less than 5 seconds. Δ: More than 5 seconds to less than 20 seconds. ×: more than 20 seconds.
<TSP感度> 在使用ESD試驗中所製作之內嵌觸控感測機能之液晶顯示裝置的輸入顯示裝置之狀態下進行肉眼觀察,確認有無故障。 〇:無故障。 ×:有故障。<TSP Sensitivity> Observe with naked eyes in the state of using the input display device of the liquid crystal display device with built-in touch sensing function produced in the ESD test to confirm whether there is any failure. 〇: No failure. X: There is a malfunction.
<導通可靠性:ESD加濕試驗後> 將偏光薄膜側面部已塗佈銀糊之前述內置型液晶單元在60℃/90%RH之氣體環境下施行500小時處理後,實施上述ESD試驗。<Continuity reliability: after ESD humidification test> The above-mentioned ESD test was carried out after treating the built-in liquid crystal cell with the silver paste coated on the side of the polarizing film for 500 hours in an atmosphere of 60°C/90%RH.
[表1]表1中,Li-TFSI表示雙(三氟甲烷磺醯基)醯亞胺鋰,MPP-TFSI表示雙(三氟甲烷磺醯基)醯亞胺甲基丙基吡咯啶鎓,EMI‐FSI表示雙(氟磺醯基)醯亞胺1-乙基-3-甲基咪唑啉鎓,EMP‐TFSI表示雙(三氟甲烷磺醯基)醯亞胺乙基甲基吡咯啶鎓。[Table 1] In Table 1, Li-TFSI means lithium bis(trifluoromethanesulfonyl)imide, MPP-TFSI means bis(trifluoromethanesulfonyl)imidomethylpropylpyrrolidinium, and EMI-FSI means Bis(fluorosulfonyl)imide 1-ethyl-3-methylimidazolinium, EMP-TFSI stands for bis(trifluoromethanesulfonyl)imide ethylmethylpyrrolidinium.
1‧‧‧第1偏光薄膜
2‧‧‧第1黏著劑層
3‧‧‧錨定層
4‧‧‧表面處理層
11‧‧‧第2偏光薄膜
12‧‧‧第2黏著劑層
20‧‧‧液晶層
31‧‧‧觸控感測器部
32‧‧‧驅動電極兼感測器部
41‧‧‧第1透明基板
42‧‧‧第2透明基板
50、51‧‧‧導通結構
A‧‧‧附黏著劑層之偏光薄膜
B‧‧‧內置型液晶單元
C‧‧‧內置型液晶面板1‧‧‧The first
圖1係顯示本發明之附內嵌觸控感測機能之液晶單元用黏著劑層之偏光薄膜一例的截面圖。 圖2係顯示本發明之內嵌觸控感測機能之液晶面板(內置型)一例的截面圖。FIG. 1 is a cross-sectional view showing an example of a polarizing film with an adhesive layer for a liquid crystal cell embedded with a touch sensing function of the present invention. FIG. 2 is a cross-sectional view showing an example of a liquid crystal panel (built-in type) with embedded touch sensing function according to the present invention.
1‧‧‧第1偏光薄膜 1‧‧‧The first polarizing film
2‧‧‧第1黏著劑層 2‧‧‧The first adhesive layer
3‧‧‧錨定層 3‧‧‧anchor layer
4‧‧‧表面處理層 4‧‧‧Surface treatment layer
11‧‧‧第2偏光薄膜 11‧‧‧The second polarizing film
12‧‧‧第2黏著劑層 12‧‧‧The second adhesive layer
20‧‧‧液晶層 20‧‧‧LCD layer
31‧‧‧觸控感測器部 31‧‧‧Touch sensor department
32‧‧‧驅動電極兼感測器部 32‧‧‧Drive electrode and sensor part
41‧‧‧第1透明基板 41‧‧‧The first transparent substrate
42‧‧‧第2透明基板 42‧‧‧Second transparent substrate
50、51‧‧‧導通結構 50, 51‧‧‧conduction structure
A‧‧‧附黏著劑層之偏光薄膜 A‧‧‧Polarizing film with adhesive layer
B‧‧‧內置型液晶單元 B‧‧‧Built-in LCD unit
C‧‧‧內置型液晶面板 C‧‧‧Built-in LCD panel
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JP7058815B1 (en) | 2019-12-13 | 2022-04-22 | 日東電工株式会社 | Optical film and liquid crystal panel with adhesive layer |
KR102670167B1 (en) * | 2020-08-10 | 2024-05-28 | 삼성에스디아이 주식회사 | Polarizing plate and optical display apparatus comprising the same |
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Also Published As
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WO2017057102A1 (en) | 2017-04-06 |
KR20180062460A (en) | 2018-06-08 |
KR102686627B1 (en) | 2024-07-22 |
JP6913435B2 (en) | 2021-08-04 |
TW201721244A (en) | 2017-06-16 |
JP2017068026A (en) | 2017-04-06 |
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