TW202332942A - Sensor laminate - Google Patents
Sensor laminate Download PDFInfo
- Publication number
- TW202332942A TW202332942A TW111147182A TW111147182A TW202332942A TW 202332942 A TW202332942 A TW 202332942A TW 111147182 A TW111147182 A TW 111147182A TW 111147182 A TW111147182 A TW 111147182A TW 202332942 A TW202332942 A TW 202332942A
- Authority
- TW
- Taiwan
- Prior art keywords
- transparent conductive
- layer
- conductive film
- polarizer
- conductive layer
- Prior art date
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K59/10—OLED displays
Abstract
Description
本發明涉及一種感測器積層體。The present invention relates to a sensor laminate.
以往，作為用於觸控感測器之電極等的透明導電性薄膜，大多使用透明樹脂薄膜上形成有銦-錫複合氧化物層(ITO層)等金屬氧化物層的透明導電性薄膜。但，形成有金屬氧化物層之透明導電性薄膜其撓曲性不足，故不易使用於撓性顯示器等需要撓曲性之用途上。因此，近年來針對撓曲性優異之透明導電性薄膜，提出了一種具備含金屬奈米線之導電層的透明導電性薄膜。Conventionally, as transparent conductive films used for electrodes of touch sensors, etc., a transparent conductive film in which a metal oxide layer such as an indium-tin composite oxide layer (ITO layer) is formed on a transparent resin film is often used. However, the transparent conductive film formed with the metal oxide layer has insufficient flexibility, so it is not easy to be used in applications requiring flexibility such as flexible displays. Therefore, in recent years, as a transparent conductive film having excellent flexibility, a transparent conductive film having a conductive layer containing metal nanowires has been proposed.
另一方面，近年來以液晶顯示裝置及電致發光(EL)顯示裝置(例如有機EL顯示裝置、無機EL顯示裝置)為代表之影像顯示裝置急速普及。影像顯示裝置代表上係使用偏光板及相位差板。在實際應用上，係廣泛使用偏光板、相位差板及黏著劑層一體化而成的附相位差層之偏光板(例如專利文獻1)。 先前技術文獻 專利文獻 On the other hand, in recent years, image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices (eg, organic EL display devices, inorganic EL display devices) have rapidly become popular. Typical image display devices use polarizing plates and phase difference plates. In practical applications, polarizing plates with a retardation layer that are integrated with a polarizing plate, a retardation plate and an adhesive layer are widely used (for example, Patent Document 1). Prior technical literature patent documents
專利文獻1：日本專利第3325560號公報 專利文獻2：日本專利特表2009-505358號公報 Patent Document 1: Japanese Patent No. 3325560 Patent Document 2: Japanese Patent Publication No. 2009-505358
發明欲解決之課題 本發明人等發現，若使用具備上述這種含金屬奈米線的透明導電層之透明導電性薄膜作為電極，並將偏光板配置於該透明導電性薄膜上而構成感測器積層體，該金屬奈米線的劣化會變顯著，從而發生透明導電性薄膜之導電性降低。本發明是為了解決所述課題而成者，其主要目的在於提供一種感測器積層體，其具備偏光板與含金屬奈米線之透明導電性薄膜，且已抑制住透明導電性薄膜之導電性降低。 The problem to be solved by the invention The present inventors discovered that if a transparent conductive film having a transparent conductive layer containing metal nanowires as described above is used as an electrode, and a polarizing plate is disposed on the transparent conductive film to form a sensor laminate, the sensor laminate can achieve The deterioration of the metal nanowires will become significant, resulting in a decrease in the conductivity of the transparent conductive film. The present invention is made in order to solve the above-mentioned problems, and its main purpose is to provide a sensor laminate that includes a polarizing plate and a transparent conductive film containing metal nanowires, and has suppressed conductivity of the transparent conductive film. Sexuality is reduced.
用以解決課題之手段 本發明感測器積層體具備：透明導電性薄膜；及配置於該透明導電性薄膜之至少單側的偏光板；該透明導電性薄膜具備含金屬奈米線之透明導電層；該偏光板具備偏光件；且該偏光件與該透明導電層之距離為25µm以上且小於70µm。 在一實施形態中，係利用配置於該偏光件與該透明導電層之間的透明導電性薄膜側結構體，來確保上述偏光件與透明導電層之距離，且該透明導電性薄膜側結構體係上述偏光板之該偏光件以外的結構體。 在一實施形態中，上述透明導電性薄膜側結構體係從偏光件側起依序具備第1相位差層、第2相位差層及黏著劑層。 在一實施形態中，上述透明導電性薄膜具備透明基材與配置於該透明基材之至少單側的上述透明導電層；且該透明基材係由環烯烴系樹脂構成。 means to solve problems The sensor laminate of the present invention is provided with: a transparent conductive film; and a polarizing plate arranged on at least one side of the transparent conductive film; the transparent conductive film is provided with a transparent conductive layer containing metal nanowires; the polarizing plate is provided with Polarizer; and the distance between the polarizer and the transparent conductive layer is more than 25µm and less than 70µm. In one embodiment, a transparent conductive film side structure disposed between the polarizer and the transparent conductive layer is used to ensure the distance between the polarizer and the transparent conductive layer, and the transparent conductive film side structure system A structure other than the polarizer of the above-mentioned polarizing plate. In one embodiment, the transparent conductive film side structural system includes a first retardation layer, a second retardation layer and an adhesive layer in order from the polarizer side. In one embodiment, the transparent conductive film includes a transparent base material and the transparent conductive layer disposed on at least one side of the transparent base material; and the transparent base material is made of a cycloolefin-based resin.
發明效果 根據本發明實施形態，可提供一種感測器積層體，其具備偏光板與含金屬奈米線之透明導電性薄膜，且已抑制住透明導電性薄膜之導電性降低。 Invention effect According to an embodiment of the present invention, it is possible to provide a sensor laminate that includes a polarizing plate and a transparent conductive film containing metal nanowires, and in which conductivity reduction of the transparent conductive film is suppressed.
以下說明本發明之實施形態，惟本發明不受該等實施形態所限。Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
(用語及符號之定義) 本說明書中之用語及符號之定義如下。 (1)折射率(nx、ny、nz) 「nx」為面內折射率達最大之方向(亦即慢軸方向)的折射率，「ny」為在面內與慢軸正交之方向(亦即快軸方向)的折射率，而「nz」為厚度方向的折射率。 (2)面內相位差(Re) 「Re(λ)」係在23℃下以波長λnm之光測定之面內相位差。例如，「Re(550)」係在23℃下以波長550nm之光測定之面內相位差。Re(λ)可於令層(薄膜)之厚度為d(nm)時，藉由式：Re(λ)=(nx-ny)×d求出。 (3)厚度方向之相位差(Rth) 「Rth(λ)」係在23℃下以波長λnm之光測定之厚度方向之相位差。例如，「Rth(550)」係在23℃下以波長550nm之光測定之厚度方向之相位差。Rth(λ)可於令層(薄膜)厚度為d(nm)時，藉由式：Rth(λ)=(nx-nz)×d求出。 (4)Nz係數 Nz係數可藉由Nz=Rth/Re求出。 (5)角度 本說明書中提及角度時，該角度包含相對於基準方向往順時針方向及逆時針方向兩者。因此，例如「45°」係指±45°。 (Definition of terms and symbols) The definitions of terms and symbols in this manual are as follows. (1)Refractive index (nx, ny, nz) "nx" is the refractive index in the direction where the in-plane refractive index reaches the maximum (that is, the slow axis direction), "ny" is the refractive index in the direction that is orthogonal to the slow axis in the plane (that is, the fast axis direction), and " nz" is the refractive index in the thickness direction. (2) In-plane phase difference (Re) "Re(λ)" is the in-plane phase difference measured with light of wavelength λnm at 23°C. For example, "Re(550)" is the in-plane phase difference measured using light with a wavelength of 550 nm at 23°C. Re(λ) can be calculated by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (thin film) is d(nm). (3) Phase difference in thickness direction (Rth) "Rth(λ)" is the phase difference in the thickness direction measured with light of wavelength λnm at 23°C. For example, "Rth(550)" is the phase difference in the thickness direction measured at 23°C using light with a wavelength of 550 nm. Rth(λ) can be calculated by the formula: Rth(λ)=(nx-nz)×d when the layer (film) thickness is d(nm). (4)Nz coefficient The Nz coefficient can be found by Nz=Rth/Re. (5)Angle When an angle is mentioned in this specification, the angle includes both clockwise and counterclockwise directions relative to the reference direction. So, for example, "45°" means ±45°.
A.感測器積層體的整體構成
圖1係本發明一實施形態之感測器積層體的概略截面圖。感測器積層體100具備透明導電性薄膜10與配置於透明導電性薄膜10之至少單側的偏光板20。透明導電性薄膜10具備透明導電層11。代表上，透明導電性薄膜10係於透明基材12之至少單側具備透明導電層11。透明導電層11包含金屬奈米線(未圖示)。偏光板20具備偏光件21。代表上，係於偏光件21之至少一面(圖1中為偏光件21之與透明導電性薄膜10相反側的面)配置保護層23。
A. Overall composition of sensor laminate
FIG. 1 is a schematic cross-sectional view of a sensor laminate according to an embodiment of the present invention. The
本發明中，偏光件21與透明導電層11之距離A為25µm以上且小於70µm。在一實施形態中，係利用配置於偏光件21與透明導電層11之間的透明導電性薄膜側結構體22，來確保偏光件21與透明導電層11之距離A，且該透明導電性薄膜側結構體22係偏光板20之偏光件21以外的結構體22。又，雖未圖示，但亦可於偏光板與透明導電性薄膜之間配置任意適當之層(例如相位差層、黏著劑層、接著劑層、液晶層等)，並利用該層與偏光板之透明導電性薄膜側結構體22，來確保有偏光件與透明導電層之距離A。In the present invention, the distance A between the polarizer 21 and the transparent
透明導電性薄膜側結構體22係由任意適當之層來構成。構成透明導電性薄膜側結構體22之層可舉例如相位差層、黏著劑層、接著劑層等、液晶層等。以下，圖2中顯示透明導電性薄膜側結構體22之一例，惟透明導電性薄膜側結構體22之構成不受此限，可製成任意適當之構成。The transparent conductive film-
圖2係本發明一實施形態之感測器積層體的概略截面圖。感測器積層體100'中，偏光板20係附相位差層之偏光板，其依序具備保護層23、偏光件21、第1相位差層22a、第2相位差層22b及黏著劑層22c。偏光板20係配置成使黏著劑層22c在透明導電性薄膜10側，並貼合黏著劑層22c與透明導電層11而構成感測器積層體100'。本實施形態中，第1相位差層22a、第2相位差層22b及黏著劑層22c係構成透明導電性薄膜側結構體22。各層可透過任意適當之接著劑層積層(未圖示)。本實施形態中，透明導電性薄膜側結構體22的厚度A相當於偏光件21與透明導電層11之距離A。即，透明導電性薄膜側結構體22之厚度為25µm以上且小於70µm。FIG. 2 is a schematic cross-sectional view of a sensor laminate according to an embodiment of the present invention. In the sensor laminated body 100', the polarizing
雖未示於圖式中，但偏光板與透明導電性薄膜之間亦可配置有障壁層。例如，作為透明導電性薄膜側結構體22之一要素，可於黏著劑層22c與第2相位差層22b之間配置障壁層。障壁層係一可防止碘成分移動之層。Although not shown in the drawings, a barrier layer may be disposed between the polarizing plate and the transparent conductive film. For example, as an element of the transparent conductive
本發明中可提供一種感測器積層體，其具備透明導電性薄膜，該透明導電性薄膜藉由將偏光件與透明導電層之距離設為25µm以上且小於70µm，可防止透明導電層中金屬奈米線因碘造成之劣化，而可展現優異導電性。本發明感測器積層體在加濕下之可靠性優異之方面來看有利。又，藉由將偏光件與透明導電層之距離設為小於70µm，可獲得展現優異撓曲性之感測器積層體，且藉由透明導電性薄膜由金屬奈米線構成之相乘下，撓曲性提升效果顯著。偏光件與透明導電層之距離宜為30µm~65µm，較宜為40µm~60µm。若在所述範圍內，上述效果便顯著。The present invention can provide a sensor laminate having a transparent conductive film that can prevent metal in the transparent conductive layer by setting the distance between the polarizer and the transparent conductive layer to 25 µm or more and less than 70 µm. Nanowires exhibit excellent electrical conductivity due to degradation caused by iodine. The sensor laminate of the present invention is advantageous in that it has excellent reliability under humidification. Furthermore, by setting the distance between the polarizer and the transparent conductive layer to less than 70µm, a sensor laminate showing excellent flexibility can be obtained, and by multiplying the transparent conductive film by metal nanowires, The flexibility improvement effect is significant. The distance between the polarizer and the transparent conductive layer should be 30µm~65µm, more preferably 40µm~60µm. If it is within the above range, the above-mentioned effects will be significant.
配置於偏光件與透明導電層之間的積層結構(代表上為上述透明導電性薄膜側結構體22)在23℃下之彎曲彈性模數宜為1000MPa~9000MPa，較宜為1300MPa~6000MPa，更宜為1500MPa~5000MPa。The bending elastic modulus of the laminated structure arranged between the polarizer and the transparent conductive layer (representatively the above-mentioned transparent conductive film side structure 22) at 23°C is preferably 1000MPa~9000MPa, more preferably 1300MPa~6000MPa, and more It should be 1500MPa~5000MPa.
配置於偏光件與透明導電層之間的積層結構(代表上為上述透明導電性薄膜側結構體22)在40℃92%環境下投入24h後之透濕度宜為5g/m 2以上且1500g/m 2以下，較宜為10g/m 2以上且1000g/m 2以下，更宜為10g/m 2以上且700g/m 2以下。上述透濕度若過低，恐在高溫環境下於積層體發生透光之虞。上述透濕度若過高，恐在高濕度環境下於積層體發生不均。 The moisture permeability of the laminated structure disposed between the polarizer and the transparent conductive layer (representatively the above-mentioned transparent conductive film side structure 22) after being put into the environment for 24 hours at 40°C and 92% is preferably 5g/m2 or more and 1500g/ m 2 or less, preferably 10 g/m 2 or more and 1000 g/m 2 or less, more preferably 10 g/m 2 or more and 700 g/m 2 or less. If the above-mentioned moisture permeability is too low, light transmission may occur in the laminate in a high-temperature environment. If the above-mentioned moisture permeability is too high, unevenness may occur in the laminate in a high-humidity environment.
B.偏光板 B-1.偏光件 偏光件可採用任意適當之偏光件。例如，形成偏光件之樹脂薄膜可為單層樹脂薄膜亦可為二層以上之積層體。 B.Polarizing plate B-1.Polarizer The polarizing element can be any suitable polarizing element. For example, the resin film forming the polarizer may be a single-layer resin film or a laminate of two or more layers.
由單層樹脂薄膜構成之偏光件的具體例，可舉：利用碘或二色性染料等二色性物質對聚乙烯醇(PVA)系薄膜、部分縮甲醛化PVA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進行染色處理及延伸處理而成者；PVA之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系定向薄膜等。由光學特性優異來看，宜使用以碘將PVA系薄膜染色並進行單軸延伸所得之偏光件。Specific examples of polarizers composed of a single-layer resin film include polyvinyl alcohol (PVA)-based films, partially formalized PVA-based films, and ethylene-vinyl acetate films using dichroic substances such as iodine or dichroic dyes. Ester copolymers are hydrophilic polymer films such as partially saponified films that are dyed and stretched; polyene oriented films such as PVA dehydrated products or PVC dehydrochloric acid treated products, etc. Since it has excellent optical properties, it is preferable to use a polarizer obtained by dyeing a PVA-based film with iodine and uniaxially stretching it.
上述利用碘進行之染色，例如可藉由將PVA系薄膜浸漬於碘水溶液中來進行。上述單軸延伸之延伸倍率宜為3~7倍。延伸可在染色處理後進行，亦可邊染色邊進行。又，亦可延伸後再染色。視需要，對PVA系薄膜施行膨潤處理、交聯處理、洗淨處理、乾燥處理等。例如，藉由在染色前將PVA系薄膜浸漬於水中進行水洗，不僅可洗淨PVA系薄膜表面之污垢或抗黏結劑，還可使PVA系薄膜膨潤，防止染色不均等情況。The above-described dyeing with iodine can be performed, for example, by immersing a PVA-based film in an iodine aqueous solution. The extension ratio of the above-mentioned uniaxial extension is preferably 3 to 7 times. Extending can be done after dyeing or while dyeing. Also, it can be dyed after stretching. If necessary, the PVA film is subjected to swelling treatment, cross-linking treatment, washing treatment, drying treatment, etc. For example, by immersing the PVA film in water and washing it before dyeing, not only can the dirt or anti-adhesive agent on the surface of the PVA film be washed away, but the PVA film can also be swollen to prevent uneven dyeing.
作為使用積層體而得之偏光件的具體例可舉：使用樹脂基材與積層在該樹脂基材之PVA系樹脂層(PVA系樹脂薄膜)之積層體、或者是使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層之積層體而得之偏光件。使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體而得之偏光件，例如可藉由以下步驟來製作：將PVA系樹脂溶液塗佈於樹脂基材並使其乾燥，於樹脂基材上形成PVA系樹脂層，而獲得樹脂基材與PVA系樹脂層的積層體；及，將該積層體延伸及染色，以將PVA系樹脂層製成偏光件。在本實施形態中，延伸在代表上包含使積層體浸漬於硼酸水溶液中並延伸。並且視需求，延伸可更包含在硼酸水溶液中進行延伸前將積層體在高溫(例如95℃以上)下進行空中延伸。所得樹脂基材/偏光件之積層體可直接使用(即，亦可將樹脂基材作為偏光件之保護層)，亦可從樹脂基材/偏光件之積層體剝離樹脂基材並於該剝離面上積層符合目的之任意適當的保護層後來使用。所述偏光件之製造方法之詳細內容記載於例如日本專利特開2012-73580號公報、日本專利第6470455號中。本說明書中係引用該等公報整體之記載作為參考。Specific examples of polarizers using a laminate include a laminate using a resin base material and a PVA-based resin layer (PVA-based resin film) laminated on the resin base material, or using a resin base material and coating A polarizing element formed from a laminate of PVA-based resin layers on the resin base material. A polarizing element using a laminate of a resin base material and a PVA-based resin layer coated on the resin base material can be produced, for example, by applying a PVA-based resin solution to the resin base material and allowing it to Drying, forming a PVA-based resin layer on the resin base material to obtain a laminate of the resin base material and the PVA-based resin layer; and extending and dyeing the laminate to make the PVA-based resin layer into a polarizer. In this embodiment, stretching typically includes immersing the laminate in a boric acid aqueous solution and stretching. And if necessary, stretching may further include stretching the laminate in the air at a high temperature (for example, above 95° C.) before stretching in a boric acid aqueous solution. The obtained resin base material/polarizing element laminated body can be used directly (that is, the resin base material can also be used as a protective layer of the polarizing element), or the resin base material can be peeled off from the resin base material/polarizing element laminated body and then peeled off. Any suitable protective layer suitable for the purpose shall be applied later. Details of the manufacturing method of the polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The entire description of these publications is cited in this specification as a reference.
偏光件之厚度宜為15µm以下，較宜為1µm~12µm，更宜為3µm~12µm，尤宜為3µm~8µm。The thickness of the polarizer should be less than 15µm, preferably 1µm~12µm, more preferably 3µm~12µm, especially 3µm~8µm.
偏光件宜在波長380nm~780nm之任一波長下顯示吸收二色性。偏光件之單體透射率宜為41.5%~46.0%，較宜為43.0%~46.0%，更宜為44.5%~46.0%。偏光件之偏光度宜為97.0%以上，較宜為99.0%以上，更宜為99.9%以上。The polarizer should show absorption dichroism at any wavelength between 380nm and 780nm. The single transmittance of the polarizer is preferably 41.5%~46.0%, more preferably 43.0%~46.0%, and even more preferably 44.5%~46.0%. The polarization degree of the polarizer is preferably above 97.0%, more preferably above 99.0%, more preferably above 99.9%.
B-2.保護層 保護層可以任意適當之薄膜構成。薄膜之構成材料的代表例可列舉：三醋酸纖維素(TAC)等之纖維素系樹脂、或聚酯系、聚乙烯醇系、聚碳酸酯系、聚醯胺系、聚醯亞胺系、聚醚碸系、聚碸系、聚苯乙烯系、聚降𦯉烯系、聚烯烴系、(甲基)丙烯酸系及乙酸酯系等之透明樹脂等。又，亦可舉(甲基)丙烯酸系、胺甲酸酯系、(甲基)丙烯酸胺甲酸酯系、環氧系、聚矽氧系等之熱硬化型樹脂或紫外線硬化型樹脂等。本說明書中，「(甲基)丙烯酸」意指丙烯酸及/或甲基丙烯酸。 B-2.Protective layer The protective layer can be composed of any suitable film. Representative examples of the constituent materials of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, Transparent resins of polyether series, polystyrene series, polystyrene series, polynorphene series, polyolefin series, (meth)acrylic series and acetate series, etc. Furthermore, thermosetting resins such as (meth)acrylic type, urethane type, (meth)acrylic urethane type, epoxy type, polysilicone type, etc., or ultraviolet curing type resins may also be mentioned. In this specification, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid.
保護層之厚度宜為10µm~40µm，較宜為10µm~30µm。The thickness of the protective layer should be 10µm~40µm, more preferably 10µm~30µm.
B-3.相位差層 在一實施形態中，相位差層可為液晶化合物之定向固化層。例如，圖2所示第1相位差層及第2相位差層各自可為液晶化合物之定向固化層。本說明書中所謂「定向固化層」係指液晶化合物在層內於預定方向定向，且其定向狀態經固定之層。此外，「定向固化層」之概念包含如後述使液晶單體硬化而得之定向硬化層。以第1相位差層及第2相位差層來說，代表上係棒狀液晶化合物沿第1相位差層及第2相位差層之慢軸方向排列之狀態下定向(沿面定向)。 B-3. Phase difference layer In one embodiment, the retardation layer may be a directionally solidified layer of a liquid crystal compound. For example, each of the first retardation layer and the second retardation layer shown in FIG. 2 may be a directionally solidified layer of a liquid crystal compound. The so-called "orientation solidified layer" in this specification refers to a layer in which the liquid crystal compound is oriented in a predetermined direction within the layer and its orientation state is fixed. In addition, the concept of "directionally hardened layer" includes a directionally hardened layer obtained by hardening a liquid crystal monomer as described later. For the first retardation layer and the second retardation layer, it means that the rod-shaped liquid crystal compounds are aligned along the slow axis direction of the first retardation layer and the second retardation layer (epiplane orientation).
液晶化合物可舉例如液晶相為向列相之液晶化合物(向列型液晶)。所述液晶化合物例如可使用液晶聚合物或液晶單體。液晶化合物之液晶性的表現機構可為溶致亦可為熱致。液晶聚合物及液晶單體各自可單獨使用，亦可組合。Examples of the liquid crystal compound include a liquid crystal compound whose liquid crystal phase is a nematic phase (nematic liquid crystal). As the liquid crystal compound, a liquid crystal polymer or a liquid crystal monomer can be used, for example. The liquid crystallinity expression mechanism of the liquid crystal compound may be either lyotropic or thermotropic. The liquid crystal polymer and the liquid crystal monomer can each be used alone or in combination.
液晶化合物為液晶單體時，該液晶單體宜為聚合性單體及交聯性單體。原因在於，藉由使液晶單體聚合或交聯(亦即硬化)可固定液晶單體的定向狀態。在使液晶單體定向之後，例如若使液晶單體彼此聚合或交聯，便可藉此固定上述定向狀態。在此係藉由聚合來形成聚合物，藉由交聯來形成3維網目結構，而該等為非液晶性。因此，所形成之相位差層例如不會發生液晶性化合物特有之因溫度變化而轉變為液晶相、玻璃相、結晶相之情形。結果，相位差層會成為不受溫度變化影響而穩定性極優異的相位差層。When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. The reason is that the orientation state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (that is, hardening) the liquid crystal monomer. After the liquid crystal monomers are oriented, for example, if the liquid crystal monomers are polymerized or cross-linked with each other, the above-mentioned orientation state can be fixed. Here, the polymer is formed by polymerization, and the three-dimensional network structure is formed by cross-linking, and these are non-liquid crystalline. Therefore, the formed retardation layer does not undergo transformation into a liquid crystal phase, a glass phase, or a crystal phase due to temperature changes, which is unique to liquid crystalline compounds. As a result, the retardation layer becomes a retardation layer that is not affected by temperature changes and has extremely excellent stability.
液晶單體展現液晶性之溫度範圍會因其種類而異。具體來說，該溫度範圍宜為40℃~120℃，更宜為50℃~100℃，最宜為60℃~90℃。The temperature range in which liquid crystal monomers exhibit liquid crystallinity varies depending on their type. Specifically, the temperature range is preferably 40°C to 120°C, more preferably 50°C to 100°C, and most preferably 60°C to 90°C.
上述液晶單體可採用任意適當之液晶單體。例如可使用日本專利特表2002-533742(WO00/37585)、EP358208(US5211877)、EP66137(US4388453)、WO93/22397、EP0261712、DE19504224、DE4408171及GB2280445等中記載之聚合性液晶原化合物等。所述聚合性液晶原化合物之具體例可舉例如BASF公司之商品名LC242、Merck公司之商品名E7、Wacker-Chem公司之商品名LC-Sillicon-CC3767。液晶單體宜為例如向列性液晶單體。Any appropriate liquid crystal monomer can be used as the above-mentioned liquid crystal monomer. For example, polymerizable mesogen compounds described in Japanese Patent List 2002-533742 (WO00/37585), EP358208 (US5211877), EP66137 (US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, and GB2280445 can be used. . Specific examples of the polymerizable mesogen compound include LC242, a trade name of BASF, E7, a trade name of Merck, and LC-Sillicon-CC3767, a trade name of Wacker-Chem. The liquid crystal monomer is preferably a nematic liquid crystal monomer, for example.
液晶定向固化層可藉由以下方式來形成：對預定基材之表面施行定向處理，並於該表面塗敷含液晶化合物的塗敷液使該液晶化合物於對應上述定向處理之方向定向，並固定該定向狀態。The liquid crystal orientation solidified layer can be formed by performing orientation treatment on the surface of a predetermined base material, and coating a coating liquid containing a liquid crystal compound on the surface so that the liquid crystal compound is oriented in a direction corresponding to the orientation treatment and fixed. the orientation status.
上述定向處理可採用任意適當之定向處理。具體上可舉機械性定向處理、物理性定向處理、化學性定向處理。機械性定向處理的具體例可舉磨擦處理、延伸處理。物理性定向處理的具體例可舉磁場定向處理、電場定向處理。化學性定向處理的具體例可舉斜向蒸鍍法、光定向處理。各種定向處理的處理條件可按目的採用任意適當之條件。The above orientation processing may adopt any appropriate orientation processing. Specifically, mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment can be cited. Specific examples of mechanical orientation treatment include friction treatment and stretching treatment. Specific examples of physical orientation processing include magnetic field orientation processing and electric field orientation processing. Specific examples of chemical orientation treatment include oblique evaporation and photo-orientation treatment. The processing conditions for various targeted treatments can be any appropriate conditions depending on the purpose.
液晶化合物的定向可因應液晶化合物的種類在可展現液晶相之溫度下進行處理來進行。藉由進行所述溫度處理，液晶化合物會變為液晶狀態，而該液晶化合物會因應基材表面之定向處理方向而定向。The orientation of the liquid crystal compound can be carried out by treating the liquid crystal compound at a temperature that can exhibit a liquid crystal phase according to the type of the liquid crystal compound. By performing the temperature treatment, the liquid crystal compound will change into a liquid crystal state, and the liquid crystal compound will be oriented according to the direction of the orientation treatment on the surface of the substrate.
在一實施形態中，定向狀態之固定係藉由冷卻依上述方式定向之液晶化合物來進行。當液晶化合物為聚合性單體或交聯性單體時，定向狀態之固定係藉由對依上述方式定向之液晶化合物施行聚合處理或交聯處理來進行。In one embodiment, the alignment state is fixed by cooling the liquid crystal compound aligned in the above manner. When the liquid crystal compound is a polymerizable monomer or a cross-linking monomer, the alignment state is fixed by subjecting the liquid crystal compound oriented in the above manner to a polymerization treatment or a cross-linking treatment.
液晶化合物之具體例及定向固化層的形成方法的詳細內容係記載於日本專利特開2006-163343號公報中。本說明書中係援用該公報之記載作為參考。Specific examples of the liquid crystal compound and details of the formation method of the orientationally solidified layer are described in Japanese Patent Application Laid-Open No. 2006-163343. The records in this publication are cited in this specification as a reference.
第1相位差層及第2相位差層代表上各自之折射率特性展現nx＞ny=nz之關係。此外，關於「ny=nz」，不只是ny與nz完全相同之情況，還包含實質上相同之情況。因此，在不損及本發明效果之範圍下，有可能會出現ny＞nz或ny＜nz之情形。The respective refractive index characteristics of the first phase difference layer and the second phase difference layer represent the relationship of nx>ny=nz. In addition, "ny=nz" means not only the case where ny and nz are exactly the same, but also the case where they are substantially the same. Therefore, within the scope that does not impair the effect of the present invention, the situation of ny>nz or ny<nz may occur.
代表上，第1相位差層或第2相位差層中之任一者可作為λ/2板發揮功能，而另一者可作為λ/4板發揮功能。例如，當第1相位差層作為λ/2板發揮功能、第2相位差層作為λ/4板發揮功能時，第1相位差層的Re(550)宜為200nm~300nm，且其慢軸與偏光件的吸收軸形成之角度宜為10°~20°；第2相位差層之Re(550)宜為100nm~190nm，且其慢軸與偏光件的吸收軸形成之角度宜為70°~80°。Representatively, either the first retardation layer or the second retardation layer can function as a λ/2 plate, and the other can function as a λ/4 plate. For example, when the first retardation layer functions as a λ/2 plate and the second retardation layer functions as a λ/4 plate, Re (550) of the first retardation layer is preferably 200 nm to 300 nm, and its slow axis The angle formed with the absorption axis of the polarizer should be 10°~20°; the Re(550) of the second phase difference layer should be 100nm~190nm, and the angle formed by its slow axis with the absorption axis of the polarizer should be 70°. ~80°.
第1相位差層及第2相位差層各自之Nz係數宜為0.9~1.5，較宜為0.9~1.3。The respective Nz coefficients of the first phase difference layer and the second phase difference layer are preferably 0.9~1.5, more preferably 0.9~1.3.
第1相位差層及第2相位差層各自在40℃92%環境下投入24h後之透濕度宜為5g/m 2以上且1500g/m 2以下，較宜為10g/m 2以上且1000g/m 2以下，更宜為10g/m 2以上且700g/m 2以下。上述透濕度若過低，恐有積層體在高溫環境下透光之虞。上述透濕度若過高，恐發生積層體在高濕度環境下不均。 The moisture permeability of the first retardation layer and the second retardation layer after being put into the environment for 24 hours at 40°C and 92% is preferably 5g/m 2 or more and 1500g/m 2 or less, and more preferably 10g/m 2 or more and 1000g/m 2 or more. m 2 or less, more preferably 10g/m 2 or more and 700g/m 2 or less. If the above-mentioned moisture permeability is too low, there is a risk that the laminate may transmit light in a high-temperature environment. If the above-mentioned moisture permeability is too high, the laminate may become uneven in a high-humidity environment.
在另一實施形態中，相位差層亦可為單一層。在一實施形態中，單一層之相位差層代表上可展現逆色散波長特性且可作為λ/4板發揮功能。具體而言，相位差層之Re(550)宜為100nm~190nm，Re(450)/Re(550)宜為0.8~0.95，且相位差層的慢軸與偏光件的吸收軸形成之角度宜為40°~50°。並且，此時適宜的是，可於相位差層之與偏光件相反側，設置折射率特性展現nz＞nx=ny之關係的另一相位差層(所謂正C板)。In another embodiment, the phase difference layer may also be a single layer. In one embodiment, a single layer of retardation layer can typically exhibit inverse dispersion wavelength characteristics and function as a λ/4 plate. Specifically, Re(550) of the retardation layer should be 100nm~190nm, Re(450)/Re(550) should be 0.8~0.95, and the slow axis of the retardation layer and the absorption axis of the polarizer should form an appropriate angle. is 40°~50°. Moreover, it is appropriate at this time to provide another retardation layer (so-called positive C plate) whose refractive index characteristics exhibit the relationship nz>nx=ny on the side of the retardation layer opposite to the polarizer.
B-4.黏著劑層 構成黏著劑層之黏著劑可採用任意適當之構成。構成黏著劑層之黏著劑之具體例可舉丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、聚酯系黏著劑、胺甲酸酯系黏著劑、環氧系黏著劑及聚醚系黏著劑。藉由調整形成黏著劑之基底樹脂的單體的種類、數量、組合及摻混比、以及交聯劑的摻混量、反應溫度、反應時間等，可調製出具有符合目的之所期望特性的黏著劑。黏著劑之基底樹脂可單獨使用亦可組合2種以上來使用。由透明性、加工性及耐久性等觀點來看宜為丙烯酸系黏著劑(丙烯酸系黏著劑組成物)。 B-4. Adhesive layer The adhesive constituting the adhesive layer can adopt any appropriate composition. Specific examples of the adhesive constituting the adhesive layer include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, urethane adhesives, epoxy adhesives and polyester adhesives. Ether adhesive. By adjusting the type, quantity, combination and blending ratio of the monomers that form the base resin of the adhesive, as well as the blending amount of the cross-linking agent, reaction temperature, reaction time, etc., it is possible to prepare a product with the desired characteristics that meets the purpose. Adhesive. The base resin of the adhesive can be used alone or in combination of two or more types. From the viewpoint of transparency, processability, durability, etc., an acrylic adhesive (acrylic adhesive composition) is suitable.
黏著劑層之厚度宜為5µm~30µm，較宜為10µm~20µm。The thickness of the adhesive layer is preferably 5µm~30µm, more preferably 10µm~20µm.
B-5.接著劑層 構成接著劑層之接著劑可採用任意且適當之接著劑。接著劑代表上可舉活性能量線硬化型接著劑。活性能量線硬化型接著劑可舉例如紫外線硬化型接著劑、電子束硬化型接著劑。又，由硬化機制之觀點來看，活性能量線硬化型接著劑可舉例如自由基硬化型、陽離子硬化型、陰離子硬化型、自由基硬化型與陽離子硬化型之混合型。代表上，可使用自由基硬化型紫外線硬化型接著劑。原因在於廣用性優異、及容易調整特性(構成)。 B-5. Adhesive layer Any appropriate adhesive may be used as the adhesive constituting the adhesive layer. Typical examples of adhesives include active energy ray-hardening adhesives. Examples of active energy ray curing adhesives include ultraviolet curing adhesives and electron beam curing adhesives. In addition, from the viewpoint of the curing mechanism, examples of the active energy ray curable adhesive include a radical curing type, a cation curing type, an anion curing type, and a mixture of a radical curing type and a cation curing type. Typically, radical curing UV curing adhesives can be used. The reason is that it has excellent versatility and is easy to adjust the characteristics (structure).
接著劑代表上含有硬化成分與光聚合引發劑。硬化成分代表上可舉具有(甲基)丙烯酸酯基、(甲基)丙烯醯胺基等官能基之單體及/或寡聚物。硬化成分之具體例可列舉：三丙二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯、三環癸烷二甲醇二丙烯酸酯、苯氧基二乙二醇丙烯酸酯、環狀三羥甲丙烷縮甲醛丙烯酸酯、二㗁烷二醇二丙烯酸酯、EO改質二甘油四丙烯酸酯、γ-丁內酯丙烯酸酯、丙烯醯基嗎福林、不飽和脂肪酸羥烷基酯改質ε-己內酯、N-甲基吡咯啶酮、羥乙基丙烯醯胺、N-羥甲基丙烯醯胺、N-甲氧基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺。該等硬化成分可單獨使用亦可併用2種以上。The adhesive typically contains a hardening component and a photopolymerization initiator. Typical examples of the curing component include monomers and/or oligomers having functional groups such as (meth)acrylate groups and (meth)acrylamide groups. Specific examples of the hardening component include: tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, phenoxydiethylene glycol acrylate, and cyclic trimethylol Propane formal acrylate, diethylene glycol diacrylate, EO modified diglyceryl tetraacrylate, γ-butyrolactone acrylate, acrylomorphine, unsaturated fatty acid hydroxyalkyl ester modified ε- Caprolactone, N-methylpyrrolidone, hydroxyethylacrylamide, N-hydroxymethylacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide. These hardening components may be used individually or in combination of 2 or more types.
光聚合引發劑可以業界周知之摻混量使用業界周知之光聚合引發劑，故省略詳細說明。As the photopolymerization initiator, a photopolymerization initiator well known in the industry can be used in a blending amount well known in the industry, so detailed description is omitted.
接著劑層(接著劑硬化後)之厚度宜為0.1µm~3.0µm。The thickness of the adhesive layer (after the adhesive is hardened) is preferably 0.1µm~3.0µm.
接著劑之詳細內容例如記載於日本專利特開2018-017996號公報中。本說明書中係援用該公報之記載作為參考。Details of the adhesive are described in Japanese Patent Application Laid-Open No. 2018-017996, for example. The records in this publication are cited in this specification as a reference.
B-6.阻隔層 代表上，上述阻隔層為樹脂層。在一實施形態中，阻隔層包含丙烯酸系樹脂及/或環氧系樹脂。丙烯酸系樹脂與環氧系樹脂之含有比率(丙烯酸系樹脂：環氧系樹脂)以重量比計宜為95：5~60：40或40：60~1：99；較宜為95：5~80：20或20：80~5：95；更宜為90：10~70：30或30：70~10：90。若在所述範圍內，便可形成與鄰接層之密著性優異且透明性優異之阻隔層。 B-6. Barrier layer Typically, the barrier layer is a resin layer. In one embodiment, the barrier layer includes acrylic resin and/or epoxy resin. The content ratio of acrylic resin and epoxy resin (acrylic resin: epoxy resin) in terms of weight ratio is preferably 95:5~60:40 or 40:60~1:99; more preferably, it is 95:5~ 80:20 or 20:80~5:95; more preferably 90:10~70:30 or 30:70~10:90. If it is within the above range, a barrier layer having excellent adhesion to the adjacent layer and excellent transparency can be formed.
上述丙烯酸系樹脂宜包含源自丙烯酸系單體之構成單元與源自下述式(1)所示單體(a)之構成單元。本說明書中，有時亦會將包含源自丙烯酸系單體之構成單元與源自下述式(1)所示單體之構成單元的丙烯酸系樹脂稱為「丙烯酸系樹脂(A)」。又，下述式(1)所示單體(a)有時亦僅稱為「單體(a)」。藉由併用包含源自單體(a)之構成單元的丙烯酸系樹脂(A)與環氧系樹脂來形成阻隔層，可防止偏光件成分移動，而可獲得耐久性顯著優異的感測器積層體。 [化學式1] (式中，X表示包含反應性基之官能基，且該反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基，R 1及R 2分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基，R 1及R 2可相互連結形成環)。 The acrylic resin preferably contains a structural unit derived from an acrylic monomer and a structural unit derived from the monomer (a) represented by the following formula (1). In this specification, an acrylic resin containing a structural unit derived from an acrylic monomer and a structural unit derived from a monomer represented by the following formula (1) may be referred to as "acrylic resin (A)". In addition, the monomer (a) represented by the following formula (1) may be simply called "monomer (a)". By using together an acrylic resin (A) and an epoxy resin containing a structural unit derived from the monomer (a) to form a barrier layer, polarizer components can be prevented from moving and a sensor laminate with significantly excellent durability can be obtained. body. [Chemical formula 1] (In the formula, At least one reactive group in the group consisting of an ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amine group, an aldehyde group and a carboxyl group. R 1 and R 2 each independently represent a hydrogen atom and may be substituted. The base is an aliphatic hydrocarbon group, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and R 1 and R 2 may be connected to each other to form a ring).
上述脂肪族烴基可舉可具有取代基之碳數1~20直鏈或支鏈烷基、可具有取代基之碳數3~20環狀烷基、碳數2~20烯基。上述芳基可舉可具有取代基之碳數6~20苯基、可具有取代基之碳數10~20萘基等。雜環基可舉可具有取代基之至少包含1個雜原子的5員環基或6員環基。此外，R 1及R 2可相互連結形成環。R 1及R 2宜為氫原子或碳數1~3直鏈或支鏈烷基，較宜為氫原子。 Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent, a cyclic alkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent, a naphthyl group having 10 to 20 carbon atoms which may have a substituent, and the like. Examples of the heterocyclic group include a 5-membered cyclic group or a 6-membered cyclic group containing at least 1 heteroatom which may have a substituent. In addition, R 1 and R 2 may be linked to each other to form a ring. R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
在一實施形態中，上述X所示官能基所含之反應性基宜為(甲基)丙烯醯基及/或(甲基)丙烯醯胺基。藉由具有該等反應性基，可提升偏光件與阻隔層之密著性。In one embodiment, the reactive group contained in the functional group represented by X is preferably a (meth)acrylyl group and/or a (meth)acrylamide group. By having these reactive groups, the adhesion between the polarizer and the barrier layer can be improved.
在一實施形態中，上述X所示官能基宜為下述式所示官能基。 [化學式2] (式中，Z表示包含選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，Y表示伸苯基或伸烷基)。 In one embodiment, the functional group represented by X is preferably a functional group represented by the following formula. [Chemical formula 2] (In the formula, Z represents a group consisting of vinyl, (meth)acrylyl, styrene, (meth)acrylamide, vinyl ether, epoxy, and oxetanyl. , a functional group that is at least one reactive group in the group consisting of hydroxyl group, amine group, aldehyde group and carboxyl group, Y represents a phenyl group or an alkylene group).
通式(1)所示單體具體上可使用以下化合物。 [化學式3] Specifically, the following compounds can be used as the monomer represented by the general formula (1). [Chemical formula 3]
丙烯酸系樹脂(A)中，相對於丙烯酸系樹脂(A)100重量份，源自單體(a)之構成單元的含有比率宜大於0重量份且小於50重量份，較宜為0.01重量份以上且小於50重量份，更宜為0.05重量份~20重量份，且更宜為0.1重量份~10重量份。若為所述範圍，便可獲得耐久性優異之感測器積層體。In the acrylic resin (A), the content ratio of the structural unit derived from the monomer (a) is preferably greater than 0 parts by weight and less than 50 parts by weight, preferably 0.01 parts by weight, based on 100 parts by weight of the acrylic resin (A). Above and less than 50 parts by weight, more preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight. If it is within the above range, a sensor laminate having excellent durability can be obtained.
丙烯酸系樹脂(A)中，相對於丙烯酸系樹脂(A)100重量份，源自丙烯酸系單體之構成單元的含有比率宜大於50重量份。In the acrylic resin (A), the content ratio of the structural unit derived from the acrylic monomer is preferably greater than 50 parts by weight relative to 100 parts by weight of the acrylic resin (A).
丙烯酸系單體可使用任意適當之丙烯酸系單體。可舉例如具有直鏈或支鏈結構之(甲基)丙烯酸酯系單體、及具有環狀結構之(甲基)丙烯酸酯系單體。本說明書中，(甲基)丙烯酸意指丙烯酸及/或甲基丙烯酸。Any appropriate acrylic monomer may be used as the acrylic monomer. Examples thereof include (meth)acrylate monomers having a linear or branched structure and (meth)acrylate monomers having a cyclic structure. In this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid.
具有直鏈或支鏈結構之(甲基)丙烯酸酯系單體可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸甲基2-乙基己酯、(甲基)丙烯酸2-羥乙酯等。宜可使用(甲基)丙烯酸甲酯。(甲基)丙烯酸酯系單體可僅使用1種亦可組合2種以上來使用。Examples of (meth)acrylate monomers having a linear or branched structure include: (meth)acrylate methyl ester, (meth)ethyl acrylate, (meth)acrylate n-propyl ester, (meth)acrylate Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, (meth)acrylate ) 2-hydroxyethyl acrylate, etc. Preferably, methyl (meth)acrylate can be used. (Meth)acrylate-based monomers may be used alone or in combination of two or more types.
具有環狀結構之(甲基)丙烯酸酯系單體可列舉例如：(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧乙酯、(甲基)丙烯酸二環戊酯、聯苯(甲基)丙烯酸酯、鄰聯苯氧乙基(甲基)丙烯酸酯、鄰聯苯氧基乙氧乙基(甲基)丙烯酸酯、間聯苯氧乙基丙烯酸酯、對聯苯氧乙基(甲基)丙烯酸酯、鄰聯苯氧基-2-羥丙基(甲基)丙烯酸酯、對聯苯氧基-2-羥丙基(甲基)丙烯酸酯、間聯苯氧基-2-羥丙基(甲基)丙烯酸酯、N-(甲基)丙烯醯氧基乙基-鄰聯苯=胺甲酸酯、N-(甲基)丙烯醯氧基乙基-對聯苯=胺甲酸酯、N-(甲基)丙烯醯氧基乙基-間聯苯=胺甲酸酯、鄰苯基苯酚環氧丙基醚丙烯酸酯等含聯苯基單體、三苯(甲基)丙烯酸酯、鄰三苯氧乙基(甲基)丙烯酸酯等。宜可使用(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸二環戊酯。藉由使用該等單體可獲得玻璃轉移溫度高之聚合物。該等單體可僅使用1種亦可組合2種以上來使用。Examples of the (meth)acrylate monomer having a cyclic structure include: (meth)acrylic acid cyclohexyl, (meth)acrylic acid benzyl ester, (meth)acrylic acid isocamphenyl, (meth)acrylic acid 1 -Adamantyl ester, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, biphenyl (meth)acrylate, ortho Biphenoxyethyl (meth)acrylate, o-biphenoxyethyl (meth)acrylate, meta-biphenoxyethyl acrylate, p-biphenoxyethyl (meth)acrylate, o-biphenoxyethyl (meth)acrylate Biphenyloxy-2-hydroxypropyl (meth)acrylate, p-biphenyloxy-2-hydroxypropyl (meth)acrylate, m-biphenyloxy-2-hydroxypropyl (meth)acrylic acid Ester, N-(meth)acryloxyethyl-p-biphenyl=carbamate, N-(meth)acryloxyethyl-p-biphenyl=carbamate, N-(methyl ) Acryloxyethyl-m-biphenyl = urethane, o-phenylphenol glycidyl ether acrylate and other biphenyl-containing monomers, triphenyl (meth)acrylate, o-triphenoxyethyl (meth)acrylate, etc. Preferably, 1-adamantyl (meth)acrylate and dicyclopentyl (meth)acrylate can be used. By using these monomers, polymers with high glass transition temperatures can be obtained. These monomers may be used only 1 type or in combination of 2 or more types.
又，亦可使用具有(甲基)丙烯醯基之矽倍半氧烷化合物取代上述(甲基)丙烯酸酯系單體。藉由使用矽倍半氧烷化合物，可獲得玻璃轉移溫度高之丙烯酸系聚合物。已知矽倍半氧烷化合物係具有各種骨架結構例如籠型結構、梯型結構、無規結構等之骨架者。矽倍半氧烷化合物可為僅具有1種該等結構者，亦可為具有2種以上者。矽倍半氧烷化合物可僅使用1種亦可組合2種以上來使用。Furthermore, a silsesquioxane compound having a (meth)acrylyl group may be used instead of the (meth)acrylate monomer. By using a silsesquioxane compound, an acrylic polymer with a high glass transition temperature can be obtained. It is known that silsesquioxane compounds have various skeleton structures such as cage structures, ladder structures, random structures, and the like. The silsesquioxane compound may have only one type of these structures, or may have two or more types. As for the silsesquioxane compound, only one type may be used or two or more types may be used in combination.
具有(甲基)丙烯醯基之矽倍半氧烷化合物可使用例如東亞合成股份公司SQ系列之MAC grade及AC grade。MAC grade為含有甲基丙烯醯基之矽倍半氧烷化合物，具體可舉例如MAC-SQ TM-100、MAC-SQ SI-20、MAC-SQ HDM等。AC grade為含有丙烯醯基之矽倍半氧烷化合物，具體可舉例如AC-SQ TA-100、AC-SQ SI-20等。As the silsesquioxane compound having a (meth)acrylyl group, for example, MAC grade and AC grade of Toa Gosei Co., Ltd.'s SQ series can be used. MAC grade is a silsesquioxane compound containing methacrylyl groups. Specific examples include MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM, etc. AC grade is a silsesquioxane compound containing an acryl group. Specific examples include AC-SQ TA-100, AC-SQ SI-20, etc.
丙烯酸系樹脂(A)宜可藉由將丙烯酸系單體及單體(a)等單體成分進行溶液聚合而得。溶液聚合所使用之溶劑可使用任意適當之溶劑。可列舉例如：水；甲醇、乙醇、異丙醇等醇；苯、甲苯、二甲苯、環己烷、正己烷等芳香族或脂肪族烴；乙酸乙酯等酯化合物；丙酮、甲基乙基酮等酮化合物；四氫呋喃、二㗁烷等環狀醚化合物等。該等溶劑可僅使用1種亦可組合2種以上來使用。且，亦可併用有機溶劑與水。聚合反應可以任意適當之溫度及時間進行。例如，可於50℃~100℃、較宜於60℃~80℃之範圍下進行聚合反應。又，反應時間例如為1小時~8小時，宜為3小時~5小時。The acrylic resin (A) is preferably obtained by solution polymerization of monomer components such as an acrylic monomer and the monomer (a). Any appropriate solvent can be used as the solvent used in solution polymerization. Examples include: water; alcohols such as methanol, ethanol, and isopropanol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; acetone, methylethyl Ketone compounds such as ketones; cyclic ether compounds such as tetrahydrofuran and dihexane, etc. Only one type of these solvents may be used, or two or more types may be used in combination. Furthermore, an organic solvent and water may be used together. The polymerization reaction can be carried out at any appropriate temperature and time. For example, the polymerization reaction can be carried out in the range of 50°C to 100°C, preferably 60°C to 80°C. Moreover, the reaction time is, for example, 1 hour to 8 hours, preferably 3 hours to 5 hours.
上述環氧系樹脂可使用任意適當之環氧系樹脂。環氧系樹脂宜可使用具有芳香族環之環氧系樹脂。藉由使用具有芳香族環之環氧系樹脂，可形成與偏光件之密著性更優異的阻隔層。具有芳香族環之環氧系樹脂可列舉例如：雙酚A型環氧系樹脂、雙酚F型環氧系樹脂、雙酚S型環氧系樹脂等雙酚型環氧系樹脂；苯酚酚醛清漆環氧系樹脂、甲酚酚醛清漆環氧系樹脂、羥苯甲醛苯酚酚醛清漆環氧系樹脂等酚醛清漆型環氧系樹脂；四羥甲苯之環氧丙基醚、四羥基二苯基酮之環氧丙基醚、環氧化聚乙烯苯酚等多官能型環氧系樹脂、萘酚型環氧樹脂、萘型環氧系樹脂、聯苯型環氧系樹脂等。宜可使用雙酚A型環氧系樹脂、聯苯型環氧系樹脂、雙酚F型環氧系樹脂。藉由使用該等環氧系樹脂，可形成可適宜阻止碘成分移動的阻隔層。環氧樹脂可僅使用1種亦可組合2種以上來使用。Any appropriate epoxy resin can be used as the above-mentioned epoxy resin. As the epoxy resin, it is preferable to use an epoxy resin having an aromatic ring. By using an epoxy resin having an aromatic ring, a barrier layer with better adhesion to the polarizer can be formed. Examples of epoxy resins having aromatic rings include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; phenol novolac Novolak-type epoxy resins such as varnish epoxy resin, cresol novolak epoxy resin, hydroxybenzaldehyde phenol novolak epoxy resin, etc.; tetrahydroxytoluene glycidyl ether, tetrahydroxydiphenyl ketone Polyfunctional epoxy resins such as glycidyl ether and epoxidized polyvinyl phenol, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, etc. Bisphenol A-type epoxy resin, biphenyl-type epoxy resin, and bisphenol F-type epoxy resin can be used. By using these epoxy resins, a barrier layer that can appropriately prevent the movement of iodine components can be formed. As for the epoxy resin, only one type may be used or two or more types may be used in combination.
環氧系樹脂之重量平均分子量(Mw)宜為20,000以上，較宜為30,000以上，更宜為37,000以上。藉由環氧系樹脂之重量平均分子量為上述範圍，可形成可適宜阻止碘成分移動的阻隔層。重量平均分子量例如可藉由GPC來測定。The weight average molecular weight (Mw) of the epoxy resin is preferably 20,000 or more, more preferably 30,000 or more, and more preferably 37,000 or more. When the weight average molecular weight of the epoxy resin is within the above range, a barrier layer that can appropriately prevent the movement of the iodine component can be formed. The weight average molecular weight can be measured by GPC, for example.
阻隔層之單層厚度宜為0.1µm~8µm，較宜為0.2µm~3µm，更宜為0.4µm~1µm。The single layer thickness of the barrier layer is preferably 0.1µm~8µm, more preferably 0.2µm~3µm, more preferably 0.4µm~1µm.
上述阻隔層之總厚度宜為0.1µm~16µm，較宜為0.1µm~8µm，更宜為0.2µm~6µm，又更宜為0.2µm~3µm，再更宜為0.2µm~2µm，尤宜為0.4µm~1µm。所謂阻隔層之總厚度，當阻隔層為單層時相當於單層厚度，而當阻隔層為複數層時相當於各層厚度合計後之厚度。The total thickness of the above-mentioned barrier layer is preferably 0.1µm~16µm, more preferably 0.1µm~8µm, more preferably 0.2µm~6µm, more preferably 0.2µm~3µm, further preferably 0.2µm~2µm, especially 0.2µm~2µm. 0.4µm~1µm. The so-called total thickness of the barrier layer is equivalent to the thickness of a single layer when the barrier layer is a single layer, and is equivalent to the total thickness of each layer when the barrier layer is multiple layers.
C.透明導電性薄膜 C-1.透明導電層 在一實施形態中，透明導電層包含金屬奈米線及聚合物基質。若形成含金屬奈米線的透明導電層，便可獲得撓曲性優異且光透射率優異之透明導電性薄膜。金屬奈米線係被聚合物基質保護。結果，可防止金屬奈米線腐蝕，而可獲得耐久性更優異的透明導電性薄膜。 C.Transparent conductive film C-1. Transparent conductive layer In one embodiment, the transparent conductive layer includes metal nanowires and a polymer matrix. If a transparent conductive layer containing metal nanowires is formed, a transparent conductive film with excellent flexibility and light transmittance can be obtained. The metal nanowires are protected by a polymer matrix. As a result, corrosion of the metal nanowires can be prevented, and a transparent conductive film with improved durability can be obtained.
上述透明導電層之厚度宜為10nm~1000nm，較宜為20nm~500nm。The thickness of the above-mentioned transparent conductive layer is preferably 10nm~1000nm, more preferably 20nm~500nm.
上述透明導電層之全光線透射率宜為85%以上，較宜為90%以上，更宜為95%以上。The total light transmittance of the above-mentioned transparent conductive layer is preferably above 85%, more preferably above 90%, and more preferably above 95%.
上述透明導電層之薄片電阻值宜為200Ω/□以下，較宜為150Ω/□以下，更宜為100Ω/□以下。透明導電性薄膜之薄片電阻值越小越好，惟其下限例如為1Ω/□(宜為0.5Ω/□，較宜為0.1Ω/□)。The sheet resistance value of the above-mentioned transparent conductive layer is preferably 200Ω/□ or less, more preferably 150Ω/□ or less, and more preferably 100Ω/□ or less. The sheet resistance of the transparent conductive film is as small as possible, but its lower limit is, for example, 1Ω/□ (preferably 0.5Ω/□, more preferably 0.1Ω/□).
(金屬奈米線) 所謂金屬奈米線係指：材質為金屬、形狀為針狀或線狀、且直徑為奈米尺寸之導電性物質。金屬奈米線可為直線狀亦可為曲線狀。若使用以金屬奈米線構成之透明導電層，藉由使金屬奈米線呈網目狀，即便為少量金屬奈米線仍可形成良好的電傳導路徑，而可獲得電阻小的透明導電性薄膜。並且，藉由使金屬奈米線呈網目狀，於網目間隙形成開口部，而可獲得光透射率高的透明導電性薄膜。 (metal nanowire) The so-called metal nanowires refer to conductive substances made of metal, needle-like or linear in shape, and nanometer-sized in diameter. Metal nanowires can be linear or curved. If a transparent conductive layer composed of metal nanowires is used, by making the metal nanowires into a mesh shape, even a small amount of metal nanowires can still form a good electrical conduction path, and a transparent conductive film with low resistance can be obtained . Furthermore, by forming the metal nanowires into a mesh shape and forming openings in the gaps between the meshes, a transparent conductive film with high light transmittance can be obtained.
上述金屬奈米線的粗度d與長度L之比(長寬比：L/d)宜為10~100,000，較宜為50~100,000，尤宜為100~10,000。如上述，若使用長寬比大的金屬奈米線，金屬奈米線會良好地相交，而利用少量的金屬奈米線便可展現更高的導電性。結果可獲得光透射率高的透明導電性薄膜。此外，在本說明書中，所謂「金屬奈米線的粗度」，在金屬奈米線之截面為圓形時意指其直徑，當為橢圓狀時意指其短徑，當為多邊形時則指最長的對角線。金屬奈米線的粗度及長度可藉由掃描型電子顯微鏡或穿透型電子顯微鏡確認。The ratio of the thickness d to the length L (aspect ratio: L/d) of the above-mentioned metal nanowire is preferably 10~100,000, more preferably 50~100,000, especially 100~10,000. As mentioned above, if metal nanowires with a large aspect ratio are used, the metal nanowires will intersect well, and a small amount of metal nanowires can exhibit higher conductivity. As a result, a transparent conductive film with high light transmittance can be obtained. In addition, in this specification, the so-called "thickness of the metal nanowire" means its diameter when the cross section of the metal nanowire is circular, its short diameter when it is elliptical, and its short diameter when it is polygonal. Refers to the longest diagonal. The thickness and length of metal nanowires can be confirmed by scanning electron microscopy or transmission electron microscopy.
上述金屬奈米線的粗度宜小於500nm，較宜小於200nm，尤宜為10nm~100nm，最宜為10nm~50nm。若為所述範圍，便可形成光透射率高之透明導電層。The thickness of the above-mentioned metal nanowires is preferably less than 500nm, more preferably less than 200nm, especially preferably 10nm~100nm, most preferably 10nm~50nm. If it is within the above range, a transparent conductive layer with high light transmittance can be formed.
上述金屬奈米線的長度宜為1µm~1000µm，較宜為10µm~500µm，尤宜為10µm~100µm。若為所述範圍，便可獲得導電性高之透明導電性薄膜。The length of the above-mentioned metal nanowires is preferably 1µm~1000µm, more preferably 10µm~500µm, especially 10µm~100µm. If it is within the above range, a transparent conductive film with high conductivity can be obtained.
構成上述金屬奈米線的金屬只要為導電性金屬，便可使用任意適當之金屬。構成上述金屬奈米線的金屬可舉例如銀、金、銅、鎳等。又，亦可使用已對該等金屬進行鍍敷處理(例如鍍金處理)的材料。其中由導電性之觀點來看，宜為銀、銅或金，較宜為銀。As the metal constituting the metal nanowires, any appropriate metal can be used as long as it is a conductive metal. Examples of metals constituting the metal nanowires include silver, gold, copper, nickel, and the like. In addition, materials in which these metals have been plated (for example, gold plated) may be used. Among them, from the viewpoint of electrical conductivity, silver, copper or gold is preferred, and silver is more preferred.
上述金屬奈米線的製造方法可採用任意適當之方法。可舉例如：在溶液中還原硝酸銀的方法；從探針之前端部使施加電壓或電流對前驅物表面作用，並以探針前端部拉出金屬奈米線，連續形成該金屬奈米線的方法等。在溶液中還原硝酸銀的方法中，可藉由在乙二醇等多元醇及聚乙烯吡咯啶酮存在下，將硝酸銀等之銀鹽之液相還原，來合成銀奈米線。均一尺寸之銀奈米線例如可依循例如Xia, Y.etal., Chem.Mater.(2002)，14, 4736-4745、Xia, Y.etal., Nano letters(2003)3(7)，955-960中記載之方法來大量生產。The above-mentioned manufacturing method of metal nanowires can adopt any appropriate method. Examples include: a method of reducing silver nitrate in a solution; applying voltage or current from the front end of the probe to the surface of the precursor, and pulling out metal nanowires with the front end of the probe to continuously form the metal nanowires. Methods etc. In the method of reducing silver nitrate in solution, silver nanowires can be synthesized by reducing the liquid phase of silver salts such as silver nitrate in the presence of polyhydric alcohols such as ethylene glycol and polyvinylpyrrolidone. Silver nanowires of uniform size can be produced according to, for example, Xia, Y. et al., Chem. Mater. (2002), 14, 4736-4745, Xia, Y. et al., Nano letters (2003) 3 (7), 955 - Mass production using the method recorded in -960.
上述含金屬奈米線之透明導電層可將已使上述金屬奈米線分散於溶劑中之分散液塗佈於上述透明基材上之後，使塗佈層乾燥而形成。The above-mentioned transparent conductive layer containing metal nanowires can be formed by applying a dispersion liquid in which the above-mentioned metal nanowires are dispersed in a solvent onto the above-mentioned transparent substrate, and then drying the coating layer.
上述溶劑可列舉水、醇系溶劑、酮系溶劑、醚系溶劑、烴系溶劑、芳香族系溶劑等。由減低環境負荷之觀點來看，宜使用水。Examples of the solvent include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, and the like. From the viewpoint of reducing environmental load, it is appropriate to use water.
上述金屬奈米線分散液中金屬奈米線的分散濃度宜為0.1重量%~1重量%。若為所述範圍，便可形成導電性及光透射性優異的透明導電層。The dispersion concentration of the metal nanowires in the above-mentioned metal nanowire dispersion liquid is preferably 0.1% by weight to 1% by weight. If it is within the above range, a transparent conductive layer excellent in conductivity and light transmittance can be formed.
上述金屬奈米線分散液可因應目的進一步含有任意適當之添加劑。上述添加劑可舉例如用以防止金屬奈米線腐蝕的抗腐蝕材、用以防止金屬奈米線凝集的界面活性劑等。所使用之添加劑的種類、數量及量可按目的適當設定。The above-mentioned metal nanowire dispersion may further contain any appropriate additives according to the purpose. Examples of the additives include anti-corrosion materials to prevent corrosion of metal nanowires, surfactants to prevent aggregation of metal nanowires, and the like. The type, quantity and amount of additives used can be appropriately set according to the purpose.
上述金屬奈米線分散液的塗佈方法可採用任意適當之方法。塗佈方法可舉例如噴塗、棒塗、輥塗、模塗、噴墨塗佈、網版塗佈、浸塗、凸版印刷法、凹版印刷法、輪轉凹版印刷法等。塗佈層之乾燥方法可採用任意適當之乾燥方法(例如自然乾燥、送風乾燥、加熱乾燥)。例如，加熱乾燥時，乾燥溫度代表上為50℃~200℃，乾燥時間代表上為1~10分鐘。Any appropriate method may be used for coating the metal nanowire dispersion liquid. Examples of coating methods include spray coating, bar coating, roller coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing, gravure printing, rotogravure printing, and the like. The coating layer can be dried using any appropriate drying method (such as natural drying, air drying, and heating drying). For example, when heating and drying, the drying temperature is typically 50°C to 200°C, and the drying time is typically 1 to 10 minutes.
上述透明導電層中，相對於透明導電層之總重量，金屬奈米線的含有比率宜為30重量%~90重量%，較宜為45重量%~80重量%。若為所述範圍，便可獲得導電性及光透射性優異的透明導電性薄膜。In the above-mentioned transparent conductive layer, the content ratio of metal nanowires is preferably 30% to 90% by weight, more preferably 45% to 80% by weight relative to the total weight of the transparent conductive layer. Within the above range, a transparent conductive film excellent in conductivity and light transmittance can be obtained.
上述金屬奈米線為銀奈米線時，透明導電層之密度宜為1.3g/cm 3~10.5g/cm 3，較宜為1.5g/cm 3~3.0g/cm 3。若為所述範圍，便可獲得導電性及光透射性優異的透明導電性薄膜。 When the above-mentioned metal nanowires are silver nanowires, the density of the transparent conductive layer is preferably 1.3g/cm 3 ~10.5g/cm 3 , more preferably 1.5g/cm 3 ~3.0g/cm 3 . Within the above range, a transparent conductive film excellent in conductivity and light transmittance can be obtained.
在一實施形態中，上述透明導電層業經圖案化。圖案化之方法可因應透明導電層之形態採用任意適當之方法。透明導電層之圖案的形狀可因應用途為任意適當之形狀。可列舉例如：日本專利特表2011-511357號公報、日本專利特開2010-164938號公報、日本專利特開2008-310550號公報、日本專利特表2003-511799號公報、日本專利特表2010-541109號公報中記載之圖案。透明導電層可在形成於透明基材上之後，因應透明導電層之形態使用任意適當之方法進行圖案化。In one embodiment, the transparent conductive layer is patterned. The patterning method can adopt any appropriate method according to the shape of the transparent conductive layer. The shape of the pattern of the transparent conductive layer can be any appropriate shape according to the purpose. Examples include: Japanese Patent Application Publication No. 2011-511357, Japanese Patent Application Publication No. 2010-164938, Japanese Patent Application Publication No. 2008-310550, Japanese Patent Application Publication No. 2003-511799, Japanese Patent Application Publication No. 2010- The pattern recorded in Gazette No. 541109. After the transparent conductive layer is formed on the transparent substrate, it can be patterned using any appropriate method according to the shape of the transparent conductive layer.
(聚合物基質) 構成上述聚合物基質之聚合物可使用任意適當之聚合物。作為該聚合物可列舉例如：丙烯酸系聚合物；聚對苯二甲酸乙二酯等聚酯系聚合物；聚苯乙烯、聚乙烯基甲苯、聚乙烯基二甲苯、聚醯亞胺、聚醯胺、聚醯胺醯亞胺等芳香族系聚合物；聚胺甲酸酯系聚合物；環氧系聚合物；聚烯烴系聚合物；丙烯腈-丁二烯-苯乙烯共聚物(ABS)；纖維素；矽系聚合物；聚氯乙烯；聚乙酸酯；聚降𦯉烯；合成橡膠；氟系聚合物等。宜可使用：由新戊四醇三丙烯酸酯(PETA)、新戊二醇二丙烯酸酯(NPGDA)、二新戊四醇六丙烯酸酯(DPHA)、二新戊四醇五丙烯酸酯(DPPA)、三羥甲丙烷三丙烯酸酯(TMPTA)等多官能丙烯酸酯構成之硬化型樹脂(宜為紫外線硬化型樹脂)。 (polymer matrix) Any suitable polymer may be used as the polymer constituting the above-mentioned polymer matrix. Examples of the polymer include: acrylic polymers; polyester polymers such as polyethylene terephthalate; polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, and polyamide. Aromatic polymers such as amines and polyamide imines; polyurethane polymers; epoxy polymers; polyolefin polymers; acrylonitrile-butadiene-styrene copolymer (ABS) ; Cellulose; Silicone polymers; Polyvinyl chloride; Polyacetate; Polynorphene; Synthetic rubber; Fluorine polymers, etc. Suitable to use: composed of neopentyl erythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dineopenterythritol hexaacrylate (DPHA), and dineopenterythritol pentaacrylate (DPPA) , trimethylolpropane triacrylate (TMPTA) and other multifunctional acrylates (preferably UV curable resin).
上述聚合物基質如上述，可於透明基材上形成由金屬奈米線構成之層後，於該層上塗佈聚合物溶液，然後使塗佈層乾燥或硬化而形成。藉由該操作，可形成於聚合物基質中存在有金屬奈米線的透明導電層。The polymer matrix can be formed as described above by forming a layer of metal nanowires on a transparent substrate, coating the layer with a polymer solution, and then drying or hardening the coating layer. Through this operation, a transparent conductive layer in which metal nanowires exist in the polymer matrix can be formed.
上述聚合物溶液包含構成上述聚合物基質之聚合物、或該聚合物之前驅物(構成該聚合物之單體)。The above-mentioned polymer solution contains the polymer constituting the above-mentioned polymer matrix, or the polymer precursor (monomer constituting the polymer).
上述聚合物溶液可包含溶劑。上述聚合物溶液所含之溶劑可舉例如醇系溶劑、酮系溶劑、四氫呋喃、烴系溶劑或芳香族系溶劑等。該溶劑宜為揮發性。該溶劑之沸點宜為200℃以下，較宜為150℃以下，更宜為100℃以下。The above polymer solution may contain a solvent. Examples of the solvent contained in the polymer solution include alcohol solvents, ketone solvents, tetrahydrofuran, hydrocarbon solvents, and aromatic solvents. The solvent is preferably volatile. The boiling point of the solvent is preferably below 200°C, more preferably below 150°C, more preferably below 100°C.
C-2.透明基材 上述透明基材之厚度宜為8µm~500µm，較宜為10µm~250µm，更宜為10µm~150µm，尤宜為15µm~100µm。 C-2.Transparent substrate The thickness of the above-mentioned transparent substrate is preferably 8µm~500µm, more preferably 10µm~250µm, more preferably 10µm~150µm, especially 15µm~100µm.
上述透明基材之全光線透射率宜為80%以上，較宜為85%以上，尤宜為90%以上。若為所述範圍，便可獲得適於設置於觸控面板等之透明導電性薄膜的透明導電性薄膜。The total light transmittance of the above-mentioned transparent substrate is preferably above 80%, more preferably above 85%, especially above 90%. If it is within the above range, a transparent conductive film suitable for a transparent conductive film provided on a touch panel or the like can be obtained.
構成上述透明基材之樹脂只要可獲得本發明之效果，便可使用任意適當之樹脂。構成透明基材之樹脂可舉例如環烯烴系樹脂、聚醯亞胺系樹脂、聚二氯亞乙烯系樹脂、聚氯乙烯系樹脂、聚對苯二甲酸乙二酯系樹脂、聚萘二甲酸乙二酯系樹脂等。宜為環烯烴系樹脂。若使用環烯烴系樹脂，便可低價獲得具有高水分障壁性之透明基材。As the resin constituting the transparent base material, any appropriate resin may be used as long as the effects of the present invention can be obtained. Examples of the resin constituting the transparent base material include cycloolefin resin, polyimide resin, polyvinylidene chloride resin, polyvinyl chloride resin, polyethylene terephthalate resin, and polynaphthalenedicarboxylic acid. Ethylene glycol resin, etc. Preferably it is a cycloolefin resin. By using cycloolefin-based resin, a transparent base material with high moisture barrier properties can be obtained at low cost.
上述環烯烴系樹脂例如可適宜使用聚降𦯉烯。聚降𦯉莰烯係指於一部分或全部起始原料(單體)使用具有降𦯉烯環之降莰烯系單體而得的(共)聚合物。As the above-mentioned cycloolefin-based resin, for example, polynorphene can be suitably used. Polynorbornene refers to a (co)polymer obtained by using norbornene-based monomers having a norbornene ring as part or all of the starting materials (monomers).
上述聚降𦯉烯在市面上販售有各種製品。具體例可舉日本ZEON公司製之商品名「ZEONEX」、「ZEONOR」、JSR公司製之商品名「Arton」、TICONA公司製之商品名「TOPAS」、三井化學公司製之商品名「APEL」。The above-mentioned polynorphene is sold in various products on the market. Specific examples include the trade names "ZEONEX" and "ZEONOR" manufactured by Japan ZEON Co., Ltd., the trade name "Arton" manufactured by JSR Co., Ltd., the trade name "TOPAS" manufactured by TICONA Co., Ltd., and the trade name "APEL" manufactured by Mitsui Chemicals Co., Ltd.
構成上述透明基材之樹脂的玻璃轉移溫度宜為50℃~200℃，較宜為60℃~180℃，更宜為70℃~160℃。 若為具有所述範圍之玻璃轉移溫度的透明基材，便可防止形成透明導電層時之劣化。 The glass transition temperature of the resin constituting the transparent base material is preferably 50°C to 200°C, more preferably 60°C to 180°C, and more preferably 70°C to 160°C. If the transparent base material has a glass transition temperature within the above range, deterioration during formation of the transparent conductive layer can be prevented.
上述透明基材可視需要進一步含有任意適當之添加劑。添加劑之具體例可列舉：塑化劑、熱穩定劑、光穩定劑、滑劑、抗氧化劑、紫外線吸收劑、阻燃劑、著色劑、抗靜電劑、增容劑、交聯劑及增稠劑等。所使用之添加劑的種類及量可按目的適當設定。The above-mentioned transparent substrate may further contain any appropriate additives if necessary. Specific examples of additives include: plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, ultraviolet absorbers, flame retardants, colorants, antistatic agents, compatibilizers, cross-linking agents and thickening agents. Agents, etc. The type and amount of additives used can be appropriately set according to the purpose.
獲得上述透明基材之方法可使用任意適當之成形加工法，例如可從壓縮成形法、轉注成形法、射出成形法、擠製成形法、吹塑成形法、粉末成形法、FRP成形法及溶劑澆鑄法等選擇適當適切者。該等製法之中，又宜使用擠製成形法或溶劑澆鑄法。原因在於，可提高所得透明基材之平滑性，因而可獲得良好的光學均一性。成形條件可因應所使用樹脂之組成或種類等適當設定。The method for obtaining the above-mentioned transparent substrate can use any appropriate molding process, such as compression molding, transfer molding, injection molding, extrusion molding, blow molding, powder molding, FRP molding and solvent Choose the appropriate casting method, etc. Among these manufacturing methods, extrusion forming method or solvent casting method is preferably used. The reason is that the smoothness of the obtained transparent substrate can be improved, and therefore good optical uniformity can be obtained. Molding conditions can be appropriately set according to the composition or type of resin used.
亦可視需求對上述透明基材進行各種表面處理。表面處理可按目的採用任意適當之方法。可例如舉：低壓電漿處理、紫外線照射處理、電暈處理、火焰處理、酸或鹼處理。在一實施形態中，對透明基材進行表面處理使透明基材表面親水化。Various surface treatments can also be performed on the above-mentioned transparent substrates as required. Surface treatment can be carried out by any suitable method according to the purpose. Examples include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment. In one embodiment, the surface of the transparent substrate is treated to make the surface of the transparent substrate hydrophilic.
實施例 以下，藉由實施例來具體說明本發明，惟本發明不受該等實施例所限。各特性之測定方法如以下所述。此外，只要無特別註記，實施例及比較例中之「份」及「%」即為重量基準。 (1)可靠性評估 以非接觸電阻測定器(Napson(股) NC-80)，測定將感測器積層體(長50mm×寬50mm)投入65℃90%RH中240小時後之電阻值上升率。相對於初始電阻值，表面電阻值之上升率若為20%以下視為合格，上升率大於20%時則視為不合格。 (2)撓曲性評估 測定使感測器積層體撓曲後之電阻值。 於感測器積層體(長100mm×寬20mm)之導電層側長邊方向兩端塗佈Ag糊料而獲得試驗片。將該試驗片設成導電層為外側且覆於不鏽鋼圓棒(半徑：Rmm)上，並使其沿該圓棒撓曲180°，使長邊方向彎曲。接著，於長邊方向之兩端部透過夾具垂吊砝碼(各500g)，並在該狀態下保持10秒。 在上述操作之後，取下砝碼-夾具，並以測試機確認Ag糊料部間之表面電阻值(撓曲後之電阻值)。相對於撓曲前之表面電阻值，表面電阻值之上升率若為20%以下視為合格，上升率大於20%時則視為不合格。 Example Hereinafter, the present invention will be specifically described through examples, but the present invention is not limited by these examples. The measurement method of each characteristic is as follows. In addition, unless otherwise noted, "parts" and "%" in the examples and comparative examples are based on weight. (1)Reliability assessment A non-contact resistance measuring device (Napson Co., Ltd. NC-80) was used to measure the resistance value increase rate after the sensor laminate (length 50 mm × width 50 mm) was placed in 65°C 90% RH for 240 hours. Relative to the initial resistance value, if the increase rate of the surface resistance value is less than 20%, it is considered qualified, and if the increase rate is greater than 20%, it is considered unqualified. (2)Flexibility evaluation The resistance value after bending the sensor laminate is measured. Ag paste was applied to both ends in the longitudinal direction of the conductive layer side of the sensor laminate (100 mm long x 20 mm wide) to obtain a test piece. The test piece was covered with a stainless steel round rod (radius: Rmm) with the conductive layer on the outside, and was bent 180° along the round rod to bend in the long side direction. Then, weights (500g each) were hung from the two ends in the longitudinal direction through the clamps, and kept in this state for 10 seconds. After the above operation, remove the weight-clamp, and use a testing machine to confirm the surface resistance value (resistance value after deflection) between the Ag paste parts. Relative to the surface resistance value before deflection, if the increase rate of the surface resistance value is less than 20%, it is deemed to be qualified, and if the increase rate is greater than 20%, it is deemed to be unqualified.
[實施例1] (透明導電層形成用組成物(PN)之調製) 以上述銀奈米纖維分散液25重量份、純水75重量份稀釋，而調製出固體成分濃度0.05重量%之透明導電層形成用組成物(PN)。 (單體組成物之調製) 將新戊四醇三丙烯酸酯(大阪有機化學工業公司製，商品名「Viscoat #300」)1重量份、光聚合引發劑(BASF公司製，商品名「IRGACURE 907」)0.2重量份以異丙醇80重量份、二丙酮醇19重量份稀釋，而獲得固體成分濃度1重量%之單體組成物。 (透明導電性薄膜之製作) 於基材(環烯烴薄膜(日本ZEON公司製，商品名「ZEONOR(註冊商標)」，厚度55µm)之一側塗佈上述透明導電層形成用組成物(PN)，使其乾燥。並於透明導電層形成用組成物(PN)塗佈層上塗佈上述單體組成物，在90℃下乾燥1分鐘後，照射300mJ/cm 2之紫外線而形成透明導電層。 (相位差薄膜之製作) 將異山梨醇(Roquette Frères公司製，商品名：POLYSORB)445.1重量份、9,9-(4-(2-羥乙氧基)苯基)茀(Osaka Gas Chemicals Co., Ltd.製)906.2重量份、分子量1000之聚乙二醇15.4重量份、碳酸二苯酯(三洋化成工業(股)製)1120.4重量份及作為觸媒之碳酸銫(0.2重量%水溶液)6.27重量份分別投入反應器中，在氮氣環境下，在反應第1階段步驟中將反應容器之加熱介質溫度設為150℃，一邊視需求攪拌一邊使原料溶解(約15分鐘)。接著將反應容器內之壓力從常壓變更至13.3kPa，一邊以1小時使反應容器之加熱介質溫度升溫至190℃，一邊將產生之酚排出反應容器外。歷經該步驟而製出聚碳酸酯。 在80℃下將製出之聚碳酸酯真空乾燥5小時後，使用具備單軸擠製機(Isuzu Chemical Industries Co.,Ltd.製，螺桿徑25mm，缸筒設定溫度：220℃，T型模(寬200mm，設定溫度：220℃)，冷卻輥(設定溫度：120~130℃))及捲取機之薄膜製膜裝置，而獲得厚度100µm之原板薄膜。將該試料以分批式雙軸延伸裝置(東洋精機公司製)，一邊在127~177℃下調節延伸溫度，一邊以延伸速度720mm/分鐘(應變速度1200%/分鐘)進行1×2.0倍的單軸延伸，使R1(550)成為140±10nm，而獲得厚度35µm之λ/4相位差薄膜。 (貼合有偏光板之感測器積層體) 於具有保護薄膜/偏光件/相位差薄膜之構成的圓偏光板，透過丙烯酸系黏著劑層貼合厚度之相位差薄膜與上述透明導電層使該等鄰接，而獲得感測器積層體。丙烯酸系黏著劑層之厚度係設為15µm，且如上述，相位差薄膜之厚度係設為35µm，亦即將偏光件與該透明導電層之距離A設為50µm。 將所得感測器積層體供於上述評估。將結果顯示於表1。 [Example 1] (Preparation of a transparent conductive layer forming composition (PN)) Dilute 25 parts by weight of the silver nanofiber dispersion and 75 parts by weight of pure water to prepare a transparent conductive composition with a solid content concentration of 0.05% by weight. Layer forming composition (PN). (Preparation of monomer composition) 1 part by weight of neopentylerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #300"), photopolymerization initiator (manufactured by BASF Co., Ltd., trade name "IRGACURE 907") ") 0.2 parts by weight was diluted with 80 parts by weight of isopropyl alcohol and 19 parts by weight of diacetone alcohol to obtain a monomer composition with a solid content concentration of 1% by weight. (Preparation of transparent conductive film) The above-mentioned transparent conductive layer forming composition (PN) is applied to one side of the base material (cycloolefin film (manufactured by Japan ZEON Co., Ltd., trade name "ZEONOR (registered trademark)", thickness 55 μm)) , and let it dry. The above-mentioned monomer composition is coated on the transparent conductive layer forming composition (PN) coating layer, dried at 90°C for 1 minute, and then irradiated with ultraviolet rays of 300mJ/cm 2 to form a transparent conductive layer. . (Preparation of retardation film) 445.1 parts by weight of isosorbide (manufactured by Roquette Frères, trade name: POLYSORB), 9,9-(4-(2-hydroxyethoxy)phenyl)quinone (Osaka Gas Chemicals Co., Ltd.), 15.4 parts by weight of polyethylene glycol with a molecular weight of 1000, 1120.4 parts by weight of diphenyl carbonate (manufactured by Sanyo Chemical Industry Co., Ltd.) and cesium carbonate (0.2% by weight aqueous solution) as a catalyst )6.27 parts by weight were put into the reactor respectively. In the first stage of the reaction under a nitrogen atmosphere, set the heating medium temperature of the reaction vessel to 150°C and dissolve the raw materials while stirring as needed (about 15 minutes). Then The pressure in the reaction vessel was changed from normal pressure to 13.3 kPa, and the generated phenol was discharged out of the reaction vessel while raising the temperature of the heating medium in the reaction vessel to 190°C for 1 hour. Polycarbonate was produced through this step. After vacuum drying the produced polycarbonate at 80°C for 5 hours, use a single-screw extruder (manufactured by Isuzu Chemical Industries Co., Ltd., screw diameter 25mm, cylinder set temperature: 220°C, T-die ( Width 200mm, set temperature: 220℃), cooling roller (set temperature: 120~130℃)) and film forming device of the winding machine to obtain an original film with a thickness of 100µm. The sample was biaxially stretched in batches The device (manufactured by Toyo Seiki Co., Ltd.) performs uniaxial stretching of 1×2.0 times at a stretching speed of 720 mm/min (strain rate of 1200%/min) while adjusting the stretching temperature at 127 to 177°C, so that R1 (550) becomes 140±10nm to obtain a λ/4 retardation film with a thickness of 35µm. (Sensor laminate with polarizing plate attached) On a circularly polarizing plate composed of a protective film/polarizer/retardation film, through an acrylic The adhesive layer is bonded to a thick retardation film and the above-mentioned transparent conductive layer so that they are adjacent to each other to obtain a sensor laminate. The thickness of the acrylic adhesive layer is set to 15µm, and as mentioned above, the thickness of the retardation film is Set to 35µm, that is, the distance A between the polarizer and the transparent conductive layer is set to 50µm. The obtained sensor laminate was submitted to the above evaluation. The results are shown in Table 1.
[實施例2] 除了將丙烯酸系黏著劑層之厚度設為23µm(將距離A設為58µm)外，依與實施例1相同方式而獲得感測器積層體。將所得感測器積層體供於上述評估。將結果顯示於表1。 [Example 2] A sensor laminate was obtained in the same manner as in Example 1, except that the thickness of the acrylic adhesive layer was set to 23 μm (the distance A was set to 58 μm). The obtained sensor laminate was used for the above evaluation. The results are shown in Table 1.
[比較例1] 除了將相位差薄膜之厚度設為60µm(將距離A設為75µm)外，依與實施例1相同方式而獲得感測器積層體。將所得感測器積層體供於上述評估。將結果顯示於表1。 [Comparative example 1] A sensor laminate was obtained in the same manner as in Example 1, except that the thickness of the retardation film was set to 60 µm (the distance A was set to 75 µm). The obtained sensor laminate was used for the above evaluation. The results are shown in Table 1.
[實施例3] 使用具有保護薄膜/偏光件/第1相位差薄膜(厚度：5µm之液晶性相位差層)/第2相位差層(厚度：3µm之液晶性相位差層)之構成的圓偏光板來取代具有保護薄膜/偏光件/相位差薄膜之構成的圓偏光板，且將丙烯酸系黏著劑層之厚度設為30µm，除此之外依與實施例1相同方式而獲得感測器積層體(距離A：38µm)。將所得感測器積層體供於上述評估。將結果顯示於表1。 [Example 3] Use a circular polarizing plate composed of a protective film/polarizer/first retardation film (thickness: 5 µm liquid crystal retardation layer)/second retardation layer (thickness: 3 µm liquid crystal retardation layer). A circularly polarizing plate composed of a protective film/polarizer/retardation film, and the thickness of the acrylic adhesive layer was set to 30 µm. In addition, a sensor laminate (distance A) was obtained in the same manner as in Example 1. :38µm). The obtained sensor laminate was used for the above evaluation. The results are shown in Table 1.
[實施例4] 除了將丙烯酸系黏著劑層之厚度設為45µm(將距離A設為53µm)外，依與實施例3相同方式而獲得感測器積層體。將所得感測器積層體供於上述評估。將結果顯示於表1。 [Example 4] A sensor laminate was obtained in the same manner as in Example 3, except that the thickness of the acrylic adhesive layer was set to 45 μm (the distance A was set to 53 μm). The obtained sensor laminate was used for the above evaluation. The results are shown in Table 1.
[比較例2] 除了將丙烯酸系黏著劑層之厚度設為15µm(將距離A設為23µm)外，依與實施例3相同方式而獲得感測器積層體。將所得感測器積層體供於上述評估。將結果顯示於表1。 [Comparative example 2] A sensor laminate was obtained in the same manner as in Example 3, except that the thickness of the acrylic adhesive layer was set to 15 μm (the distance A was set to 23 μm). The obtained sensor laminate was used for the above evaluation. The results are shown in Table 1.
[參考例1] 於形成有硬化樹脂層之環烯烴薄膜上，透過15µm之丙烯酸系黏著劑層貼合下述透明導電性薄膜與具有保護薄膜/偏光件/第1相位差薄膜/第2相位差層之構成的圓偏光板，使第2相位差層與透明導電層鄰接，該透明導電性薄膜係將厚度為25nm之由非晶質銦-錫氧化物構成的透明導電層利用反應性濺鍍成膜而成者，藉此獲得貼合有偏光板之感測器積層體。將該貼合有偏光板之感測器積層體供於上述撓曲性評估後，結果不合格。 [Reference example 1] The following transparent conductive film and a protective film/polarizer/first retardation film/second retardation layer are bonded to a cycloolefin film with a hardened resin layer formed on it through a 15µm acrylic adhesive layer. Circularly polarizing plate with the second retardation layer adjacent to the transparent conductive layer. The transparent conductive film is formed by reactive sputtering of a 25 nm thick transparent conductive layer composed of amorphous indium-tin oxide. In this way, a sensor laminate laminated with a polarizing plate is obtained. When the sensor laminate with the polarizing plate was subjected to the above-mentioned flexibility evaluation, the result was found to be unsatisfactory.
[表1] [Table 1]
10:透明導電性薄膜
11:透明導電層
12:透明基材
20:偏光板
21:偏光件
22:透明導電性薄膜側結構體
22a:第1相位差層
22b:第2相位差層
22c:黏著劑層
23:保護層
100,100':感測器積層體
A:距離
10:Transparent conductive film
11:Transparent conductive layer
12:Transparent substrate
20:Polarizing plate
21:Polarizer
22: Transparent conductive
圖1係本發明一實施形態之感測器積層體的概略截面圖。 圖2係本發明另一實施形態之感測器積層體的概略截面圖。 FIG. 1 is a schematic cross-sectional view of a sensor laminate according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a sensor laminate according to another embodiment of the present invention.
10:透明導電性薄膜 10:Transparent conductive film
11:透明導電層 11:Transparent conductive layer
12:透明基材 12:Transparent substrate
20:偏光板 20:Polarizing plate
21:偏光件 21:Polarizer
22:透明導電性薄膜側結構體 22: Transparent conductive film side structure
23:保護層 23:Protective layer
100:感測器積層體 100: Sensor laminate
A:距離 A:Distance
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