TWI881085B - Adhesive optical film - Google Patents
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- TWI881085B TWI881085B TW110110676A TW110110676A TWI881085B TW I881085 B TWI881085 B TW I881085B TW 110110676 A TW110110676 A TW 110110676A TW 110110676 A TW110110676 A TW 110110676A TW I881085 B TWI881085 B TW I881085B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
本發明提供一種包含光透射性構件與積層於該光透射性構件上之黏著劑層的黏著型光學薄膜。上述黏著型光學薄膜具有藉由上述黏著劑層構成之黏著面。上述黏著劑層之折射率大於1.570,全光線透射率為86%以上,且霧度值為3.0%以下。The present invention provides an adhesive optical film comprising a light-transmitting member and an adhesive layer laminated on the light-transmitting member. The adhesive optical film has an adhesive surface formed by the adhesive layer. The adhesive layer has a refractive index greater than 1.570, a total light transmittance of greater than 86%, and a haze value of less than 3.0%.
Description
本發明涉及黏著型光學薄膜,詳細而言涉及包含光透射性構件與接合於該光透射性構件之黏著劑層的黏著型光學薄膜。 本申請案主張依據已於2020年3月24提申之日本專利申請案2020-052408號、已於2020年9月30日提申之日本專利申請案2020-166427號、及已於2021年3月23日提申之日本專利申請案2021-049060號的優先權,並將該等申請案之全部內容納入本說明書中作為參照。The present invention relates to an adhesive optical film, and more specifically, to an adhesive optical film comprising a light-transmitting member and an adhesive layer bonded to the light-transmitting member. This application claims priority based on Japanese Patent Application No. 2020-052408 filed on March 24, 2020, Japanese Patent Application No. 2020-166427 filed on September 30, 2020, and Japanese Patent Application No. 2021-049060 filed on March 23, 2021, and all the contents of these applications are incorporated into this specification by reference.
一般而言,黏著劑(亦稱壓敏接著劑,以下亦同)在室溫附近之溫度區域下呈現軟質固體(黏彈性體)之狀態,具有可藉由壓力簡單地接著於被黏著體之性質。而活用這種性質,黏著劑在從家電製品至汽車、各種機械、電氣機器、電子機器等各種產業領域中,於接合或固定、保護等之目的下被廣泛利用。作為黏著劑之用途之一例,可舉在液晶顯示裝置或有機EL顯示裝置等這類顯示裝置中,接合偏光薄膜、相位差薄膜、覆蓋窗構件、其他各種光透射性構件及其他構件之用途。有關光學構件用黏著劑之技術文獻可舉專利文獻1、2。
先前技術文獻
專利文獻Generally speaking, adhesives (also called pressure-sensitive adhesives, the same below) are in the state of soft solids (viscoelastic bodies) in the temperature range near room temperature, and have the property of being able to be simply bonded to the adherend by pressure. By utilizing this property, adhesives are widely used in various industrial fields, from home appliances to automobiles, various machinery, electrical machinery, electronic machinery, etc., for the purpose of bonding, fixing, and protection. As an example of the use of adhesives, it can be cited that in display devices such as liquid crystal display devices or organic EL display devices, polarizing films, phase difference films, cover window components, other various light-transmitting components, and other components are bonded. Technical documents related to adhesives for optical components include
專利文獻1:日本專利申請案公開2014-169382號公報 專利文獻2:日本專利申請案公開2017-128732號公報Patent document 1: Japanese patent application publication No. 2014-169382 Patent document 2: Japanese patent application publication No. 2017-128732
發明欲解決之課題
專利文獻1、2中提出了一種以(甲基)丙烯酸酯聚合物為主成分之黏著劑組成物、及使該黏著劑組成物交聯而成之黏著劑,且該(甲基)丙烯酸酯聚合物含有具有複數個芳香環之單體作為單體單元,但未揭示折射率大於1.570之具體的黏著劑。另一方面,亦已知一種將由高折射率的無機材料構成之粒子(例如氧化鋯粒子或氧化鈦粒子等無機粒子)摻混於樹脂中來提升折射率的技術,但摻混有無機粒子的黏著劑因折射率與黏著特性(例如剝離強度、柔軟性等)處於抵換關係,故難以應用於黏著劑領域。尤其以供於光學用途之黏著劑來說,在摻混無機粒子時亦須考量到對光學特性(例如全光線透射率、霧度等)之影響。因此,不易實現以下黏著型光學薄膜:於光透射性構件(例如光學薄膜)上具備兼顧了大於1.570的折射率與良好光學特性(透明性)之黏著劑層,且顯示實用黏著性能者。Problems to be solved by the
本發明係有鑑於上述狀況而創造者,其目的在於提供一種具有兼具高折射率與良好光學特性之黏著劑層的黏著型光學薄膜。本發明之其他目的在於提供一種包含上述黏著型光學薄膜之附剝離襯墊之黏著型光學薄膜。The present invention is created in view of the above situation, and its purpose is to provide an adhesive optical film having an adhesive layer with both high refractive index and good optical properties. Another purpose of the present invention is to provide an adhesive optical film with a peel-off pad including the above adhesive optical film.
用以解決課題之手段 根據本說明書,可提供一種包含光透射性構件與積層於該光透射性構件上之黏著劑層的黏著型光學薄膜。上述黏著型光學薄膜具有藉由上述黏著劑層構成之黏著面。上述黏著劑層之折射率大於1.570,全光線透射率為86%以上,且霧度值為3.0%以下。所述黏著型光學薄膜中光透射性構件與黏著劑層已一體化,故藉由使用該黏著型光學薄膜,可有效率地且精度良好地形成上述光透射性構件與被黏著體透過上述黏著劑層積層之結構。Means for solving the problem According to the present specification, an adhesive optical film comprising a light-transmitting member and an adhesive layer laminated on the light-transmitting member can be provided. The adhesive optical film has an adhesive surface formed by the adhesive layer. The adhesive layer has a refractive index greater than 1.570, a total light transmittance of greater than 86%, and a haze value of less than 3.0%. In the adhesive optical film, the light-transmitting member and the adhesive layer are integrated, so by using the adhesive optical film, a structure in which the light-transmitting member and the adherend are laminated through the adhesive layer can be formed efficiently and with good precision.
在數個態樣中,上述黏著劑層之厚度為5µm以上。藉由具有所述厚度之黏著劑層,便容易獲得良好之黏著特性。又,具有所述厚度之黏著劑層會吸收可能存在於被黏著體表面之凹凸而容易密著性良好地接合於該被黏著體,因此可於被黏著體上適當設置高折射率之黏著劑層。In several aspects, the thickness of the adhesive layer is 5µm or more. With the adhesive layer having the above thickness, good adhesive properties can be easily obtained. In addition, the adhesive layer having the above thickness can absorb the unevenness that may exist on the surface of the adherend and can be easily bonded to the adherend with good adhesion, so an adhesive layer with a high refractive index can be appropriately set on the adherend.
在數個態樣中,上述黏著型光學薄膜對玻璃板之剝離強度(黏著力)為3N/25mm以上。由與被黏著體之接合可靠性之觀點來看,宜具有所述黏著力。In some embodiments, the peel strength (adhesion force) of the adhesive optical film to the glass plate is 3N/25mm or more. From the perspective of reliability of bonding with an adherend, it is desirable to have such adhesion force.
在數個態樣中,上述黏著面之算術平均粗度Ra為100nm以下。由光學均質性之觀點來看,宜具有所述高平滑之黏著面。例如,在通過上述黏著面擷取光之使用態樣(在發光裝置中上述黏著劑層配置於較自發光元件更靠視點側之態樣等)中,便可抑制因黏著劑層之表面狀態而發生亮度不均。In several embodiments, the arithmetic mean roughness Ra of the adhesive surface is less than 100 nm. From the viewpoint of optical homogeneity, it is preferable to have the highly smooth adhesive surface. For example, in the use embodiment in which light is captured by the adhesive surface (in the light-emitting device, the adhesive layer is arranged on the viewpoint side relative to the light-emitting element, etc.), it is possible to suppress uneven brightness caused by the surface state of the adhesive layer.
在數個態樣中,上述黏著劑層之吸水率為1.0%以下。藉由吸水率低之黏著劑層,可抑制該黏著劑層中之水分量的變動造成黏著劑層之尺寸變化。藉此,可抑制黏著型光學薄膜或包含該黏著型光學薄膜之積層體的翹曲。In some embodiments, the water absorption rate of the adhesive layer is less than 1.0%. The adhesive layer with low water absorption rate can suppress the change of the water content in the adhesive layer and cause the dimensional change of the adhesive layer. Thereby, the warping of the adhesive optical film or the laminate including the adhesive optical film can be suppressed.
在數個態樣中,上述黏著型光學薄膜係以包含上述黏著劑層與作為上述光透射性構件之樹脂薄膜的積層體之形式構成。藉由將所述構成之黏著型光學薄膜貼附於被黏著體,可輕易形成該被黏著體與上述光透射性構件透過高折射率之黏著劑層積層之結構。In some embodiments, the adhesive optical film is formed in the form of a laminate including the adhesive layer and the resin film as the light-transmitting member. By attaching the adhesive optical film formed in the above manner to an adherend, a structure in which the adherend and the light-transmitting member are laminated through the adhesive layer with a high refractive index can be easily formed.
又,根據本說明書,可提供一種附剝離襯墊之黏著型光學薄膜,其包含在此揭示之任一黏著型光學薄膜與配置於上述黏著型光學薄膜之黏著面上的剝離襯墊。在此揭示之黏著型光學薄膜可適宜在以下態樣下使用:其以如前所述於黏著面上配置有剝離襯墊之附剝離襯墊之黏著型光學薄膜的形態進行製造、保管、流通、加工等,並在貼附於被黏著體之前從黏著面剝除剝離襯墊。Furthermore, according to the present specification, an adhesive optical film with a peel-off liner can be provided, which includes any of the adhesive optical films disclosed herein and a peel-off liner disposed on the adhesive surface of the adhesive optical film. The adhesive optical film disclosed herein can be suitably used in the following manner: the adhesive optical film with a peel-off liner disposed on the adhesive surface as described above is manufactured, stored, distributed, processed, etc., and the peel-off liner is peeled off from the adhesive surface before being attached to an adherend.
此外,適當組合本說明書所記載之各要素而成者亦可包含於藉由本件專利申請案尋求專利保護之發明範圍中。In addition, an appropriate combination of the elements described in this specification may also be included in the scope of the invention for which patent protection is sought through this patent application.
以下說明本發明之理想實施形態。本說明書中未特別言及之事項以外且為本發明實施所需之情事,乃熟知此項技藝之人士可根據關於本說明書所載發明實施之教示及申請時之技術常識而理解。本發明得以根據本說明書中所揭示之內容及該領域之技術常識來實施。 此外,在以下圖式中,對於發揮相同作用之構件、部位有賦予相同符號來說明之情形,且重複之說明有省略或簡化之情形。又,圖式中記載之實施形態係為了清楚說明本發明而業經示意化,並非完全正確表示實際提供之製品的尺寸或比例尺。The following describes the ideal implementation form of the present invention. Matters other than those specifically mentioned in this specification and necessary for the implementation of the present invention can be understood by those familiar with this art based on the teachings on the implementation of the invention contained in this specification and the technical common sense at the time of application. The present invention can be implemented based on the contents disclosed in this specification and the technical common sense in this field. In addition, in the following figures, components and parts that play the same role are given the same symbols for description, and repeated descriptions are omitted or simplified. In addition, the implementation forms recorded in the figures are schematic for the purpose of clearly explaining the present invention, and do not completely correctly represent the size or scale of the actual product provided.
本說明書中,自發光元件意指可藉由流通的電流值來控制發光亮度的發光元件。自發光元件可以單一體構成,亦可以集合體來構成。自發光元件之具體例包含發光二極體(LED)及有機EL,惟不受該等限定。在本說明書中提及發光裝置時,該發光裝置可包含所述自發光元件作為構成要素。在上述發光裝置之例中,還包含作為照明利用之光源模組裝置(例如面狀發光體模組)或形成有畫素之顯示裝置,惟不受該等限定。In this specification, a self-luminous element means a light-emitting element whose luminance can be controlled by the value of the current flowing therethrough. A self-luminous element can be constituted as a single body or as an aggregate. Specific examples of self-luminous elements include light-emitting diodes (LEDs) and organic ELs, but are not limited thereto. When a light-emitting device is mentioned in this specification, the light-emitting device may include the self-luminous element as a constituent element. The examples of the above-mentioned light-emitting devices also include light source module devices (such as planar light-emitting body modules) used for lighting or display devices formed with pixels, but are not limited thereto.
<黏著型光學薄膜之構成例>
將藉由本說明揭示之黏著型光學薄膜的一構成例顯示於圖1。該黏著型光學薄膜1係構成為單面接著性之黏著型光學薄膜(單面黏著片),其包含:黏著劑層10,其係第1表面10A成為貼附於被黏著體之貼附面(黏著面)者;及光透射性構件20,其係積層於黏著劑層10之第2表面10B者。黏著劑層10之第2表面10B係接合於光透射性構件20之第1面(非剝離性表面)20A。光透射性構件20例如可為光學用樹脂薄膜。光透射性構件20亦可為偏光板等之光學薄膜。使用前(貼附於被黏著體前)之黏著型光學薄膜1例如可如圖1所示,為黏著面10A被剝離襯墊30保護之附剝離襯墊之黏著型光學薄膜50的形態,而該剝離襯墊30係至少該黏著劑層側成為剝離性表面(剝離面)者。或者,亦可為以下形態:光透射性構件20之第2面20B(與第1面20A相反之側的表面,亦稱背面)成為剝離面,且以使黏著面10A抵接該第2面20B之方式捲繞或積層,藉以保護黏著面10A。黏著劑層10可為單層結構,亦可為2層以上組成相異之子黏著劑層直接接觸(亦即,未被非黏著性材料之層隔開)積層而成之積層結構。<Configuration example of adhesive optical film>
An example of the configuration of the adhesive optical film disclosed by the present description is shown in FIG1. The adhesive
在此揭示之黏著型光學薄膜可為黏著劑層之至少一表面接合有光學構件的光學積層體的構成要素。例如,圖1所示黏著型光學薄膜1可如圖2所示,為黏著劑層10之第1表面10A接合有光學構件70的光學積層體100的構成要素。上述光學構件例如可為玻璃板、樹脂薄膜、金屬板等。又,在圖1所示之黏著型光學薄膜1中,當光透射性構件20為光學薄膜等之光學構件時,該黏著型光學薄膜1可視為黏著劑層10之第2表面10B接合有光學構件的光學積層體。The adhesive optical film disclosed herein may be a constituent element of an optical laminate in which an optical component is bonded to at least one surface of an adhesive layer. For example, the adhesive
又,雖無特別圖示,在此揭示之黏著型光學薄膜亦可為下述雙面接著性之黏著型光學薄膜之形態:具備具有非剝離性之第1面及第2面的光透射性構件,並且上述第1面上固定積層有第1黏著劑層,且上述第2面上固定積層有第2黏著劑層。作為所述雙面接著性之黏著型光學薄膜(以下,亦稱雙面黏著型光學薄膜)的構成例,可舉下述形態:在圖1所示黏著型光學薄膜(單面黏著片)1中,光透射性構件20之第2面20B為非剝離性表面且該第2面20B上設有第2黏著劑層,上述第2黏著劑層之第2表面接合於光透射性構件20之第2面20B,且上述第2黏著劑層之第1表面(與第2表面相反之側的表面)成為雙面黏著型光學薄膜的第2黏著面。構成第2黏著劑層之黏著劑之組成可與構成第1黏著劑層之黏著劑之組成相同,亦可互異。使用前之雙面黏著型光學薄膜可為第1黏著面及第2黏著面被剝離襯墊保護之形態。Furthermore, although not specifically illustrated, the adhesive optical film disclosed herein may also be in the form of a double-sided adhesive optical film: a light-transmissive member having a first non-releasable surface and a second surface, wherein a first adhesive layer is fixedly laminated on the first surface, and a second adhesive layer is fixedly laminated on the second surface. As an example of the structure of the double-sided adhesive optical film (hereinafter, also referred to as the double-sided adhesive optical film), the following form can be cited: in the adhesive optical film (single-sided adhesive sheet) 1 shown in FIG. 1, the
此外,在此揭示之黏著型光學薄膜可為卷狀亦可為薄片狀。或者亦可為進一步加工成各種形狀之形態的黏著型光學薄膜。In addition, the adhesive optical film disclosed herein may be in a roll or sheet form, or may be an adhesive optical film further processed into various shapes.
<黏著劑層之特性> (折射率) 在此揭示之黏著型光學薄膜具有折射率大於1.570之黏著劑層。所述黏著劑層可藉由利用折射率大於1.570之黏著劑構成該黏著劑層之至少一表面(黏著面)來實現。根據在此揭示之技術,可提供:折射率大於1.570之黏著劑、可形成該黏著劑之黏著劑組成物、及包含上述黏著劑之黏著型光學薄膜。<Characteristics of adhesive layer> (Refractive index) The adhesive optical film disclosed herein has an adhesive layer having a refractive index greater than 1.570. The adhesive layer can be realized by using an adhesive having a refractive index greater than 1.570 to constitute at least one surface (adhesive surface) of the adhesive layer. According to the technology disclosed herein, there can be provided: an adhesive having a refractive index greater than 1.570, an adhesive composition that can form the adhesive, and an adhesive optical film containing the above-mentioned adhesive.
此外,本說明書中,黏著劑之折射率意指該黏著劑之表面(黏著面)的折射率。黏著劑之折射率可使用市售的折射率測定裝置(阿貝折射計),在測定波長589nm、測定溫度25℃之條件下進行測定。阿貝折射計例如可使用ATAGO公司製之型式「DR-M4」或其等效品。測定試樣可使用由評估對象之黏著劑構成之黏著劑層。黏著劑之折射率具體上可以後述實施例記載之方法來測定。黏著劑之折射率可藉由例如該黏著劑之組成(例如構成基底聚合物之單體成分的組成、可因應需要使用之添加劑等)來調節。In addition, in this specification, the refractive index of the adhesive means the refractive index of the surface (adhesive surface) of the adhesive. The refractive index of the adhesive can be measured using a commercially available refractive index measuring device (Abbe refractometer) under the conditions of a measuring wavelength of 589nm and a measuring temperature of 25°C. The Abbe refractometer can use, for example, the model "DR-M4" manufactured by ATAGO or its equivalent. The measuring sample can use an adhesive layer composed of the adhesive of the evaluation object. The refractive index of the adhesive can be specifically measured by the method described in the embodiments described later. The refractive index of the adhesive can be adjusted by, for example, the composition of the adhesive (for example, the composition of the monomer components constituting the base polymer, additives that can be used as needed, etc.).
在數個態樣中,上述黏著劑之折射率宜為1.580以上,較宜為1.585以上,更宜為1.590以上(例如1.595以上)。藉由具有所述折射率之黏著劑,可利用該黏著劑與被黏著體之相對性之折射率之關係,來有效控制透射該黏著劑之光的行為。在此揭示之黏著劑之數個態樣中,該黏著劑之折射率例如可為1.600以上或大於1.600,1.605以上或大於1.605,或者1.610以上或大於1.610。黏著劑之折射率的理想上限可因應被黏著體的折射率等而不同,故不受特定範圍所限。在數個態樣中,考量到與黏著特性或透明性之平衡,黏著劑之折射率例如可為1.700以下,可為1.670以下,亦可為1.650以下。In several aspects, the refractive index of the above-mentioned adhesive is preferably above 1.580, more preferably above 1.585, and more preferably above 1.590 (for example, above 1.595). By using an adhesive having the above-mentioned refractive index, the behavior of light transmitted through the adhesive can be effectively controlled by utilizing the relationship between the relative refractive indices of the adhesive and the adherend. In several aspects of the adhesive disclosed herein, the refractive index of the adhesive can be, for example, above 1.600 or greater, above 1.605 or greater, or above 1.610 or greater. The ideal upper limit of the refractive index of the adhesive can vary depending on the refractive index of the adherend, etc., and is therefore not limited to a specific range. In some aspects, in consideration of the balance with adhesive properties or transparency, the refractive index of the adhesive may be, for example, 1.700 or less, 1.670 or less, or 1.650 or less.
在此揭示之黏著型光學薄膜為其中一面成為第1黏著面且另一面成為第2黏著面之雙面黏著型光學薄膜之形態時,只要至少第1黏著面滿足上述任一折射率即可,而第2黏著面之折射率無特別限制。 在數個態樣中,第2黏著面之折射率n2 可為與第1黏著面之折射率n1 大致相同程度。更具體而言,兩黏著面之折射率之差的絕對值、亦即|n1 -n2 |,可為例如小於0.05,或小於0.03,或小於0.01。|n1 -n2 |的下限可為0.00,亦可大於0.00。兩黏著面之折射率的相對關係可為n1 >n2 ,可為n1 <n2 ,亦可為n1 =n2 。 在其他數個態樣中,雙面黏著型光學薄膜之第1黏著面的折射率n1 與第2黏著面的折射率n2 之差、亦即n1 -n2 ,例如可大於0.00,可為0.01以上,可為0.03以上,可為0.05以上,可為0.10以上,可為0.15以上,可為0.20以上,亦可為0.25以上。n1 與n2 之大小關係亦可相反。在第1黏著面與第2黏著面之折射率相異的雙面黏著型光學薄膜例如可藉由於光透射性構件之第1面及第2面積層折射率相異之第1、第2黏著劑層來實現。When the adhesive optical film disclosed herein is a double-sided adhesive optical film in which one side is the first adhesive side and the other side is the second adhesive side, it is sufficient that at least the first adhesive side satisfies any of the above-mentioned refractive indices, and the refractive index of the second adhesive side is not particularly limited. In several aspects, the refractive index n2 of the second adhesive side can be substantially the same as the refractive index n1 of the first adhesive side. More specifically, the absolute value of the difference in refractive index between the two adhesive sides, i.e., | n1 - n2 |, can be, for example, less than 0.05, or less than 0.03, or less than 0.01. The lower limit of | n1 - n2 | can be 0.00 or greater than 0.00. The relative relationship of the refractive index of the two adhesive surfaces may be n 1 >n 2 , n 1 <n 2 , or n 1 =n 2 . In several other aspects, the difference between the refractive index n 1 of the first adhesive surface and the refractive index n 2 of the second adhesive surface of the double-sided adhesive optical film, i.e., n 1 -n 2 , may be, for example, greater than 0.00, may be greater than 0.01, may be greater than 0.03, may be greater than 0.05, may be greater than 0.10, may be greater than 0.15, may be greater than 0.20, or may be greater than 0.25. The magnitude relationship between n 1 and n 2 may also be opposite. A double-sided adhesive optical film having different refractive indices on the first adhesive surface and the second adhesive surface can be realized by, for example, forming first and second adhesive layers having different refractive indices on the first and second surfaces of a light-transmitting member.
(全光線透射率) 在此揭示之黏著型光學薄膜具備具有上述高折射率且全光線透射率為86%以上的黏著劑層。在數個態樣中,上述黏著劑層之全光線透射率宜為88%以上,90%以上(例如大於90.0%)較佳,可為90.5%以上,可為93%以上,亦可為95%以上。全光線透射率的上限在理論上係從100%排除在空氣界面產生之反射所造成之光損失(弗芮耳損失(Fresnel loss))所得之值,實用上可為大約98%以下,可為大約96%以下,亦可為大約95%以下。在數個態樣中,考量到折射率或黏著特性,黏著劑層之全光線透射率可為大約94%以下,可為大約93%以下,亦可為大約92%以下。全光線透射率係根據JIS K 7136:2000,使用市售的透射率計來測定。透射率計可使用村上色彩技術研究所製之商品名「HAZEMETER HM-150」或其等效品。更具體來說,例如可依後述實施例來測定黏著劑層之全光線透射率。黏著劑層之全光線透射率可藉由例如選擇該黏著劑層之組成或厚度等來調節。(Total light transmittance) The adhesive optical film disclosed herein has an adhesive layer having the above-mentioned high refractive index and a total light transmittance of 86% or more. In several embodiments, the total light transmittance of the above-mentioned adhesive layer is preferably 88% or more, preferably 90% or more (for example, greater than 90.0%), and can be 90.5% or more, 93% or more, or 95% or more. The upper limit of the total light transmittance is theoretically the value obtained by 100% excluding the light loss (Fresnel loss) caused by reflection generated at the air interface, and can be practically less than about 98%, less than about 96%, or less than about 95%. In several aspects, taking into account the refractive index or adhesive properties, the total light transmittance of the adhesive layer may be less than about 94%, less than about 93%, or less than about 92%. The total light transmittance is measured according to JIS K 7136:2000 using a commercially available transmittance meter. The transmittance meter may use the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Laboratory or its equivalent. More specifically, for example, the total light transmittance of the adhesive layer may be measured according to the embodiments described below. The total light transmittance of the adhesive layer may be adjusted by, for example, selecting the composition or thickness of the adhesive layer.
在此揭示之黏著型光學薄膜為第1黏著劑層及第2黏著劑層被固定積層在光透射性構件的第1面及第2面上之雙面黏著型光學薄膜之形態時,只要至少第1黏著劑層滿足上述任一全光線透射率即可,而第2黏著劑層之全光線透射率無特別限制。於光在黏著型光學薄膜之厚度方向上穿透之使用態樣中,第2黏著劑層之全光線透射率宜滿足上述第1黏著劑層之全光線透射率中之任一者。兩黏著劑層之全光線透射率的相對關係可為第1黏著劑層>第2黏著劑層,可為第1黏著劑層<第2黏著劑層,亦可為第1黏著劑層=第2黏著劑層。When the adhesive optical film disclosed herein is a double-sided adhesive optical film in which the first adhesive layer and the second adhesive layer are fixedly laminated on the first surface and the second surface of the light-transmitting member, it is sufficient that at least the first adhesive layer satisfies any of the above-mentioned total light transmittances, and the total light transmittance of the second adhesive layer is not particularly limited. In the use mode in which light penetrates in the thickness direction of the adhesive optical film, the total light transmittance of the second adhesive layer preferably satisfies any of the total light transmittances of the above-mentioned first adhesive layer. The relative relationship of the total light transmittance of the two adhesive layers may be: the first adhesive layer > the second adhesive layer, the first adhesive layer < the second adhesive layer, or the first adhesive layer = the second adhesive layer.
(霧度值) 在此揭示之黏著型光學薄膜具備具有上述高折射率且霧度值為3.0%以下的黏著劑層。在數個態樣中,上述黏著劑層之霧度值宜為2.0%以下,1.0%以下較佳,0.9%以下更佳,可為0.8%以下,可為0.5%以下,亦可為0.3%以下。黏著劑層之霧度值的下限無特別限制,由提升透明性之觀點來看霧度值越小越好。另一方面,在數個態樣中,考量到折射率或黏著特性,霧度值例如可為0.05%以上,可為0.1%以上,可為0.2%以上,可為0.3%以上,亦可為0.4%以上。(Haze value) The adhesive optical film disclosed herein has an adhesive layer having the above-mentioned high refractive index and a haze value of 3.0% or less. In several embodiments, the haze value of the above-mentioned adhesive layer is preferably 2.0% or less, preferably 1.0% or less, and more preferably 0.9% or less, and can be 0.8% or less, 0.5% or less, or 0.3% or less. There is no particular restriction on the lower limit of the haze value of the adhesive layer. From the perspective of improving transparency, the smaller the haze value, the better. On the other hand, in several embodiments, considering the refractive index or adhesive properties, the haze value can be, for example, 0.05% or more, 0.1% or more, 0.2% or more, 0.3% or more, or 0.4% or more.
在此「霧度值」意指對測定對象照射可見光時漫透射光相對於全透射光之比率。亦稱為Haze Value。霧度值可以下式表示。 Th(%)=Td/Tt×100 上述式中,Th為霧度值(%),Td為散射光透射率,Tt為全光透射率。霧度值之測定可依照後述實施例記載之方法來進行。黏著劑層之霧度值可藉由例如選擇該黏著劑層之組成或厚度等來調節。Here, "haze value" means the ratio of diffuse light to total light when the measured object is irradiated with visible light. It is also called Haze Value. The haze value can be expressed by the following formula. Th(%)=Td/Tt×100 In the above formula, Th is the haze value (%), Td is the diffuse light transmittance, and Tt is the total light transmittance. The haze value can be measured according to the method described in the embodiment described below. The haze value of the adhesive layer can be adjusted by, for example, selecting the composition or thickness of the adhesive layer.
在此揭示之黏著型光學薄膜為第1黏著劑層及第2黏著劑層被固定積層在光透射性構件的第1面及第2面上之雙面黏著型光學薄膜之形態時,只要至少第1黏著劑層滿足上述任一霧度值即可,而第2黏著劑層之霧度值無特別限制。於光在黏著型光學薄膜之厚度方向上穿透之使用態樣中,第2黏著劑層之霧度值宜滿足上述第1黏著劑層之霧度值中之任一者。兩黏著劑層之霧度值的相對關係可為第1黏著劑層>第2黏著劑層,可為第1黏著劑層<第2黏著劑層,亦可為第1黏著劑層=第2黏著劑層。When the adhesive optical film disclosed herein is a double-sided adhesive optical film in which the first adhesive layer and the second adhesive layer are fixedly laminated on the first surface and the second surface of the light-transmitting member, it is sufficient that at least the first adhesive layer satisfies any of the above-mentioned haze values, and the haze value of the second adhesive layer is not particularly limited. In the use mode in which light penetrates in the thickness direction of the adhesive optical film, the haze value of the second adhesive layer preferably satisfies any of the above-mentioned haze values of the first adhesive layer. The relative relationship of the mist values of the two adhesive layers may be the first adhesive layer > the second adhesive layer, the first adhesive layer < the second adhesive layer, or the first adhesive layer = the second adhesive layer.
(黏著面之表面平滑性) 在此揭示之黏著型光學薄膜之數個態樣中,該黏著型光學薄膜之黏著面宜具有高表面平滑性。(Surface smoothness of adhesive surface) In several aspects of the adhesive optical film disclosed herein, the adhesive surface of the adhesive optical film preferably has high surface smoothness.
例如,上述黏著面之算術平均粗度Ra宜被限制在預定值以下。由光學均質性之觀點來看,宜為具備設計成算術平均粗度Ra變低之黏著面的構成。藉由限制算術平均粗度Ra,例如在通過上述黏著面擷取光之使用態樣(在發光裝置中上述黏著劑層配置於較自發光元件更靠視點側之態樣等)中,便可發揮抑制因黏著劑層之表面狀態而發生亮度不均的效果。黏著面之算術平均粗度Ra低一事亦有利於抑制光學應變,而光學應變之抑制亦有助於提升光學均質性。具有第1黏著面及第2黏著面之雙面黏著型光學薄膜中,宜至少第1黏著面之算術平均粗度Ra被限制在預定值以下,較佳為兩黏著面之算術平均粗度Ra皆被限制在預定值以下。藉由雙面黏著型光學薄膜之各黏著面具有高表面平滑性,可適宜實現光學均質性優異之接著。For example, the arithmetic mean roughness Ra of the adhesive surface is preferably limited to below a predetermined value. From the perspective of optical homogeneity, it is preferable to have an adhesive surface designed to have a lower arithmetic mean roughness Ra. By limiting the arithmetic mean roughness Ra, for example, in a usage state where light is captured through the adhesive surface (in a light-emitting device, the adhesive layer is arranged closer to the viewpoint than the light-emitting element), it is possible to suppress uneven brightness due to the surface state of the adhesive layer. The low arithmetic mean roughness Ra of the adhesive surface is also beneficial for suppressing optical strain, and suppressing optical strain also helps to improve optical homogeneity. In a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, it is preferred that at least the arithmetic mean roughness Ra of the first adhesive surface is limited to a predetermined value, and it is preferred that the arithmetic mean roughness Ra of both adhesive surfaces is limited to a predetermined value. By having each adhesive surface of the double-sided adhesive optical film have high surface smoothness, it is possible to achieve a bonding with excellent optical homogeneity.
在數個態樣中,黏著面之算術平均粗度Ra宜為大約70nm以下,較宜為大約65nm以下,更宜為大約55nm以下,可小於50nm,可小於45nm,亦可小於40nm。由生產效率等觀點來看,在數個態樣中,黏著面的算術平均粗度Ra例如可為大約10nm以上,可為大約20nm以上,亦可為大約30nm以上(例如大約40nm以上)。在黏著型光學薄膜具有第1黏著面及第2黏著面之態樣中,第1黏著面之算術平均粗度Ra與第2黏著面之算術平均粗度Ra可為相同程度,亦可不同。In several aspects, the arithmetic mean roughness Ra of the adhesive surface is preferably less than about 70 nm, more preferably less than about 65 nm, more preferably less than about 55 nm, less than 50 nm, less than 45 nm, or less than 40 nm. From the perspective of production efficiency, in several aspects, the arithmetic mean roughness Ra of the adhesive surface can be, for example, more than about 10 nm, more than about 20 nm, or more than about 30 nm (for example, more than about 40 nm). In the aspect where the adhesive optical film has a first adhesive surface and a second adhesive surface, the arithmetic mean roughness Ra of the first adhesive surface and the arithmetic mean roughness Ra of the second adhesive surface can be the same or different.
又,例如,上述黏著面之最大高度Rz宜被限制在預定值以下。由光學均質性之觀點來看,宜為具備設計成最大高度Rz變低之黏著面的構成。藉由限制最大高度Rz,例如在如上述通過上述黏著面擷取光之使用態樣中,便可發揮抑制因黏著劑層之表面狀態而發生亮度不均的效果。黏著面之最大高度Rz低一事亦有利於抑制光學應變。具有第1黏著面及第2黏著面之雙面黏著型光學薄膜中,宜至少第1黏著面之最大高度Rz被限制在預定值以下,較佳為兩黏著面之最大高度Rz皆被限制在預定值以下。藉由雙面黏著型光學薄膜之各黏著面具有高表面平滑性,可適宜實現光學均質性優異之接著。Furthermore, for example, the maximum height Rz of the adhesive surface is preferably limited to below a predetermined value. From the viewpoint of optical homogeneity, it is preferable to have an adhesive surface designed so that the maximum height Rz becomes lower. By limiting the maximum height Rz, for example, in the above-mentioned usage mode of capturing light through the adhesive surface, the effect of suppressing uneven brightness due to the surface state of the adhesive layer can be exerted. The low maximum height Rz of the adhesive surface is also beneficial to suppressing optical strain. In a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, it is preferable that at least the maximum height Rz of the first adhesive surface is limited to below a predetermined value, and it is preferable that the maximum height Rz of both adhesive surfaces is limited to below a predetermined value. Since each adhesive surface of the double-sided adhesive optical film has high surface smoothness, it is possible to achieve excellent optical homogeneity.
在數個態樣中,黏著面之最大高度Rz宜為大約600nm以下,較宜為大約500nm以下,更宜為大約450nm以下,尤宜為大約400nm以下,可小於350nm,可小於300nm,亦可小於250nm。由生產效率等觀點來看,在數個態樣中,黏著面的最大高度Rz例如可為大約10nm以上,可為大約50nm以上,可為大約100nm以上,亦可為大約200nm以上。在具有第1黏著面及第2黏著面之黏著型光學薄膜之形態中,第1黏著面之最大高度Rz與第2黏著面之最大高度Rz可為相同程度,亦可不同。In several aspects, the maximum height Rz of the adhesive surface is preferably less than about 600nm, more preferably less than about 500nm, more preferably less than about 450nm, and particularly preferably less than about 400nm. It may be less than 350nm, less than 300nm, or less than 250nm. From the perspective of production efficiency, in several aspects, the maximum height Rz of the adhesive surface may be, for example, more than about 10nm, more than about 50nm, more than about 100nm, or more than about 200nm. In the form of an adhesive optical film having a first adhesive surface and a second adhesive surface, the maximum height Rz of the first adhesive surface and the maximum height Rz of the second adhesive surface may be the same or different.
黏著面之算術平均粗度Ra及最大高度Rz係使用非接觸式表面粗度測定裝置測定。非接觸式表面粗度測定裝置可使用光干涉方式表面粗度測定裝置,例如可使用3維光學輪廓儀(商品名「NewView7300」,ZYGO公司製)或其等效品。具體之測定操作及測定條件可依照後述實施例記載之測定條件來設定,或以可獲得與依照該測定條件之情況同等或對應之結果之方式來設定。The arithmetic mean roughness Ra and the maximum height Rz of the adhesive surface are measured using a non-contact surface roughness measuring device. The non-contact surface roughness measuring device can use an optical interference surface roughness measuring device, for example, a 3D optical profiler (trade name "NewView7300", manufactured by ZYGO) or its equivalent. The specific measurement operation and measurement conditions can be set according to the measurement conditions described in the embodiments described below, or in a manner that can obtain results that are equivalent to or corresponding to the situation according to the measurement conditions.
黏著面之算術平均粗度Ra及最大高度Rz可藉由用於形成黏著劑層之黏著劑組成物之組成或性狀(黏度、調平性等)、保護黏著面之剝離襯墊之表面(剝離面)的性狀等來調節。The arithmetic mean roughness Ra and the maximum height Rz of the adhesive surface can be adjusted by the composition or properties (viscosity, leveling properties, etc.) of the adhesive composition used to form the adhesive layer, the properties of the surface (peel surface) of the peel pad protecting the adhesive surface, etc.
(吸水率) 在此揭示之黏著型光學薄膜之數個態樣中,構成該黏著型光學薄膜之黏著劑層之吸水率宜被限制在預定值以下。例如,宜滿足上述折射率、全光線透射率及霧度值,且吸水率被限制在預定值以下。藉由限制黏著劑層之吸水率,有抑制該黏著劑層中之水分量的變動(例如環境中之濕氣等水分的吸收及釋放)造成黏著劑層的尺寸變化之傾向。藉此,可抑制黏著劑層與鄰接其之層(可為光透射性構件、剝離襯墊、被黏著體等)之尺寸變化的不一致造成之黏著型光學薄膜或包含該黏著型光學薄膜之光學積層體的翹曲。可抑制黏著劑層中之水分量的變動一事由可將黏著劑層之平坦性、透明性、折射率等固定維持之觀點來看亦佳。又,吸水率低之黏著劑層不易吸留水分,所以適合作為例如用於有機EL元件這類包含不喜水分之要素的構件或製品之黏著型光學薄膜。(Water absorption) In several aspects of the adhesive optical film disclosed herein, the water absorption of the adhesive layer constituting the adhesive optical film is preferably limited to a predetermined value or less. For example, the above-mentioned refractive index, total light transmittance and haze value are preferably satisfied, and the water absorption is limited to a predetermined value or less. By limiting the water absorption of the adhesive layer, there is a tendency to suppress the change in the size of the adhesive layer caused by the change in the amount of water in the adhesive layer (for example, the absorption and release of water such as humidity in the environment). This can suppress the warping of the adhesive optical film or the optical laminate containing the adhesive optical film caused by the inconsistency of the dimensional changes between the adhesive layer and the adjacent layer (which can be a light-transmitting component, a peeling pad, an adherend, etc.). The fact that the change of the amount of water in the adhesive layer can be suppressed is also good from the perspective of maintaining the flatness, transparency, refractive index, etc. of the adhesive layer. In addition, an adhesive layer with a low water absorption rate is not easy to absorb water, so it is suitable as an adhesive optical film used for components or products such as organic EL elements that contain elements that do not like water.
在數個態樣中,黏著劑層之吸水率為大約1.0%以下是適當的,宜為0.7%以下,較宜為0.5%以下(例如小於0.5%),可為0.4%以下,可為0.3%以下,亦可為0.2%以下。黏著劑層之吸水率的下限無特別限制,由兼顧與黏著特性等實用上之觀點來看,例如可為0.01%以上,可為0.05%以上,可為0.1%以上,可為0.15%以上,亦可為0.25%以上。具有第1黏著劑層及第2黏著劑層之雙面黏著型光學薄膜中,至少第1黏著劑層之吸水率被限制在預定值以下為佳。由獲得更高效果之觀點來看,第1、第2黏著劑層之吸水率宜皆被限制在預定值以下。In several aspects, the water absorption rate of the adhesive layer is preferably about 1.0% or less, preferably 0.7% or less, more preferably 0.5% or less (e.g., less than 0.5%), and can be 0.4% or less, 0.3% or less, or 0.2% or less. There is no particular restriction on the lower limit of the water absorption rate of the adhesive layer. From the practical point of view of both the adhesive property and the adhesive property, for example, it can be 0.01% or more, 0.05% or more, 0.1% or more, 0.15% or more, or 0.25% or more. In a double-sided adhesive optical film having a first adhesive layer and a second adhesive layer, it is preferred that the water absorption rate of at least the first adhesive layer is limited to below a predetermined value. From the perspective of obtaining a higher effect, the water absorption of the first and second adhesive layers should be limited to below a predetermined value.
此外,黏著劑層之吸水率(亦稱為水分率)係利用以下方法測定。在後述之實施例中亦可採用相同之方法。 [水分率之測定] 將評價對象之黏著劑層與配置於其中一面及另一面上之2片剝離襯墊一同裁切成4cm×5cm(面積:20cm2 )之尺寸,去除其中一面上之剝離襯墊後,貼合至預先秤量好之鋁箔上。接著,去除黏著劑層之另一面上之剝離襯墊,投入溫度60℃、相對濕度90%之恆溫恆濕槽中,並於72小時後取出。秤量積層有黏著劑層與鋁箔之試驗片後,使用具備加熱汽化裝置(三菱化學Analytech VA-200型)之水分計(三菱化學Analytech CA-200型),藉由卡耳費雪(Karl Fischer)電量滴定法在以下之條件下測定水分率。 陽極液:AQUAMICRON AKX(三菱化學製) 陰極液:AQUAMICRON CXU(三菱化學製) 加熱汽化溫度:150℃In addition, the water absorption rate (also called moisture content) of the adhesive layer is measured using the following method. The same method can also be used in the embodiments described below. [Measurement of moisture content] The adhesive layer of the evaluation object and the two peeling pads arranged on one side and the other side are cut into a size of 4cm×5cm (area: 20cm2 ), and after removing the peeling pad on one side, it is attached to the pre-weighed aluminum foil. Then, the peeling pad on the other side of the adhesive layer is removed, and it is placed in a constant temperature and humidity tank with a temperature of 60℃ and a relative humidity of 90%, and taken out after 72 hours. After weighing the test piece with the adhesive layer and the aluminum foil, the moisture content was measured by Karl Fischer electrometric titration under the following conditions using a moisture meter (Mitsubishi Chemical Analytech CA-200) equipped with a heating vaporization device (Mitsubishi Chemical Analytech VA-200). Anode liquid: AQUAMICRON AKX (Mitsubishi Chemical) Cathode liquid: AQUAMICRON CXU (Mitsubishi Chemical) Heating vaporization temperature: 150℃
(凝膠分率) 黏著劑層之凝膠分率可因應使用目的或使用態樣等適當設定,不受特定範圍所限。上述凝膠分率例如為大約99%以下,大約97%以下為適當。由容易適宜兼顧高折射率與黏著特性之觀點來看,在數個理想態樣中,上述凝膠分率為大約95%以下,較宜可為大約92%以下(例如大約90%以下)。凝膠分率不過高一事由可適當跟隨會存在於被黏著體表面之凹凸(例如在發光裝置中為了提升光擷取效率等而設置之凹凸結構)從而良好密著之觀點來看亦佳。在數個態樣中,凝膠分率可為大約88%以下,可為大約75%以下,亦可為大約65%以下。又,由賦予黏著劑適度的凝集性而適當展現黏著特性之觀點來看,黏著劑層之凝膠分率例如為大約10%以上,且設為大約20%以上是適當的,亦可為大約30%以上。由黏著劑層之耐變形性(防止因壓力造成之溢出或因夾入異物造成之氣泡等)之觀點來看,上述凝膠分率宜為大約30%以上,較宜為大約40%以上,可為大約45%以上,可為大約50%以上,可為大約65%以上,亦可為大約75%以上。凝膠分率可藉由基底聚合物之分子量或分子結構、濃度、交聯度等來調節。凝膠分率係以下述方法測定。(Gel fraction) The gel fraction of the adhesive layer can be appropriately set according to the purpose of use or the usage mode, and is not limited to a specific range. The gel fraction is, for example, about 99% or less, and about 97% or less is appropriate. From the perspective of easily and appropriately taking into account both high refractive index and adhesive properties, in several ideal modes, the gel fraction is about 95% or less, and preferably about 92% or less (for example, about 90% or less). The gel fraction is not too high because it can appropriately follow the unevenness that may exist on the surface of the adherend (for example, the uneven structure provided in the light-emitting device to improve the light extraction efficiency, etc.), thereby achieving good adhesion. In several aspects, the gel fraction may be less than about 88%, less than about 75%, or less than about 65%. In addition, from the perspective of giving the adhesive a proper cohesiveness and appropriately exhibiting adhesive properties, the gel fraction of the adhesive layer is, for example, more than about 10%, and it is appropriate to set it to more than about 20%, and it may also be more than about 30%. From the perspective of the deformation resistance of the adhesive layer (preventing overflow caused by pressure or bubbles caused by the inclusion of foreign objects, etc.), the above-mentioned gel fraction is preferably more than about 30%, more preferably more than about 40%, can be more than about 45%, can be more than about 50%, can be more than about 65%, and can also be more than about 75%. The gel fraction can be adjusted by the molecular weight or molecular structure, concentration, crosslinking degree, etc. of the base polymer. The gel fraction is determined by the following method.
[凝膠分率之測定] 將預定量之黏著劑試樣(重量Wg1 )以平均孔徑0.2µm之多孔質聚四氟乙烯膜(重量Wg2 )包成小袋狀,並用風箏線(重量Wg3 )綁住開口。上述多孔質聚四氟乙烯(PTFE)薄膜係使用可從日東電工公司取得之商品名「Nitoflon(註冊商標)NTF1122」(平均孔徑0.2µm,氣孔率75%,厚度85µm)或其等效品。 將該捆包浸漬於充分量之乙酸乙酯中,在室溫(典型上為23℃)下保持7天,僅使黏著劑中之溶膠份溶出上述膜外後,取出上述捆包並擦拭附著於外表面之乙酸乙酯,使該捆包在130℃下乾燥2小時,測定該捆包之重量(Wg4 )。黏著劑層之凝膠分率可藉由將各值代入以下式而求得。 凝膠分率(%)=[(Wg4 -Wg2 -Wg3 )/Wg1 ]×100[Determination of gel fraction] A predetermined amount of adhesive sample (weight Wg 1 ) is wrapped in a small bag with a porous polytetrafluoroethylene film (weight Wg 2 ) with an average pore size of 0.2µm, and the opening is tied with a kite line (weight Wg 3 ). The porous polytetrafluoroethylene (PTFE) film is a product name "Nitoflon (registered trademark) NTF1122" (average pore size 0.2µm, porosity 75%, thickness 85µm) available from Nitto Denko Corporation or its equivalent. The bundle is immersed in a sufficient amount of ethyl acetate and kept at room temperature (typically 23°C) for 7 days until only the sol in the adhesive is dissolved out of the above film. Then the bundle is taken out and the ethyl acetate attached to the outer surface is wiped off. The bundle is dried at 130°C for 2 hours and the weight of the bundle is measured (Wg 4 ). The gel fraction of the adhesive layer can be obtained by substituting each value into the following formula. Gel fraction (%) = [(Wg 4 -Wg 2 -Wg 3 )/Wg 1 ] × 100
具有第1黏著面及第2黏著面之雙面黏著型光學薄膜之形態中,上述凝膠分率至少應用於構成第1黏著面之黏著劑層,且宜應用於構成第1黏著面之黏著劑層及構成第2黏著面之黏著劑層兩者。構成第1黏著面之黏著劑層的凝膠分率與構成第2黏著面之黏著劑層的凝膠分率可為相同程度,亦可不同。In the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, the above-mentioned gel fraction is applied to at least the adhesive layer constituting the first adhesive surface, and is preferably applied to both the adhesive layer constituting the first adhesive surface and the adhesive layer constituting the second adhesive surface. The gel fraction of the adhesive layer constituting the first adhesive surface and the gel fraction of the adhesive layer constituting the second adhesive surface may be the same or different.
(儲存彈性模數G') 在此揭示之黏著型光學薄膜中,構成黏著劑層之黏著劑在25℃下之儲存彈性模數G'(以下亦稱「儲存彈性模數G'(25)」)可因應使用目的或使用態樣等適當設定,不受特定範圍所限。黏著劑之儲存彈性模數G'(25)例如可為大約700kPa以下。在數個態樣中,由對被黏著體之貼附容易性等觀點來看,黏著劑之儲存彈性模數G'(25)為大約600kPa以下是有利的,宜為500kPa以下,較宜為400kPa以下(例如350kPa以下)。在數個態樣中,由提高黏著劑在室溫區域(例如25℃)下之柔軟性而易密著於被黏著體之觀點來看,黏著劑之儲存彈性模數G'(25)為大約330kPa以下是有利的,且宜為300kPa以下。在更重視在室溫區域下之貼附性或柔軟性之數個態樣中,黏著劑之儲存彈性模數G'(25)例如可小於270kPa或小於250kPa,而小於200kPa是有利的,且宜小於180kPa,較宜小於160kPa(例如小於140kPa)。在數個態樣中,黏著劑之儲存彈性模數G'(25)可小於100kPa,亦可小於90kPa。黏著劑之儲存彈性模數G'(25)的下限無特別限制,惟由加工性或處理性等觀點來看,例如可為30kPa以上,可為50kPa以上,亦可為70kPa以上。在數個態樣中,考量到高折射率化,儲存彈性模數G'(25)可為100kPa以上,可為150kPa以上,可為200kPa以上,可為250kPa以上,亦可為300kPa以上。(Storage modulus of elasticity G') In the adhesive optical film disclosed herein, the storage modulus of elasticity G' (hereinafter also referred to as "storage modulus of elasticity G'(25)") of the adhesive constituting the adhesive layer at 25°C can be appropriately set according to the purpose of use or the usage mode, and is not limited to a specific range. The storage modulus of elasticity G'(25) of the adhesive can be, for example, about 700 kPa or less. In several embodiments, from the perspective of ease of attachment to the adherend, it is advantageous for the storage modulus of elasticity G'(25) of the adhesive to be about 600 kPa or less, preferably 500 kPa or less, and more preferably 400 kPa or less (for example, 350 kPa or less). In several aspects, from the perspective of improving the flexibility of the adhesive at room temperature (e.g., 25° C.) and making it easier to adhere to the adherend, the storage elastic modulus G'(25) of the adhesive is advantageously about 330 kPa or less, and preferably 300 kPa or less. In several aspects where more emphasis is placed on adhesion or flexibility at room temperature, the storage elastic modulus G'(25) of the adhesive may be, for example, less than 270 kPa or less than 250 kPa, and is advantageously less than 200 kPa, and is preferably less than 180 kPa, and more preferably less than 160 kPa (e.g., less than 140 kPa). In several aspects, the storage elastic modulus G'(25) of the adhesive may be less than 100 kPa or less than 90 kPa. The lower limit of the storage elastic modulus G'(25) of the adhesive is not particularly limited, but from the perspective of processability or handling, it may be, for example, 30 kPa or more, 50 kPa or more, or 70 kPa or more. In several aspects, considering the high refractive index, the storage elastic modulus G'(25) may be 100 kPa or more, 150 kPa or more, 200 kPa or more, 250 kPa or more, or 300 kPa or more.
在此揭示之黏著型光學薄膜中,構成黏著劑層之黏著劑在50℃下之儲存彈性模數G'(以下亦稱「儲存彈性模數G'(50)」)無特別限定,例如可小於100kPa。在數個態樣中,儲存彈性模數G'(50)小於60kPa是適當的,且宜小於40kPa,較宜小於38kPa(例如小於36kPa)。如所述儲存彈性模數G'(50)經限制之黏著劑,可視需求藉由進行適度之加熱來輕易地提高對被黏著體之密著性,藉此可提升對被黏著體之接著性。黏著劑之儲存彈性模數G'(50)的下限無特別限制。在數個態樣中,由黏著劑之耐熱特性之觀點來看,儲存彈性模數G'(50)例如可為10kPa以上,可為15kPa以上,可為20kPa以上,亦可為23kPa以上。In the adhesive optical film disclosed herein, the storage modulus G' (hereinafter also referred to as "storage modulus G'(50)") of the adhesive constituting the adhesive layer at 50°C is not particularly limited, and may be, for example, less than 100 kPa. In several embodiments, it is appropriate for the storage modulus G'(50) to be less than 60 kPa, and preferably less than 40 kPa, and more preferably less than 38 kPa (for example, less than 36 kPa). The adhesive having a limited storage modulus G'(50) as described above can easily improve its adhesion to the adherend by appropriately heating as required, thereby improving its adhesion to the adherend. There is no particular limitation on the lower limit of the storage modulus G'(50) of the adhesive. In several aspects, from the perspective of the heat resistance of the adhesive, the storage elastic modulus G'(50) may be, for example, greater than 10 kPa, greater than 15 kPa, greater than 20 kPa, or greater than 23 kPa.
在此揭示之黏著型光學薄膜之數個態樣中,構成黏著劑層之黏著劑宜滿足以下條件之至少一者: (a)在25℃下之儲存彈性模數G'(25)為350kPa以下(宜小於200kPa,例如180kPa以下);及 (b)在50℃下之儲存彈性模數G'(50)小於60kPa(宜小於50kPa,較宜小於40kPa,例如小於38kPa)。 至少滿足上述條件(a)之黏著劑,由在室溫區域(例如25℃)下對被黏著體之密著性之觀點來看實為理想。至少滿足上述條件(b)之黏著劑因可藉由加熱至較室溫稍高之程度的溫度來輕易地提升對被黏著體之密著性(接著性),故為佳。不滿足上述條件(a)且滿足上述(b)之黏著劑可作為熱活化型黏著劑來利用,其在室溫區域下貼附之初始時重工性(重新貼合性)佳,藉由加熱至較室溫稍高之程度的溫度就可有效提升從被黏著體剝離之剝離強度。上述熱活化亦可在貼附於被黏著體時,藉由將黏著劑加熱至較室溫稍高之程度的溫度來進行。上述所謂較室溫稍高之程度的溫度例如為60℃左右或其以下,且宜為55℃左右或其以下(例如為50℃左右或其以下)。In the several aspects of the adhesive optical film disclosed herein, the adhesive constituting the adhesive layer preferably meets at least one of the following conditions: (a) the storage elastic modulus G'(25) at 25°C is less than 350 kPa (preferably less than 200 kPa, for example, less than 180 kPa); and (b) the storage elastic modulus G'(50) at 50°C is less than 60 kPa (preferably less than 50 kPa, more preferably less than 40 kPa, for example, less than 38 kPa). An adhesive that at least meets the above condition (a) is ideal from the perspective of adhesion to the adherend at room temperature (e.g., 25°C). Adhesives that at least meet the above condition (b) are preferred because they can easily improve the adhesion to the adherend by heating to a temperature slightly higher than room temperature. Adhesives that do not meet the above condition (a) but meet the above condition (b) can be used as heat-activated adhesives, which have good reworkability (re-adhesion) when attached at room temperature, and can effectively improve the peeling strength from the adherend by heating to a temperature slightly higher than room temperature. The above heat activation can also be performed by heating the adhesive to a temperature slightly higher than room temperature when attached to the adherend. The temperature slightly higher than room temperature is, for example, about 60°C or lower, and preferably about 55°C or lower (for example, about 50°C or lower).
在此揭示之黏著型光學薄膜之數個態樣中,構成黏著劑層之黏著劑之儲存彈性模數G'(50)[kPa]相對於儲存彈性模數G'(25)[kPa]之比、亦即儲存彈性模數比G'(50)/G'(25),例如為70%以下,可為40%以下,可為30%以下,亦可為20%以下。G'(50)/G'(25)小之黏著劑適於作為上述熱活化型黏著劑使用。G'(50)/G'(25)的下限無特別限制。G'(50)/G'(25)例如為5%以上,而由黏著劑之耐熱特性之觀點來看,宜為10%以上,可為12%以上,亦可為15%以上。In several aspects of the adhesive optical film disclosed herein, the ratio of the storage modulus G'(50) [kPa] of the adhesive constituting the adhesive layer to the storage modulus G'(25) [kPa], i.e., the storage modulus ratio G'(50)/G'(25), is, for example, less than 70%, less than 40%, less than 30%, or less than 20%. An adhesive with a small G'(50)/G'(25) is suitable for use as the above-mentioned heat-activated adhesive. There is no particular restriction on the lower limit of G'(50)/G'(25). G'(50)/G'(25) is, for example, 5% or more. From the viewpoint of the heat resistance of the adhesive, it is preferably 10% or more, and may be 12% or more, or may be 15% or more.
儲存彈性模數G'(25)及G'(50)可藉由動態黏彈性測定求得,並可從其結果算出G'(50)/G'(25)。動態黏彈性測定可使用市售之動態黏彈性測定裝置以常法來進行,例如可使用TA Instruments公司製之「Advanced Rheometric Expansion System (ARES)」或其等效品,在以下測定條件下進行。測定用試樣係使用將評估對象之黏著劑層因應需求進行積層等調整成厚度約1.5mm者。 [測定條件] 變形模式:扭轉 測定頻率:1Hz 升溫速度:5℃/分鐘 形狀:平行板 7.9mmφThe storage elastic modulus G'(25) and G'(50) can be obtained by dynamic viscoelasticity measurement, and G'(50)/G'(25) can be calculated from the result. Dynamic viscoelasticity measurement can be performed in a conventional manner using a commercially available dynamic viscoelasticity measurement device, such as the "Advanced Rheometric Expansion System (ARES)" manufactured by TA Instruments or its equivalent, under the following measurement conditions. The test specimen is a test specimen in which the adhesive layer of the evaluation object is adjusted to a thickness of about 1.5 mm by lamination as required. [Measurement conditions] Deformation mode: Torsion Measurement frequency: 1 Hz Heat rise rate: 5°C/min Shape: Parallel plate 7.9 mm φ
黏著劑層之儲存彈性模數G'(25)、G'(50)及儲存彈性模數比,可藉由選擇構成黏著劑之基底聚合物的單體成分之組成(例如選擇單體(m1)之種類及含量)、有無使用交聯劑以及選擇種類及使用量、有無使用後述之折射率提升劑或塑化材料以及選擇種類及使用量等來調節。例如,作為單體(m1),除了屬該單體(m1)之主成分的第1單體外,還可使用較少量之與該第1單體之化學結構不同的第2單體並組合上述第1單體來使用,藉此除了在單獨使用第1單體作為單體(m1)時能縮小G'(50),還可使G’(50)/G'(25)降低。The storage elastic modulus G'(25), G'(50) and storage elastic modulus ratio of the adhesive layer can be adjusted by selecting the composition of the monomer components of the base polymer constituting the adhesive (for example, selecting the type and content of the monomer (m1)), whether or not a crosslinking agent is used, and selecting the type and amount of use, whether or not a refractive index enhancer or plasticizer described later is used, and selecting the type and amount of use, etc. For example, as the monomer (m1), in addition to the first monomer that is the main component of the monomer (m1), a second monomer having a chemical structure different from that of the first monomer can be used in a relatively small amount and combined with the first monomer, thereby reducing G'(50) when the first monomer is used alone as the monomer (m1), and also reducing G'(50)/G'(25).
具有第1黏著面及第2黏著面之雙面黏著型光學薄膜之形態中,上述儲存彈性模數G'(25)、G'(50)及儲存彈性模數比至少應用於構成第1黏著面之黏著劑層,且宜應用於構成第1黏著面之黏著劑層及構成第2黏著面之黏著劑層兩者。構成第1黏著面之黏著劑層的儲存彈性模數G'與構成第2黏著面之黏著劑層的儲存彈性模數G'可為相同程度,亦可不同。In the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, the above-mentioned storage elastic modulus G'(25), G'(50) and storage elastic modulus ratio are applied to at least the adhesive layer constituting the first adhesive surface, and are preferably applied to both the adhesive layer constituting the first adhesive surface and the adhesive layer constituting the second adhesive surface. The storage elastic modulus G' of the adhesive layer constituting the first adhesive surface and the storage elastic modulus G' of the adhesive layer constituting the second adhesive surface may be of the same degree or may be different.
在此揭示之技術之數個態樣中,構成黏著劑層之黏著劑的tanδ之峰值溫度宜大約-50℃以上,且宜大約50℃以下。在此,黏著劑之tanδ(耗損正切)意指該黏著劑之損耗彈性模數G”相對於儲存彈性模數G'的比。亦即,tanδ=G”/G’。黏著劑之tanδ可將厚度約2mm、直徑7.9mm之圓盤狀的黏著劑試樣以平行板包夾,一邊使用黏彈性試驗裝置賦予頻率1Hz之剪切應變,一邊在測定溫度範圍-60℃~60℃、升溫速度5℃/分鐘之條件下,以剪切模式進行該黏著劑之溫度分散試驗,並從此時之儲存彈性模數G'(Pa)及損耗彈性模數G"(Pa)藉由下式:tanδ=G”/G’來求得。可從在上述溫度範圍中之tanδ的推移,求得黏著劑之tanδ的峰值溫度(以下有表記為Tpeak之情形)。黏彈性試驗裝置可使用TA Instruments公司製之ARES或其等效品。In several aspects of the technology disclosed herein, the peak temperature of tanδ of the adhesive constituting the adhesive layer is preferably above about -50°C and preferably below about 50°C. Here, tanδ (loss tangent) of the adhesive means the ratio of the loss elastic modulus G" to the storage elastic modulus G' of the adhesive. That is, tanδ=G"/G'. The tanδ of the adhesive can be determined by sandwiching a disc-shaped adhesive sample with a thickness of about 2mm and a diameter of 7.9mm with parallel plates, applying a shear strain of 1Hz using a viscoelastic tester, and performing a temperature dispersion test of the adhesive in a shear mode at a temperature range of -60℃~60℃ and a heating rate of 5℃/min. The storage elastic modulus G'(Pa) and loss elastic modulus G"(Pa) at this time can be obtained by the following formula: tanδ=G"/G'. The peak temperature of the tanδ of the adhesive (hereinafter referred to as Tpeak) can be obtained from the transition of tanδ in the above temperature range. The viscoelastic tester can use ARES manufactured by TA Instruments or its equivalent.
在數個態樣中,黏著劑之Tpeak為45℃以下或35℃以下是有利的,且宜為30℃以下(例如25℃以下),可為20℃以下,亦可為15℃以下。藉由Tpeak較低之黏著劑,有在室溫區域下容易獲得良好之初始接著性或密著性的傾向。另一方面,黏著劑之Tpeak不過低一事由賦予黏著劑適度之凝集性之觀點來看實為理想,且有適於兼顧高折射率化之傾向。由所述觀點來看,在數個態樣中,黏著劑之Tpeak例如可為-40℃以上,可為-30℃以上,可為-20℃以上,可為-5℃以上,可為5℃以上,可為15℃以上,更可為25℃以上。Tpeak較高之黏著劑在貼附於被黏著體時,可適宜在視需求將黏著劑與被黏著體之其中一者或兩者加熱至較室溫稍高之程度的溫度之態樣下使用。黏著劑的Tpeak可藉由選擇該黏著劑之組成(例如構成基底聚合物之單體成分的組成、有無使用折射率提升劑或塑化材料以及選擇種類及使用量)等來調節。 具有第1黏著面及第2黏著面之雙面黏著型光學薄膜之形態中,上述黏著劑的Tpeak宜至少應用於構成第1黏著面之黏著劑層,且較宜應用於構成第1黏著面之黏著劑層及構成第2黏著面之黏著劑層兩者。構成第1黏著面之黏著劑層的Tpeak與構成第2黏著面之黏著劑層的Tpeak可為相同程度,亦可不同。In several aspects, it is advantageous for the Tpeak of the adhesive to be below 45°C or below 35°C, and preferably below 30°C (for example, below 25°C), below 20°C, or below 15°C. With an adhesive having a lower Tpeak, it tends to be easy to obtain good initial adhesion or tightness at room temperature. On the other hand, it is ideal for the Tpeak of the adhesive to be not too low from the perspective of giving the adhesive a moderate degree of cohesion, and it tends to be suitable for taking into account a high refractive index. From the above viewpoint, in several aspects, the Tpeak of the adhesive can be, for example, above -40°C, above -30°C, above -20°C, above -5°C, above 5°C, above 15°C, or even above 25°C. When an adhesive with a higher Tpeak is attached to an adherend, it is appropriate to use it in a state where one or both of the adhesive and the adherend are heated to a temperature slightly higher than room temperature as required. The Tpeak of the adhesive can be adjusted by selecting the composition of the adhesive (for example, the composition of the monomer components constituting the base polymer, whether a refractive index enhancer or plasticizer is used, and the type and amount of use). In the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, the Tpeak of the above-mentioned adhesive should be applied to at least the adhesive layer constituting the first adhesive surface, and preferably applied to both the adhesive layer constituting the first adhesive surface and the adhesive layer constituting the second adhesive surface. The Tpeak of the adhesive layer constituting the first adhesive surface and the Tpeak of the adhesive layer constituting the second adhesive surface may be of the same level or may be different.
<黏著劑層> (基底聚合物) 在此揭示之技術中,構成黏著劑層之黏著劑的種類無特別限定。上述黏著劑可為包含可在黏著劑領域中使用之丙烯酸系聚合物、橡膠系聚合物(例如天然橡膠、合成橡膠、該等之混合物等)、聚酯系聚合物、胺甲酸酯系聚合物、聚醚系聚合物、聚矽氧系聚合物、聚醯胺系聚合物、氟系聚合物等之各種橡膠狀聚合物之1種或2種以上作為黏著性聚合物(意指可將黏著劑塑形之結構聚合物,以下亦稱「基底聚合物」)者。由黏著性能或成本等觀點來看,可適宜採用包含丙烯酸系聚合物或橡膠系聚合物作為基底聚合物之黏著劑。其中,以丙烯酸系聚合物作為基底聚合物之黏著劑(丙烯酸系黏著劑)為宜。在此揭示之技術適宜在使用丙烯酸系黏著劑之態樣下實施。<Adhesive layer> (Base polymer) In the technology disclosed herein, the type of adhesive constituting the adhesive layer is not particularly limited. The above-mentioned adhesive may be one or more of various rubber-like polymers including acrylic polymers, rubber polymers (such as natural rubber, synthetic rubber, mixtures thereof, etc.), polyester polymers, urethane polymers, polyether polymers, polysilicone polymers, polyamide polymers, fluorine polymers, etc. that can be used in the adhesive field as adhesive polymers (meaning structural polymers that can shape the adhesive, hereinafter also referred to as "base polymers"). From the perspective of adhesive performance or cost, an adhesive including an acrylic polymer or a rubber polymer as a base polymer can be appropriately used. Among them, an adhesive with an acrylic polymer as the base polymer (acrylic adhesive) is preferred. The technology disclosed herein is preferably implemented in the state of using an acrylic adhesive.
以下,主要說明藉由丙烯酸系黏著劑構成之黏著劑層、即具有丙烯酸系黏著劑層之黏著型光學薄膜,惟非意在將在此揭示之黏著型光學薄膜的黏著劑層限定為以丙烯酸系黏著劑構成者。Hereinafter, the adhesive layer formed of an acrylic adhesive, that is, the adhesive optical film having the acrylic adhesive layer, will be mainly described, but it is not intended to limit the adhesive layer of the adhesive optical film disclosed herein to that formed of an acrylic adhesive.
此外,在本說明書中,黏著劑之「基底聚合物」意指該黏著劑中所含橡膠狀聚合物之主成分,除此之外不作任何限定解釋。上述橡膠狀聚合物係指於室溫附近之溫度區域中展現橡膠彈性之聚合物。又,在本說明書中,「主成分」在未特別註記時,意指包含大於50重量%之成分。 又,在本說明書中,「丙烯酸系聚合物」意指包含下述單體單元作為構成該聚合物之單體單元的聚合物:該單體單元係源自1分子中具有至少1個(甲基)丙烯醯基之單體。以下,1分子中具有至少1個(甲基)丙烯醯基之單體亦稱「丙烯酸系單體」。因此,本說明書中之丙烯酸系聚合物係定義為包含源自丙烯酸系單體之單體單元的聚合物。丙烯酸系聚合物之典型例可舉可用於該丙烯酸系聚合物之合成之總單體中丙烯酸系單體之比率大於50重量%(宜大於70重量%,例如大於90重量%)之聚合物。 又,在本說明書中「(甲基)丙烯醯基」係指總括丙烯醯基及甲基丙烯醯基之意。同樣地,「(甲基)丙烯酸酯」係指總括丙烯酸酯及甲基丙烯酸酯之意,而「(甲基)丙烯酸」係指總括丙烯酸及甲基丙烯酸之意。因此,在此所提丙烯酸系單體之概念可包含具有丙烯醯基之單體(丙烯酸系單體)及具有甲基丙烯醯基之單體(甲基丙烯酸系單體)兩者。In addition, in this specification, the "base polymer" of the adhesive means the main component of the rubbery polymer contained in the adhesive, and no other limiting interpretation is given. The above-mentioned rubbery polymer refers to a polymer that exhibits rubber elasticity in a temperature range near room temperature. In addition, in this specification, "main component" means a component containing more than 50% by weight when not specifically noted. In addition, in this specification, "acrylic polymer" means a polymer containing the following monomer units as monomer units constituting the polymer: the monomer unit is derived from a monomer having at least one (meth)acryl group in one molecule. Hereinafter, a monomer having at least one (meth)acryl group in one molecule is also referred to as an "acrylic monomer". Therefore, the acrylic polymer in this specification is defined as a polymer containing monomer units derived from acrylic monomers. Typical examples of acrylic polymers include polymers in which the ratio of acrylic monomers in the total monomers that can be used to synthesize the acrylic polymer is greater than 50% by weight (preferably greater than 70% by weight, for example greater than 90% by weight). In addition, in this specification, "(meth)acryl" refers to acryl and methacryl. Similarly, "(meth)acrylate" refers to acrylate and methacrylate, and "(meth)acrylic acid" refers to acrylic acid and methacrylic acid. Therefore, the concept of acrylic monomers mentioned here can include both monomers having an acryl group (acrylic monomers) and monomers having a methacryl group (methacrylic monomers).
(丙烯酸系聚合物(A)) 在此揭示之黏著型光學薄膜,適宜在包含下述丙烯酸系黏著劑層之態樣下實施,該丙烯酸系黏著劑層之折射率大於1.570,全光線透射率為86%以上,且霧度值為3.0%以下(宜為2.0%以下,較宜為1.0%以下)。屬上述丙烯酸系黏著劑層之基底聚合物的丙烯酸系聚合物宜為包含含芳香環單體(m1)作為構成該丙烯酸系聚合物之單體成分者。亦即,宜為包含含芳香環單體(m1)作為單體單元之丙烯酸系聚合物。以下,亦將所述丙烯酸系聚合物稱為「丙烯酸系聚合物(A)」。在此,本說明書中所謂「構成丙烯酸系聚合物之單體成分」,意指無論是以預先形成之聚合物(可為寡聚物)之形態包含於黏著劑組成物中、或是以未聚合單體之形態包含於黏著劑組成物中,皆會在由該黏著劑組成物形成之黏著劑中構成丙烯酸系聚合物之重複單元的單體。亦即,構成丙烯酸系聚合物之單體成分可在聚合物、未聚合物、部分聚合物之任一形態下包含於上述黏著劑組成物中。由黏著劑組成物之調製容易性等觀點來看,在數個態樣中宜為將單體成分之實質上全部(例如95重量%以上,宜為99重量%以上)以聚合物之形態包含的黏著劑組成物。將單體成分之實質上全部以聚合物之形態包含的黏著劑組成物,由容易形成少有應變或翹曲的黏著型光學薄膜之觀點來看亦佳。(Acrylic polymer (A)) The adhesive optical film disclosed herein is preferably implemented in a state including the following acrylic adhesive layer, wherein the refractive index of the acrylic adhesive layer is greater than 1.570, the total light transmittance is greater than 86%, and the haze value is less than 3.0% (preferably less than 2.0%, more preferably less than 1.0%). The acrylic polymer that is the base polymer of the above-mentioned acrylic adhesive layer is preferably one that contains an aromatic ring-containing monomer (m1) as a monomer component constituting the acrylic polymer. In other words, it is preferably an acrylic polymer that contains an aromatic ring-containing monomer (m1) as a monomer unit. Hereinafter, the acrylic polymer is also referred to as "acrylic polymer (A)". Here, the "monomer components constituting acrylic polymers" in this specification means monomers that constitute repeating units of acrylic polymers in the adhesive formed by the adhesive composition, whether they are included in the adhesive composition in the form of a pre-formed polymer (which may be an oligomer) or in the form of an unpolymerized monomer. That is, the monomer components constituting acrylic polymers may be included in the above-mentioned adhesive composition in any form of a polymer, an unpolymerized polymer, or a partially polymerized polymer. From the viewpoint of the ease of preparation of the adhesive composition, in several aspects, it is preferable that substantially all (e.g., more than 95% by weight, preferably more than 99% by weight) of the monomer components are included in the form of a polymer. An adhesive composition containing substantially all monomer components in the form of a polymer is also preferred from the viewpoint of being easy to form an adhesive optical film with little strain or warping.
(單體(m1)) 單體(m1)可使用1分子中包含至少1個芳香環與至少1個乙烯性不飽和基之化合物。單體(m1)可單獨使用1種所述化合物或組合2種以上來使用。(Monomer (m1)) Monomer (m1) can be a compound containing at least one aromatic ring and at least one ethylenically unsaturated group in one molecule. Monomer (m1) can be used alone or in combination of two or more.
上述乙烯性不飽和基之例可舉(甲基)丙烯醯基、乙烯基、(甲基)烯丙基等。由聚合反應性之觀點來看宜為(甲基)丙烯醯基,而由柔軟性或黏著性之觀點來看以丙烯醯基較佳。由抑制黏著劑之柔軟性降低之觀點來看,單體(m1)可適宜使用1分子中所含乙烯性不飽和基之數量為1的化合物(即單官能單體)。Examples of the above-mentioned ethylenically unsaturated group include (meth)acrylic group, vinyl group, (meth)allyl group, etc. From the viewpoint of polymerization reactivity, (meth)acrylic group is preferred, and from the viewpoint of flexibility or adhesiveness, acryl group is more preferred. From the viewpoint of suppressing the decrease in the flexibility of the adhesive, the monomer (m1) can be suitably a compound having 1 ethylenically unsaturated group contained in one molecule (i.e., a monofunctional monomer).
可作為單體(m1)使用之化合物1分子中所含芳香環之數量可為1,亦可為2以上。單體(m1)所含芳香環之數量的上限無特別限制,例如可為16以下。在數個態樣中,由丙烯酸系聚合物(A)之調製容易性或黏著劑之透明性之觀點來看,上述芳香環之數量例如可為12以下,宜為8以下,較宜為6以下,可為5以下,可為4以下,可為3以下,亦可為2以下。The number of aromatic rings contained in the molecule of the
可作為單體(m1)使用之化合物具有之芳香環可為例如苯環(可為構成聯苯結構或茀結構之一部分的苯環);萘環、茚環、薁環、蒽環、菲環之縮合環等之碳環;亦可為例如吡啶環、嘧啶環、嗒𠯤環、吡𠯤環、三𠯤環、吡咯環、吡唑環、咪唑環、三唑環、㗁唑環、異㗁唑環、噻唑環、噻吩環等之雜環。上述雜環中作為環構成原子所含雜原子例如可為選自於由氮、硫及氧所構成群組中之1或種2以上。在數個態樣中,上述構成雜環之雜原子可為氮及硫之一者或兩者。單體(m1)例如亦可如二萘并噻吩結構般,具有1或2個以上碳環與1或2個以上雜環已行縮合之結構。The aromatic ring possessed by the compound that can be used as the monomer (m1) may be, for example, a benzene ring (which may be a benzene ring constituting a part of a biphenyl structure or a fluorene structure); a carbon ring such as a condensed ring of a naphthalene ring, an indene ring, an azulene ring, an anthracene ring, and a phenanthrene ring; or a heterocyclic ring such as a pyridine ring, a pyrimidine ring, an indole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxadiazole ring, an isoxadiazole ring, a thiazole ring, and a thiophene ring. The heteroatom contained in the heterocyclic ring as a ring-constituting atom may be, for example, one or more selected from the group consisting of nitrogen, sulfur and oxygen. In several embodiments, the heteroatom constituting the heterocyclic ring may be one or both of nitrogen and sulfur. The monomer (m1) may also have a structure in which one or more carbon rings and one or more heterocyclic rings are condensed, such as a dinaphthothiophene structure.
上述芳香環(宜為碳環)可於環構成原子上具有1或2個以上取代基,亦可不具有取代基。具有取代基時,該取代基可例示烷基、烷氧基、芳氧基、羥基、鹵素原子(氟原子、氯原子、溴原子等)、羥烷基、羥烷氧基、環氧丙氧基等,惟不受該等限定。在包含碳原子之取代基中,該取代基所含碳原子數宜為1~4,較宜為1~3,且例如可為1或2。在數個態樣中,上述芳香環可為於環構成原子上不具有取代基之芳香環、或可為於環構成原子上具有選自於由烷基、烷氧基及鹵素原子(例如溴原子)所構成群組中之1或2個以上取代基之芳香環。此外,單體(m1)具有之芳香環於環構成原子上具有取代基,係指該芳香環具有具乙烯性不飽和基之取代基以外之取代基。The above aromatic ring (preferably a carbocyclic ring) may have 1 or 2 or more substituents on the ring-constituting atoms, or may have no substituents. When having a substituent, the substituent may be exemplified by an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkoxy group, a glycidoxy group, etc., but is not limited thereto. In a substituent containing a carbon atom, the number of carbon atoms contained in the substituent is preferably 1 to 4, more preferably 1 to 3, and may be, for example, 1 or 2. In several aspects, the above aromatic ring may be an aromatic ring having no substituents on the ring-constituting atoms, or may be an aromatic ring having 1 or 2 or more substituents selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom (e.g., a bromine atom) on the ring-constituting atoms. Furthermore, the fact that the aromatic ring of the monomer (m1) has a substituent on an atom constituting the ring means that the aromatic ring has a substituent other than a substituent having an ethylenically unsaturated group.
芳香環與乙烯性不飽和基可直接鍵結,亦可隔著連結基來鍵結。上述連結基例如可為包含選自伸烷基、氧伸烷基、聚(氧伸烷基)基、苯基、烷基苯基、烷氧基苯基、該等基中之1或2個以上氫原子被羥基取代之結構的基團(例如羥伸烷基)、氧基(-O-基)、硫代氧基(-S-基)等中之1或2種以上結構的基團。在數個態樣中,可適宜採用芳香環與乙烯性不飽和基直接鍵結之結構的含芳香環單體、或隔著選自於由伸烷基、氧伸烷基及聚(氧伸烷基)基所構成群組中之連結基而鍵結之結構的含芳香環單體。上述伸烷基及上述氧伸烷基之碳原子數宜為1~4,較宜為1~3,例如可為1或2。上述聚(氧伸烷基)基中之氧伸烷基單元的重複數例如可為2~3。The aromatic ring and the ethylenically unsaturated group may be bonded directly or via a linking group. The linking group may be, for example, a group including one or more structures selected from an alkylene group, an oxyalkylene group, a poly(oxyalkylene) group, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, a group having a structure in which one or more hydrogen atoms in these groups are replaced by a hydroxyl group (e.g., a hydroxyalkylene group), an oxy group (-O-group), a thiooxy group (-S-group), etc. In several aspects, an aromatic ring-containing monomer having a structure in which the aromatic ring and the ethylenically unsaturated group are bonded directly or via a linking group selected from the group consisting of an alkylene group, an oxyalkylene group, and a poly(oxyalkylene) group may be suitably used. The carbon number of the alkylene group and the oxyalkylene group is preferably 1-4, more preferably 1-3, for example 1 or 2. The number of repetitions of the oxyalkylene unit in the poly(oxyalkylene) group may be, for example, 2-3.
可適宜採用作為單體(m1)之化合物之例可舉含芳香環(甲基)丙烯酸酯及含芳香環乙烯基化合物。含芳香環(甲基)丙烯酸酯及含芳香環乙烯基化合物可分別單獨使用1種或組合2種以上來使用。亦可組合1種或2種以上含芳香環(甲基)丙烯酸酯與1種或2種以上含芳香環乙烯基化合物來使用。Examples of compounds that can be suitably used as the monomer (m1) include aromatic ring-containing (meth)acrylates and aromatic ring-containing vinyl compounds. The aromatic ring-containing (meth)acrylates and aromatic ring-containing vinyl compounds can be used alone or in combination of two or more. One or more aromatic ring-containing (meth)acrylates and one or more aromatic ring-containing vinyl compounds can also be used in combination.
構成丙烯酸系聚合物(A)之單體成分中之單體(m1)之含量無特別限制,可設定成可實現兼顧所期望之折射率與黏著特性(例如剝離強度、柔軟性等)及/或光學特性(例如全光線透射性、霧度值等)之黏著劑層。在數個態樣中,上述單體成分中之單體(m1)之含量例如可為30重量%以上,且宜為50重量%以上,可為60重量%以上,亦可為70重量%以上。由容易獲得更高折射率之觀點來看,在數個理想態樣中,上述單體(m1)之含量例如可大於70重量%,可為75重量%以上,可為80重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。上述單體成分中之單體(m1)之含量的上限為100重量%。由平衡兼顧高折射率與黏著特性及/或光學特性之觀點來看,上述單體(m1)之含量設為小於100重量%是有利的,例如宜為大約99重量%以下,較宜為98重量%以下,可為97重量%以下,亦可為96重量%以下。在數個態樣中,上述單體(m1)之含量可為93重量%以下,可為90重量%以下,可為80重量%以下,亦可為75重量%以下。在更重視黏著特性及/或光學特性之數個態樣中,上述單體成分中之上述單體(m1)之含量可為70重量%以下,可為60重量%以下,亦可為45重量%以下。The content of the monomer (m1) in the monomer component constituting the acrylic polymer (A) is not particularly limited, and can be set to achieve an adhesive layer that takes into account the desired refractive index and adhesive properties (such as peel strength, flexibility, etc.) and/or optical properties (such as total light transmittance, haze value, etc.). In several aspects, the content of the monomer (m1) in the above-mentioned monomer component can be, for example, 30% by weight or more, and preferably 50% by weight or more, can be 60% by weight or more, and can also be 70% by weight or more. From the perspective of easily obtaining a higher refractive index, in several ideal aspects, the content of the above-mentioned monomer (m1) can be, for example, greater than 70% by weight, can be 75% by weight or more, can be 80% by weight or more, can be 85% by weight or more, can be 90% by weight or more, and can also be 95% by weight or more. The upper limit of the content of the monomer (m1) in the above-mentioned monomer component is 100 weight %. From the perspective of balancing the high refractive index with the adhesion properties and/or optical properties, it is advantageous to set the content of the above-mentioned monomer (m1) to be less than 100 weight %, for example, it is preferably about 99 weight % or less, more preferably 98 weight % or less, it can be 97 weight % or less, and it can also be 96 weight % or less. In several aspects, the content of the above-mentioned monomer (m1) can be 93 weight % or less, 90 weight % or less, 80 weight % or less, or 75 weight % or less. In several aspects that attach more importance to the adhesion properties and/or optical properties, the content of the above-mentioned monomer (m1) in the above-mentioned monomer component can be 70 weight % or less, 60 weight % or less, or 45 weight % or less.
在此揭示之技術之數個態樣中,由容易獲得較高的高折射率化效果來看,可適宜採用1分子中具有2個以上芳香環(宜為碳環)之單體作為單體(m1)。1分子內具有2個以上芳香環之單體(以下亦稱「含複數個芳香環之單體」)之例可列舉:具有2個以上非縮合芳香環隔著連結基鍵結之結構的單體、具有2個以上非縮合芳香環直接(亦即不隔著其他原子)化學鍵結之結構的單體、具有縮合芳香環結構之單體、具有茀結構之單體、具有二萘并噻吩結構之單體、具有二苯并噻吩結構之單體等。含複數個芳香環之單體可單獨使用1種或組合2種以上來使用。In several aspects of the technology disclosed herein, a monomer having two or more aromatic rings (preferably a carbon ring) in one molecule can be suitably used as the monomer (m1) in order to easily obtain a higher refractive index effect. Examples of monomers having two or more aromatic rings in one molecule (hereinafter also referred to as "monomers containing multiple aromatic rings") include: monomers having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, monomers having a structure in which two or more non-condensed aromatic rings are directly (i.e., not separated by other atoms) chemically bonded, monomers having a condensed aromatic ring structure, monomers having a fluorene structure, monomers having a dinaphthothiophene structure, monomers having a dibenzothiophene structure, etc. The monomer containing plural aromatic rings may be used alone or in combination of two or more.
上述連結基可為例如氧基(-O-)、硫代氧基(-S-)、氧伸烷基(例如-O-(CH2 )n -基,在此n為1~3,且宜為1)、硫代氧基伸烷基(例如-S-(CH2 )n -基,在此n為1~3,且宜為1)、直鏈伸烷基(亦即-(CH2 )n -基,在此n為1~6,且宜為1~3)、上述氧伸烷基、上述硫代氧基伸烷基及上述直鏈伸烷基中之伸烷基已部分鹵化或完全鹵化之基團等。由黏著劑之柔軟性等觀點來看,上述連結基之適當例可舉氧基、硫代氧基、氧伸烷基及直鏈伸烷基。具有2個以上非縮合芳香環隔著連結基鍵結之結構的單體之具體例可舉苯氧基苄基(甲基)丙烯酸酯(例如間苯氧基苄基(甲基)丙烯酸酯)、硫代苯氧基苄基(甲基)丙烯酸酯、(甲基)丙烯酸苄基苄酯等。The linking group may be, for example, an oxy group (—O—), a thiooxy group (—S—), an oxyalkylene group (for example, an —O—(CH 2 ) n -group, where n is 1 to 3 and preferably 1), a thiooxyalkylene group (for example, an —S—(CH 2 ) n -group, where n is 1 to 3 and preferably 1), a linear alkylene group (i.e., a —(CH 2 ) n -group, where n is 1 to 6 and preferably 1 to 3), the above oxyalkylene groups, the above thiooxyalkylene groups, and the above linear alkylene groups in which the alkylene groups are partially or completely halogenated. From the viewpoint of the softness of the adhesive, suitable examples of the linking group include an oxy group, a thiooxy group, an oxyalkylene group, and a linear alkylene group. Specific examples of the monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group include phenoxybenzyl (meth)acrylate (e.g., m-phenoxybenzyl (meth)acrylate), thiophenoxybenzyl (meth)acrylate, and benzylbenzyl (meth)acrylate.
上述2個以上非縮合芳香環直接化學鍵結之結構的單體例如可為含聯苯結構之(甲基)丙烯酸酯、含三苯基結構之(甲基)丙烯酸酯、含乙烯基之聯苯等。具體例可舉鄰苯基苯酚(甲基)丙烯酸酯、聯苯甲基(甲基)丙烯酸酯等。The monomer having a structure in which two or more non-condensed aromatic rings are directly chemically bonded may be, for example, a (meth)acrylate containing a biphenyl structure, a (meth)acrylate containing a triphenyl structure, a biphenyl containing a vinyl group, etc. Specific examples include o-phenylphenol (meth)acrylate, biphenylmethyl (meth)acrylate, etc.
上述具有縮合芳香環結構之單體之例可舉含萘環(甲基)丙烯酸酯、含蒽環(甲基)丙烯酸酯、含乙烯基萘、含乙烯基蒽等。具體例可舉:1-萘基甲基(甲基)丙烯酸酯(別名:1-萘甲基(甲基)丙烯酸酯)、羥乙基化β-萘酚丙烯酸酯、2-萘乙基(甲基)丙烯酸酯、2-萘氧乙基丙烯酸酯、2-(4-甲氧基-1-萘氧基)乙基(甲基)丙烯酸酯等。Examples of the monomer having a condensed aromatic ring structure include naphthalene ring-containing (meth)acrylate, anthracene ring-containing (meth)acrylate, vinyl naphthalene-containing, vinyl anthracene-containing, etc. Specific examples include 1-naphthylmethyl (meth)acrylate (also known as 1-naphthylmethyl (meth)acrylate), hydroxyethylated β-naphthol acrylate, 2-naphthylethyl (meth)acrylate, 2-naphthyloxyethyl acrylate, 2-(4-methoxy-1-naphthyloxy)ethyl (meth)acrylate, etc.
上述具有茀結構之單體的具體例可舉9,9-雙(4-羥苯基)茀(甲基)丙烯酸酯、9,9-雙[4-(2-羥乙氧基)苯基]茀(甲基)丙烯酸酯等。此外,具有茀結構之單體因包含2個苯環直接化學鍵結之結構部分,故包含在具有上述2個以上非縮合芳香環直接化學鍵結之結構的單體的概念中。Specific examples of the monomer having a fluorene structure include 9,9-bis(4-hydroxyphenyl)fluorene(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene(meth)acrylate, etc. In addition, since the monomer having a fluorene structure includes a structural portion in which two benzene rings are directly chemically bonded, it is included in the concept of the monomer having a structure in which two or more non-condensed aromatic rings are directly chemically bonded.
上述具有二萘并噻吩結構之單體可舉含(甲基)丙烯醯基之二萘并噻吩、含乙烯基之二萘并噻吩、含(甲基)烯丙基之二萘并噻吩等。具體例可舉:(甲基)丙烯醯氧基甲基二萘并噻吩(例如於二萘并噻吩環之5位或6位鍵結有CH2 CH(R1 )C(O)OCH2 -之結構的化合物;此處,R1 為氫原子或甲基)、(甲基)丙烯醯氧基乙基二萘并噻吩(例如於二萘并噻吩環之5位或6位鍵結有CH2 CH(R1 )C(O)OCH(CH3 )-或CH2 CH(R1 )C(O)OCH2 CH2 -之結構的化合物;此處,R1 為氫原子或甲基)、乙烯基二萘并噻吩(例如於萘并噻吩環之5位或6位鍵結有乙烯基之結構的化合物)、(甲基)烯丙氧基二萘并噻吩等。此外,具有二萘并噻吩結構之單體係藉由包含萘結構、還有具有噻吩環與2個萘結構已行縮合之結構,而亦包含於上述具有縮合芳香環結構之單體的概念中。Examples of the monomer having a dinaphthothiophene structure include dinaphthothiophene containing a (meth)acryl group, dinaphthothiophene containing a vinyl group, and dinaphthothiophene containing a (meth)allyl group. Specific examples include: (meth)acryloyloxymethyl dinaphthothiophene (for example, a compound having a structure of CH2CH ( R1 )C(O) OCH2- bonded to the 5-position or 6-position of the dinaphthothiophene ring; here, R1 is a hydrogen atom or a methyl group), (meth)acryloyloxyethyl dinaphthothiophene (for example, a compound having a structure of CH2CH ( R1 )C(O)OCH(CH3)- or CH2CH ( R1 )C(O) OCH2CH2- bonded to the 5-position or 6-position of the dinaphthothiophene ring; here, R1 is a hydrogen atom or a methyl group), vinyl dinaphthothiophene (for example, a compound having a structure of vinyl bonded to the 5-position or 6-position of the naphthothiophene ring), (meth)allyloxy dinaphthothiophene, and the like. In addition, the monomer having a dinaphthothiophene structure is also included in the concept of the monomer having a condensed aromatic ring structure by including a naphthalene structure and a structure in which a thiophene ring and two naphthalene structures are condensed.
上述具有二苯并噻吩結構之單體可舉含(甲基)丙烯醯基之二苯并噻吩、含乙烯基之二苯并噻吩等。此外,具有二苯并噻吩結構之單體由於具有噻吩環與2個苯環已行縮合之結構,而包含於上述具有縮合芳香環結構之單體的概念中。 此外,二萘并噻吩結構及二苯并噻吩結構皆不屬於2個以上非縮合芳香環直接化學鍵結之結構。Examples of the above-mentioned monomers having a dibenzothiophene structure include dibenzothiophene containing a (meth)acryloyl group and dibenzothiophene containing a vinyl group. In addition, since the monomers having a dibenzothiophene structure have a structure in which a thiophene ring and two benzene rings are condensed, they are included in the concept of the above-mentioned monomers having a condensed aromatic ring structure. In addition, the dinaphthothiophene structure and the dibenzothiophene structure are not structures in which two or more non-condensed aromatic rings are directly chemically bonded.
作為在此揭示之技術之單體(m1)亦可採用1分子中具有1個芳香環(宜為碳環)之單體。1分子中具有1個芳香環之單體例如有助於提升黏著劑之柔軟性或調整黏著特性、提升透明性等。在數個態樣中,由提升黏著劑之折射率之觀點來看,1分子中具有1個芳香環之單體宜與含複數個芳香環之單體組合來使用。As the monomer (m1) of the technology disclosed herein, a monomer having one aromatic ring (preferably a carbon ring) in one molecule may also be used. A monomer having one aromatic ring in one molecule, for example, helps to improve the flexibility of the adhesive or adjust the adhesive properties, improve the transparency, etc. In several aspects, from the perspective of improving the refractive index of the adhesive, a monomer having one aromatic ring in one molecule is preferably used in combination with a monomer containing multiple aromatic rings.
1分子中具有1個芳香環之單體之例可舉:(甲基)丙烯酸苄酯、(甲基)丙烯酸甲氧基苄酯、(甲基)丙烯酸苯酯、乙氧基化苯酚(甲基)丙烯酸酯、(甲基)丙烯酸苯氧丙酯、(甲基)丙烯酸苯氧丁酯、(甲基)丙烯酸甲苯酯、2-羥-3-苯氧丙基(甲基)丙烯酸酯、氯苄基(甲基)丙烯酸酯等含碳芳香環(甲基)丙烯酸酯;2-(4,6-二溴-2-二級丁基苯氧基)乙基(甲基)丙烯酸酯、2-(4,6-二溴-2-異丙基苯氧基)乙基(甲基)丙烯酸酯、6-(4,6-二溴-2-二級丁基苯氧基)己基(甲基)丙烯酸酯、6-(4,6-二溴-2-異丙基苯氧基)己基(甲基)丙烯酸酯、2,6-二溴-4-壬基苯基丙烯酸酯、2,6-二溴-4-十二基苯基丙烯酸酯等含溴取代芳香環(甲基)丙烯酸酯;苯乙烯、α-甲基苯乙烯、乙烯基甲苯、三級丁基苯乙烯等含碳芳香環之乙烯基化合物;N-乙烯吡啶、N-乙烯嘧啶、N-乙烯吡𠯤、N-乙烯吡咯、N-乙烯咪唑、N-乙烯基㗁唑等雜芳香環上具有乙烯基取代基之化合物等。Examples of monomers having one aromatic ring in one molecule include: carbon-containing aromatic ring (meth)acrylates such as benzyl (meth)acrylate, methoxybenzyl (meth)acrylate, phenyl (meth)acrylate, ethoxylated phenol (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxybutyl (meth)acrylate, toluene (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and benzyl (meth)acrylate; 2-(4,6-dibromo-2-dibutylphenoxy)ethyl (meth)acrylate, 2-(4,6-dibromo-2-isopropylphenoxy)ethyl (meth)acrylate, 6-( Bromine-substituted aromatic ring (meth)acrylates such as 4,6-dibromo-2-dibutylphenoxy)hexyl (meth)acrylate, 6-(4,6-dibromo-2-isopropylphenoxy)hexyl (meth)acrylate, 2,6-dibromo-4-nonylphenyl acrylate, 2,6-dibromo-4-dodecylphenyl acrylate; vinyl compounds containing carbon aromatic rings such as styrene, α-methylstyrene, vinyltoluene, tertiary butylstyrene; compounds having vinyl substituents on heteroaromatic rings such as N-vinylpyridine, N-vinylpyrimidine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, etc.
單體(m1)亦可使用如上述之各種含芳香環單體中之乙烯性不飽和基與芳香環之間包夾有氧伸乙基鏈之結構的單體。如所述使乙烯性不飽和基與芳香環之間包夾有氧伸乙基鏈之單體可視為原本單體的乙氧基化物。上述氧伸乙基鏈中之氧伸乙基單元(-CH2 CH2 O-)的重複數典型上為1~4,宜為1~3,較宜為1~2,且例如為1。經乙氧基化之含芳香環單體的具體例可舉:乙氧基化鄰苯基苯酚(甲基)丙烯酸酯、乙氧基化壬苯酚(甲基)丙烯酸酯、乙氧基化甲酚(甲基)丙烯酸酯、(甲基)丙烯酸苯氧乙酯、苯氧基二乙二醇二(甲基)丙烯酸酯等。The monomer (m1) may also be a monomer having a structure in which an oxyethylene chain is sandwiched between an ethylenically unsaturated group and an aromatic ring, as in the above-mentioned various aromatic ring-containing monomers. The monomer having an oxyethylene chain sandwiched between an ethylenically unsaturated group and an aromatic ring as described above may be regarded as an ethoxylate of the original monomer. The number of repetitions of the oxyethylene unit (-CH 2 CH 2 O-) in the above-mentioned oxyethylene chain is typically 1 to 4, preferably 1 to 3, more preferably 1 to 2, and for example 1. Specific examples of the ethoxylated aromatic ring-containing monomer include ethoxylated o-phenylphenol (meth)acrylate, ethoxylated nonoxyphenol (meth)acrylate, ethoxylated cresol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol di(meth)acrylate, and the like.
單體(m1)中之含複數個芳香環之單體之含量無特別限制,例如可為5重量%以上,可為25重量%以上,亦可為40重量%以上。在數個態樣中,由容易實現具有更高折射率之黏著劑之觀點來看,單體(m1)中之含複數個芳香環之單體之含量例如可為50重量%以上,且宜為70重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。單體(m1)實質上亦可100重量%為含複數個芳香環之單體。亦即,單體(m1)亦可僅使用1種或2種以上含複數個芳香環之單體。又,在數個態樣中,例如考量到高折射率與黏著特性及/或光學特性之平衡,單體(m1)中之含複數個芳香環之單體之含量可小於100重量%,可為98重量%以下,可為90重量%以下,可為80重量%以下,亦可為65重量%以下。在數個態樣中,考量到黏著特性及/或光學特性,單體(m1)中之含複數個芳香環之單體之含量可為70重量%以下,可為50重量%以下,可為25重量%以下,亦可為10重量%以下。在此揭示之技術即便在單體(m1)中之含複數個芳香環之單體之含量小於5重量%之態樣下仍可實施。亦可不使用含複數個芳香環之單體。The content of the monomer containing multiple aromatic rings in the monomer (m1) is not particularly limited, and can be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In several aspects, from the perspective of easily achieving an adhesive with a higher refractive index, the content of the monomer containing multiple aromatic rings in the monomer (m1) can be, for example, 50% by weight or more, and preferably 70% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The monomer (m1) can also be substantially 100% by weight of a monomer containing multiple aromatic rings. That is, the monomer (m1) can also use only one or more monomers containing multiple aromatic rings. Furthermore, in several aspects, for example, considering the balance between high refractive index and adhesion and/or optical properties, the content of monomers containing multiple aromatic rings in monomer (m1) may be less than 100% by weight, may be less than 98% by weight, may be less than 90% by weight, may be less than 80% by weight, or may be less than 65% by weight. In several aspects, considering adhesion and/or optical properties, the content of monomers containing multiple aromatic rings in monomer (m1) may be less than 70% by weight, may be less than 50% by weight, may be less than 25% by weight, or may be less than 10% by weight. The technology disclosed herein can be implemented even in the aspect that the content of monomers containing multiple aromatic rings in monomer (m1) is less than 5% by weight. Monomers containing multiple aromatic rings may also not be used.
構成丙烯酸系聚合物之單體成分中之含複數個芳香環之單體之含量無特別限制,可設定成可實現兼顧所期望之折射率與黏著特性(例如剝離強度、柔軟性等)及/或光學特性(例如全光線透射性、霧度值等)之黏著劑層。上述單體成分中之含複數個芳香環之單體之含量例如可為3重量%以上,可為10重量%以上,亦可為25重量%以上。在數個態樣中,由容易實現具有更高折射率之黏著劑之觀點來看,上述單體成分中之含複數個芳香環之單體之含量例如可大於35重量%,宜大於50重量%,可大於70重量%,可為75重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。上述單體成分中之含複數個芳香環之單體之含量可為100重量%,惟由平衡兼顧高折射率與黏著特性及/或光學特性之觀點來看,設為小於100重量%是有利的,宜設為大約99重量%以下,較宜為98重量%以下,可為96重量%以下,可為93重量%以下,可為90重量%以下,可為85重量%以下,可為80重量%以下,亦可為75重量%以下。在數個態樣中,考量到黏著特性及/或光學特性,上述單體成分中之含複數個芳香環之單體之含量可為70重量%以下,可為50重量%以下,可為25重量%以下,可為15重量%以下,亦可為5重量%以下。在此揭示之技術即便在上述單體成分中之含複數個芳香環之單體之含量小於3重量%之態樣下仍可實施。The content of the monomer containing multiple aromatic rings in the monomer component constituting the acrylic polymer is not particularly limited, and can be set to achieve an adhesive layer that takes into account the desired refractive index and adhesive properties (such as peel strength, flexibility, etc.) and/or optical properties (such as total light transmittance, haze value, etc.). The content of the monomer containing multiple aromatic rings in the above-mentioned monomer component can be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In several aspects, from the perspective of easily achieving an adhesive with a higher refractive index, the content of the monomer containing multiple aromatic rings in the above-mentioned monomer component can be, for example, greater than 35% by weight, preferably greater than 50% by weight, greater than 70% by weight, greater than 75% by weight, greater than 85% by weight, greater than 90% by weight, or greater than 95% by weight. The content of the monomer containing multiple aromatic rings in the above-mentioned monomer component can be 100% by weight, but from the perspective of balancing the high refractive index with the adhesive property and/or the optical property, it is advantageous to set it to less than 100% by weight, preferably to be about 99% by weight or less, preferably to be 98% by weight or less, to be 96% by weight or less, to be 93% by weight or less, to be 90% by weight or less, to be 85% by weight or less, to be 80% by weight or less, or to be 75% by weight or less. In several aspects, considering the adhesive property and/or the optical property, the content of the monomer containing multiple aromatic rings in the above-mentioned monomer component can be 70% by weight or less, to be 50% by weight or less, to be 25% by weight or less, to be 15% by weight or less, or to be 5% by weight or less. The technology disclosed herein can be implemented even when the content of the monomer containing multiple aromatic rings in the above-mentioned monomer component is less than 3% by weight.
在此揭示之技術之數個態樣中,作為單體(m1)之至少一部份宜可採用高折射率單體。在此,「高折射率單體」意指其折射率例如大約1.510以上、宜為大約1.530以上、較宜為大約1.550以上之單體。高折射率單體之折射率的上限無特別限制,惟由黏著劑組成物之調製容易性或與適合作為黏著劑之柔軟性之兼顧容易性之觀點來看,例如為3.000以下,可為2.500以下,可為2.000以下,可為1.900以下,可為1.800以下,亦可為1.700以下。高折射率單體可單獨使用1種或組合2種以上來使用。 此外,單體之折射率係使用阿貝折射計在測定波長589nm、測定溫度25℃之條件下進行測定。阿貝折射計可使用ATAGO公司製之型式「DR-M4」或其等效品。當有從製造商等提供了在25℃下之折射率的標稱值時,可採用該標稱值。In several aspects of the technology disclosed herein, a high refractive index monomer may be preferably used as at least a part of the monomer (m1). Here, "high refractive index monomer" means a monomer whose refractive index is, for example, about 1.510 or more, preferably about 1.530 or more, and more preferably about 1.550 or more. There is no particular upper limit on the refractive index of the high refractive index monomer, but from the perspective of ease of preparation of the adhesive composition or ease of balance between flexibility and suitability as an adhesive, for example, it may be 3.000 or less, 2.500 or less, 2.000 or less, 1.900 or less, 1.800 or less, or 1.700 or less. The high refractive index monomer may be used alone or in combination of two or more. The refractive index of the monomer is measured using an Abbe refractometer at a measurement wavelength of 589 nm and a measurement temperature of 25°C. The Abbe refractometer may be a "DR-M4" model manufactured by ATAGO or an equivalent. When a nominal value of the refractive index at 25°C is provided by a manufacturer, the nominal value may be used.
上述高折射率單體可從在此揭示之含芳香環單體(m1)之概念所含化合物(例如上述所例示之化合物及化合物群)之中適當採用具有該折射率者。具體例可舉:間苯氧基苄基丙烯酸酯(折射率:1.566,均聚物之Tg:-35℃)、1-萘甲基丙烯酸酯(折射率:1.595,均聚物之Tg:31℃)、乙氧基化鄰苯基苯酚丙烯酸酯(氧伸乙基單元之重複數:1,折射率:1.578)、丙烯酸苄酯(折射率(nD20):1.519,均聚物之Tg:6℃)、丙烯酸苯氧乙酯(折射率(nD20):1.517,均聚物之Tg:2℃)、苯氧基二乙二醇丙烯酸酯(折射率:1.510,均聚物之Tg:-35℃)、6-丙烯醯氧基甲基二萘并噻吩(6MDNTA,折射率:1.75)、6-甲基丙烯醯氧基甲基二萘并噻吩(6MDNTMA,折射率:1.726)、5-丙烯醯氧基乙基二萘并噻吩(5EDNTA,折射率:1.786)、6-丙烯醯氧基乙基二萘并噻吩(6EDNTA,折射率:1.722)、6-乙烯基二萘并噻吩(6VDNT,折射率:1.802)、5-乙烯基二萘并噻吩(縮寫:5VDNT,折射率:1.793)等,惟不受該等限定。The high refractive index monomer can be appropriately selected from the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (e.g., the compounds and compound groups exemplified above) and have the refractive index. Specific examples include: m-phenoxybenzyl acrylate (refractive index: 1.566, Tg of homopolymer: -35°C), 1-naphthylmethyl acrylate (refractive index: 1.595, Tg of homopolymer: 31°C), ethoxylated o-phenylphenol acrylate (number of repetitions of oxyethylidene units: 1, refractive index: 1.578), benzyl acrylate (refractive index (nD20): 1.519, Tg of homopolymer: 6°C), phenoxyethyl acrylate (refractive index (nD20): 1.517, Tg of homopolymer: 2°C), phenoxydiethylene glycol acrylate (refractive index: 1.510, Tg of homopolymer: -35°C), 6-acryloxymethyl dinaphthothiophene (6MDNTA, refractive index: 1.75), 6-methacryloxymethyl dinaphthothiophene (6MDNTMA, refractive index: 1.726), 5-acryloxyethyl dinaphthothiophene (5EDNTA, refractive index: 1.786), 6-acryloxyethyl dinaphthothiophene (6EDNTA, refractive index: 1.722), 6-vinyl dinaphthothiophene (6VDNT, refractive index: 1.802), 5-vinyl dinaphthothiophene (abbreviation: 5VDNT, refractive index: 1.793), etc., but are not limited thereto.
單體(m1)中之高折射率單體(亦即折射率為大約1.510以上、宜為大約1.530以上、較宜為大約1.550以上之含芳香環單體)之含量無特別限制,例如可為5重量%以上,可為25重量%以上,可為35重量%以上,亦可為40重量%以上。在數個態樣中,由容易獲得更高折射率之觀點來看,單體(m1)中之高折射率單體之含量例如可為50重量%以上,且宜為70重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。單體(m1)實質上亦可100重量%為高折射率單體。又,在數個態樣中,例如由平衡兼顧高折射率與黏著特性及/或光學特性之觀點來看,單體(m1)中之高折射率單體之含量可小於100重量%,可為98重量%以下,可為90重量%以下,可為80重量%以下,亦可為65重量%以下。在數個態樣中,考量到黏著特性及/或光學特性,單體(m1)中之高折射率單體之含量可為70重量%以下,可為50重量%以下,可為25重量%以下,可為15重量%以下,亦可為10重量%以下。在此揭示之技術即便在單體成分(m1)中之高折射率單體之含量小於5重量%之態樣下仍可實施。亦可不使用高折射率單體。The content of the high refractive index monomer (i.e., an aromatic ring-containing monomer having a refractive index of about 1.510 or more, preferably about 1.530 or more, and more preferably about 1.550 or more) in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, 35% by weight or more, or 40% by weight or more. In several aspects, from the perspective of easily obtaining a higher refractive index, the content of the high refractive index monomer in the monomer (m1) may be, for example, 50% by weight or more, preferably 70% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The monomer (m1) may also be substantially 100% by weight of a high refractive index monomer. Furthermore, in several aspects, for example, from the perspective of balancing the high refractive index with the adhesion and/or optical properties, the content of the high refractive index monomer in the monomer (m1) may be less than 100 wt%, may be less than 98 wt%, may be less than 90 wt%, may be less than 80 wt%, or may be less than 65 wt%. In several aspects, considering the adhesion and/or optical properties, the content of the high refractive index monomer in the monomer (m1) may be less than 70 wt%, may be less than 50 wt%, may be less than 25 wt%, may be less than 15 wt%, or may be less than 10 wt%. The technology disclosed herein can be implemented even in the aspect that the content of the high refractive index monomer in the monomer component (m1) is less than 5 wt%. It is also possible not to use a high refractive index monomer.
構成丙烯酸系聚合物之單體成分中之高折射率單體之含量無特別限制,可設定成可實現兼顧所期望之折射率與黏著特性(例如剝離強度、柔軟性等)及/或光學特性(例如全光線透射性、霧度值等)之黏著劑層。上述單體成分中之高折射率單體之含量例如可為3重量%以上,可為10重量%以上,亦可為25重量%以上。在數個態樣中,由容易實現具有更高折射率之黏著劑之觀點來看,上述單體成分中之高折射率單體之含量例如可大於35重量%,宜大於50重量%,可大於70重量%,可為75重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。上述單體成分中之高折射率單體之含量可為100重量%,惟由平衡兼顧高折射率與黏著特性及/或光學特性之觀點來看,設為小於100重量%是有利的,宜設為99重量%以下,較宜為98重量%以下,可為96重量%以下,可為93重量%以下,可為90重量%以下,可為85重量%以下,可為80重量%以下,亦可為75重量%以下。在數個態樣中,考量到黏著特性及/或光學特性,上述單體成分中之高折射率單體之含量可為70重量%以下,可為50重量%以下,可為25重量%以下,可為15重量%以下,亦可為5重量%以下。在此揭示之技術即便在上述單體成分中之高折射率單體之含量小於3重量%之態樣下仍可實施。The content of the high refractive index monomer in the monomer component constituting the acrylic polymer is not particularly limited, and can be set to achieve an adhesive layer that takes into account the desired refractive index and adhesive properties (such as peel strength, flexibility, etc.) and/or optical properties (such as total light transmittance, haze value, etc.). The content of the high refractive index monomer in the above-mentioned monomer component can be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In several aspects, from the perspective of easily achieving an adhesive with a higher refractive index, the content of the high refractive index monomer in the above-mentioned monomer component can be, for example, greater than 35% by weight, preferably greater than 50% by weight, greater than 70% by weight, greater than 75% by weight, greater than 85% by weight, greater than 90% by weight, or greater than 95% by weight. The content of the high refractive index monomer in the above-mentioned monomer component can be 100 weight %, but from the perspective of balancing the high refractive index with the adhesion characteristics and/or optical characteristics, it is advantageous to set it to less than 100 weight %, preferably 99 weight % or less, more preferably 98 weight % or less, 96 weight % or less, 93 weight % or less, 90 weight % or less, 85 weight % or less, 80 weight % or less, or 75 weight % or less. In several aspects, considering the adhesion characteristics and/or optical characteristics, the content of the high refractive index monomer in the above-mentioned monomer component can be 70 weight % or less, 50 weight % or less, 25 weight % or less, 15 weight % or less, or 5 weight % or less. The technology disclosed herein can be implemented even in the aspect that the content of the high refractive index monomer in the above-mentioned monomer component is less than 3 weight %.
在此揭示之技術之數個理想態樣中,作為單體(m1)之至少一部分係採用均聚物之Tg為10℃以下(宜為5℃以下或0℃以下,較宜為-10℃以下,更宜為-20℃以下,例如-25℃以下)之含芳香環單體(以下有表記為「單體L」之情形)。當增加單體成分中之含芳香環單體(m1)(尤其是相當於上述含複數個芳香環之單體及高折射率單體中之一者或兩者的含芳香環單體(m1))之含量時,有黏著劑之儲存彈性模數G'大致會上升之傾向,但藉由採用單體L作為該單體(m1)之一部分或全部,可抑制儲存彈性模數G'之上升。藉此,可更良好地維持適合作為黏著劑之柔軟性,並可提升折射率。單體L之Tg的下限無特別限制。考量到與折射率提升效果之平衡,在數個態樣中,單體L之Tg例如可為-70℃以上,可為-55℃以上,亦可為-45℃以上。單體L可單獨使用1種或組合2種以上來使用。In several ideal aspects of the technology disclosed herein, at least a portion of the monomer (m1) is an aromatic ring-containing monomer (hereinafter referred to as "monomer L") having a homopolymer Tg of 10°C or less (preferably 5°C or less or 0°C or less, more preferably -10°C or less, and even more preferably -20°C or less, for example -25°C or less). When the content of the aromatic ring-containing monomer (m1) in the monomer component is increased (especially an aromatic ring-containing monomer (m1) equivalent to one or both of the above-mentioned monomer containing multiple aromatic rings and the high refractive index monomer), the storage modulus G' of the adhesive tends to increase. However, by using the monomer L as part or all of the monomer (m1), the increase in the storage modulus G' can be suppressed. Thereby, the softness suitable for use as an adhesive can be better maintained, and the refractive index can be increased. The lower limit of the Tg of the monomer L is not particularly limited. Considering the balance with the refractive index increase effect, in several aspects, the Tg of the monomer L can be, for example, above -70°C, above -55°C, or above -45°C. The monomer L can be used alone or in combination of two or more.
單體L可從在此揭示之含芳香環單體(m1)之概念所含化合物(例如上述所例示之化合物及化合物群)之中適當採用具有該Tg者。可作為單體L使用之含芳香環單體之一適當例可舉間苯氧基苄基丙烯酸酯(均聚物之Tg:-35℃)。其他一適當例可舉苯氧基二乙二醇丙烯酸酯(均聚物之Tg:-35℃)。The monomer L can be appropriately selected from the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (e.g., the compounds and compound groups exemplified above) and having the Tg. One appropriate example of the aromatic ring-containing monomer that can be used as the monomer L is m-phenoxybenzyl acrylate (homopolymer Tg: -35°C). Another appropriate example is phenoxydiethylene glycol acrylate (homopolymer Tg: -35°C).
單體(m1)中之單體L之含量無特別限制,例如可為5重量%以上,可為25重量%以上,亦可為40重量%以上。在數個態樣中,由容易獲得以更高水準兼顧高折射率與柔軟性之黏著劑之觀點來看,單體(m1)中之單體L之含量例如可為50重量%以上,可為60重量%以上,可為70重量%以上,可為75重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。單體(A1)實質上亦可100重量%為單體L。又,在數個態樣中,例如由平衡兼顧適合作為黏著劑之柔軟性與高折射率之觀點來看,單體(m1)中之單體L之含量可小於100重量%,可為98重量%以下,可為90重量%以下,可為80重量%以下,可為70重量%以下,可為50重量%以下,可為25重量%以下,亦可為10重量%以下。在此揭示之技術即便在單體(m1)中之單體L之含量小於5重量%之態樣下仍可實施。亦可不使用單體L。The content of monomer L in monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In several aspects, from the perspective of easily obtaining an adhesive having both high refractive index and softness at a higher level, the content of monomer L in monomer (m1) may be, for example, 50% by weight or more, 60% by weight or more, 70% by weight or more, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. Monomer (A1) may also be substantially 100% by weight of monomer L. In some aspects, for example, from the perspective of balancing the softness and high refractive index suitable for use as an adhesive, the content of monomer L in monomer (m1) may be less than 100 wt%, 98 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 50 wt% or less, 25 wt% or less, or 10 wt% or less. The technology disclosed herein can be implemented even when the content of monomer L in monomer (m1) is less than 5 wt%. Monomer L may not be used.
構成丙烯酸系聚合物之單體成分中之單體L之含量例如可為3重量%以上,可為10重量%以上,亦可為25重量%以上。在數個態樣中,由容易獲得以更高水準兼顧高折射率與柔軟性之黏著劑之觀點來看,單體成分中之單體L之含量例如可大於35重量%,可大於50重量%,可大於70重量%,可為75重量%以上,可為85重量%以上,可為90重量%以上,亦可為95重量%以上。上述單體成分中之單體L之含量可為100重量%,惟考量到高折射率與黏著特性及/或光學特性之平衡,設為小於100重量%是有利的,且宜為大約99重量%以下,較宜為98重量%以下,可為96重量%以下,可為95重量%以下,可為93重量%以下,可為90重量%以下,可為85重量%以下,可為80重量%以下,亦可為75重量%以下。在數個態樣中,上述單體成分中之單體L之含量可為70重量%以下,可為50重量%以下,可為25重量%以下,可為15重量%以下,亦可為5重量%以下。在此揭示之技術即便在上述單體成分中之單體L之含量小於3重量%之態樣下仍可實施。The content of monomer L in the monomer component constituting the acrylic polymer may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In several aspects, from the viewpoint of easily obtaining an adhesive having both high refractive index and flexibility at a higher level, the content of monomer L in the monomer component may be, for example, greater than 35% by weight, greater than 50% by weight, greater than 70% by weight, greater than 75% by weight, greater than 85% by weight, greater than 90% by weight, or greater than 95% by weight. The content of monomer L in the above-mentioned monomer component can be 100 weight %, but considering the balance between high refractive index and adhesion characteristics and/or optical characteristics, it is advantageous to set it to less than 100 weight %, and preferably it is about 99 weight % or less, preferably 98 weight % or less, can be 96 weight % or less, can be 95 weight % or less, can be 93 weight % or less, can be 90 weight % or less, can be 85 weight % or less, can be 80 weight % or less, and can also be 75 weight % or less. In several aspects, the content of monomer L in the above-mentioned monomer component can be 70 weight % or less, can be 50 weight % or less, can be 25 weight % or less, can be 15 weight % or less, and can also be 5 weight % or less. The technology disclosed herein can still be implemented even in the aspect that the content of monomer L in the above-mentioned monomer component is less than 3 weight %.
在數個態樣中,由黏著劑之柔軟性之觀點來看,根據單體(m1)之組成的玻璃轉移溫度Tgm1 為大約20℃以下是有利的,宜為10℃以下(例如5℃以下),較宜為0℃以下,更宜為-10℃以下,可為-20℃以下,亦可為-25℃以下。玻璃轉移溫度Tgm1 的下限無特別限制。考量到與折射率提升效果之平衡,在數個態樣中,玻璃轉移溫度Tgm1 例如可為-70℃以上,可為-55℃以上,亦可為-45℃以上。在此揭示之技術即便在玻璃轉移溫度Tgm1 為例如-40℃以上、-35℃以上、-33℃以上、-30℃以上或-25℃以上之態樣下仍可適宜實施。In several aspects, from the viewpoint of the softness of the adhesive, it is advantageous for the glass transition temperature Tg m1 of the composition of the monomer (m1) to be about 20°C or less, preferably 10°C or less (e.g., 5°C or less), more preferably 0°C or less, more preferably -10°C or less, -20°C or less, or -25°C or less. There is no particular restriction on the lower limit of the glass transition temperature Tg m1 . Considering the balance with the refractive index enhancement effect, in several aspects, the glass transition temperature Tg m1 may be, for example, above -70°C, above -55°C, or above -45°C. The technology disclosed herein can be suitably implemented even in aspects where the glass transition temperature Tg m1 is, for example, above -40°C, above -35°C, above -33°C, above -30°C, or above -25°C.
在此,根據單體(m1)之組成的玻璃轉移溫度Tgm1 意指僅根據構成丙烯酸系聚合物之單體成分中之單體(m1)的組成,藉由後述Fox式求得之Tg。玻璃轉移溫度Tgm1 可僅將構成丙烯酸系聚合物之單體成分中之單體(m1)作為對象來應用後述Fox式,並從作為單體(m1)使用之各含芳香環單體之均聚物的玻璃轉移溫度與單體(m1)之合計量中各含芳香環單體所佔之重量分率來算出。在僅使用1種單體作為單體(m1)之態樣中,該單體之均聚物的Tg與玻璃轉移溫度Tgm1 一致。Here, the glass transition temperature Tg m1 according to the composition of the monomer (m1) means Tg obtained by the Fox equation described below based on the composition of only the monomer (m1) among the monomer components constituting the acrylic polymer. The glass transition temperature Tg m1 can be calculated from the glass transition temperature of the homopolymer of each aromatic ring-containing monomer used as the monomer (m1) and the weight fraction of each aromatic ring-containing monomer in the total amount of the monomer (m1) by applying the Fox equation described below to only the monomer (m1) among the monomer components constituting the acrylic polymer. In the case where only one monomer is used as the monomer (m1), the Tg of the homopolymer of the monomer is consistent with the glass transition temperature Tg m1 .
在數個態樣中,含芳香環單體(m1)可組合單體L(亦即為均聚物的Tg為10℃以下、且宜為5℃以下或0℃以下、較宜為-10℃以下、更宜為-20℃以下、例如-25℃以下之含芳香環單體)與Tg高於10℃之單體H來使用。單體H之Tg例如可高於10℃,可高於15℃,亦可高於20℃。藉由組合單體L與單體H來使用,例如在單體成分中之含芳香環單體(m1)之含量較多之構成中,可以更高水準兼顧黏著劑之高折射率與柔軟性。單體L與單體H之使用量比可設定成可適宜展現所述效果,並無特別限定。例如,宜將單體L與單體H之使用量比設定成可滿足上述任一玻璃轉移溫度Tgm1 。In several aspects, the aromatic ring-containing monomer (m1) can be used in combination with a monomer L (i.e., an aromatic ring-containing monomer whose homopolymer Tg is below 10°C, preferably below 5°C or below 0°C, more preferably below -10°C, more preferably below -20°C, for example, below -25°C) and a monomer H having a Tg higher than 10°C. The Tg of monomer H can be, for example, higher than 10°C, higher than 15°C, or higher than 20°C. By using a combination of monomer L and monomer H, for example, in a configuration in which the content of the aromatic ring-containing monomer (m1) in the monomer component is relatively high, a high refractive index and softness of the adhesive can be taken into account at a higher level. The usage ratio of monomer L and monomer H can be set to appropriately exhibit the above-mentioned effects, and there is no particular limitation. For example, the usage ratio of monomer L to monomer H is preferably set to satisfy any of the above-mentioned glass transition temperatures Tg m1 .
在數個態樣中,含芳香環單體(m1)可適宜自不含2個以上非縮合芳香環直接化學鍵結之結構(例如聯苯結構)的化合物中選擇。例如,宜為藉由下述組成之單體成分構成之丙烯酸系聚合物:包含2個以上非縮合芳香環直接化學鍵結之結構的化合物之含量小於5重量%(較宜為小於3重量%,亦可為0重量%)。如所述限制包含2個以上非縮合芳香環直接化學鍵結之結構的化合物的使用量一事,由實現平衡兼顧柔軟性或黏著性與高折射率之黏著劑之觀點來看是有利的。In several aspects, the aromatic ring-containing monomer (m1) can be suitably selected from compounds that do not contain a structure in which two or more non-condensed aromatic rings are directly chemically bonded (e.g., a biphenyl structure). For example, it is preferably an acrylic polymer composed of the following monomer components: the content of the compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded is less than 5% by weight (preferably less than 3% by weight, and may also be 0% by weight). As described above, limiting the amount of the compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded is advantageous from the perspective of achieving an adhesive that balances softness or adhesion with a high refractive index.
(單體(m2)) 在此揭示之技術之數個態樣中,構成丙烯酸系聚合物之單體成分除了上述單體(m1),可更含有單體(m2)。上述單體(m2)係相當於具有羥基之單體(含羥基單體)及具有羧基之單體(含羧基單體)中之至少一者的單體。上述含羥基單體係1分子內具有至少1個羥基與至少1個乙烯性不飽和基之化合物。上述含羧基單體係1分子內包含至少1個羧基與至少1個乙烯性不飽和基之化合物。單體(m2)有助於用以將交聯點導入丙烯酸系聚合物、或賦予黏著劑適度的凝集性。單體(m2)可單獨使用1種或組合2種以上來使用。單體(m2)典型上為不含芳香環之單體。(Monomer (m2)) In several aspects of the technology disclosed herein, the monomer components constituting the acrylic polymer may contain monomer (m2) in addition to the above-mentioned monomer (m1). The above-mentioned monomer (m2) is a monomer equivalent to at least one of a monomer having a hydroxyl group (hydroxyl-containing monomer) and a monomer having a carboxyl group (carboxyl-containing monomer). The above-mentioned hydroxyl-containing monomer is a compound having at least one hydroxyl group and at least one ethylenically unsaturated group in one molecule. The above-mentioned carboxyl-containing monomer is a compound having at least one carboxyl group and at least one ethylenically unsaturated group in one molecule. Monomer (m2) helps to introduce crosslinking points into the acrylic polymer or to give the adhesive a moderate cohesiveness. Monomer (m2) can be used alone or in combination of two or more. The monomer (m2) is typically a monomer not containing an aromatic ring.
單體(m2)具有之乙烯性不飽和基之例可舉(甲基)丙烯醯基、乙烯基、(甲基)烯丙基等。由聚合反應性之觀點來看宜為(甲基)丙烯醯基,而由柔軟性或黏著性之觀點來看以丙烯醯基較佳。由抑制黏著劑之柔軟性降低之觀點來看,單體(m2)可適宜使用1分子中所含乙烯性不飽和基之數量為1的化合物(即單官能單體)。Examples of the ethylenically unsaturated group possessed by the monomer (m2) include (meth)acrylic group, vinyl group, (meth)allyl group, etc. From the viewpoint of polymerization reactivity, a (meth)acrylic group is preferred, and from the viewpoint of flexibility or adhesiveness, an acryl group is more preferred. From the viewpoint of suppressing the decrease in the flexibility of the adhesive, the monomer (m2) can be suitably a compound having 1 ethylenically unsaturated group contained in one molecule (i.e., a monofunctional monomer).
含羥基單體之例可舉:(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-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、(4-羥甲基環己基)甲基(甲基)丙烯酸酯等(甲基)丙烯酸羥烷基酯,惟不受該等限定。可適宜使用之含羥基單體之例可舉丙烯酸4-羥丁酯(Tg:-40℃)及丙烯酸2-羥乙酯(Tg:-15℃)。由提升在室溫區域下中之柔軟性之觀點來看,以Tg更低之丙烯酸4-羥丁酯較佳。在理想之一態樣中,單體(m2)之50重量%以上(例如大於50重量%、大於70重量%或大於85重量%)可為丙烯酸4-羥丁酯。含羥基單體可單獨使用1種或組合2種以上來使用。Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate and other hydroxyalkyl (meth)acrylates, but are not limited thereto. Examples of hydroxyl-containing monomers that can be suitably used include 4-hydroxybutyl acrylate (Tg: -40°C) and 2-hydroxyethyl acrylate (Tg: -15°C). From the viewpoint of improving the flexibility at room temperature, 4-hydroxybutyl acrylate having a lower Tg is preferred. In an ideal embodiment, 50% by weight or more (e.g., greater than 50% by weight, greater than 70% by weight, or greater than 85% by weight) of the monomer (m2) may be 4-hydroxybutyl acrylate. The hydroxyl group-containing monomer may be used alone or in combination of two or more.
在使用含羥基單體作為單體(m2)之數個態樣中,上述含羥基單體可為選自不具甲基丙烯醯基之化合物中之1種或2種以上。不具甲基丙烯醯基之含羥基單體的適當例可舉上述各種丙烯酸羥烷基酯。例如,以作為單體(m2)使用之含羥基單體中大於50重量%、大於70重量%或大於85重量%為丙烯酸羥烷基酯為佳。藉由使用丙烯酸羥烷基酯,可將有助於提供交聯點或賦予適度凝集性的羥基導入丙烯酸系聚合物,且相較於僅使用對應之甲基丙烯酸羥烷基之情況更容易獲得在室溫區域下之柔軟性或黏著性佳的黏著劑。In several aspects of using a hydroxyl-containing monomer as the monomer (m2), the hydroxyl-containing monomer may be one or more selected from compounds without a methacryloyl group. Suitable examples of hydroxyl-containing monomers without a methacryloyl group include the above-mentioned various hydroxyalkyl acrylates. For example, it is preferred that more than 50% by weight, more than 70% by weight, or more than 85% by weight of the hydroxyl-containing monomer used as the monomer (m2) is a hydroxyalkyl acrylate. By using a hydroxyalkyl acrylate, a hydroxyl group that helps to provide a crosslinking point or impart a moderate cohesiveness can be introduced into the acrylic polymer, and it is easier to obtain an adhesive with good flexibility or adhesion at room temperature than when only the corresponding methacrylic acid hydroxyalkyl is used.
含羧基單體之例除了(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯等丙烯酸系單體外,還可舉伊康酸、馬來酸、延胡索酸、巴豆酸及異巴豆酸等,惟不受該等限定。可適宜使用之含羧基單體之例可舉例如丙烯酸、甲基丙烯酸。含羧基單體可單獨使用1種或組合2種以上來使用。亦可併用含羥基單體與含羧基單體。Examples of carboxyl group-containing monomers include acrylic acid monomers such as (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate, but are not limited to these. Examples of carboxyl group-containing monomers that can be suitably used include acrylic acid and methacrylic acid. Carboxyl group-containing monomers can be used alone or in combination of two or more. Hydroxyl group-containing monomers and carboxyl group-containing monomers can also be used in combination.
構成丙烯酸系聚合物之單體成分中之單體(m2)之含量無特別限制,可按目的作設定。在數個態樣中,上述單體(m2)之含量例如可為0.01重量%以上、0.1重量%以上或0.5重量%以上。由獲得更高之使用效果之觀點來看,在數個態樣中,上述單體(A2)之含量宜設為1重量%以上,可設為2重量%以上,亦可設為4重量%以上。單體成分中之單體(m2)之含量的上限係設定成與其他單體之含量的合計不超過100重量%。在數個態樣中,上述單體(m2)之含量例如設為30重量%以下或25重量%以下是適當的,而由使單體(m1)之含量相對較多而容易高折射率化之觀點來看,宜設為20重量%以下,較宜設為15重量%以下,可小於12重量%,可小於10重量%,亦可小於7重量%。The content of the monomer (m2) in the monomer component constituting the acrylic polymer is not particularly limited and can be set according to the purpose. In several aspects, the content of the above-mentioned monomer (m2) can be, for example, 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more. From the perspective of obtaining a higher use effect, in several aspects, the content of the above-mentioned monomer (A2) is preferably set to 1% by weight or more, can be set to 2% by weight or more, and can also be set to 4% by weight or more. The upper limit of the content of the monomer (m2) in the monomer component is set so that the total content of the monomer (m2) and other monomers does not exceed 100% by weight. In several aspects, it is appropriate to set the content of the above-mentioned monomer (m2) to, for example, less than 30 weight % or less than 25 weight %. From the perspective of making the content of the monomer (m1) relatively large and easily increasing the refractive index, it is preferably set to less than 20 weight %, more preferably less than 15 weight %, and can be less than 12 weight %, less than 10 weight %, or less than 7 weight %.
在使用含羥基單體作為單體(m2)之態樣中,單體成分中之含羥基單體之含量無特別限制,例如可為0.01重量%以上(宜為0.1重量%以上,較宜為0.5重量%以上)。在數個態樣中,上述含羥基單體之含量宜設為上述單體成分的1重量%以上,可設為2重量%以上,亦可設為4重量%以上。單體成分中之含羥基單體之含量的上限係設定成與其他單體之含量的合計不超過100重量%,例如設為30重量%以下或25重量%以下是適當的,而由使單體(m1)之含量相對較多而容易高折射率化之觀點來看,宜設為20重量%以下,較宜設為15重量%以下,可小於12重量%,可小於10重量%,亦可小於7重量%。In the embodiment of using a hydroxyl-containing monomer as the monomer (m2), the content of the hydroxyl-containing monomer in the monomer component is not particularly limited, and can be, for example, 0.01 wt % or more (preferably 0.1 wt % or more, more preferably 0.5 wt % or more). In several embodiments, the content of the hydroxyl-containing monomer is preferably 1 wt % or more of the monomer component, can be 2 wt % or more, and can also be 4 wt % or more. The upper limit of the content of the hydroxyl-containing monomer in the monomer component is set so that the total content of the hydroxyl-containing monomer and other monomers does not exceed 100 weight %, for example, it is appropriate to set it to 30 weight % or less or 25 weight % or less. From the perspective of making the content of the monomer (m1) relatively large and facilitating a high refractive index, it is preferably set to 20 weight % or less, more preferably to 15 weight % or less, and can be less than 12 weight %, less than 10 weight %, or less than 7 weight %.
在使用含羧基單體作為單體(m2)之態樣中,單體成分中之含羧基單體之含量無特別限制,例如可為0.01重量%以上(宜為0.1重量%以上,較宜為0.3重量%以上)。在數個態樣中,上述含羧基單體之含量可設為1重量%以上,可設為2重量%以上,亦可設為4重量%以上。單體成分中之含羧基單體之含量的上限係設定成與其他單體之使用量的合計不超過100重量%,例如設為30重量%以下或25重量%以下是適當的,而由使單體(m1)之含量相對較多而容易高折射率化之觀點來看,宜設為20重量%以下,較宜設為15重量%以下,可小於12重量%,亦可小於10重量%。在數個態樣中,由提升黏著劑之柔軟性之觀點來看,上述含羧基單體之含量設為小於7重量%是有利的,宜設為小於5重量%,可設為小於3重量%,可設為小於1重量%,亦可設為小於0.5重量%。在此揭示之技術例如可適宜在僅使用含羥基單體作為單體(m2)之態樣下實施,亦即在不使用含羧基單體之態樣下實施。In the aspect of using a carboxyl-containing monomer as a monomer (m2), the content of the carboxyl-containing monomer in the monomer component is not particularly limited, for example, it can be 0.01% by weight or more (preferably 0.1% by weight or more, preferably 0.3% by weight or more). In several aspects, the content of the above-mentioned carboxyl-containing monomer can be set to 1% by weight or more, can be set to 2% by weight or more, and can also be set to 4% by weight or more. The upper limit of the content of the carboxyl-containing monomer in the monomer component is set to a total of no more than 100% by weight with the amount of other monomers used, for example, it is appropriate to set it to 30% by weight or less or 25% by weight or less, and from the viewpoint of making the content of the monomer (m1) relatively large and easy to high refractive index, it is preferably set to 20% by weight or less, preferably set to 15% by weight or less, can be less than 12% by weight, and can also be less than 10% by weight. In several aspects, from the perspective of improving the softness of the adhesive, it is advantageous to set the content of the carboxyl-containing monomer to less than 7 wt %, preferably less than 5 wt %, less than 3 wt %, less than 1 wt %, or less than 0.5 wt %. The technology disclosed herein can be suitably implemented in an aspect in which only hydroxyl-containing monomers are used as monomers (m2), that is, in an aspect in which no carboxyl-containing monomers are used.
構成丙烯酸系聚合物之單體成分中之單體(m1)與單體(m2)之合計含量例如可為31重量%以上,且宜為51重量%以上,可為61重量%以上,亦可為71重量%以上。在數個態樣中,構成丙烯酸系聚合物之單體成分中之單體(m1)與單體(m2)之合計含量由容易適宜發揮該等單體之效果之觀點來看,例如可為76重量%以上,宜為81重量%以上,可為86重量%以上,可為91重量%以上,可為96重量%以上,可為99重量%以上,亦可實質上為100重量%。The total content of the monomer (m1) and the monomer (m2) in the monomer components constituting the acrylic polymer may be, for example, 31% by weight or more, preferably 51% by weight or more, 61% by weight or more, or 71% by weight or more. In several aspects, the total content of the monomer (m1) and the monomer (m2) in the monomer components constituting the acrylic polymer may be, for example, 76% by weight or more, preferably 81% by weight or more, 86% by weight or more, 91% by weight or more, 96% by weight or more, 99% by weight or more, or substantially 100% by weight, from the viewpoint of facilitating and appropriately exerting the effects of the monomers.
(單體m3) 構成丙烯酸系聚合物之單體成分亦可視需求包含有上述單體(m1)及上述單體(m2)以外之單體。所述任意成分之一例可舉(甲基)丙烯酸烷基酯(以下亦稱「單體(m3)」)。單體(m3)有助於調整黏著劑之柔軟性或改善在黏著劑內之相溶性。(Monomer m3) The monomer components constituting the acrylic polymer may also include monomers other than the above-mentioned monomer (m1) and the above-mentioned monomer (m2) as required. An example of the above-mentioned arbitrary component is alkyl (meth)acrylate (hereinafter also referred to as "monomer (m3)"). Monomer (m3) helps to adjust the softness of the adhesive or improve the compatibility in the adhesive.
單體(m3)可適宜使用於酯末端具有碳原子數1~20之(即C1-20 之)直鏈或支鏈狀烷基之(甲基)丙烯酸烷基酯。(甲基)丙烯酸C1-20 烷基酯之具體例可舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十五酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十七酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸異十八酯、(甲基)丙烯酸十九酯、(甲基)丙烯酸二十酯等,惟不受該等限定。The monomer (m3) can be suitably used in an alkyl (meth)acrylate having a linear or branched alkyl group with 1 to 20 carbon atoms (i.e., C1-20 ) at the end of the ester. Specific examples of the C1-20 alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecanyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecanyl (meth)acrylate, eicosyl (meth)acrylate, etc., but are not limited thereto.
在數個態樣中,單體(m3)之至少一部分可適宜採用均聚物之Tg為-20℃以下(較宜為-40℃以下,例如-50℃以下)之(甲基)丙烯酸烷基酯。所述低Tg之(甲基)丙烯酸烷基酯有助於提升黏著劑之柔軟性。上述(甲基)丙烯酸烷基酯之Tg的下限無特別限制,例如可為-85℃以上,可為-75℃以上,可為-65℃以上,亦可為-60℃以上。上述低Tg(甲基)丙烯酸烷基酯之具體例可舉丙烯酸正丁酯(BA)、丙烯酸2-乙基己酯(2EHA)、丙烯酸異壬酯(iNA)等。In several aspects, at least a portion of the monomer (m3) may be suitably an alkyl (meth)acrylate having a homopolymer Tg of below -20°C (preferably below -40°C, for example below -50°C). The low Tg alkyl (meth)acrylate helps to improve the softness of the adhesive. There is no particular restriction on the lower limit of the Tg of the above-mentioned alkyl (meth)acrylate, for example, it may be above -85°C, above -75°C, above -65°C, or above -60°C. Specific examples of the above-mentioned low Tg alkyl (meth)acrylate include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), isononyl acrylate (iNA), etc.
在使用單體(m3)之數個態樣中,由柔軟性或黏著性等觀點來看,上述單體(m3)之至少一部分宜為丙烯酸烷基酯。例如,以單體(m3)中50重量%以上(較宜為75重量%以上,更宜為90重量%以上)為丙烯酸烷基酯為佳。亦可為作為單體(m3)僅使用1種或2種以上丙烯酸烷基酯且不使用甲基丙烯酸烷基酯之態樣。In several aspects of using the monomer (m3), from the viewpoint of flexibility or adhesion, at least a part of the monomer (m3) is preferably an alkyl acrylate. For example, it is preferred that 50% by weight or more (preferably 75% by weight or more, and more preferably 90% by weight or more) of the monomer (m3) is an alkyl acrylate. It is also possible to use only one or two or more alkyl acrylates as the monomer (m3) and no alkyl methacrylate.
在單體成分包含(甲基)丙烯酸烷基酯之態樣中,單體成分中之(甲基)丙烯酸烷基酯之含量可設定成可適當發揮其使用效果。在數個態樣中,上述(甲基)丙烯酸烷基酯之含量例如可為1重量%以上,可為3重量%以上,可為5重量%以上,亦可為8重量%以上。在數個態樣中,上述(甲基)丙烯酸烷基酯之含量可為15重量%以上,可為30重量%以上,亦可為45重量%以上。單體成分中之單體(m3)之含量的上限係設定成與其他單體之含量的合計不超過100重量%,例如可小於50重量%。在數個態樣中,上述單體(m3)之含量例如可小於35重量%。一般而言,(甲基)丙烯酸烷基酯之折射率較低,因此為了高折射率化,限制單體成分中之單體(m3)之含量,使單體(m1)之含量相對較多是有利的。由所述觀點來看,單體(m3)之含量為單體成分之24重量%以下是有利的,宜小於23重量%,較宜小於20重量%,可小於17重量%,可小於12重量%,可小於7重量%,可小於3重量%,亦可小於1重量%。亦可實質上不使用單體(m3)。In the aspect that the monomer component includes (meth) alkyl acrylate, the content of the (meth) alkyl acrylate in the monomer component can be set to properly exert its use effect. In several aspects, the content of the above-mentioned alkyl (meth) acrylate can be, for example, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more. In several aspects, the content of the above-mentioned alkyl (meth) acrylate can be 15% by weight or more, 30% by weight or more, or 45% by weight or more. The upper limit of the content of the monomer (m3) in the monomer component is set so that the total content of the monomer (m3) and the content of other monomers does not exceed 100% by weight, for example, it can be less than 50% by weight. In several aspects, the content of the above-mentioned monomer (m3) can be, for example, less than 35% by weight. Generally speaking, the refractive index of alkyl (meth)acrylate is relatively low, so in order to increase the refractive index, it is advantageous to limit the content of the monomer (m3) in the monomer component and to make the content of the monomer (m1) relatively high. From the above point of view, it is advantageous for the content of the monomer (m3) to be 24 wt % or less of the monomer component, preferably less than 23 wt %, more preferably less than 20 wt %, less than 17 wt %, less than 12 wt %, less than 7 wt %, less than 3 wt %, or less than 1 wt %. It is also possible not to use the monomer (m3) substantially.
(其他單體) 構成丙烯酸系聚合物之單體成分亦可視需求包含有上述單體(m1)、(m2)、(m3)以外之單體(以下稱作「其他單體」)。上述其他單體例如可為了調整丙烯酸系聚合物之Tg、調整黏著性能、改善在黏著劑層內之相溶性等來使用。上述其他單體可單獨使用1種或組合2種以上來使用。(Other monomers) The monomer components constituting the acrylic polymer may also include monomers other than the above-mentioned monomers (m1), (m2), and (m3) (hereinafter referred to as "other monomers") as required. The above-mentioned other monomers may be used, for example, to adjust the Tg of the acrylic polymer, adjust the adhesive performance, improve the compatibility in the adhesive layer, etc. The above-mentioned other monomers may be used alone or in combination of two or more.
上述其他單體之例可舉具有羥基及羧基以外之官能基的單體(含官能基單體)。例如,可使黏著劑之凝集力或耐熱性提升之其他單體可舉含磺酸基單體、含磷酸基單體、含氰基單體等。又,作為可於丙烯酸系聚合物中導入可成為交聯基點之官能基、或是可有助於提升剝離強度或改善在黏著劑層內之相溶性的單體,可舉含醯胺基單體(例如(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺等)、含胺基單體(例如胺乙基(甲基)丙烯酸酯、N,N-二甲基胺乙基(甲基)丙烯酸酯等)、具有含氮原子環之單體(例如N-乙烯基-2-吡咯啶酮、N-(甲基)丙烯醯基嗎福林等)、含醯亞胺基單體、含環氧基單體、含酮基單體、含異氰酸酯基單體、含烷氧矽基單體等。此外,具有含氮原子環之單體中有例如像N-乙烯基-2-吡咯啶酮般亦相當於含醯胺基單體之物。關於上述具有含氮原子環之單體與含胺基單體之關係亦同。Examples of the other monomers include monomers having functional groups other than hydroxyl and carboxyl groups (functional group-containing monomers). For example, other monomers that can improve the cohesive force or heat resistance of the adhesive include sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, and the like. In addition, as monomers that can introduce functional groups that can become crosslinking points into acrylic polymers, or that can help to enhance peel strength or improve compatibility in the adhesive layer, there can be exemplified amide group-containing monomers (e.g., (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, etc.), amine group-containing monomers (e.g., aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, etc.), monomers having a nitrogen atom-containing ring (e.g., N-vinyl-2-pyrrolidone, N-(meth)acryloylmethacrylate, etc.), imide group-containing monomers, epoxy group-containing monomers, ketone group-containing monomers, isocyanate group-containing monomers, alkoxysilyl group-containing monomers, and the like. In addition, some monomers having a nitrogen atom ring, such as N-vinyl-2-pyrrolidone, are also equivalent to amide group-containing monomers. The relationship between the above-mentioned monomers having a nitrogen atom ring and amine group-containing monomers is also the same.
上述含官能基單體外可使用之其他單體可舉:乙酸乙烯酯等乙烯酯系單體;(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯等含非芳香族性環(甲基)丙烯酸酯;乙烯、丁二烯、異丁烯等烯烴系單體;氯乙烯等含氯單體;甲氧基乙基(甲基)丙烯酸酯、乙氧基乙基(甲基)丙烯酸酯、乙氧基乙氧基乙基(甲基)丙烯酸酯等含烷氧基單體;甲基乙烯基醚等乙烯基醚系單體等。在提升黏著劑之柔軟性等目的下使用之其他單體的一適當例可舉乙氧基乙氧基乙基丙烯酸酯(別名:乙基卡必醇丙烯酸酯,均聚物之Tg:-67℃)。Other monomers that can be used in addition to the above-mentioned functional group-containing monomers include: vinyl ester monomers such as vinyl acetate; non-aromatic ring-containing (meth)acrylates such as cyclohexyl (meth)acrylate and isoborneol (meth)acrylate; olefin monomers such as ethylene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride; alkoxy-containing monomers such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and ethoxyethoxyethyl (meth)acrylate; vinyl ether monomers such as methyl vinyl ether, etc. An appropriate example of other monomers used for the purpose of improving the softness of the adhesive is ethoxyethoxyethyl acrylate (also known as ethyl carbitol acrylate, Tg of the homopolymer: -67°C).
使用上述其他單體時,其使用量無特別限制,可在單體成分之合計量不超過100重量%之範圍內適當設定。在數個態樣中,由容易發揮使用單體(m1)所得折射率提升效果之觀點來看,單體成分中之上述其他單體之含量可設為例如大約35重量%以下,設為大約25重量%以下(例如0~25重量%)是適當的,可大約20重量%以下(例如0~20重量%),可大約10重量%以下,可大約5重量%以下,亦可例如大約1重量%以下。在此揭示之技術可適宜在單體成分實質上不含上述其他單體之態樣下實施。When the above-mentioned other monomers are used, their usage amount is not particularly limited and can be appropriately set within the range where the total amount of the monomer components does not exceed 100 weight %. In several aspects, from the perspective of easily exerting the refractive index enhancement effect obtained by using the monomer (m1), the content of the above-mentioned other monomers in the monomer components can be set to, for example, about 35 weight % or less, about 25 weight % or less (for example, 0-25 weight %) is appropriate, about 20 weight % or less (for example, 0-20 weight %), about 10 weight % or less, about 5 weight % or less, and about 1 weight % or less. The technology disclosed herein can be appropriately implemented in an aspect where the monomer components do not substantially contain the above-mentioned other monomers.
在數個態樣中,構成丙烯酸系聚合物之單體成分可為含甲基丙烯醯基單體之使用量經抑制在預定以下之組成。單體成分中之含甲基丙烯醯基單體之使用量例如可小於5重量%,可小於3重量%,可小於1重量%,亦可小於0.5重量%。如所述限制含甲基丙烯醯基單體之使用量一事,由實現平衡兼顧柔軟性或黏著性與高折射率之黏著劑之觀點來看是有利的。構成丙烯酸系聚合物的單體成分亦可為不含含甲基丙烯醯基單體之組成(例如僅由含丙烯醯基單體構成之組成)。In several aspects, the monomer components constituting the acrylic polymer may be a composition in which the amount of methacrylic monomers is suppressed to a predetermined amount or less. The amount of methacrylic monomers in the monomer components may be, for example, less than 5% by weight, less than 3% by weight, less than 1% by weight, or less than 0.5% by weight. Limiting the amount of methacrylic monomers as described above is advantageous from the perspective of achieving an adhesive that balances flexibility or adhesion with a high refractive index. The monomer components constituting the acrylic polymer may also be a composition that does not contain methacrylic monomers (e.g., a composition consisting only of acryl monomers).
在數個態樣中,由抑制黏著劑之著色或變色(例如黃變)之觀點來看,構成黏著劑層之基底聚合物(例如丙烯酸系聚合物)之單體成分中含羧基單體之使用量宜業經限制。單體成分中之含羧基單體之使用量例如可小於1重量%,宜小於0.5重量%,較宜小於0.3重量%,可小於0.1重量%,亦可小於0.05重量%。如所述含羧基單體之使用量被限制一事,由抑制可接觸或與在此揭示之黏著劑鄰近配置的金屬材料(例如可存在於被黏著體上之金屬配線或金屬膜等)之腐蝕之觀點來看亦有利。在此揭示之技術可適宜在上述單體成分不含含羧基單體之態樣下實施。 基於同樣理由,在數個態樣中,構成黏著劑層之基底聚合物之單體成分中具有酸性官能基(除羧基以外,還包含磺酸基、磷酸基等)之單體之使用量宜業經限制。所述態樣之單體成分中之含酸性官能基單體之使用量可應用上述含羧基單體之理想使用量。在此揭示之技術可適宜在上述單體成分不含含酸性基單體之態樣(亦即黏著劑層之基底聚合物為無酸之態樣)下實施。In several aspects, from the perspective of inhibiting the coloring or discoloration (e.g., yellowing) of the adhesive, the amount of carboxyl-containing monomers used in the monomer components of the base polymer (e.g., acrylic polymer) constituting the adhesive layer is preferably limited. The amount of carboxyl-containing monomers used in the monomer components may be, for example, less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, less than 0.1% by weight, or less than 0.05% by weight. The fact that the amount of carboxyl-containing monomers used is limited is also beneficial from the perspective of inhibiting corrosion of metal materials (e.g., metal wiring or metal films that may exist on the adherend) that may contact or be arranged adjacent to the adhesive disclosed herein. The technology disclosed herein may be appropriately implemented in the aspect that the above-mentioned monomer components do not contain carboxyl-containing monomers. For the same reason, in several aspects, the amount of monomers having acidic functional groups (including sulfonic acid groups, phosphoric acid groups, etc. in addition to carboxyl groups) in the monomer components of the base polymer constituting the adhesive layer is preferably limited. The amount of monomers containing acidic functional groups in the monomer components of the above aspects can be applied to the ideal amount of carboxyl-containing monomers. The technology disclosed herein can be appropriately implemented in the aspect that the above monomer components do not contain acidic monomers (i.e., the base polymer of the adhesive layer is acid-free).
(基底聚合物之玻璃轉移溫度TgT ) 在數個態樣中,黏著劑層之基底聚合物(例如丙烯酸系聚合物)中,根據構成該聚合物之單體成分之組成的玻璃轉移溫度TgT 為大約20℃以下是適當的,宜大約10℃以下,較宜為0℃以下,可為-10℃以下,可為-20℃以下,可為-25℃以下,可為-28℃以下,亦可為-30℃以下。由提升黏著劑之柔軟性之觀點來看,玻璃轉移溫度TgT 低是有利的。又,玻璃轉移溫度TgT 例如可為-60℃以上,而由容易進行黏著劑之高折射率化之觀點來看,宜為-50℃以上,較宜高於-45℃,可高於-40℃,可高於-35℃,可高於-25℃,可為-15℃以上,亦可為-5℃以上。(Glass transition temperature Tg T of base polymer) In several aspects, the base polymer (e.g., acrylic polymer) of the adhesive layer has a glass transition temperature Tg T of about 20°C or less, preferably about 10°C or less, more preferably 0°C or less, -10°C or less, -20°C or less, -25°C or less, -28°C or less, or -30°C or less. From the perspective of improving the flexibility of the adhesive, a low glass transition temperature Tg T is advantageous. The glass transition temperature TgT may be, for example, above -60°C, but from the viewpoint of facilitating the high refractive index of the adhesive, it is preferably above -50°C, more preferably above -45°C, may be above -40°C, may be above -35°C, may be above -25°C, may be above -15°C, and may also be above -5°C.
在此,聚合物之玻璃轉移溫度TgT 在未特別記載的情況下,意指根據構成該聚合物之單體成分的組成藉由Fox式求得之玻璃轉移溫度。Fox式如以下所示,係共聚物之Tg與構成該共聚物之單體各自均聚合後之均聚物的玻璃轉移溫度Tgi的關係式。 1/Tg=Σ(Wi/Tgi) 在上述Fox式中,Tg表示共聚物之玻璃轉移溫度(單位:K),Wi表示該共聚物中之單體i的重量分率(重量基準之共聚比率),Tgi表示單體i之均聚物的玻璃轉移溫度(單位:K)。 關於使用於Tg之計算之均聚物的玻璃轉移溫度,係使用「Polymer Handbook」(第3版,John Wiley & Sons, Inc., 1989年)等公知資料中記載之值。關於上述Polymer Handbook中記載之複數種值的單體,係採用最高之值。公知資料中未記載均聚物之Tg時,係使用藉由日本專利申請案公開2007-51271號公報中記載之測定方法所得之值。Here, the glass transition temperature Tg T of a polymer means the glass transition temperature obtained by the Fox equation based on the composition of the monomer components constituting the polymer unless otherwise specified. The Fox equation is shown below, and is a relationship between the Tg of a copolymer and the glass transition temperature Tgi of a homopolymer after each monomer constituting the copolymer is polymerized. 1/Tg=Σ(Wi/Tgi) In the above Fox equation, Tg represents the glass transition temperature of the copolymer (unit: K), Wi represents the weight fraction of monomer i in the copolymer (copolymerization ratio based on weight), and Tgi represents the glass transition temperature of the homopolymer of monomer i (unit: K). The glass transition temperature of the homopolymer used for the calculation of Tg is a value described in known materials such as "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989). For monomers with multiple values listed in the above-mentioned Polymer Handbook, the highest value is used. When the Tg of the homopolymer is not listed in the public data, the value obtained by the measurement method described in Japanese Patent Application Publication No. 2007-51271 is used.
(基底聚合物之調製方法) 在此揭示之技術中,獲得黏著劑層之基底聚合物(例如藉由如上述之單體成分構成之丙烯酸系聚合物(A))的方法無特別限定,可適當採用溶液聚合法、乳化聚合法、整體聚合法、懸浮聚合法、光聚合法等公知的聚合方法。在數個態樣中,可適宜採用溶液聚合法。進行溶液聚合時之聚合溫度可因應使用之單體及溶劑之種類、聚合引發劑之種類等適當選擇,例如可設為20℃~170℃左右(典型上為40℃~140℃左右)。(Preparation method of base polymer) In the technology disclosed herein, the method for obtaining the base polymer of the adhesive layer (for example, an acrylic polymer (A) composed of the above-mentioned monomer components) is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization can be appropriately adopted. In several aspects, solution polymerization can be appropriately adopted. The polymerization temperature during solution polymerization can be appropriately selected according to the types of monomers and solvents used, the type of polymerization initiator, etc., and can be set to about 20°C~170°C (typically about 40°C~140°C).
溶液聚合所用溶劑(聚合溶劑)可從以往公知之有機溶劑適當選擇。例如,可使用選自下述中之任1種溶劑或2種以上之混合溶劑:甲苯等芳香族化合物類(典型上為芳香族烴類);乙酸乙酯等乙酸酯類;己烷或環己烷等脂肪族或脂環式烴類;1,2-二氯乙烷等鹵烷類;異丙醇等低級醇類(例如碳原子數1~4之一元醇類);三級丁基甲基醚等醚類;甲基乙基酮等酮類等。The solvent used for solution polymerization (polymerization solvent) can be appropriately selected from conventionally known organic solvents. For example, any one solvent or a mixed solvent of two or more solvents selected from the following can be used: aromatic compounds such as toluene (typically aromatic hydrocarbons); acetates such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane or cyclohexane; halides such as 1,2-dichloroethane; lower alcohols such as isopropanol (e.g., monohydric alcohols with 1 to 4 carbon atoms); ethers such as tertiary butyl methyl ether; ketones such as methyl ethyl ketone, etc.
聚合所用之引發劑可因應聚合方法之種類從公知之聚合引發劑適當選擇。例如可適宜使用2,2'-偶氮雙異丁腈(AIBN)等偶氮系聚合引發劑之1種或2種以上。作為聚合引發劑之其他例可舉:過硫酸鉀等過硫酸鹽;苯甲醯基過氧化物、過氧化氫等過氧化物系引發劑;苯基取代乙烷等取代乙烷系引發劑;芳香族羰基化合物等。聚合引發劑之又其他例可舉過氧化物與還原劑組合而成之氧還系引發劑。聚合引發劑可單獨使用1種或組合2種以上來使用。聚合引發劑之使用量為通常之使用量即可,例如可相對於單體成分100重量份自大約0.005~1重量份左右(典型上為大約0.01~1重量份左右)之範圍內選擇。The initiator used for the polymerization can be appropriately selected from known polymerization initiators according to the type of polymerization method. For example, one or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be appropriately used. Other examples of polymerization initiators include: persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds, etc. Another example of the polymerization initiator is a redox-based initiator composed of a peroxide and a reducing agent. The polymerization initiator can be used alone or in combination of two or more. The amount of the polymerization initiator used may be a normal amount, for example, it may be selected from the range of about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) relative to 100 parts by weight of the monomer component.
上述聚合中可因應需要使用以往公知之各種鏈轉移劑。例如可使用正十二基硫醇、三級十二基硫醇、硫代乙醇酸、α-硫甘油等硫醇類。或者,亦可使用不含硫原子之鏈轉移劑(非硫系鏈轉移劑)。非硫系鏈轉移劑之例可舉N,N-二甲基苯胺、N,N-二乙基苯胺等苯胺類;α-蒎烯、萜品油烯等類萜類;α-甲基苯乙烯、α-甲基苯乙烯二聚物等之苯乙烯類等。鏈轉移劑可單獨使用1種或組合2種以上來使用。使用鏈轉移劑時之使用量相對於單體原料100重量份,例如可設為大約0.01~1重量份左右。In the above-mentioned polymerization, various conventionally known chain transfer agents may be used as needed. For example, thiols such as n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, and α-thioglycerol may be used. Alternatively, a chain transfer agent that does not contain a sulfur atom (non-sulfur chain transfer agent) may also be used. Examples of non-sulfur chain transfer agents include anilines such as N,N-dimethylaniline and N,N-diethylaniline; terpenes such as α-pinene and terpinolene; styrenes such as α-methylstyrene and α-methylstyrene dimer, and the like. Chain transfer agents may be used alone or in combination of two or more. When a chain transfer agent is used, the amount used may be, for example, about 0.01 to 1 part by weight relative to 100 parts by weight of the monomer raw material.
基底聚合物之重量平均分子量(Mw)無特別限定,可為例如大約10×104 ~500×104 之範圍。由黏著性能之觀點來看,基底聚合物之Mw宜在大約20×104 ~400×104 (較宜為大約30×104 ~150×104 ,例如大約50×104 ~130×104 )之範圍內。The weight average molecular weight (Mw) of the base polymer is not particularly limited, and may be, for example, in the range of about 10×10 4 to 500×10 4. From the viewpoint of adhesion performance, the Mw of the base polymer is preferably in the range of about 20×10 4 to 400×10 4 (preferably about 30×10 4 to 150×10 4 , for example, about 50×10 4 to 130×10 4 ).
在此,聚合物之Mw可藉由凝膠滲透層析法(GPC)換算成聚苯乙烯而求得。具體上,可使用商品名「HLC-8220GPC」(Tosoh公司製)作為GPC測定裝置,以下述條件測定來求得。 [GPC之測定條件] 試樣濃度:0.2重量%(四氫呋喃溶液) 試樣注入量:10µL 溶析液:四氫呋喃(THF) 流量(流速):0.6mL/分鐘 管柱溫度(測定溫度):40℃ 管柱: 試樣管柱:商品名「TSKguardcolumn SuperHZ-H」1支+商品名「TSKgel SuperHZM-H」2支」(Tosoh公司製) 參考管柱:商品名「TSKgel SuperH-RC」1支(Tosoh公司製) 檢測器:示差折射計(RI) 標準試料:聚苯乙烯Here, the Mw of the polymer can be obtained by converting it into polystyrene by gel permeation chromatography (GPC). Specifically, it can be obtained by using the trade name "HLC-8220GPC" (manufactured by Tosoh Corporation) as a GPC measuring device and measuring under the following conditions. [GPC measurement conditions] Sample concentration: 0.2 wt% (tetrahydrofuran solution) Sample injection volume: 10µL Eluent: tetrahydrofuran (THF) Flow rate: 0.6mL/min Column temperature (measurement temperature): 40℃ Column: Sample column: 1 piece of "TSKguardcolumn SuperHZ-H" + 2 pieces of "TSKgel SuperHZM-H" (manufactured by Tosoh) Reference column: 1 piece of "TSKgel SuperH-RC" (manufactured by Tosoh) Detector: Differential refractometer (RI) Standard sample: Polystyrene
(折射率提升劑) 在此揭示之技術之數個態樣中,上述黏著劑層(例如丙烯酸系黏著劑層)中除了基底聚合物,還可視需求含有折射率提升劑。在此,本說明書中折射率提升劑意指可藉由使用其來提高黏著劑層之折射率的材料。折射率提升劑可適宜使用折射率較包含該折射率提升劑之黏著劑層之折射率更高之材料。又,折射率提升劑可適宜使用折射率較包含該折射率提升劑之黏著劑層的基底聚合物(例如丙烯酸系聚合物(A))更高之材料。藉由適當使用折射率提升劑,可適宜兼顧更高之折射率與實用之黏著性能。在數個態樣中,折射率提升劑宜為有機材料。可作為折射率提升劑使用之有機材料可為聚合物,亦可為非聚合物。又,可具有聚合性官能基,亦可不具聚合性官能基。折射率提升劑可單獨使用1種或組合2種以上來使用。(Refractive index enhancer) In several aspects of the technology disclosed herein, the above-mentioned adhesive layer (e.g., acrylic adhesive layer) may contain a refractive index enhancer in addition to the base polymer as required. Here, the refractive index enhancer in this specification means a material that can be used to enhance the refractive index of the adhesive layer. The refractive index enhancer may be suitably a material having a higher refractive index than the refractive index of the adhesive layer containing the refractive index enhancer. In addition, the refractive index enhancer may be suitably a material having a higher refractive index than the base polymer (e.g., acrylic polymer (A)) of the adhesive layer containing the refractive index enhancer. By appropriately using the refractive index enhancer, a higher refractive index and practical adhesive performance can be suitably taken into account. In several aspects, the refractive index enhancer is preferably an organic material. The organic material that can be used as the refractive index enhancer may be a polymer or a non-polymer. Also, it may have a polymerizable functional group or may not have a polymerizable functional group. The refractive index enhancer may be used alone or in combination of two or more.
折射率提升劑(例如後述之添加劑((HRO ))之折射率可在與基底聚合物之折射率的相對關係下設定為適當的範圍,因此不受特定範圍所限。折射率提升劑之折射率例如大於1.55、大於1.56或大於1.57,且可自較基底聚合物之折射率更高之範圍中選擇。由黏著劑之高折射率化之觀點來看,在數個態樣中,折射率提升劑之折射率為1.58以上是有利的,且宜為1.60以上,較宜為1.63以上,可為1.65以上,可為1.70以上,亦可為1.75以上。藉由折射率較高之折射率提升劑,即便藉由使用較少量之折射率提升劑仍可達成目標折射率。此事由抑制黏著特性或光學特性降低之觀點來看實為理想。折射率提升劑之折射率的上限無特別限制,惟由在黏著劑內之相溶性、高折射率化與適合作為黏著劑之柔軟性之兼顧容易性等觀點來看,例如為3.000以下,可為2.500以下,可為2.000以下,可為1.950以下,可為1.900以下,亦可為1.850以下。The refractive index of the refractive index enhancer (e.g., the additive ((H RO ) described later)) can be set to an appropriate range in relation to the refractive index of the base polymer and is therefore not limited to a specific range. The refractive index of the refractive index enhancer is, for example, greater than 1.55, greater than 1.56, or greater than 1.57, and can be selected from a range higher than the refractive index of the base polymer. From the perspective of increasing the refractive index of the adhesive, in several aspects, it is advantageous for the refractive index of the refractive index enhancer to be greater than 1.58, preferably greater than 1.60, more preferably greater than 1.63, may be greater than 1.65, may be greater than 1.70, and may also be greater than 1.75. By using a refractive index enhancer with a higher refractive index, the target refractive index can be achieved even by using a smaller amount of the refractive index enhancer. This is ideal from the viewpoint of suppressing the reduction of adhesive properties or optical properties. There is no particular upper limit on the refractive index of the refractive index enhancer, but from the viewpoint of compatibility in the adhesive, ease of achieving a high refractive index and suitability as an adhesive for flexibility, for example, it may be 3.000 or less, 2.500 or less, 2.000 or less, 1.950 or less, 1.900 or less, or 1.850 or less.
在數個態樣中,折射率提升劑(例如後述添加劑(HRO ))之折射率nb 與基底聚合物之折射率na 之差、亦即nb -na (以下亦稱「ΔnA 」)係設定為大於0。在數個態樣中,ΔnA 例如為0.02以上,可為0.05以上,可為0.07以上,可為0.10以上,可為0.15以上,亦可為0.20以上或0.25以上。藉由以使ΔnA 變更大之方式來選擇基底聚合物及折射率提升劑,使用折射率提升劑來提升折射率之效果有變高之傾向。又,由在黏著劑層內之相溶性或黏著劑層之透明性等觀點來看,在數個態樣中,ΔnA 例如可為0.70以下,可為0.60以下,可為0.50以下,亦可為0.40以下或0.35以下。In some embodiments, the difference between the refractive index nb of the refractive index enhancer (e.g., the additive ( HRO ) described below) and the refractive index na of the base polymer, i.e., nb - na (hereinafter also referred to as "ΔnA " ), is set to be greater than 0. In some embodiments, ΔnA is, for example, greater than 0.02, greater than 0.05, greater than 0.07, greater than 0.10, greater than 0.15, greater than 0.20, or greater than 0.25. By selecting the base polymer and the refractive index enhancer so as to increase ΔnA , the effect of increasing the refractive index using the refractive index enhancer tends to be higher. Furthermore, from the viewpoint of compatibility in the adhesive layer or transparency of the adhesive layer, in several aspects, Δn A may be, for example, less than 0.70, less than 0.60, less than 0.50, less than 0.40, or less than 0.35.
在數個態樣中,折射率提升劑(例如後述添加劑(HRO ))之折射率nb 與包含該折射率提升劑之黏著劑層之折射率nT 之差、亦即nb -nT (以下亦稱「ΔnB 」)係設定為大於0。在數個態樣中,ΔnB 例如為0.02以上,可為0.05以上,可為0.07以上,可為0.10以上,可為0.15以上,亦可為0.20以上或0.25以上。藉由以使ΔnB 變更大之方式來選擇黏著劑層之組成及折射率提升劑,使用折射率提升劑來提升折射率之效果有變高之傾向。又,由在黏著劑層內之相溶性或黏著劑層之透明性等觀點來看,在數個態樣中,ΔnB 例如可為0.70以下,可為0.60以下,可為0.50以下,亦可為0.40以下或0.35以下。In some embodiments, the difference between the refractive index nb of the refractive index raising agent (e.g., the additive ( HRO ) described later) and the refractive index nT of the adhesive layer containing the refractive index raising agent, i.e., nb - nT (hereinafter also referred to as " ΔnB "), is set to be greater than 0. In some embodiments, ΔnB is, for example, greater than 0.02, greater than 0.05, greater than 0.07, greater than 0.10, greater than 0.15, greater than 0.20, or greater than 0.25. By selecting the composition of the adhesive layer and the refractive index raising agent so as to increase ΔnB , the effect of raising the refractive index using the refractive index raising agent tends to be higher. Furthermore, from the viewpoint of compatibility in the adhesive layer or transparency of the adhesive layer, in several aspects, Δn B may be, for example, 0.70 or less, 0.60 or less, 0.50 or less, 0.40 or less, or 0.35 or less.
折射率提升劑相對於基底聚合物100重量份之使用量(使用複數種折射率提升劑時為其等之合計量)無特別限定,可按目的作設定。由黏著劑之高折射率化之觀點來看,折射率提升劑相對於基底聚合物100重量份之使用量可設為例如1重量份以上,設為3重量份以上是有利的,宜設為5重量份以上,可為7重量份以上,可為10重量份以上,可為15重量份以上,亦可為20重量份以上。又,在數個態樣中,折射率提升劑相對於基底聚合物100重量份之使用量可設為例如80重量份以下,而由平衡兼顧黏著劑之高折射率化與抑制黏著特性或光學特性降低之觀點來看,設為60重量份以下是有利的,且宜設為45重量份以下。在更重視黏著特性或光學特性之數個態樣中,折射率提升劑相對於基底聚合物100重量份之使用量例如可為30重量份以下,可為20重量份以下,可為15重量份以下,可為10重量份以下,可為5重量份以下,亦可為3重量份以下。在此揭示之技術即使在折射率提升劑相對於黏著劑層中之基底聚合物100重量份的使用量小於1重量份、或實質上不使用折射率提升劑之態樣下仍可適宜實施。在此,實質上不使用係指至少非刻意使用。The amount of the refractive index enhancer used relative to 100 parts by weight of the base polymer (the total amount of the refractive index enhancers when multiple refractive index enhancers are used) is not particularly limited and can be set according to the purpose. From the perspective of increasing the refractive index of the adhesive, the amount of the refractive index enhancer used relative to 100 parts by weight of the base polymer can be set to, for example, 1 part by weight or more, and it is advantageous to set it to 3 parts by weight or more, preferably to set it to 5 parts by weight or more, and it can be 7 parts by weight or more, it can be 10 parts by weight or more, it can be 15 parts by weight or more, and it can also be 20 parts by weight or more. In addition, in several aspects, the amount of the refractive index enhancer used relative to 100 parts by weight of the base polymer can be set to, for example, 80 parts by weight or less, and from the perspective of balancing the high refractive index of the adhesive and suppressing the reduction of adhesion characteristics or optical characteristics, it is advantageous to set it to 60 parts by weight or less, and it is preferably set to 45 parts by weight or less. In several aspects where the adhesive property or the optical property is more important, the amount of the refractive index enhancer used relative to 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less. The technology disclosed herein can be appropriately implemented even when the amount of the refractive index enhancer used relative to 100 parts by weight of the base polymer in the adhesive layer is less than 1 part by weight, or when the refractive index enhancer is not substantially used. Here, substantially not used means at least not intentionally used.
(添加劑(HRO )) 在數個態樣中,折射率提升劑可適宜採用折射率較基底聚合物更高之有機材料。以下,有將所述有機材料表記為「添加劑(HRO )」之情形。在此,上述「HRO 」係表示高折射率(High Refractive index)之有機材料(Organic material)。藉由組合基底聚合物(例如丙烯酸系聚合物,宜為丙烯酸系聚合物(A))與添加劑(HRO )來使用,可實現可更適宜兼顧折射率與黏著特性(剝離強度、柔軟性等)及/或光學特性(全光線透射率、霧度值等)之黏著劑。可作為添加劑(HRO )使用之有機材料可為聚合物,亦可為非聚合物。又,可具有聚合性官能基,亦可不具聚合性官能基。添加劑劑(HRO )可單獨使用1種或組合2種以上來使用。(Additive (H RO )) In several aspects, the refractive index enhancer may be preferably an organic material having a higher refractive index than the base polymer. In the following, the organic material is sometimes referred to as "additive (H RO )". Here, the "H RO " refers to an organic material having a high refractive index. By combining a base polymer (e.g., an acrylic polymer, preferably an acrylic polymer (A)) and an additive (H RO ), an adhesive may be achieved that more appropriately takes into account both the refractive index and adhesive properties (peel strength, flexibility, etc.) and/or optical properties (total light transmittance, haze value, etc.). The organic material that may be used as an additive (H RO ) may be a polymer or a non-polymer. Furthermore, it may or may not have a polymerizable functional group. The additive (H RO ) may be used alone or in combination of two or more.
添加劑(HRO )之折射率係與單體之折射率同樣地,使用阿貝折射計在測定波長589nm、測定溫度25℃之條件下進行測定。當有從製造商等提供了在25℃下之折射率的標稱值時,可採用該標稱值。The refractive index of the additive (H RO ) is measured using an Abbe refractometer at a wavelength of 589 nm and a temperature of 25° C., similarly to the refractive index of the monomer. If a nominal value of the refractive index at 25° C. is provided by a manufacturer, the nominal value may be used.
作為添加劑(HRO )使用之有機材料的分子量無特別限定,可按目的作選擇。由平衡兼顧高折射率化之效果與其他特性(例如適於黏著劑之柔軟性、霧度等光學特性)之觀點來看,在數個態樣中,添加劑(HRO )之分子量為大約小於10000是適當的,宜小於5000,較宜小於3000(例如小於1000),可小於800,可小於600,可小於500,亦可小於400。添加劑(HRO )之分子量不過大一事由提升在黏著劑層內之相溶性之觀點來看是有利的。又,添加劑(HRO )之分子量例如可為130以上,亦可為150以上。在數個態樣中,由該添加劑(HRO )之高折射率化之觀點來看,添加劑(HRO )之分子量宜為170以上,較宜為200以上,可為230以上,可為250以上,可為270以上,可為500以上,可為1000以上,亦可為2000以上。在數個態樣中,可將分子量為1000~10000左右(例如1000以上且小於5000)之聚合物作為添加劑(HRO )來使用。 添加劑(HRO )之分子量可使用針對非聚合物或低聚合度(例如2~5聚物左右)之聚合物依據化學結構算出之分子量、或使用基質輔助雷射脫附游離飛行時間型質量分析法(MALDI-TOF-MS)所得之測定值。添加劑(HRO )為聚合度更高之聚合物時,可使用根據以適當條件進行之GPC的重量平均分子量(Mw)。當有從製造商等提供了分子量的標稱值時,可採用該標稱值。The molecular weight of the organic material used as the additive (H RO ) is not particularly limited and can be selected according to the purpose. From the perspective of balancing the effect of high refractive index and other properties (such as optical properties such as flexibility and haze suitable for adhesives), in several aspects, the molecular weight of the additive (H RO ) is preferably less than about 10,000, preferably less than 5,000, more preferably less than 3,000 (for example, less than 1,000), less than 800, less than 600, less than 500, or less than 400. It is beneficial to not have an additive (H RO ) with a molecular weight that is too large in order to improve the compatibility in the adhesive layer. In addition, the molecular weight of the additive (H RO ) can be, for example, 130 or more, or 150 or more. In several aspects, from the viewpoint of increasing the refractive index of the additive (H RO ), the molecular weight of the additive (H RO ) is preferably 170 or more, preferably 200 or more, 230 or more, 250 or more, 270 or more, 500 or more, 1000 or more, or 2000 or more. In several aspects, a polymer having a molecular weight of about 1000 to 10000 (e.g., 1000 or more and less than 5000) can be used as the additive (H RO ). The molecular weight of the additive (H RO ) can be a molecular weight calculated based on the chemical structure of a non-polymer or a polymer with a low degree of polymerization (e.g., about 2 to 5 polymers), or a measured value obtained using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). When the additive (H RO ) is a polymer with a higher degree of polymerization, the weight average molecular weight (Mw) obtained by GPC under appropriate conditions can be used. When a nominal value of the molecular weight is provided by the manufacturer, the nominal value can be used.
可成為添加劑(HRO )之選項的有機材料之例包含具有芳香環之有機化合物、具有雜環(可為芳香環,亦可為非芳香族性雜環)之有機化合物等,惟不受該等限定。Examples of organic materials that can be selected as the additive (H RO ) include organic compounds having an aromatic ring, organic compounds having a heterocyclic ring (which may be an aromatic ring or a non-aromatic heterocyclic ring), etc., but are not limited thereto.
可作為添加劑(HRO )使用之上述具有芳香環之有機化合物(以下亦稱「含芳香環化合物」)所具有之芳香環,可自與可作為單體(m1)使用之化合物所具有之芳香環相同之物來選擇。The aromatic ring of the organic compound having an aromatic ring (hereinafter also referred to as "aromatic ring-containing compound") which can be used as the additive (H RO ) can be selected from the same aromatic rings as those of the compound which can be used as the monomer (m1).
上述芳香環可於環構成原子上具有1或2個以上取代基,亦可不具有取代基。具有取代基時,該取代基可例示烷基、烷氧基、芳氧基、羥基、鹵素原子(氟原子、氯原子、溴原子等)、羥烷基、羥烷氧基、環氧丙氧基等,惟不受該等限定。在包含碳原子之取代基中,該取代基所含碳原子數例如為1~10,1~6為有利,宜為1~4,較宜為1~3,且例如可為1或2。在數個態樣中,上述芳香環可為於環構成原子上不具有取代基之芳香環、或可為於環構成原子上具有選自於由烷基、烷氧基及鹵素原子(例如溴原子)所構成群組中之1或2個以上取代基之芳香環。The aromatic ring may have 1 or 2 or more substituents on the ring-constituting atoms, or may have no substituents. When having substituents, the substituents may be alkyl, alkoxy, aryloxy, hydroxyl, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), hydroxyalkyl, hydroxyalkoxy, glycidoxy, etc., but are not limited thereto. In the substituent containing carbon atoms, the number of carbon atoms contained in the substituent is, for example, 1 to 10, 1 to 6 is advantageous, 1 to 4 is preferably, 1 to 3 is more preferably, and may be, for example, 1 or 2. In several aspects, the aromatic ring may be an aromatic ring having no substituents on the ring-constituting atoms, or may be an aromatic ring having 1 or 2 or more substituents selected from the group consisting of alkyl, alkoxy and halogen atoms (e.g., bromine atoms) on the ring-constituting atoms.
作為可作為添加劑(HRO )使用之含芳香環化合物之例可舉例如:可作為單體(m1)使用之化合物;包含可作為單體(m1)使用之化合物作為單體單元的寡聚物;從可作為單體(m1)使用之化合物中去除具有乙烯性不飽和基之基團(可為鍵結於環構成原子之取代基)或該基團中構成乙烯性不飽和基之部分且取代成氫原子或不具乙烯性不飽和基之基團(例如羥基、胺基、鹵素原子、烷基、烷氧基、羥烷基、羥烷氧基、環氧丙氧基等)之結構的化合物等,惟不受該等限定。可作為添加劑(HRO )使用之含芳香環化合物的非限定具體例中可包含:丙烯酸苄酯、間苯氧基苄基丙烯酸酯、2-(鄰苯基苯氧基)乙基丙烯酸酯、丙烯酸苯氧乙酯、苯氧基二乙二醇丙烯酸酯、苯氧基聚乙二醇丙烯酸酯、2-羥-3-苯氧基丙基丙烯酸酯、上述具有茀結構之單體、具有二萘并噻吩結構之單體、具有二苯并噻吩結構之單體等含芳香環單體;3-苯氧基苯甲醇、二萘并噻吩及其衍生物(例如於二萘并噻吩環上鍵結有1或2個以上選自羥基、甲醇基、二乙醇基及環氧丙基等中之1種或2種以上取代基之結構的化合物)等不具乙烯性不飽和基之含芳香環化合物等。又,含芳香環化合物可為包含所述含芳香環單體作為單體單元之寡聚物(宜為分子量大約5000以下、較宜為大約1000以下之寡聚物;例如為2~5聚物左右之低聚合物)。上述寡聚物例如可為:含芳香環單體的均聚物;1種或2種以上含芳香環單體的共聚物;1種或2種以上含芳香環單體與其他單體的共聚物等。上述其他單體可使用不具芳香環之單體之1種或2種以上。Examples of aromatic ring-containing compounds that can be used as additives (H RO ) include compounds that can be used as monomers (m1); oligomers containing compounds that can be used as monomers (m1) as monomer units; compounds having a structure in which a group having an ethylenically unsaturated group (which may be a substituent bonded to a ring-constituting atom) or a portion of the group that constitutes an ethylenically unsaturated group is removed from the compound that can be used as a monomer (m1) and replaced with a hydrogen atom or a group that does not have an ethylenically unsaturated group (e.g., a hydroxyl group, an amine group, a halogen atom, an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, a glycidoxy group, etc.), etc., but are not limited thereto. Non-limiting specific examples of aromatic ring-containing compounds that can be used as additives (H RO ) include: benzyl acrylate, m-phenoxybenzyl acrylate, 2-(o-phenylphenoxy)ethyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, the above-mentioned monomers having a fluorene structure, monomers having a dinaphthothiophene structure, monomers having a dibenzothiophene structure and other aromatic ring-containing monomers; 3-phenoxybenzyl alcohol, dinaphthothiophene and its derivatives (for example, compounds having a structure in which one or two or more substituents selected from hydroxyl, methanol, diethanol and glycidyl groups are bonded to the dinaphthothiophene ring) and other aromatic ring-containing compounds without ethylenically unsaturated groups. Furthermore, the aromatic ring-containing compound may be an oligomer (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less; for example, a dimer to pentamer) containing the aromatic ring-containing monomer as a monomer unit. The oligomer may be, for example: a homopolymer of the aromatic ring-containing monomer; a copolymer of one or more aromatic ring-containing monomers; a copolymer of one or more aromatic ring-containing monomers and other monomers. The other monomers may be one or more monomers without an aromatic ring.
在數個態樣中,由容易獲得較高的高折射率化效果來看,可適宜採用1分子中具有2個以上芳香環之有機化合物(以下亦稱「含複數個芳香環之化合物」)作為添加劑(HRO )。含複數個芳香環之化合物可具有乙烯性不飽和基等聚合性官能基,亦可不具有。又,含複數個芳香環之化合物可為聚合物,亦可為非聚合物。又,上述聚合物可為包含含複數個芳香環之單體作為單體單元之寡聚物(宜為分子量大約5000以下、較宜為大約1000以下之寡聚物;例如為2~5聚物左右之低聚合物)。上述寡聚物例如可為:含複數個芳香環之單體的均聚物;1種或2種以上含複數個芳香環之單體的共聚物;1種或2種以上含複數個芳香環之單體與其他單體的共聚物等。上述其他單體可為不屬於含複數個芳香環之單體的含芳香環單體,可為不具芳香環之單體,亦可為該等之組合。In several aspects, from the perspective of easily obtaining a higher refractive index-enhancing effect, an organic compound having two or more aromatic rings in one molecule (hereinafter also referred to as a "compound containing multiple aromatic rings") can be suitably used as an additive (H RO ). The compound containing multiple aromatic rings may or may not have polymerizable functional groups such as ethylenic unsaturated groups. Furthermore, the compound containing multiple aromatic rings may be a polymer or a non-polymer. Furthermore, the above-mentioned polymer may be an oligomer containing a monomer containing multiple aromatic rings as a monomer unit (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less; for example, a low polymer of about 2 to 5 polymers). The oligomers may be, for example, homopolymers of monomers containing multiple aromatic rings; copolymers of one or more monomers containing multiple aromatic rings; copolymers of one or more monomers containing multiple aromatic rings and other monomers, etc. The other monomers may be aromatic ring-containing monomers that are not monomers containing multiple aromatic rings, monomers without aromatic rings, or combinations thereof.
含複數個芳香環之化合物之非限定例可舉:具有2個以上非縮合芳香環隔著連結基鍵結之結構的化合物、具有2個以上非縮合芳香環直接(亦即不隔著其他原子)化學鍵結之結構的化合物、具有縮合芳香環結構之化合物、具有茀結構之化合物、具有二萘并噻吩結構之化合物、具有二苯并噻吩結構之化合物等。含複數個芳香環之化合物可單獨使用1種或組合2種以上來使用。Non-limiting examples of compounds containing multiple aromatic rings include compounds having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, compounds having a structure in which two or more non-condensed aromatic rings are directly (i.e., not separated by other atoms) chemically bonded, compounds having a condensed aromatic ring structure, compounds having a fluorene structure, compounds having a dinaphthothiophene structure, compounds having a dibenzothiophene structure, etc. Compounds containing multiple aromatic rings may be used alone or in combination of two or more.
上述具有茀結構之化合物的具體例除了上述具有茀結構之單體、或是所述單體之均聚物或共聚物之寡聚物外,還可舉9,9-雙(4-羥苯基)茀(折射率:1.68)、9,9-雙(4-胺基苯基)茀(折射率:1.73)、9,9-雙(4-羥-3-甲基苯基)茀(折射率:1.68)、9,9-雙[4-(2-羥基乙氧基)苯基]茀(折射率:1.65)等9,9-雙苯基茀及其衍生物。Specific examples of the above-mentioned compound having a fluorene structure include, in addition to the above-mentioned monomer having a fluorene structure, or an oligomer of a homopolymer or copolymer of the above-mentioned monomer, 9,9-bis(4-hydroxyphenyl)fluorene (refractive index: 1.68), 9,9-bis(4-aminophenyl)fluorene (refractive index: 1.73), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (refractive index: 1.68), 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (refractive index: 1.65), and other 9,9-bisphenylfluorene and its derivatives.
上述具有二萘并噻吩結構之化合物的具體例除了上述具有二萘并噻吩結構之單體、或是所述單體之均聚物或共聚物之寡聚物外,還可舉:二萘并噻吩(折射率:1.808);6-羥甲基二萘并噻吩(折射率:1.766)等之羥烷基二萘并噻吩;2,12-二羥基二萘并噻吩(折射率:1.750)等之二羥基二萘并噻吩;2,12-二羥乙基氧基二萘并噻吩(折射率:1.677)等之二羥烷基氧基二萘并噻吩;2,12-二環氧丙基氧基二萘并噻吩(折射率1.723)等之二環氧丙基氧基二萘并噻吩;2,12-二烯丙基氧基二萘并噻吩(縮寫:2,12-DAODNT,折射率1.729)等具有2個以上乙烯性不飽和基之二萘并噻吩等之二萘并噻吩及其衍生物。Specific examples of the compound having a dinaphthothiophene structure include, in addition to the monomer having a dinaphthothiophene structure, or a homopolymer or copolymer of the monomer, dinaphthothiophene (refractive index: 1.808); hydroxyalkyl dinaphthothiophene such as 6-hydroxymethyl dinaphthothiophene (refractive index: 1.766); dihydroxy dinaphthothiophene such as 2,12-dihydroxy dinaphthothiophene (refractive index: 1.750); 2,12-dihydroxy dinaphthothiophene (refractive index: 1.766); Dihydroxyalkyloxy dinaphthothiophene such as hydroxyethyloxy dinaphthothiophene (refractive index: 1.677); diglycidyloxy dinaphthothiophene such as 2,12-diglycidyloxy dinaphthothiophene (refractive index 1.723); dinaphthothiophene having two or more ethylenically unsaturated groups such as 2,12-diallyloxy dinaphthothiophene (abbreviation: 2,12-DAODNT, refractive index 1.729) and their derivatives.
上述具有二苯并噻吩結構之化合物的具體例除了上述具有二苯并噻吩結構之單體、或是所述單體之均聚物或共聚物之寡聚物外,還可舉二苯并噻吩(折射率:1.607)、4-二甲基二苯并噻吩(折射率:1.617)、4,6-二甲基二苯并噻吩(折射率:1.617)等。Specific examples of the above-mentioned compound having a dibenzothiophene structure include, in addition to the above-mentioned monomer having a dibenzothiophene structure, or a homopolymer or copolymer oligomer of the above-mentioned monomer, dibenzothiophene (refractive index: 1.607), 4-dimethyldibenzothiophene (refractive index: 1.617), 4,6-dimethyldibenzothiophene (refractive index: 1.617), etc.
可成為添加劑(HRO )之選項的具有雜環的有機化合物(以下亦稱為含雜環有機化合物)之例可舉硫代環氧化合物、具有三𠯤環之化合物等。硫代環氧化合物之例可舉日本專利第3712653號公報中記載之雙(2,3-環硫代丙基)二硫化物及其聚合物(折射率1.74)。具有三𠯤環之化合物之例可舉1分子內具有至少1個(例如3~40個,宜為5~20個))三𠯤環之化合物。此外,三𠯤環具有芳香族性,故具有三𠯤環之化合物亦包含於上述含芳香環化合物之概念中,且,具有複數個三𠯤環之化合物亦包含於上述含複數個芳香環之化合物之概念中。Examples of heterocyclic organic compounds (hereinafter also referred to as heterocyclic organic compounds) that can be selected as additives (H RO ) include thioepoxy compounds and compounds having tricyclic rings. Examples of thioepoxy compounds include bis(2,3-cyclothiopropyl) disulfide and its polymer (refractive index 1.74) described in Japanese Patent No. 3712653. Examples of compounds having tricyclic rings include compounds having at least one (e.g., 3 to 40, preferably 5 to 20) tricyclic rings in one molecule. In addition, the tricyclic ring has aromatic properties, and thus a compound having a tricyclic ring is also included in the concept of the above-mentioned compound containing an aromatic ring, and a compound having a plurality of tricyclic rings is also included in the concept of the above-mentioned compound containing a plurality of aromatic rings.
在數個態樣中,可適宜採用不具乙烯性不飽和基之化合物作為添加劑(HRO )。藉此,可抑制黏著劑組成物因熱或光而變質(凝膠化之進行或黏度上升造成調平性降低),提高保存穩定性。採用不具乙烯性不飽和基之添加劑(HRO )一事,由在具有包含該添加劑(HRO )之黏著劑層的黏著型光學薄膜或包含該黏著型光學薄膜之積層體等中,抑制乙烯性不飽和基之反應造成之尺寸變化或變形(翹曲、起伏等)、光學應變之產生等之觀點來看亦佳。In several aspects, a compound without ethylenically unsaturated groups can be suitably used as an additive (H RO ). This can inhibit the adhesive composition from being deteriorated by heat or light (gelation or viscosity increase resulting in reduced leveling properties), thereby improving storage stability. The use of an additive without ethylenically unsaturated groups (H RO ) is also preferred from the viewpoint of inhibiting dimensional changes or deformations (warping, undulation, etc.) caused by the reaction of ethylenically unsaturated groups, the generation of optical strain, etc. in an adhesive optical film having an adhesive layer containing the additive (H RO ) or a laminate containing the adhesive optical film.
在使用寡聚物作為添加劑(HRO )之態樣中,該寡聚物可藉由以公知方法使對應之單體成分聚合來獲得。利用自由基聚合製造上述寡聚物時,可於上述單體成分中適當添加可用於進行自由基聚合的聚合引發劑、鏈轉移劑、乳化劑等,進行聚合。上述可用於自由基聚合之聚合引發劑、鏈轉移劑、乳化劑等無特別限定,可適當選擇並使用。此外,寡聚物之重量平均分子量可藉由聚合引發劑、鏈轉移劑之使用量、反應條件來控制,並因應該等之種類來適當地調整其使用量。 上述鏈轉移劑可舉例如月桂基硫醇、環氧丙基硫醇、巰乙酸、2-巰基乙醇、α-硫甘油、硫代乙醇酸、硫代乙醇酸2-乙基己酯、2,3-二巰基-1-丙醇等。鏈轉移劑可單獨使用1種,亦可混合2種以上使用。鏈轉移劑之使用量可因應可用於寡聚物之合成的單體成分之組成或鏈轉移劑之種類等,設定成可獲得所期望之重量平均分子量的寡聚物。在數個態樣中,鏈轉移劑相對於可用於寡聚物之合成的單體之總量100重量份的使用量設為大約15重量份以下是適當的,可為10重量份以下,亦可為5重量份左右以下。鏈轉移劑相對於可用於寡聚物之合成的單體之總量100重量份之使用量的下限無特別限制,例如可為0.01重量份以上,可為0.1重量份以上,可為0.5重量份以上,亦可為1重量份以上。In the case where an oligomer is used as an additive (H RO ), the oligomer can be obtained by polymerizing the corresponding monomer component by a known method. When the above-mentioned oligomer is produced by free radical polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, etc. that can be used for free radical polymerization can be appropriately added to the above-mentioned monomer component to carry out polymerization. The above-mentioned polymerization initiator, chain transfer agent, emulsifier, etc. that can be used for free radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of the oligomer can be controlled by the amount of polymerization initiator and chain transfer agent used and the reaction conditions, and the amount used can be appropriately adjusted according to the type of the polymerization initiator and chain transfer agent. The chain transfer agent may be, for example, lauryl mercaptan, glycidyl mercaptan, isethanoic acid, 2-isobutyl ethanol, α-thioglycerol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-diisobutyl-1-propanol, etc. The chain transfer agent may be used alone or in combination of two or more. The amount of the chain transfer agent used may be set so as to obtain an oligomer having a desired weight average molecular weight, depending on the composition of the monomer components that can be used for the synthesis of the oligomer or the type of the chain transfer agent. In several embodiments, the amount of the chain transfer agent used is appropriately set to about 15 parts by weight or less, and may be 10 parts by weight or less, or may be about 5 parts by weight or less, relative to 100 parts by weight of the total amount of monomers that can be used for the synthesis of the oligomer. The lower limit of the amount of the chain transfer agent used relative to 100 parts by weight of the total amount of monomers that can be used to synthesize the oligomer is not particularly limited, and can be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more.
在使用添加劑(HRO )作為折射率提升劑之態樣中,添加劑(HRO )相對於基底聚合物100重量份之使用量(使用複數種化合物時為其等之合計量)無特別限定,可按目的作設定。由黏著劑之高折射率化之觀點來看,添加劑(HRO )相對於基底聚合物100重量份之使用量可設為例如1重量份以上,設為3重量份以上是有利的,宜設為5重量份以上,可為7重量份以上,可為10重量份以上,可為15重量份以上,亦可為20重量份以上。在數個態樣中,添加劑(HRO )相對於基底聚合物100重量份之使用量可設為例如80重量份以下,而由平衡兼顧黏著劑之高折射率化與抑制黏著特性或光學特性降低之觀點來看,設為60重量份以下是有利的,且宜設為45重量份以下。在更重視黏著特性或光學特性之數個態樣中,添加劑(HRO )相對於基底聚合物100重量份之使用量例如可為30重量份以下,可為20重量份以下,可為15重量份以下,亦可為10重量份以下。In the embodiment of using the additive (H RO ) as the refractive index enhancer, the amount of the additive (H RO ) used relative to 100 parts by weight of the base polymer (the total amount thereof when using a plurality of compounds) is not particularly limited and can be set according to the purpose. From the viewpoint of increasing the refractive index of the adhesive, the amount of the additive (H RO ) used relative to 100 parts by weight of the base polymer can be set to, for example, 1 part by weight or more, 3 parts by weight or more is advantageous, 5 parts by weight or more is preferred, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, and 20 parts by weight or more. In several aspects, the amount of the additive (H RO ) used relative to 100 parts by weight of the base polymer can be set to, for example, 80 parts by weight or less, and from the perspective of balancing the high refractive index of the adhesive and suppressing the decrease in adhesion or optical properties, it is advantageous to set it to 60 parts by weight or less, and preferably to set it to 45 parts by weight or less. In several aspects where adhesion or optical properties are more important, the amount of the additive (H RO ) used relative to 100 parts by weight of the base polymer can be, for example, 30 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less.
(塑化材料) 在此揭示之黏著型光學薄膜之數個態樣中,黏著劑層除了如上述之基底聚合物(例如丙烯酸系聚合物(A)),還可包含分子量較該基底聚合物更低的塑化材料。藉由使用塑化材料,可提升黏著劑層之柔軟性,從而可提升對被黏著體之密著性、或是作為黏著型光學薄膜整體之柔軟性或對變形之追隨性。由在黏著劑層內之相溶性或透明性之觀點來看,塑化材料可適宜採用有機材料。塑化材料亦可為可作為上述折射率提升劑(例如上述添加劑(HRO ))使用之材料。(Plasticizer) In several aspects of the adhesive optical film disclosed herein, the adhesive layer may include, in addition to the base polymer (e.g., acrylic polymer (A)) as described above, a plasticizer having a lower molecular weight than the base polymer. By using a plasticizer, the flexibility of the adhesive layer can be improved, thereby improving the adhesion to the adherend, or the flexibility of the adhesive optical film as a whole or the ability to follow deformation. From the perspective of compatibility or transparency in the adhesive layer, the plasticizer may be an organic material. The plasticizer may also be a material that can be used as the above-mentioned refractive index enhancer (e.g., the above-mentioned additive (H RO )).
塑化材料之分子量較基底聚合物更低即可,無特別限定。在數個態樣中,由容易展現塑化效果之觀點來看,塑化材料之分子量可為30000以下,可為25000以下,可小於10000,宜小於5000,較宜小於3000(例如小於1000),可小於800,可小於600,可小於500,亦可小於400。塑化材料之分子量不過大一事由提升在黏著劑層內之相溶性等觀點來看是有利的。又,在數個態樣中,由容易發揮充分之塑化效果之觀點來看,塑化材料之分子量為130以上是適當的,且宜為150以上,較宜為170以上,可為200以上,可為250以上,亦可為300以上。在數個態樣中,塑化材料之分子量可為500以上,可為1000以上,亦可為2000以上。塑化材料之分子量不過低一事由耐熱性能或抑制被黏著體之污染之觀點來看亦佳。The molecular weight of the plasticizer is not particularly limited as long as it is lower than that of the base polymer. In several aspects, from the perspective of easy plasticization effect, the molecular weight of the plasticizer may be less than 30,000, less than 25,000, less than 10,000, preferably less than 5,000, more preferably less than 3,000 (for example, less than 1,000), less than 800, less than 600, less than 500, or less than 400. The fact that the molecular weight of the plasticizer is not too large is advantageous from the perspective of improving the compatibility in the adhesive layer. In addition, in several aspects, from the perspective of easy plasticization effect, the molecular weight of the plasticizer is appropriate to be 130 or more, preferably 150 or more, more preferably 170 or more, may be 200 or more, may be 250 or more, or may be 300 or more. In several aspects, the molecular weight of the plasticizing material may be greater than 500, greater than 1000, or greater than 2000. The molecular weight of the plasticizing material is preferably not too low from the perspective of heat resistance or suppression of contamination of the adherend.
可成為塑化材料之選項的化合物之非限定例中包含:可作為單體(m1)使用之化合物(例如具有苄基、苯氧基、萘基等芳香環(甲基)丙烯酸酯、具有茀結構之單體、具有二萘并噻吩結構之單體、具有二苯并噻吩結構之單體等);包含可作為單體(m1)使用之化合物作為單體單元的寡聚物;從可作為單體(m1)使用之化合物去除具有乙烯性不飽和基之部分且取代成氫原子或不具乙烯性不飽和基之基團的結構之化合物(例如3-苯氧基苯甲醇)等。由提升柔軟性之觀點來看,包含可作為單體(m1)使用之化合物作為單體單元之寡聚物中例如丙烯酸正丁酯或丙烯酸2-乙基己酯等低Tg單體亦可已共聚。作為塑化材料,亦可利用公知之塑化劑(例如鄰苯二甲酸酯系、對苯二甲酸酯系、己二酸酯系、己二酸系聚酯、苯甲酸乙二醇酯等)之1種或2種以上。Non-limiting examples of compounds that can be selected as plasticizers include: compounds that can be used as monomers (m1) (e.g., aromatic ring (meth)acrylates having benzyl, phenoxy, naphthyl, etc., monomers having a fluorene structure, monomers having a dinaphthothiophene structure, monomers having a dibenzothiophene structure, etc.); oligomers containing compounds that can be used as monomers (m1) as monomer units; compounds having structures in which a portion having an ethylenically unsaturated group is removed from a compound that can be used as a monomer (m1) and replaced with a hydrogen atom or a group without an ethylenically unsaturated group (e.g., 3-phenoxybenzyl alcohol), etc. From the viewpoint of improving softness, low Tg monomers such as n-butyl acrylate or 2-ethylhexyl acrylate may also be copolymerized in oligomers containing compounds that can be used as monomers (m1) as monomer units. As the plasticizing material, one or more of known plasticizers (such as phthalate-based plasticizers, terephthalate-based plasticizers, adipate-based plasticizers, adipic acid-based polyesters, and ethylene glycol benzoate) may be used.
在數個態樣中,塑化材料可適宜使用折射率大約1.50以上(較宜為1.53以上)之有機材料。可成為塑化材料之選項的化合物之具體例中包含:二乙二醇二苯甲酸酯(折射率1.55)、二丙二醇二苯甲酸酯(折射率1.54)、3-苯氧基甲苯(折射率1.57)、3-乙基聯苯(折射率1.59)、3-甲氧基聯苯(折射率1.61)、4-甲氧基聯苯(折射率1.57)、聚乙二醇二苯甲酸酯、3-苯氧基苯甲醇(折射率1.59)、三苯基磷酸酯(折射率1.56)、苯甲酸苄酯(折射率1.57)、4-(三級丁基)苯基二苯基磷酸酯(折射率1.56)、三甲基苯基磷酸酯(折射率1.55)、鄰苯二甲酸丁苄酯(折射率1.54)、松香甲酯(折射率1.53)、鄰苯二甲酸烷基苄酯(折射率1.53)、丁基(苯基磺醯基)胺(折射率1.53)、偏苯三甲酸三甲酯(折射率1.52)、鄰苯二甲酸苄酯(折射率1.52)、2-乙基己基二苯基磷酸酯(折射率1.51)、亞磷酸參(2,4-二-三級丁基苯基)酯等,惟不受該等限定。由折射率及相溶性之觀點來看,可適宜採用例如二乙二醇二苯甲酸酯。塑化材料之折射率的上限無特別限制,例如可為3.00以下。在數個態樣中,由黏著劑組成物之調製容易性或在黏著劑內之相溶性等觀點來看,塑化材料之折射率為2.50以下是適當的,為2.00以下是有利的,可為1.90以下,可為1.80以下,亦可為1.70以下。 此外,塑化材料之折射率係與單體之折射率同樣地,使用阿貝折射計在測定波長589nm、測定溫度25℃之條件下進行測定。當有從製造商等提供了在25℃下之折射率的標稱值時,可採用該標稱值。In several aspects, the plasticizer may be an organic material having a refractive index of about 1.50 or more (preferably 1.53 or more). Specific examples of compounds that can be selected as plasticizers include: diethylene glycol dibenzoate (refractive index 1.55), dipropylene glycol dibenzoate (refractive index 1.54), 3-phenoxytoluene (refractive index 1.57), 3-ethylbiphenyl (refractive index 1.59), 3-methoxybiphenyl (refractive index 1.61), 4-methoxybiphenyl (refractive index 1.57), polyethylene glycol dibenzoate, 3-phenoxybenzyl alcohol (refractive index 1.59), triphenyl phosphate (refractive index 1.56), benzyl benzoate (refractive index 1.57), 4-(tert-butyl) )phenyl diphenyl phosphate (refractive index 1.56), trimethylphenyl phosphate (refractive index 1.55), butyl benzyl phthalate (refractive index 1.54), methyl rosin (refractive index 1.53), alkyl benzyl phthalate (refractive index 1.53), butyl (phenylsulfonyl) amine (refractive index 1.53), trimethyl trimellitate (refractive index 1.52), benzyl phthalate (refractive index 1.52), 2-ethylhexyl diphenyl phosphate (refractive index 1.51), tris(2,4-di-tert-butylphenyl) phosphite, etc., but are not limited thereto. From the viewpoint of refractive index and compatibility, for example, diethylene glycol dibenzoate can be suitably used. The upper limit of the refractive index of the plasticizing material is not particularly limited, and for example, it can be 3.00 or less. In several aspects, from the viewpoint of ease of preparation of the adhesive composition or compatibility in the adhesive, the refractive index of the plasticizer is suitable to be 2.50 or less, 2.00 or less is advantageous, 1.90 or less, 1.80 or less, or 1.70 or less. In addition, the refractive index of the plasticizer is measured using an Abbe refractometer at a measurement wavelength of 589 nm and a measurement temperature of 25°C, similar to the refractive index of the monomer. When a nominal value of the refractive index at 25°C is provided by a manufacturer, the nominal value may be adopted.
在使用塑化材料之態樣中,塑化材料相對於基底聚合物100重量份之使用量無特別限定,可按目的作設定。由提高塑化效果之觀點來看,塑化材料相對於基底聚合物100重量份之使用量例如可為0.1重量份以上,亦可為0.5重量份以上,而由獲得更高之塑化效果之觀點來看,宜設為1重量份以上,設為3重量份以上較佳,可為5重量份以上,可為7重量份以上,可為10重量份以上,可為15重量份以上,亦可為20重量份以上。又,由平衡兼顧黏著劑之高折射率化與透明性及塑化效果之觀點來看,塑化材料相對於基底聚合物100重量份之使用量設為大約100重量份以下是適當的,宜設為80重量份以下,設為60重量份以下較佳,可為45重量份以下,可為35重量份以下,亦可為25重量份以下。在更重視黏著特性或光學特性之數個態樣中,塑化材料相對於基底聚合物100重量份之使用量例如可為15重量份以下,可為10重量份以下,亦可為5重量份以下。In the mode of using the plasticizing material, the amount of the plasticizing material used relative to 100 parts by weight of the base polymer is not particularly limited and can be set according to the purpose. From the perspective of improving the plasticizing effect, the amount of the plasticizing material used relative to 100 parts by weight of the base polymer can be, for example, 0.1 parts by weight or more, or 0.5 parts by weight or more, and from the perspective of obtaining a higher plasticizing effect, it is preferably set to 1 part by weight or more, preferably 3 parts by weight or more, and can be 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. Furthermore, from the perspective of balancing the high refractive index of the adhesive with the transparency and the plasticizing effect, the amount of the plasticizing material used relative to 100 parts by weight of the base polymer is appropriate to be set at less than about 100 parts by weight, preferably less than 80 parts by weight, more preferably less than 60 parts by weight, less than 45 parts by weight, less than 35 parts by weight, or less than 25 parts by weight. In several aspects where the adhesive properties or optical properties are more important, the amount of the plasticizing material used relative to 100 parts by weight of the base polymer can be, for example, less than 15 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.
(調平劑) 在數個態樣中,用於形成黏著劑層的黏著劑組成物中,可為了提升由該組成物形成之黏著劑層的外觀(例如提升厚度之均勻性)或提升上述黏著劑組成物之塗敷性等,視需求含有調平劑。調平劑之非限定之例可舉丙烯酸系調平劑、氟系調平劑、聚矽氧系調平劑等。調平劑例如可從市售之調平劑選擇適當之物,利用常法來使用。(Leveling agent) In several embodiments, the adhesive composition used to form the adhesive layer may contain a leveling agent as required in order to improve the appearance of the adhesive layer formed by the composition (for example, to improve the uniformity of thickness) or to improve the coating properties of the adhesive composition. Non-limiting examples of leveling agents include acrylic leveling agents, fluorine leveling agents, silicone leveling agents, etc. The leveling agent can be selected from commercially available leveling agents and used in a conventional manner.
在數個態樣中,上述調平劑可適宜使用以下聚合物(以下亦稱「聚合物(B)」),其為包含具有聚有機矽氧烷骨架之單體(以下亦稱「單體S1」)與丙烯酸系單體之單體原料(以下亦稱「單體原料B」)的聚合物。聚合物(B)可稱為單體S1與丙烯酸系單體之共聚物。聚合物(B)可單獨使用一種或組合二種以上來使用。In several aspects, the leveling agent may suitably use the following polymer (hereinafter also referred to as "polymer (B)"), which is a polymer comprising a monomer having a polyorganosiloxane skeleton (hereinafter also referred to as "monomer S1") and a monomer raw material of an acrylic monomer (hereinafter also referred to as "monomer raw material B"). Polymer (B) may be referred to as a copolymer of monomer S1 and an acrylic monomer. Polymer (B) may be used alone or in combination of two or more.
單體S1無特別限定,可使用含有聚有機矽氧烷骨架之任意單體。單體S1可適宜使用於一末端具有聚合性反應基之結構者。其中,可適宜採用於一末端具有聚合性反應基且於另一末端不具有與基底聚合物(意指摻混該調平劑之黏著劑組成物的基底聚合物,例如為丙烯酸系聚合物)產生交聯反應之官能基之結構的單體S1。市售物可舉例如信越化學工業公司製之一末端反應性聚矽氧油(例如X-22-174ASX、X-22-2426、X-22-2475、KF-2012等之型號)。單體S1可單獨使用一種或組合二種以上來使用。Monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used. Monomer S1 can be suitably used in a structure having a polymerizable reactive group at one end. Among them, monomer S1 having a polymerizable reactive group at one end and having no functional group at the other end that produces a cross-linking reaction with a base polymer (meaning a base polymer of the adhesive composition mixed with the leveling agent, such as an acrylic polymer) can be suitably used. Commercially available materials include, for example, one-terminal reactive polysilicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (such as models such as X-22-174ASX, X-22-2426, X-22-2475, KF-2012, etc.). Monomer S1 can be used alone or in combination of two or more.
單體S1之官能基當量例如可為100g/mol~30000g/mol左右。在數個理想態樣中,上述官能基當量例如為500g/mol以上,可為800g/mol以上,可為1500g/mol以上,亦可為2000g/mol以上。又,上述官能基當量例如可為20000g/mol以下,可小於10000g/mol,可為7000g/mol以下,亦可為5500g/mol以下。單體S1之官能基當量若在上述範圍內,便容易發揮良好之調平效果。 另,使用官能基當量相異之二種以上單體作為單體S1時,單體S1之官能基當量可使用各種類之單體的官能基當量與該單體之重量分率的乘積總和。The functional group equivalent of monomer S1 can be, for example, about 100 g/mol to 30,000 g/mol. In several ideal embodiments, the functional group equivalent is, for example, 500 g/mol or more, 800 g/mol or more, 1,500 g/mol or more, or 2,000 g/mol or more. In addition, the functional group equivalent can be, for example, less than 20,000 g/mol, less than 10,000 g/mol, less than 7,000 g/mol, or less than 5,500 g/mol. If the functional group equivalent of monomer S1 is within the above range, it is easy to exert a good leveling effect. In addition, when two or more monomers with different functional group equivalents are used as monomer S1, the functional group equivalent of monomer S1 can be the sum of the products of the functional group equivalents of each type of monomer and the weight fraction of the monomer.
在此,「官能基當量」意指與每個官能基鍵結之主骨架(例如聚二甲基矽氧烷)的重量。有關標記單位g/mol係換算成官能基1mol。單體S1之官能基當量例如可從根據核磁共振(NMR)之1 H-NMR(質子NMR)之光譜強度算出。根據1 H-NMR之光譜強度進行之單體S1之官能基當量(g/mol)的計算,可根據有關1 H-NMR光譜解析之一般結構解析手法,且若有需要即參照日本專利第5951153號公報之記載來進行。在單體S1之官能基當量中,上述官能基意指聚合性官能基(例如(甲基)丙烯醯基、乙烯基、烯丙基等乙烯性不飽和基)。Here, "functional group equivalent" means the weight of the main skeleton (e.g., polydimethylsiloxane) bonded to each functional group. The relevant marked unit g/mol is converted into 1 mol of functional groups. The functional group equivalent of monomer S1 can be calculated, for example, from the spectral intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). The calculation of the functional group equivalent (g/mol) of monomer S1 based on the spectral intensity of 1 H-NMR can be based on the general structural analysis method of 1 H-NMR spectrum analysis, and if necessary, refer to the description of Japanese Patent Gazette No. 5951153. In the functional group equivalent of monomer S1, the above-mentioned functional group means a polymerizable functional group (e.g., ethylenically unsaturated groups such as (meth)acryl, vinyl, and allyl).
單體原料B中之單體S1之含量可在使用該單體S1能發揮所期望之效果的範圍內採用適當之值,不受特定範圍所限。在數個態樣中,單體原料B中之單體S1之含量例如可為5~60重量%,可為10~50重量%,亦可為15~40重量%。The content of monomer S1 in monomer raw material B can be an appropriate value within the range in which the desired effect can be exerted by using the monomer S1, and is not limited to a specific range. In several aspects, the content of monomer S1 in monomer raw material B can be, for example, 5-60% by weight, 10-50% by weight, or 15-40% by weight.
單體原料B除了單體S1外,還包含可與單體S1共聚之丙烯酸系單體。藉此,可改善聚合物(B)在黏著劑層內之相溶性。可用於單體原料B之丙烯酸系單體可舉例如丙烯酸烷基酯。此處所提「烷基」係指鏈狀(包含直鏈狀、支鏈狀)烷基(基),而不包含後述脂環式烴基。在數個態樣中,單體原料B可含有(甲基)丙烯酸C4-12 烷基酯(宜為(甲基)丙烯酸C4-10 烷基酯,例如(甲基)丙烯酸C6-10 烷基酯)之至少一種。在其他數個態樣中,單體原料B可含有甲基丙烯酸C1-18 烷基酯(宜為甲基丙烯酸C1-14 烷基酯,例如(甲基)丙烯酸C1-10 烷基酯)之至少一種。單體原料B例如可包含選自甲基丙烯酸甲酯(MMA)、甲基丙烯酸正丁酯(BMA)及甲基丙烯酸2-乙基己酯(2EHMA)中之一種或二種以上作為丙烯酸系單體。In addition to monomer S1, monomer raw material B also includes an acrylic monomer that can be copolymerized with monomer S1. Thereby, the compatibility of polymer (B) in the adhesive layer can be improved. Examples of acrylic monomers that can be used for monomer raw material B include alkyl acrylates. The "alkyl" mentioned here refers to a chain (including straight chain and branched chain) alkyl (group), and does not include the alicyclic hydrocarbon group described later. In several aspects, monomer raw material B may contain at least one C 4-12 alkyl (meth)acrylate (preferably C 4-10 alkyl (meth)acrylate, such as C 6-10 alkyl (meth)acrylate). In several other aspects, monomer raw material B may contain at least one C 1-18 alkyl methacrylate (preferably C 1-14 alkyl methacrylate, such as C 1-10 alkyl (meth)acrylate). The monomer raw material B may contain, as the acrylic monomer, one or more selected from methyl methacrylate (MMA), n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA).
上述丙烯酸系單體之其他例可舉具有脂環式烴基之(甲基)丙烯酸酯。例如可使用(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸1-金剛烷基酯等。亦可不使用具有脂環式烴基之(甲基)丙烯酸酯。Other examples of the acrylic monomers include (meth)acrylates having alicyclic alkyl groups. For example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc. can be used. (Meth)acrylates having alicyclic alkyl groups do not need to be used.
單體原料B中具有上述(甲基)丙烯酸烷基酯及上述脂環式烴基之(甲基)丙烯酸酯之含量例如可為10重量%以上且95重量%以下,可為20重量%以上且95重量%以下,可為30重量%以上且90重量%以下,可為40重量%以上且90重量%以下,亦可為50重量%以上且85重量%以下。The content of the (meth)acrylate having the above-mentioned (meth)acrylate alkyl ester and the above-mentioned alicyclic hydrocarbon group in the monomer raw material B may be, for example, 10% by weight or more and 95% by weight or less, 20% by weight or more and 95% by weight or less, 30% by weight or more and 90% by weight or less, 40% by weight or more and 90% by weight or less, or 50% by weight or more and 85% by weight or less.
可與單體S1一同包含於單體原料B之單體的其他例可舉:作為可用於丙烯酸系聚合物而於上述所例示之含羧基單體、含酸酐基單體、含羥基單體、含環氧基單體、含氰基單體、含異氰酸酯基單體、含醯胺基單體、具有含氮原子環之單體、(甲基)丙烯酸胺基烷基酯類、乙烯酯類、乙烯基醚類、烯烴類、具有芳香族烴基之(甲基)丙烯酸酯、含鹵素原子之(甲基)丙烯酸酯等。Other examples of monomers that can be included in the monomer raw material B together with the monomer S1 include: carboxyl group-containing monomers, anhydride group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, isocyanate group-containing monomers, amide group-containing monomers, monomers having a nitrogen atom-containing ring, (meth)acrylic acid aminoalkyl esters, vinyl esters, vinyl ethers, olefins, (meth)acrylates having aromatic hydrocarbon groups, and (meth)acrylates containing halogen atoms, etc., which can be used in acrylic polymers.
聚合物(B)之Mw例如可為5,000以上,宜為10,000以上,亦可為15,000以上。又,聚合物(B)之Mw例如可為200,000以下,宜為100,000以下,可為50,000以下,亦可為30,000以下。藉由將聚合物(B)之Mw設定在適當範圍內,可發揮良好之相溶性及調平性。The Mw of the polymer (B) may be, for example, 5,000 or more, preferably 10,000 or more, or 15,000 or more. Also, the Mw of the polymer (B) may be, for example, 200,000 or less, preferably 100,000 or less, 50,000 or less, or 30,000 or less. By setting the Mw of the polymer (B) within an appropriate range, good compatibility and leveling properties can be exhibited.
聚合物(B)例如可藉由溶液聚合法、乳化聚合法、整體聚合法、懸浮聚合法、光聚合法等公知之手法使上述單體聚合來製作。 為了調整聚合物(B)之分子量,可因應需求使用鏈轉移劑。所使用之鏈轉移劑之例可舉:三級十二基硫醇、巰乙醇、α-硫甘油等具有巰基之化合物;硫代乙醇酸、硫代乙醇酸甲酯等硫代乙醇酸酯類;α-甲基苯乙烯二聚物等。鏈轉移劑之使用量無特別限制,可適當設定成可獲得具有所期望之分子量的聚合物(B)。在數個態樣中,鏈轉移劑相對於單體100重量份之使用量例如可為0.1~5重量份,可為0.2~3重量份,亦可為0.5~2重量份。The polymer (B) can be prepared by polymerizing the above-mentioned monomers by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization, etc. In order to adjust the molecular weight of the polymer (B), a chain transfer agent can be used as required. Examples of the chain transfer agent used include: tertiary dodecyl mercaptan, hydroxyethyl alcohol, α-thioglycerol and other compounds having hydroxyl groups; thioglycolic acid, methyl thioglycolate and other thioglycolic acid esters; α-methylstyrene dimer, etc. The amount of the chain transfer agent used is not particularly limited and can be appropriately set to obtain a polymer (B) with a desired molecular weight. In several embodiments, the amount of the chain transfer agent used relative to 100 parts by weight of the monomer can be, for example, 0.1 to 5 parts by weight, 0.2 to 3 parts by weight, or 0.5 to 2 parts by weight.
聚合物(B)相對於基底聚合物(例如丙烯酸系聚合物)100重量份之使用量可設為例如0.001重量份以上,而由可獲得更高之使用效果之觀點來看,可設為0.01重量份以上,亦可設為0.03重量份以上。又,上述聚合物(B)之使用量例如可為3重量份以下,而由減輕對折射率之影響之觀點來看,設為1重量份以下是適當的,可為0.5重量份以下,亦可為0.1重量份以下。The amount of polymer (B) used relative to 100 parts by weight of the base polymer (e.g., acrylic polymer) may be, for example, 0.001 parts by weight or more, and from the perspective of obtaining a higher effect of use, it may be 0.01 parts by weight or more, or may be 0.03 parts by weight or more. Furthermore, the amount of polymer (B) used may be, for example, 3 parts by weight or less, and from the perspective of reducing the effect on the refractive index, it is appropriate to set it to 1 part by weight or less, and may be 0.5 parts by weight or less, or may be 0.1 parts by weight or less.
(無機粒子) 在此揭示之技術亦可適宜在實質上不使用作為折射率提升劑之無機粒子之態樣下實施。尤其,在此揭示之黏著型光學薄膜之數個態樣中,只要能滿足所期望之光學特性(全光線透射率、霧度值)且不會大幅損害作為黏著劑之特性,便可容許使用無機粒子作為折射率提升劑。可作為折射率提升劑使用之無機粒子之例可舉藉由氧化鈦(titania、TiO2 )、氧化鋯(zirconia、ZrO2 )、氧化鋁、氧化鋅、氧化錫、氧化銅、鈦酸鋇、氧化鈮(Nb2 O5 等)等之無機氧化物(具體上為金屬氧化物)所構成之無機粒子。上述無機粒子之平均粒徑(係指根據雷射散射繞射法所得之50%體積平均粒徑)可從例如10nm~100nm左右之範圍中選擇。此外,無機粒子之折射率係針對構成該無機粒子之材料的單層膜(採用可進行折射率測定之膜厚),使用市售之分光橢圓偏光儀,在測定波長589nm、測定溫度23℃之條件下進行測定。分光橢圓偏光儀例如可使用製品名「EC-400」(JA.Woolam公司製)或其等效品。使用無機粒子作為折射率提升劑時之使用量,相對於基底聚合物100重量份宜設為小於5重量份,較宜設為小於1重量份。又,在使用添加劑(HRO )之態樣中,上述無機粒子之使用量以重量基準計宜設為上述添加劑(HRO )之使用量的2倍以下,且設為1倍以下或0.5倍以下較佳。(Inorganic particles) The technology disclosed herein can also be suitably implemented in an embodiment in which inorganic particles as a refractive index enhancer are not substantially used. In particular, in several embodiments of the adhesive optical film disclosed herein, as long as the desired optical properties (total light transmittance, haze value) are satisfied and the properties as an adhesive are not significantly impaired, it is permissible to use inorganic particles as a refractive index enhancer. Examples of inorganic particles that can be used as a refractive index enhancer include inorganic particles composed of inorganic oxides (specifically metal oxides) such as titanium oxide (titania, TiO2 ), zirconium oxide (zirconia, ZrO2 ), aluminum oxide, zinc oxide, tin oxide, copper oxide, barium titanate , niobium oxide ( Nb2O5 , etc.). The average particle size of the above-mentioned inorganic particles (referring to the 50% volume average particle size obtained by laser scattering diffraction method) can be selected from a range of about 10nm to 100nm. In addition, the refractive index of the inorganic particles is measured for a single layer film of the material constituting the inorganic particles (using a film thickness that can be used for refractive index measurement) using a commercially available spectroscopic elliptical polarizer at a measurement wavelength of 589nm and a measurement temperature of 23°C. The spectroscopic elliptical polarizer can be, for example, the product name "EC-400" (manufactured by JA.Woolam) or its equivalent. When using inorganic particles as a refractive index enhancer, the amount used is preferably less than 5 parts by weight, and more preferably less than 1 part by weight, relative to 100 parts by weight of the base polymer. In the embodiment where the additive (H RO ) is used, the amount of the inorganic particles used is preferably set to be 2 times or less, and more preferably 1 time or less or 0.5 times or less, the amount of the additive (H RO ) used on a weight basis.
(交聯劑) 在此揭示之技術中,用於形成黏著劑層之黏著劑組成物中可為了調整黏著劑之凝集力等,視需求含有交聯劑。交聯劑可使用異氰酸酯系交聯劑、環氧系交聯劑、吖丙啶系交聯劑、㗁唑啉系交聯劑、三聚氰胺系樹脂、金屬螯合物系交聯劑等在黏著劑領域中公知之交聯劑。其中可適宜採用異氰酸酯系交聯劑。作為交聯劑之其他例,可舉1分子內具有2個以上乙烯性不飽和基之單體,亦即多官能性單體。交聯劑可單獨使用1種或組合2種以上來使用。(Crosslinking agent) In the technology disclosed herein, the adhesive composition used to form the adhesive layer may contain a crosslinking agent as required in order to adjust the cohesive force of the adhesive. The crosslinking agent may be an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, an oxazoline crosslinking agent, a melamine resin, a metal chelate crosslinking agent, or the like, which are known crosslinking agents in the adhesive field. Among them, an isocyanate crosslinking agent may be suitably used. As another example of a crosslinking agent, a monomer having two or more ethylenically unsaturated groups in one molecule, i.e., a multifunctional monomer, may be cited. The crosslinking agent may be used alone or in combination of two or more.
異氰酸酯系交聯劑可使用2官能以上之異氰酸酯化合物,可舉例如:三亞甲基二異氰酸酯、伸丁基二異氰酸酯、六亞甲基二異氰酸酯(HDI)、二體酸二異氰酸酯等脂肪族聚異氰酸酯類;伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛酮二異氰酸酯(IPDI)、1,3-雙(異氰酸基甲基)環己烷等脂環族異氰酸酯類;2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、伸茬基二異氰酸酯(XDI)等芳香族異氰酸酯類;經將異氰酸酯化合物藉由脲甲酸酯鍵、雙脲鍵、三聚異氰酸酯鍵、脲二酮鍵、脲鍵、碳二亞胺鍵、脲酮亞胺鍵、㗁二𠯤三酮鍵等改質之聚異氰酸酯改質物等。市售品之例可舉:商品名TAKENATE 300S、TAKENATE 500、TAKENATE 600、TAKENATE D165N、TAKENATE D178N(以上,武田藥品工業公司製)、Sumidur T80、Sumidur L、Desmodur N3400(以上,住化Bayer Urethane公司製)、Millionate MR、Millionate MT、Coronate L、Coronate HL、Coronate HX(以上,Tosoh公司製)等。異氰酸酯化合物可單獨使用1種或組合2種以上來使用。亦可併用2官能之異氰酸酯化合物與3官能以上之異氰酸酯化合物。Isocyanate crosslinking agents may be difunctional or higher-functional isocyanate compounds, for example, trimethylene diisocyanate, butyl diisocyanate, hexamethylene diisocyanate (HDI), diisocyanate and other aliphatic polyisocyanates; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cycloisocyanate; Alicyclic isocyanates such as hexane; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and isocyanate (XDI); polyisocyanate modified by modifying isocyanate compounds with allocarboxylate bonds, diurea bonds, isocyanurate bonds, uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, and diisocyanate-trione bonds, etc. Examples of commercial products include: trade names TAKENATE 300S, TAKENATE 500, TAKENATE 600, TAKENATE D165N, TAKENATE D178N (all manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur T80, Sumidur L, Desmodur N3400 (all manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (all manufactured by Tosoh Corporation), etc. The isocyanate compound may be used alone or in combination of two or more. A bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may also be used in combination.
環氧系交聯劑可舉例如雙酚A、環氧氯丙烷型環氧系樹脂、伸乙基環氧丙基醚、聚乙二醇二環氧丙基醚、甘油二環氧丙基醚、甘油三環氧丙基醚、1,6-己二醇環氧丙基醚、三羥甲丙烷三環氧丙基醚、二環氧丙基苯胺、二胺基環氧丙基胺、N,N,N',N'-四環氧丙基-間茬二胺及1,3-雙(N,N-二環氧丙基胺基甲基)環己烷等。該等可單獨使用1種或組合2種以上來使用。Examples of epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resins, ethyl glycidyl ether, polyethylene glycol diglycidyl ether, glyceryl diglycidyl ether, glyceryl triglycidyl ether, 1,6-hexanediol glycidyl ether, trihydroxymethylpropane triglycidyl ether, diglycidyl aniline, diaminoglycidylamine, N,N,N',N'-tetraglycidyl-intermediate diamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, etc. These can be used alone or in combination of two or more.
多官能性單體可舉例如:乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯、二乙烯苯、雙苯氧乙醇茀二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、環氧丙烯酸酯、聚酯丙烯酸酯、胺甲酸酯丙烯酸酯、丁基二醇二(甲基)丙烯酸酯、己基二醇二(甲基)丙烯酸酯等。多官能性單體可單獨使用1種或組合2種以上來使用。Examples of the multifunctional monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,1 2-Dodecanediol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, tetrahydroxymethylmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, bisphenoxyethanolfluorene di(meth)acrylate, bisphenol A di(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, butyl glycol di(meth)acrylate, hexyl glycol di(meth)acrylate, etc. The polyfunctional monomer may be used alone or in combination of two or more.
使用交聯劑(可為多官能性單體)時之使用量無特別限定,例如可相對於基底聚合物100重量份設為0.001重量份~5.0重量份左右之範圍。由提升黏著劑之柔軟性之觀點來看,在數個態樣中,交聯劑相對於基底聚合物100重量份之使用量宜為3.0重量份以下,較宜為2.0重量份以下,可為1.0重量份以下,可為0.5重量份以下,亦可為0.2重量份以下。又,由適當發揮交聯劑之使用效果之觀點來看,在數個態樣中,交聯劑相對於基底聚合物100重量份之使用量例如可為0.005重量份以上,可為0.01重量份以上,可為0.05重量份以上,亦可為0.08重量份以上。The amount of the crosslinking agent (which may be a multifunctional monomer) used is not particularly limited, and can be set to a range of about 0.001 to 5.0 parts by weight relative to 100 parts by weight of the base polymer, for example. From the perspective of improving the softness of the adhesive, in several aspects, the amount of the crosslinking agent used relative to 100 parts by weight of the base polymer is preferably 3.0 parts by weight or less, preferably 2.0 parts by weight or less, can be 1.0 parts by weight or less, can be 0.5 parts by weight or less, and can also be 0.2 parts by weight or less. In addition, from the perspective of properly exerting the effect of the use of the crosslinking agent, in several aspects, the amount of the crosslinking agent used relative to 100 parts by weight of the base polymer can be, for example, 0.005 parts by weight or more, can be 0.01 parts by weight or more, can be 0.05 parts by weight or more, and can also be 0.08 parts by weight or more.
為了使交聯反應更有效地進行,亦可使用交聯觸媒。交聯觸媒之例可舉:鈦酸四正丁酯、鈦酸四異丙酯、乙醯丙酮鐵(III)、丁基錫氧化物、二月桂酸二辛錫等金屬系交聯觸媒等。其中又以二月桂酸二辛錫等錫系交聯觸媒為佳。交聯觸媒之使用量無特別限制。考量到到交聯反應速度之快慢與黏著劑組成物使用期限之長短之平衡,交聯觸媒相對於基底聚合物100重量份之使用量例如可設為大約0.0001重量份以上且1重量份以下之範圍,且宜設為0.001重量份以上且0.5重量份以下之範圍。In order to make the crosslinking reaction more effective, a crosslinking catalyst can also be used. Examples of crosslinking catalysts include: tetrabutyl titanium, tetraisopropyl titanium, iron (III) acetylacetonate, butyltin oxide, dioctyltin dilaurate and other metal-based crosslinking catalysts. Among them, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferred. There is no particular restriction on the amount of crosslinking catalyst used. Considering the balance between the speed of the crosslinking reaction and the service life of the adhesive composition, the amount of the crosslinking catalyst used relative to 100 parts by weight of the base polymer can be set to, for example, a range of about 0.0001 parts by weight or more and less than 1 part by weight, and preferably a range of about 0.001 parts by weight or more and less than 0.5 parts by weight.
黏著劑組成物中可含有可產生酮-烯醇互變異構性之化合物作為交聯延遲劑。藉此,可實現延長黏著劑組成物之使用期限的效果。例如,可在包含異氰酸酯系交聯劑之黏著劑組成物中,適宜利用可產生酮-烯醇互變異構性之化合物。可產生酮-烯醇互變異構性之化合物可使用各種β-二羰基化合物。例如可適宜採用β-二酮類(乙醯丙酮、2,4-己二酮等)或乙醯乙酸酯類(乙醯乙酸甲酯、乙醯乙酸乙酯等)。可產生酮-烯醇互變異構性之化合物可單獨使用1種或組合2種以上來使用。可產生酮-烯醇互變異構性之化合物的使用量,相對於基底聚合物100重量份,可設為例如0.1重量份以上且20重量份以下,可設為0.5重量份以上且10重量份以下,亦可設為1重量份以上且5重量份以下。The adhesive composition may contain a compound that can produce keto-enol tautomerism as a crosslinking delayer. In this way, the effect of extending the service life of the adhesive composition can be achieved. For example, a compound that can produce keto-enol tautomerism can be appropriately used in an adhesive composition containing an isocyanate crosslinker. Various β-dicarbonyl compounds can be used as compounds that can produce keto-enol tautomerism. For example, β-diketones (acetylacetone, 2,4-hexanedione, etc.) or acetoacetates (methyl acetoacetate, ethyl acetoacetate, etc.) can be appropriately used. Compounds that can produce keto-enol tautomerism can be used alone or in combination of two or more. The amount of the compound capable of producing keto-enol tautomerism used can be, for example, 0.1 parts by weight to 20 parts by weight, 0.5 parts by weight to 10 parts by weight, or 1 part by weight to 5 parts by weight, relative to 100 parts by weight of the base polymer.
(賦黏劑) 在此揭示之技術中之黏著劑層中亦可含有賦黏劑。賦黏劑可使用松香系增黏樹脂、萜系增黏樹脂、酚系增黏樹脂、烴系增黏樹脂、酮系增黏樹脂、聚醯胺系增黏樹脂、環氧系增黏樹脂、彈性體系增黏樹脂等公知的增黏樹脂。該等可單獨使用1種或組合2種以上來使用。增黏樹脂之使用量無特別限定,可按目的及用途來設定成能發揮適當之黏著性能。在數個態樣中,由折射率或透明性之觀點來看,賦黏劑之使用量相對於黏著劑層之基底聚合物100重量份設為30重量份以下是適當的,宜設為10重量份以下,較宜設為5重量份以下。在此揭示之技術可適宜在不使用賦黏劑之態樣下實施。(Tackifier) The adhesive layer in the technology disclosed herein may also contain a tackifier. The tackifier may be a rosin-based tackifier resin, a terpene-based tackifier resin, a phenol-based tackifier resin, a hydrocarbon-based tackifier resin, a ketone-based tackifier resin, a polyamide-based tackifier resin, an epoxy-based tackifier resin, an elastic system-based tackifier resin, or other known tackifier resins. These may be used alone or in combination of two or more. The amount of the tackifier resin used is not particularly limited and may be set to exhibit appropriate adhesive properties according to the purpose and use. In several aspects, from the perspective of refractive index or transparency, the amount of the adhesive used is appropriately set to 30 parts by weight or less relative to 100 parts by weight of the base polymer of the adhesive layer, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. The technology disclosed herein can be appropriately implemented in an aspect without using an adhesive.
(其他添加劑) 在此揭示之技術中,用於形成黏著劑層之黏著劑組成物亦可在不顯著妨礙本發明效果之範圍內視需求包含有塑化劑、軟化劑、著色劑、抗靜電劑、抗老化劑、紫外線吸收劑、抗氧化劑、光穩定劑、防腐劑等可使用於黏著劑組成物之公知的添加劑。針對所述各種添加劑,可依常法使用以往公知者,而無特別賦予本發明任何特徵,故省略詳細說明。(Other additives) In the technology disclosed herein, the adhesive composition used to form the adhesive layer may also include plasticizers, softeners, colorants, antistatic agents, anti-aging agents, ultraviolet absorbers, antioxidants, light stabilizers, preservatives, and other known additives that can be used in adhesive compositions as needed within the scope that does not significantly hinder the effect of the present invention. For the various additives mentioned above, the previously known ones can be used according to the usual method, and no special features are given to the present invention, so detailed description is omitted.
(黏著劑層之製作) 在此揭示之技術中,構成黏著劑層之黏著劑可為藉由乾燥、交聯、聚合、冷卻等使溶劑型、活性能量線硬化型、水分散型、熱熔型等形態之黏著劑組成物硬化而成之黏著劑,亦即可為上述黏著劑組成物的硬化物。黏著劑組成物之硬化手段(例如乾燥、交聯、聚合、冷卻等)可僅應用1種,亦可同時或多階段應用2種以上。以溶劑型黏著劑組成物來說,典型上可使該組成物乾燥(宜為進一步交聯)來形成黏著劑。在活性能量線硬化型黏著劑組成物方面,典型上係藉由照射活性能量線使聚合反應及/或交聯反應進行而形成黏著劑。在必須以活性能量線硬化型黏著劑組成物進進行乾燥時,可於乾燥後照射活性能量線。(Preparation of Adhesive Layer) In the technology disclosed herein, the adhesive constituting the adhesive layer may be an adhesive formed by hardening an adhesive composition in the form of a solvent type, active energy ray hardening type, water dispersion type, hot melt type, etc. by drying, crosslinking, polymerization, cooling, etc., that is, a hardened product of the above adhesive composition. The hardening means (such as drying, crosslinking, polymerization, cooling, etc.) of the adhesive composition may be applied only one, or two or more may be applied simultaneously or in multiple stages. For a solvent type adhesive composition, the composition may be typically dried (preferably further crosslinked) to form an adhesive. In the case of an active energy ray-curable adhesive composition, the adhesive is typically formed by irradiating the active energy ray to cause a polymerization reaction and/or a crosslinking reaction to proceed. When the active energy ray-curable adhesive composition must be dried, the active energy ray may be irradiated after drying.
在此揭示之黏著型光學薄膜的黏著劑層可藉由在對適當表面賦予(例如塗佈)黏著劑組成物後使該組成物硬化來形成。黏著劑組成物之塗佈例如可使用凹版輥塗佈機、反向輥塗佈機、接觸輥塗佈機、浸漬輥塗佈機、棒塗機、刮刀塗佈機、噴塗機等慣用之塗佈機來實施。The adhesive layer of the adhesive optical film disclosed herein can be formed by applying (e.g., coating) an adhesive composition to a suitable surface and then hardening the composition. The adhesive composition can be coated using a conventional coating machine such as a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, a rod coater, a doctor blade coater, or a spray coater.
在此揭示之黏著型光學薄膜的黏著劑層可為具有後硬化性之黏著劑層,亦可為不具後硬化性之黏著劑層。在此,具有後硬化性之黏著劑層係指可藉由熱或活性能量線(例如紫外線)之照射來使其進一步硬化之黏著劑層。作為具有後硬化性之黏著劑層之例可舉:於基底聚合物之側鏈具有未反應之乙烯性不飽和基之黏著劑層、或包含未反應多官能性單體的黏著劑層。在數個態樣中,黏著劑層宜不具後硬化性。不具後硬化性之黏著劑層不會發生伴隨後硬化反應之尺寸變化(即尺寸穩定性佳),因此容易抑制黏著型光學薄膜或包含黏著型光學薄膜之積層體的翹曲。不會發生後硬化所造成之尺寸變化(例如硬化收縮)由抑制黏著劑層之光學應變之觀點來看亦有利。The adhesive layer of the adhesive optical film disclosed herein may be an adhesive layer with post-curing properties or an adhesive layer without post-curing properties. Here, the adhesive layer with post-curing properties refers to an adhesive layer that can be further cured by irradiation with heat or active energy rays (such as ultraviolet rays). Examples of adhesive layers with post-curing properties include: an adhesive layer having unreacted ethylenically unsaturated groups in the side chains of the base polymer, or an adhesive layer containing unreacted multifunctional monomers. In several aspects, the adhesive layer is preferably not post-curing. An adhesive layer without post-curing properties will not undergo dimensional changes associated with a subsequent curing reaction (i.e., it has good dimensional stability), and thus it is easy to suppress the warping of an adhesive optical film or a laminate containing an adhesive optical film. The absence of dimensional changes caused by post-curing (e.g., curing shrinkage) is also beneficial from the perspective of suppressing optical strain of the adhesive layer.
黏著劑層之厚度無特別限定,可設為例如3µm以上,且宜為5µm以上。藉由厚度5µm以上之黏著劑層,可易獲得良好之黏著特性。又,所述厚度之黏著劑層會吸收可能存在於被黏著體表面之凹凸而容易密著性良好地接合於該被黏著體。由防止光干涉造成之著色或顏色不均之觀點來看,黏著劑層之厚度為5µm以上亦佳。在數個態樣中,黏著劑層之厚度可為10µm以上,可為20µm以上,可為30µm以上,可為50µm以上,亦可為70µm以上或85µm以上。又,在數個態樣中,黏著劑層之厚度例如可為300µm以下,可為250µm以下,可為200µm以下,可為150µm以下,亦可為120µm以下。黏著劑層之厚度不過大一事由黏著型光學薄膜之薄型化等觀點來看是有利的。在此揭示之技術例如適宜在黏著劑層之厚度成為3µm~200µm(較宜為5µm~100µm)之範圍之態樣下實施。於光透射性構件之第1面及第2面具有第1黏著劑層及第2黏著劑層之形態的黏著型光學薄膜中,上述黏著劑層之厚度至少可應用於第1黏著劑層之厚度。第2黏著劑層之厚度亦可從相同範圍中選擇。The thickness of the adhesive layer is not particularly limited, and can be set to, for example, 3µm or more, and preferably 5µm or more. With an adhesive layer having a thickness of 5µm or more, good adhesive properties can be easily obtained. In addition, the adhesive layer of the thickness absorbs the unevenness that may exist on the surface of the adherend and is easily bonded to the adherend with good adhesion. From the perspective of preventing coloring or color unevenness caused by light interference, it is also preferred that the thickness of the adhesive layer is 5µm or more. In several embodiments, the thickness of the adhesive layer can be 10µm or more, 20µm or more, 30µm or more, 50µm or more, 70µm or more, or 85µm or more. Furthermore, in several embodiments, the thickness of the adhesive layer can be, for example, less than 300µm, less than 250µm, less than 200µm, less than 150µm, or less than 120µm. The fact that the thickness of the adhesive layer is not too large is advantageous from the perspective of thinning the adhesive optical film. The technology disclosed herein is suitable for implementation in an embodiment in which the thickness of the adhesive layer is in the range of 3µm to 200µm (preferably 5µm to 100µm). In an adhesive optical film having a first adhesive layer and a second adhesive layer on the first and second surfaces of a light-transmitting component, the thickness of the above-mentioned adhesive layer can be applied to at least the thickness of the first adhesive layer. The thickness of the second adhesive layer can also be selected from the same range.
(剝離強度) 在此揭示之黏著型光學薄膜之數個態樣中,該黏著型光學薄膜對玻璃板之剝離強度為大約1.0N/25mm以上(例如1.5N/25mm以上)是適當的,宜為2N/25mm以上,較宜為3N/25mm以上,可為4N/25mm以上,可為6N/25mm以上,可為8N/25mm以上,可為10N/25mm以上,亦可為12N/25mm以上。剝離強度的上限無特別限制,例如可為30N/25mm以下、25N/25mm以下或20N/25mm以下。(Peeling strength) In several aspects of the adhesive optical film disclosed herein, the peeling strength of the adhesive optical film to the glass plate is suitable to be about 1.0N/25mm or more (e.g., 1.5N/25mm or more), preferably 2N/25mm or more, more preferably 3N/25mm or more, 4N/25mm or more, 6N/25mm or more, 8N/25mm or more, 10N/25mm or more, or 12N/25mm or more. There is no particular limit to the upper limit of the peeling strength, for example, it can be less than 30N/25mm, less than 25N/25mm, or less than 20N/25mm.
在此,上述剝離強度係藉由下述方式來掌握:壓接於作為被黏著體之鹼玻璃板上並於23℃、50%RH之環境下放置30分鐘,接著投入加壓脫泡裝置(高壓釜)中在溫度50℃、壓力0.5MPa之條件下進行30分鐘高壓釜處理,再於23℃、50%RH之氣體環境下放置24小時後,在剝離角度180度、拉伸速度300mm/分鐘之條件下進行180°剝除,測定黏著力。在測定時,可視需求在測定對象之黏著型光學薄膜上貼附適當之襯底材(例如厚度25µm左右~50µm左右之聚對苯二甲酸乙二酯(PET)薄膜)來補強。剝離強度更具體而言可依據後述實施例所記載之方法來測定。 在此揭示之黏著型光學薄膜為具有第1黏著面及第2黏著面之雙面黏著型光學薄膜之形態時,在數個態樣中,上述剝離強度宜至少應用於第1黏著面,且較宜應用於第1黏著面及第2黏著面兩者。第1黏著面對玻璃板之剝離強度與第2黏著面對玻璃之剝離強度可為相同程度,亦可不同。Here, the peel strength is determined by pressing the adherend onto an alkaline glass plate and placing it in an environment of 23°C and 50% RH for 30 minutes, then placing it in a pressurized degassing device (autoclave) at a temperature of 50°C and a pressure of 0.5 MPa for 30 minutes, and then placing it in a gas environment of 23°C and 50% RH for 24 hours, and then performing 180° peeling at a peeling angle of 180 degrees and a tensile speed of 300 mm/min to measure the adhesion. During the measurement, a suitable backing material (e.g., a polyethylene terephthalate (PET) film with a thickness of about 25µm to about 50µm) can be attached to the adhesive optical film of the measurement object as required for reinforcement. The peel strength can be measured more specifically according to the method described in the embodiments described below. When the adhesive optical film disclosed herein is in the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, in several embodiments, the above peel strength should be applied to at least the first adhesive surface, and preferably to both the first adhesive surface and the second adhesive surface. The peel strength of the first adhesive surface against the glass plate and the peel strength of the second adhesive surface against the glass can be the same or different.
<光透射性構件> 在此所揭示之技術中,光透射性構件之材質無特別限定,可因應黏著型光學薄膜之使用目的或使用態樣等適當選擇。構成黏著型光學薄膜之光透射性構件之例包含後述光學構件(例如偏光板等機能性薄膜)。<Light-transmitting member> In the technology disclosed herein, the material of the light-transmitting member is not particularly limited and can be appropriately selected according to the purpose or usage of the adhesive optical film. Examples of the light-transmitting member constituting the adhesive optical film include the optical member described below (e.g., functional films such as polarizing plates).
在數個態樣中,可適宜使用各種薄膜基材作為光透射性構件。上述薄膜基材宜為包含獨立且可維持形狀之(自立型之、或是非依存性之)樹脂薄膜作為基底薄膜者。在此,「樹脂薄膜」係指非多孔質之結構且典型上為實質上不含氣泡(無孔洞)之樹脂薄膜。因此,上述樹脂薄膜係可與發泡體薄膜或不織布區別之概念。上述樹脂薄膜可適宜使用獨立且可維持形狀之(自立型之、或是非依存性之)者。上述樹脂薄膜可為單層結構,亦可為2層以上之多層結構(例如3層結構)。In several aspects, various film substrates can be suitably used as light-transmitting components. The above-mentioned film substrate is preferably a base film comprising an independent (self-supporting or non-dependent) resin film that can maintain its shape. Here, "resin film" refers to a non-porous structure and is typically a resin film that does not substantially contain bubbles (no holes). Therefore, the above-mentioned resin film is a concept that can be distinguished from foam film or non-woven fabric. The above-mentioned resin film can be suitably an independent (self-supporting or non-dependent) resin film that can maintain its shape. The above-mentioned resin film can be a single-layer structure, or a multi-layer structure of two or more layers (for example, a three-layer structure).
構成樹脂薄膜之材料可舉例如:以聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二酯(PEN)等聚酯為主成分之聚酯系樹脂、以聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-丁烯共聚物等聚烯烴為主成分之聚烯烴系樹脂、三醋酸纖維素等纖維素樹脂、乙酸酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、尼龍6、尼龍66、部分芳香族聚醯胺等聚醯胺(PA)系樹脂、聚醯亞胺(PI)系樹脂、透明聚醯亞胺樹脂、聚醯胺醯亞胺(PAI)、聚醚醚酮(PEEK)、聚醚碸(PES)、降莰烯系樹脂等環狀聚烯烴樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚二氯亞乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、乙烯-乙酸乙烯酯共聚物樹脂、乙烯-乙烯醇共聚物樹脂、聚芳酯系樹脂、聚伸苯硫醚(PPS)系樹脂、聚胺甲酸酯(PU)、乙烯-乙酸乙烯酯共聚物(EVA)、聚四氟乙烯(PTFE)或氟化聚醯亞胺等氟樹脂等。Materials constituting the resin film include, for example, polyester resins with polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) as main components, polyolefin resins with polyolefins such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, and ethylene-butylene copolymer as main components, cellulose resins such as cellulose triacetate, acetate resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, nylon 6, nylon 66, polyamide (PA) resins such as partially aromatic polyamides, polyimide (PI) resins, and polyamide (PA) resins. Resin, transparent polyimide resin, polyamide imide (PAI), polyetheretherketone (PEEK), polyether sulphate (PES), cyclic polyolefin resins such as norbornene resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, polyarylate resins, polyphenylene sulfide (PPS) resins, polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene (PTFE) or fluorinated polyimide and other fluororesins, etc.
上述樹脂薄膜可為使用單獨包含所述樹脂之1種的樹脂材料所形成者,亦可為使用摻合有2種以上之樹脂材料所形成者。上述樹脂薄膜可為無延伸,亦可為經延伸(例如單軸延伸或雙軸延伸)者。在數個態樣中,例如可適宜使用PET薄膜、PBT薄膜、PEN薄膜、無延伸聚丙烯(CPP)薄膜、雙軸延伸聚丙烯(OPP)薄膜、低密度聚乙烯(LDPE)薄膜、直鏈狀低密度聚乙烯(LLDPE)薄膜、PP/PE摻合物薄膜等。由強度或尺寸穩定性之觀點來看,理想之樹脂薄膜之例可舉PET薄膜、PEN薄膜、PPS薄膜及PEEK薄膜。由取得容易度等觀點來看,尤宜為PET薄膜及PPS薄膜,其中又以PET薄膜為佳。The above-mentioned resin film may be formed using a resin material containing only one of the above-mentioned resins, or may be formed using a resin material blended with two or more resins. The above-mentioned resin film may be unstretched, or may be stretched (for example, uniaxially stretched or biaxially stretched). In several aspects, for example, PET film, PBT film, PEN film, unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low-density polyethylene (LDPE) film, linear low-density polyethylene (LLDPE) film, PP/PE blend film, etc. may be suitably used. From the viewpoint of strength or dimensional stability, examples of ideal resin films include PET film, PEN film, PPS film, and PEEK film. From the viewpoint of ease of acquisition, PET film and PPS film are particularly suitable, among which PET film is preferred.
在樹脂薄膜中,可在不顯著妨礙本發明效果之範圍內視需求摻混光穩定劑、抗氧化劑、抗靜電劑、著色劑(染料、顏料等)、充填材、滑劑(slipping agent)、抗黏結劑等公知之添加劑。添加劑之摻混量無特別限定,可按黏著型光學薄膜之用途等適當設定。In the resin film, known additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slipping agents, and anti-adhesive agents may be mixed as needed within the range that does not significantly hinder the effect of the present invention. The mixing amount of the additives is not particularly limited and can be appropriately set according to the purpose of the adhesive optical film.
樹脂薄膜之製造方法無特別限定。例如可適當採用擠製成形、充氣成形、T型模澆鑄成形、砑光輥成形等以往公知之一般樹脂薄膜成形方法。The method for producing the resin film is not particularly limited. For example, a conventionally known general resin film forming method such as extrusion forming, inflation forming, T-die casting, calender roll forming, etc. can be appropriately adopted.
上述光透射性構件可為實質上由所述基底薄膜所構成者。或者,上述光透射性構件亦可為除了上述基底薄膜外還包含輔助性之層者。作為上述輔助性之層之例,可舉光學特性調整層(例如著色層、抗反射層)、用於賦予所期望之外觀的印刷層或層合層、抗靜電層、底塗層、剝離層等表面處理層。The light-transmitting member may be substantially composed of the base film. Alternatively, the light-transmitting member may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include an optical property adjustment layer (e.g., a coloring layer, an anti-reflection layer), a printing layer or a laminate layer for imparting a desired appearance, an antistatic layer, a primer layer, a peeling layer, and other surface treatment layers.
在數個態樣中,光透射性構件之全光線透射率例如可大於50%,亦可為70%以上。在數個理想態樣中,光透射性構件之全光線透射率為80%以上,較宜為90%以上,亦可為95%以上(例如95~100%)。上述全光線透射率係根據JIS K 7136:2000,使用市售之透射率計來測定。透射率計可使用村上色彩技術研究所製之商品名「HAZEMETER HM-150」或其等效品。上述光透射性構件之適當例可舉具有光透射性之樹脂薄膜。上述光透射性構件亦可為光學薄膜。In several embodiments, the total light transmittance of the light-transmitting component may be, for example, greater than 50%, or may be greater than 70%. In several ideal embodiments, the total light transmittance of the light-transmitting component is greater than 80%, preferably greater than 90%, or may be greater than 95% (e.g., 95-100%). The above-mentioned total light transmittance is measured according to JIS K 7136:2000 using a commercially available transmittance meter. The transmittance meter may use the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Laboratory or its equivalent. A suitable example of the above-mentioned light-transmitting component may be a resin film having light transmittance. The above-mentioned light-transmitting component may also be an optical film.
在數個態樣中,可用於上述光透射性構件之構成的材料可舉例如:銅、銀、金、鐵、錫、鈀、鋁、鎳、鈦、鉻、銦、鋅等或包含該等中之2種以上的合金等金屬材料,或是例如聚醯亞胺系樹脂、丙烯酸系樹脂、聚醚腈系樹脂、聚醚碸系樹脂、聚酯系樹脂(PET系樹脂、聚萘二甲酸乙二酯系樹脂等)、聚氯乙烯系樹脂、聚伸苯硫醚系樹脂、聚醚醚酮系樹脂、聚醯胺系樹脂(所謂的芳醯胺樹脂等)、聚芳酯系樹脂、氟系樹脂、聚碳酸酯系樹脂、二醋酸纖維素或三醋酸纖維素等纖維素系聚合物、乙烯醇縮丁醛系聚合物、液晶聚合物、奈米碳管或石墨烯等碳材料、以PEDOT(聚(3,4-伸乙基二氧噻吩))或聚苯胺等代表之高分子材料等各種樹脂材料(典型上為塑膠材)、氧化鋁、氧化鋯、氧化鈦、SiO2 、ITO(氧化銦錫)、ATO(銻摻雜氧化錫)等金屬氧化物及其混合物、氮化鋁、氮化矽、氮化鈦、氮化鎵、氮化銦等氮化物及其複合物、鹼玻璃、無鹼玻璃、石英玻璃、硼矽酸玻璃、藍寶石玻璃等無機材料、該等之混合物或複合物等,惟不受該等限定。In several aspects, the materials that can be used to form the above-mentioned light-transmitting components include, for example, copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, zinc, etc., or alloys containing two or more of these metal materials, or polyimide resins, acrylic resins, polyether nitrile resins, polyether sulfide resins, polyester resins (PET resins, polyethylene naphthalate resins, etc.), polyvinyl chloride resins, polyphenylene sulfide resins, polyether ether ketone resins. , polyamide resins (so-called aromatic amide resins, etc.), polyarylate resins, fluorine resins, polycarbonate resins, cellulose polymers such as cellulose diacetate or cellulose triacetate, vinyl butyral polymers, liquid crystal polymers, carbon materials such as carbon nanotubes or graphene, polymer materials represented by PEDOT (poly (3,4-ethylenedioxythiophene)) or polyaniline, etc., and various resin materials (typically plastic materials), aluminum oxide, zirconium oxide, titanium oxide, SiO 2. Metal oxides such as ITO (indium tin oxide) and ATO (antimony-doped tin oxide) and mixtures thereof, nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, indium nitride and complexes thereof, inorganic materials such as alkaline glass, alkali-free glass, quartz glass, borosilicate glass, sapphire glass, and mixtures or complexes thereof, but not limited thereto.
光透射性構件之厚度無特別限定,可按黏著型光學薄膜之使用目的或使用態樣等作選擇。光透射性構件之厚度例如可為500µm以下,而由處理性或加工性之觀點來看,宜為300µm以下,且可為150µm以下,可為100µm以下,可為50µm以下,可為25µm以下,亦可為10µm以下。光透射性構件之厚度若變小,有對被黏著體之表面形狀的追隨性提升之傾向。又,由處理性或加工性等觀點來看,光透射性構件之厚度例如可為2µm以上,可為10µm以上,亦可為25µm以上。The thickness of the light-transmitting member is not particularly limited, and can be selected according to the purpose of use or the usage of the adhesive optical film. The thickness of the light-transmitting member can be, for example, 500µm or less, and from the perspective of handling or processing, it is preferably 300µm or less, and can be 150µm or less, 100µm or less, 50µm or less, 25µm or less, or 10µm or less. If the thickness of the light-transmitting member is reduced, there is a tendency for the tracking performance of the surface shape of the adherend to be improved. In addition, from the perspective of handling or processing, the thickness of the light-transmitting member can be, for example, 2µm or more, 10µm or more, or 25µm or more.
光透射性構件之中要積層黏著劑層之側的面亦可視需求施行有電暈放電處理、電漿處理、紫外線照射處理、酸處理、鹼處理、藉由塗佈底塗劑(底漆)形成底塗層等之以往公知的表面處理。所述表面處理可為用以提升黏著劑層對光透射性構件之投錨性之處理。用於形成底塗層的底漆之組成無特別限定,可從公知物適當選擇。底塗層之厚度無特別限制,通常以0.01µm~1µm左右為適當,且0.1µm~1µm左右為佳。可因應需求對光透射性構件施行之其他處理可舉抗靜電層形成處理、著色層形成處理、印刷處理等。該等處理可單獨或組合來應用。The side of the light-transmitting component on which the adhesive layer is to be deposited may also be subjected to conventional surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkaline treatment, and forming a primer layer by applying a primer (primer) as required. The surface treatment may be a treatment for improving the anchoring property of the adhesive layer to the light-transmitting component. The composition of the primer used to form the primer layer is not particularly limited and can be appropriately selected from known materials. The thickness of the primer layer is not particularly limited, and is generally about 0.01µm to 1µm, and about 0.1µm to 1µm is preferred. Other treatments that may be performed on the light-transmitting member as required include antistatic layer formation, coloring layer formation, printing, etc. These treatments may be applied alone or in combination.
在此揭示之黏著型光學薄膜之厚度例如可為1000µm以下,可為350µm以下,可為200µm以下,可為120µm以下,可為75µm以下,亦可為50µm以下。又,由處理性等觀點來看,黏著型光學薄膜之厚度例如可為10µm以上,可為25µm以上,可為80µm以上,亦可為130µm以上。
此外,黏著型光學薄膜之厚度意指貼附於被黏著體之部分的厚度。例如圖1所示之構成的黏著型光學薄膜1中,係指從黏著劑層之第1表面(黏著面)10A至光透射性構件之第2面20B為止之厚度,而不包含剝離襯墊30之厚度。The thickness of the adhesive optical film disclosed herein may be, for example, less than 1000µm, less than 350µm, less than 200µm, less than 120µm, less than 75µm, or less than 50µm. Moreover, from the viewpoint of processing properties, the thickness of the adhesive optical film may be, for example, more than 10µm, more than 25µm, more than 80µm, or more than 130µm.
In addition, the thickness of the adhesive optical film refers to the thickness of the portion attached to the adherend. For example, in the adhesive
<附剝離襯墊之黏著型光學薄膜> 在此揭示之黏著型光學薄膜可採用使黏著劑層之表面(黏著面)抵接剝離襯墊之剝離面的黏著製品之形態。因此,根據本說明書可提供一種附剝離襯墊之黏著型光學薄膜(黏著製品),其包含在此揭示之任一黏著型光學薄膜與具有抵接該黏著型光學薄膜之黏著面的剝離面之剝離襯墊。<Adhesive optical film with peel-off pad> The adhesive optical film disclosed herein can be in the form of an adhesive product in which the surface (adhesive surface) of the adhesive layer abuts against the peeling surface of the peeling pad. Therefore, according to this specification, an adhesive optical film with peel-off pad (adhesive product) can be provided, which includes any adhesive optical film disclosed herein and a peeling pad having a peeling surface abutting against the adhesive surface of the adhesive optical film.
剝離襯墊無特別限定,例如可使用樹脂薄膜或紙(可為聚乙烯等樹脂層合而成之紙)等之剝離襯墊基材上具有剝離處理層之剝離襯墊、或是由藉由氟系聚合物(聚四氟乙烯等)或聚烯烴系樹脂(聚乙烯、聚丙烯等)這類低接著性材料形成之樹脂薄膜構成之剝離襯墊等。上述剝離處理層可為藉由剝離處理劑將剝離襯墊基材進行表面處理所形成者。剝離處理劑可為聚矽氧系剝離處理劑、長鏈烷基系剝離處理劑、氟系剝離處理劑、硫化鉬(IV)等公知之剝離處理劑。在數個態樣中,可適宜採用具有利用聚矽氧系剝離處理劑所得剝離處理層之剝離襯墊。剝離處理層之厚度或形成方法無特別限定,可設定成能在剝離襯墊之黏著面側表面發揮適當之剝離性。The release liner is not particularly limited, and for example, a release liner having a release treatment layer on a release liner substrate such as a resin film or paper (which may be a paper laminated with a resin such as polyethylene) or a release liner composed of a resin film formed by a low-adhesion material such as a fluorine-based polymer (polytetrafluoroethylene, etc.) or a polyolefin-based resin (polyethylene, polypropylene, etc.) can be used. The release treatment layer can be formed by surface treating the release liner substrate with a release treatment agent. The peeling agent may be a known peeling agent such as a silicone peeling agent, a long-chain alkyl peeling agent, a fluorine peeling agent, or molybdenum (IV) sulfide. In several embodiments, a peeling pad having a peeling layer obtained by using a silicone peeling agent may be appropriately used. The thickness or formation method of the peeling layer is not particularly limited, and may be set to exhibit appropriate peeling properties on the adhesive side surface of the peeling pad.
在數個態樣中,由黏著面之平滑性等觀點來看,可適宜採用作為剝離襯墊基材之樹脂薄膜(以下亦稱剝離薄膜基材)上具有剝離處理層之構成的剝離襯墊(以下亦稱剝離薄膜)。剝離薄膜基材可使用各種塑膠薄膜。在本說明書中,所謂塑膠薄膜典型上為非多孔質的片材,係例如可與不織布作區別(亦即,不包含不織布)之概念。In several aspects, from the viewpoint of the smoothness of the adhesive surface, a peeling liner (hereinafter also referred to as a peeling film) having a peeling treatment layer on a resin film (hereinafter also referred to as a peeling film substrate) as a peeling liner substrate can be appropriately used. Various plastic films can be used as the peeling film substrate. In this specification, the so-called plastic film is typically a non-porous sheet material, which is a concept that can be distinguished from non-woven fabrics (that is, it does not include non-woven fabrics).
上述塑膠薄膜之材料可舉例如聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二酯(PEN)等聚酯系樹脂、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-丁烯共聚物等聚烯烴系樹脂、三醋酸纖維素等纖維素樹脂、乙酸酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、降莰烯系樹脂等環狀聚烯烴樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚二氯亞乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、乙烯-乙酸乙烯酯共聚物樹脂、乙烯-乙烯醇共聚物樹脂、聚芳酯系樹脂、聚伸苯硫醚系樹脂等。亦可使用由該等樹脂中之任1種或2種以上混合物形成之剝離薄膜基材。其中較佳之剝離薄膜基材可舉由聚酯系樹脂形成之聚酯系樹脂薄膜(例如PET薄膜)。The material of the above-mentioned plastic film can be, for example, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyolefin resins such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-butylene copolymer, cellulose resins such as cellulose triacetate, acetate resins, polyester resins, polystyrene resins, etc. Cyclic polyolefin resins such as ether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, norbornene resins, (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, polyarylate resins, polyphenylene sulfide resins, etc. A release film substrate formed of any one or a mixture of two or more of these resins can also be used. A preferred release film substrate is a polyester resin film (e.g., PET film) formed of a polyester resin.
可作為上述剝離薄膜基材使用之塑膠薄膜可為無延伸薄膜、單軸延伸薄膜、雙軸延伸薄膜中之任一者。又,上述塑膠薄膜可為單層結構,亦可為包含2層以上子層之多層結構。上述塑膠薄膜中亦可摻混有抗氧化劑、抗老化劑、耐熱穩定劑、光穩定劑、紫外線吸收劑、顏料或染料等之著色劑、滑劑、充填劑、抗靜電劑、成核劑等可用於黏著片之剝離薄膜基材之公知的添加劑。多層結構之塑膠薄膜中,各添加劑可摻混在所有的子層中,亦可僅摻混在一部分的子層中。The plastic film that can be used as the release film substrate can be any one of an unstretched film, a uniaxially stretched film, and a biaxially stretched film. In addition, the plastic film can be a single-layer structure or a multi-layer structure including two or more sub-layers. The plastic film can also be mixed with antioxidants, anti-aging agents, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants such as pigments or dyes, lubricants, fillers, antistatic agents, nucleating agents, and other known additives that can be used for the release film substrate of the adhesive sheet. In a multi-layer plastic film, each additive may be mixed in all sub-layers or only in a part of the sub-layers.
在數個理想之態樣中,上述剝離薄膜基材(典型上為塑膠薄膜)可適宜使用在其剝離面側之層中無機粒子等粒子(例如可為顏料或滑劑、充填劑等)之含量業經限制者、或實質上不包含所述粒子者。在此所謂實質上不包含,意指該層中之粒子(例如無機粒子)之量小於1重量%,且意指宜小於0.1重量%(例如0~0.01重量%)。具備所述剝離薄膜基材之剝離薄膜容易成為剝離面之算術平均粗度Ra或最大高度Rz低者。上述剝離薄膜基材(典型上為塑膠薄膜)具有多層結構時,剝離面側之層中之粒子含量可為該剝離面側層以外之層中之粒子含量的1/10以下(例如1/50以下)。In several ideal aspects, the above-mentioned peeling film substrate (typically a plastic film) can be appropriately used in which the content of particles such as inorganic particles (such as pigments, lubricants, fillers, etc.) in the layer on the peeling surface side is limited, or substantially does not contain the particles. Here, the so-called substantially does not contain means that the amount of particles (such as inorganic particles) in the layer is less than 1% by weight, and preferably less than 0.1% by weight (for example, 0-0.01% by weight). The peeling film having the above-mentioned peeling film substrate is easy to become a peeling surface with a low arithmetic average roughness Ra or maximum height Rz. When the release film substrate (typically a plastic film) has a multi-layer structure, the particle content in the layer on the release side may be less than 1/10 (e.g., less than 1/50) of the particle content in the layer other than the release side layer.
在第1黏著面及第2黏著面上分別具有剝離襯墊之形態的附剝離襯墊之黏著型光學薄膜中,配置於其中一黏著面上的剝離襯墊(以下,亦稱為其中一剝離襯墊)與配置於另一黏著面上的剝離襯墊(以下,亦稱為另一剝離襯墊)可為具有同種材料及構成者,亦可為具有不同種材料、構成者。In an adhesive optical film with a release liner having a release liner on each of the first adhesive surface and the second adhesive surface, the release liner arranged on one of the adhesive surfaces (hereinafter, also referred to as one of the release liner) and the release liner arranged on the other adhesive surface (hereinafter, also referred to as the other release liner) may have the same material and structure or may have different materials and structures.
剝離襯墊(宜為剝離薄膜)之厚度無特別限定,例如可為10µm~500µm左右。由剝離襯墊之強度或尺寸穩定性之觀點來看,剝離襯墊之厚度為20µm以上是適當的,宜為30µm以上,可為35µm以上,可為40µm以上,亦可為45µm以上。又,由剝離襯墊之處理性(例如捲繞容易度)等觀點來看,剝離襯墊之厚度為300µm以下是適當的,且宜為250µm以下,可為200µm以下,可為150µm以下,亦可為130µm以下。在數個理想態樣中,剝離襯墊之厚度為大約125µm以下,可為大約115µm以下,可為大約105µm以下,可為大約90µm以下,亦可為大約70µm以下。藉由將剝離襯墊之厚度設為預定值以下,便不易形成做成捲狀時之捲繞痕跡,而能順利從黏著劑層去除,從而在剝離襯墊去除後之黏著面容易獲得高表面平滑性。The thickness of the peeling pad (preferably a peeling film) is not particularly limited, and may be, for example, about 10µm to 500µm. From the perspective of the strength or dimensional stability of the peeling pad, the thickness of the peeling pad is preferably 20µm or more, preferably 30µm or more, may be 35µm or more, may be 40µm or more, and may be 45µm or more. Furthermore, from the perspective of the handling properties of the peeling pad (e.g., ease of winding), the thickness of the peeling pad is preferably 300µm or less, and may be 250µm or less, may be 200µm or less, may be 150µm or less, and may be 130µm or less. In several ideal embodiments, the thickness of the peeling pad is about 125µm or less, about 115µm or less, about 105µm or less, about 90µm or less, or about 70µm or less. By setting the thickness of the peeling pad to a predetermined value or less, it is not easy to form a winding mark when the peeling pad is rolled, and it can be smoothly removed from the adhesive layer, so that the adhesive surface after the peeling pad is removed can easily obtain high surface smoothness.
在具備有其中一剝離襯墊及另一剝離襯墊之態樣中,該等剝離襯墊之厚度可相同亦可互異。在數個態樣中,由剝離作業性等觀點來看,其中一剝離襯墊與另一剝離襯墊宜具有不同之厚度,例如較厚的剝離襯墊之厚度宜為較薄的剝離襯墊之厚度的大約1.1倍以上(例如大約1.25倍以上;上限無特別限制,例如為5倍以下)。In the embodiment having one peeling liner and another peeling liner, the thickness of the peeling liner may be the same or different. In several embodiments, from the viewpoint of peeling workability, one peeling liner and the other peeling liner preferably have different thicknesses, for example, the thickness of the thicker peeling liner is preferably about 1.1 times or more (e.g., about 1.25 times or more; the upper limit is not particularly limited, for example, 5 times or less) the thickness of the thinner peeling liner.
(黏著面側表面之算術平均粗度Ra) 在數個態樣中,剝離襯墊(宜為剝離薄膜)由實現具有高表面平滑性之黏著面之觀點來看,黏著面側表面之算術平均粗度Ra宜被限制在預定值以下(例如大約100nm以下,進一步為小於50nm)。在數個態樣中,剝離襯墊之黏著面側表面之算術平均粗度Ra例如宜為大約30nm以下,較宜為大約25nm以下,可為大約20nm以下,亦可為大約18nm以下。又,由剝離襯墊之製造容易性或處理性等觀點來看,在數個態樣中,上述算術平均粗度Ra例如可為大約5nm以上,可為大約10nm以上,亦可為大約15nm以上。在第1黏著面及第2黏著面上分別配置有剝離襯墊之形態的附剝離襯墊之黏著型光學薄膜中,兩剝離襯墊之黏著面側表面皆宜滿足上述任一算術平均粗度Ra。兩剝離襯墊之黏著面側表面的算術平均粗度Ra可為相同程度,亦可不同。(Arithmetic mean roughness Ra of the adhesive side surface) In several embodiments, from the perspective of realizing an adhesive surface with high surface smoothness, the arithmetic mean roughness Ra of the adhesive side surface of the peeling pad (preferably a peeling film) is preferably limited to a predetermined value (for example, less than about 100nm, further less than 50nm). In several embodiments, the arithmetic mean roughness Ra of the adhesive side surface of the peeling pad is preferably less than about 30nm, more preferably less than about 25nm, can be less than about 20nm, and can also be less than about 18nm. In addition, from the perspective of ease of manufacturing or handling of the release pad, in several aspects, the arithmetic average roughness Ra may be, for example, about 5 nm or more, about 10 nm or more, or about 15 nm or more. In an adhesive optical film with a release pad disposed on the first adhesive surface and the second adhesive surface, the surfaces on the adhesive surface of the two release pads preferably satisfy any of the arithmetic average roughness Ra. The arithmetic average roughness Ra of the surfaces on the adhesive surface of the two release pads may be the same or different.
(黏著面側表面之最大高度Rz) 在數個態樣中,剝離襯墊(宜為剝離薄膜)由實現具有高表面平滑性之黏著面之觀點來看,黏著面側表面之最大高度Rz宜為700nm以下。在數個態樣中,剝離襯墊之黏著面側表面之最大高度Rz宜為大約600nm以下,可為大約500nm以下,可為大約400nm以下,亦可為大約300nm以下。又,由剝離襯墊之製造容易性或處理性等觀點來看,在數個態樣中,上述最大高度Rz例如可為大約50nm以上,可為大約80nm以上,可為大約100nm以上,可為大約150nm以上,亦可為大約200nm以上。在第1黏著面及第2黏著面上分別配置有剝離襯墊之形態的附剝離襯墊之黏著型光學薄膜中,兩剝離襯墊之黏著面側表面皆宜滿足上述任一最大高度Rz。兩剝離襯墊之黏著面側表面的最大高度Rz可為相同程度,亦可不同。(Maximum height Rz of the adhesive side surface) In several embodiments, the peel pad (preferably a peel film) preferably has a maximum height Rz of 700 nm or less from the viewpoint of realizing an adhesive surface with high surface smoothness. In several embodiments, the maximum height Rz of the adhesive side surface of the peel pad is preferably about 600 nm or less, and may be about 500 nm or less, about 400 nm or less, or about 300 nm or less. In addition, from the viewpoint of the ease of manufacturing or handling of the release pad, in several aspects, the maximum height Rz may be, for example, about 50 nm or more, about 80 nm or more, about 100 nm or more, about 150 nm or more, or about 200 nm or more. In the adhesive optical film with a release pad disposed on the first adhesive surface and the second adhesive surface, the adhesive surface side surfaces of the two release pads preferably satisfy any of the above-mentioned maximum heights Rz. The maximum heights Rz of the adhesive surface side surfaces of the two release pads may be the same or different.
(背面之表面性狀) 剝離襯墊(宜為剝離薄膜)之背面(黏著劑層側之相反面)的算術平均粗度Ra或最大高度Rz無特別限定。由生產性等觀點來看,剝離襯墊之背面的算術平均粗度Ra亦可例如大於30nm(例如大於35nm,進一步為大約50nm以上)。由生產性等觀點來看,剝離襯墊之背面的最大高度Rz例如可大於400nm(例如大約500nm以上),亦可大於800nm(例如1000nm以上)。(Surface properties of the back side) The arithmetic mean roughness Ra or the maximum height Rz of the back side (opposite side to the adhesive layer side) of the release pad (preferably the release film) is not particularly limited. From the perspective of productivity, the arithmetic mean roughness Ra of the back side of the release pad may be, for example, greater than 30nm (for example, greater than 35nm, further, about 50nm or more). From the perspective of productivity, the maximum height Rz of the back side of the release pad may be, for example, greater than 400nm (for example, about 500nm or more), or greater than 800nm (for example, 1000nm or more).
剝離薄膜表面之算術平均粗度Ra及最大高度Rz可藉由薄膜材料之選擇或成形方法、剝離處理等表面處理等來調節。例如可舉調節構成剝離性表面之層(抗黏結層、硬塗層、寡聚物防止層等)之平滑性,使該表面層或剝離薄膜基材中之填料粒子減量或不使用(無粒子化),其他還有調整延伸條件等。The arithmetic average roughness Ra and maximum height Rz of the peeling film surface can be adjusted by the selection of film materials or the forming method, peeling treatment and other surface treatments. For example, the smoothness of the layer constituting the peeling surface (anti-adhesion layer, hard coating layer, oligomer prevention layer, etc.) can be adjusted, the filler particles in the surface layer or the peeling film substrate can be reduced or not used (particle-free), and other methods include adjusting the stretching conditions.
剝離襯墊(宜為剝離薄膜)表面之算術平均粗度Ra及最大高度Rz係使用非接觸式表面粗度測定裝置測定。非接觸式表面粗度測定裝置可使用光干涉方式表面粗度測定裝置,例如可使用3維光學輪廓儀(商品名「NewView7300」,ZYGO公司製)或其等效品。例如可以黏著劑將玻璃板(MATSUNAMI公司製之鈉鈣玻璃板,厚度1.3mm)貼合於剝離襯墊之與測定面相反之側的面上並固定,使用3維光學輪廓儀(商品名「NewView7300」,ZYGO公司製)在23℃、50%RH之環境下測定表面形狀。The arithmetic mean roughness Ra and the maximum height Rz of the peel pad (preferably the peel film) surface are measured using a non-contact surface roughness measuring device. The non-contact surface roughness measuring device can use an optical interference surface roughness measuring device, for example, a 3D optical profiler (trade name "NewView7300", manufactured by ZYGO) or its equivalent. For example, a glass plate (sodium calcium glass plate manufactured by MATSUNAMI, thickness 1.3 mm) can be attached to the surface of the peel pad on the opposite side of the measuring surface with an adhesive and fixed, and the surface shape can be measured using a 3D optical profiler (trade name "NewView7300", manufactured by ZYGO) in an environment of 23°C and 50%RH.
<用途> 在此揭示之黏著型光學薄膜可貼合於各種被黏著體來使用。上述被黏著體之構成材料(被黏著體材料)無特別限定,可舉例如:銅、銀、金、鐵、錫、鈀、鋁、鎳、鈦、鉻、銦、鋅等或包含該等中之2種以上的合金等金屬材料,或是例如聚醯亞胺系樹脂、丙烯酸系樹脂、聚醚腈系樹脂、聚醚碸系樹脂、聚酯系樹脂(PET系樹脂、聚萘二甲酸乙二酯系樹脂等)、聚氯乙烯系樹脂、聚伸苯硫醚系樹脂、聚醚醚酮系樹脂、聚醯胺系樹脂(所謂的芳醯胺樹脂等)、聚芳酯系樹脂、氟系樹脂、聚碳酸酯系樹脂、二醋酸纖維素或三醋酸纖維素等纖維素系聚合物、乙烯醇縮丁醛系聚合物、液晶聚合物、石墨烯等碳材料等各種樹脂材料(典型上為塑膠材)、氧化鋁、氧化鋯、氧化鈦、SiO2 、ITO、ATO等金屬氧化物及其混合物、氮化鋁、氮化矽、氮化鈦、氮化鎵、氮化銦等氮化物及其複合物、鹼玻璃、無鹼玻璃、石英玻璃、硼矽酸玻璃、藍寶石玻璃等無機材料等。在此揭示之黏著型光學薄膜可至少表面貼附在由上述材料構成之構件(例如光學構件)上來使用。<Application> The adhesive optical film disclosed herein can be applied to various adherends for use. The constituent material of the adherend (adherend material) is not particularly limited, and examples thereof include: metal materials such as copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, zinc, etc., or alloys containing two or more of these, or materials such as polyimide resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, polyester resins (PET resins, polyethylene naphthalate resins, etc.), polyvinyl chloride resins, etc. Various resin materials (typically plastic materials) such as olefin resins, polyphenylene sulfide resins, polyetheretherketone resins, polyamide resins (so-called arylamide resins, etc.), polyarylate resins, fluorine resins, polycarbonate resins, cellulose polymers such as cellulose diacetate and cellulose triacetate, vinyl butyral polymers, liquid crystal polymers, carbon materials such as graphene, etc., metal oxides such as aluminum oxide, zirconium oxide, titanium oxide, SiO2 , ITO, ATO, etc., and mixtures thereof, nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, indium nitride, and complexes thereof, and inorganic materials such as alkaline glass, alkali-free glass, quartz glass, borosilicate glass, and sapphire glass, etc. The adhesive optical film disclosed herein can be used by at least one surface being attached to a component (eg, an optical component) made of the above-mentioned material.
在此揭示之黏著型光學薄膜可在下述貼附態樣下使用:在貼合於被黏著體後,不須進行加熱至較室溫左右溫度區域(例如20℃~35℃)更高之溫度的處理之貼附態樣。又,在因應黏著型光學薄膜之構成材料(例如光透射性構件之材質)或被黏著體之種類所容許之情況下,亦可在對被黏著體貼合後、貼合之時間點及貼合前之至少任一時間點進行加熱處理。加熱處理可在提升黏著劑對被黏著體之密著性或促進接著等目的下進行。加熱處理溫度可在因應黏著型光學薄膜之構成材料或被黏著體之種類所容許之範圍內,考量被黏著體之表面狀態等來適當設定成可獲得所期望之效果,例如可為100℃左右或該溫度以下,可為80℃以下,可為60℃以下,亦可為50℃以下。The adhesive optical film disclosed herein can be used in the following attachment state: after being attached to the adherend, it is not necessary to heat it to a temperature higher than room temperature (e.g., 20°C to 35°C). In addition, if the constituent material of the adhesive optical film (e.g., the material of the light-transmitting component) or the type of the adherend permits, it can also be heated at at least any time point after, at, or before the adherend is attached. The heat treatment can be performed for the purpose of improving the adhesion of the adhesive to the adherend or promoting adhesion. The heat treatment temperature can be appropriately set to obtain the desired effect within the range allowed by the constituent material of the adhesive optical film or the type of adherend, taking into account the surface condition of the adherend, etc., for example, it can be around 100°C or below, below 80°C, below 60°C, or below 50°C.
屬黏著型光學薄膜之貼附對象的構件或材料(在雙面黏著型光學薄膜中為至少一被黏著體)可為具有光透射性者。以所述被黏著體來說,可應用在此揭示之技術而容易獲得可抑制光學特性(透明性等)之降低並同時提高折射率之優點。上述被黏著體之全光線透射率例如可大於50%,亦可為70%以上。在數個理想態樣中,上述被黏著體之全光線透射率為80%以上,較宜為90%以上,更宜為95%以上(例如95~100%)。在此揭示之黏著型光學薄膜適宜在貼附於全光線透射率為預定值以上之被黏著體(例如光學構件)上之態樣下使用。上述全光線透射率係根據JIS K 7136:2000,使用市售之透射率計來測定。透射率計可使用村上色彩技術研究所製之商品名「HAZEMETER HM-150」或其等效品。The component or material to which the adhesive optical film is attached (at least one adherend in a double-sided adhesive optical film) may be light-transmissive. As for the adherend, the technology disclosed herein can be applied to easily obtain the advantages of suppressing the reduction of optical properties (transparency, etc.) and improving the refractive index at the same time. The total light transmittance of the adherend may be greater than 50%, or may be greater than 70%, for example. In several ideal embodiments, the total light transmittance of the adherend is greater than 80%, preferably greater than 90%, and more preferably greater than 95% (for example, 95~100%). The adhesive optical film disclosed herein is suitable for use in a state where it is attached to an adherend (for example, an optical component) whose total light transmittance is greater than a predetermined value. The total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000. The transmittance meter may be "HAZEMETER HM-150" manufactured by Murakami Color Research Laboratory or an equivalent thereof.
黏著劑層之折射率與被黏著體之折射率可為相同程度,亦可不同。例如,藉由相對於被黏著體的折射率,使黏著劑層的折射率相對地變高,可使從被黏著體側以臨界角以下之角度入射黏著劑層之光在正面側折射,提高正面亮度。此時,被黏著體之折射率例如可為1.55以下、1.50以下、1.48以下、1.45以下,亦可小於1.45,又例如可為1.10以上、1.20以上、1.30以上或1.35以上。又,藉由相對於黏著劑層為相對較高之折射率的被黏著體,可使從黏著劑層側入射被黏著體之光在正面側折射,提高正面亮度。此時,被黏著體之折射率例如可為1.60以上、1.65以上或1.70以上,且例如為3.00以下,可為2.50以下或2.00以下。另一方面,藉由縮小黏著劑層與被黏著體之折射率差,可抑制在界面的光反射。此時,被黏著體之折射率可為1.55~1.80左右,可為1.55~1.75左右,亦可為1.60~1.70左右。被黏著體之折射率可以與黏著劑之折射率相同之方法來測定。The refractive index of the adhesive layer and the refractive index of the adherend may be the same or different. For example, by making the refractive index of the adhesive layer relatively high relative to the refractive index of the adherend, light incident on the adhesive layer from the side of the adherend at an angle below the critical angle can be refracted on the front side, thereby increasing the front brightness. At this time, the refractive index of the adherend can be, for example, less than 1.55, less than 1.50, less than 1.48, less than 1.45, or less than 1.45, or more than 1.10, more than 1.20, more than 1.30, or more than 1.35. Furthermore, by making the adherend have a relatively high refractive index relative to the adhesive layer, light incident on the adherend from the adhesive layer side can be refracted on the front side, thereby increasing the front brightness. At this time, the refractive index of the adherend may be, for example, 1.60 or more, 1.65 or more, or 1.70 or more, and may be, for example, 3.00 or less, 2.50 or less, or 2.00 or less. On the other hand, by reducing the refractive index difference between the adhesive layer and the adherend, light reflection at the interface may be suppressed. At this time, the refractive index of the adherend may be about 1.55 to 1.80, about 1.55 to 1.75, or about 1.60 to 1.70. The refractive index of the adherend may be measured by the same method as the refractive index of the adhesive.
在數個理想態樣中,上述被黏著體可為具有上述任一折射率且具有上述任一全光線透射率者。在貼附於所述被黏著體之態樣中,尤能適宜發揮在此揭示之技術所帶來的效果。In several ideal embodiments, the adherend may have any of the above refractive indices and any of the above total light transmittances. In the embodiment of being attached to the adherend, the effect brought by the technology disclosed herein can be particularly well exerted.
較佳用途之一例可舉光學用途。更具體而言,例如可適宜將在此揭示之黏著型光學薄膜作為可用於貼合光學構件之用途(光學構件貼合用)或使用有上述光學構件之製品(光學製品)之製造用途等的光學用黏著片來使用。One example of a preferred application is optical application. More specifically, for example, the adhesive optical film disclosed herein can be suitably used as an optical adhesive sheet for bonding optical components (optical component bonding) or for manufacturing products using the above optical components (optical products).
上述光學構件係指具有光學特性(例如偏光性、光折射性、光散射性、光反射性、光透射性、光吸收性、光繞射性、旋光性、視辨性等)之構件。上述光學構件只要為具有光學特性之構件即無特別限定,可舉例如構成顯示裝置(影像顯示裝置)、輸入裝置等機器(光學機器)之構件或用於該等機器之構件,可舉例如偏光板、波長板、相位差板、光學補償薄膜、增亮薄膜、導光板、反射薄膜、抗反射薄膜、硬塗(HC)薄膜、衝擊吸收薄膜、防污薄膜、光致變色薄膜、調光薄膜、透明導電薄膜(ITO薄膜)、設計薄膜、裝飾薄膜、表面保護板、稜鏡、透鏡、彩色濾光片、透明基板,或進一步為該等積層而成之構件(該等有時統稱為「機能性薄膜」)等。此外,上述「板」及「薄膜」係分別設為包含板狀、薄膜狀、片狀等形態者,例如「偏光薄膜」係設為包含「偏光板」或「偏光片」等者,而「導光板」係設為包含「導光薄膜」或「導光片」等者。又,上述「偏光板」係設為包含圓偏光板者。The above-mentioned optical components refer to components having optical properties (such as polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.). The above-mentioned optical components are not particularly limited as long as they are components with optical properties. Examples include components constituting display devices (image display devices), input devices and other machines (optical machines) or components used in such machines, such as polarizing plates, wavelength plates, phase difference plates, optical compensation films, brightness enhancement films, light guide plates, reflective films, anti-reflective films, hard coating (HC) films, impact absorption films, anti-fouling films, photochromic films, dimming films, transparent conductive films (ITO films), design films, decorative films, surface protection plates, prisms, lenses, color filters, transparent substrates, or further components formed by layering such components (these are sometimes collectively referred to as "functional films"), etc. In addition, the above-mentioned "plate" and "film" are respectively set to include plate-shaped, film-shaped, sheet-shaped, etc. For example, "polarizing film" is set to include "polarizing plate" or "polarizing sheet", etc., and "light guide plate" is set to include "light guide film" or "light guide sheet", etc. Moreover, the above-mentioned "polarizing plate" is set to include a circular polarizing plate.
上述顯示裝置可舉例如液晶顯示裝置、有機EL(電致發光)顯示裝置、微LED(µLED)、迷你LED(miniLED)、PDP(電漿顯示器面板)、電子紙等。又,上述輸入裝置可舉觸控面板等。Examples of the display device include a liquid crystal display device, an organic EL (electroluminescent) display device, micro LED (µLED), mini LED (miniLED), PDP (plasma display panel), electronic paper, etc. Examples of the input device include a touch panel, etc.
上述光學構件無特別限定,可舉例如由玻璃、丙烯酸樹脂、聚碳酸酯、聚對苯二甲酸乙二酯、金屬薄膜等構成之構件(例如片狀或膜狀、板狀構件)等。此外,本說明書中之「光學構件」亦設為包含保持顯示裝置或輸入裝置之視辨性的同時擔任裝飾或保護功能之構件(設計薄膜、裝飾薄膜或表面保護薄膜等)。The optical component is not particularly limited, and examples thereof include components made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, metal film, etc. (e.g., sheet-shaped, film-shaped, or plate-shaped components). In addition, the "optical component" in this specification is also intended to include components that maintain the visibility of the display device or input device while serving as a decorative or protective function (design film, decorative film, or surface protection film, etc.).
在此揭示之技術例如可適宜用於將具有1或2種以上光透射、反射、擴散、波導、聚光、繞射等功能之薄膜或螢光薄膜等光學薄膜接合於其他光學構件(可為其他光學薄膜)。例如,將具備上述光學薄膜作為光透射性構件之黏著型光學薄膜貼附於作為被黏著體之上述其他光學構件,藉此可形成上述光透射性構件透過高折射率之黏著劑層(接合層)接合於上述其他光學構件之結構。又,將具備上述其他光學構件作為光透射性構件之黏著型光學薄膜貼附於作為被黏著體之上述光學薄膜,藉此可形成上述其他光學構件透過高折射率之黏著劑層接合於上述光透射性構件之結構。其中,在具有至少1種光之波導、聚光、繞射之功能的光學薄膜之接合中,接合層之全部整體宜為高折射率,而可成為在此揭示之技術的理想應用對象。The technology disclosed herein can be suitably used, for example, to bond optical films such as films or fluorescent films having one or more functions of light transmission, reflection, diffusion, waveguide, light focusing, diffraction, etc. to other optical components (which may be other optical films). For example, an adhesive optical film having the above optical film as a light-transmitting component is attached to the above other optical component as an adherend, thereby forming a structure in which the above light-transmitting component is bonded to the above other optical component through an adhesive layer (bonding layer) with a high refractive index. In addition, an adhesive optical film having the above other optical component as a light-transmitting component is attached to the above optical film as an adherend, thereby forming a structure in which the above other optical component is bonded to the above light-transmitting component through an adhesive layer with a high refractive index. Among them, in the bonding of optical films having at least one of the functions of light waveguiding, focusing, and diffusing, the entire bonding layer should have a high refractive index, which can become an ideal application object of the technology disclosed herein.
在此揭示之技術例如可適宜用於導光薄膜、擴散薄膜、螢光薄膜、調色薄膜、稜鏡片、柱鏡薄膜、微透鏡陣列薄膜等光學薄膜之接合。該等用途中,由光學構件之小型化的傾向或高性能化之觀點來看,係要求薄型化或光擷取效率之提升。在此揭示之技術可適宜作為具備可符合所述要求之黏著劑之黏著型光學薄膜來利用。更詳細而言,例如在導光薄膜或擴散薄膜之接合時,藉由調整作為接合層之黏著劑層的折射率(例如高折射率化)可有助於薄型化。螢光薄膜之接合可藉由適當調整螢光發光體與黏著劑之折射率差,來提升光擷取效率(亦可視為發光效率)。就調色薄膜之接合而言,藉由適當調整黏著劑之折射率以使與調色用顏料之折射率差變小,可降低散射成分,而有助於提升光透射性。在稜鏡片、柱鏡薄膜、微透鏡陣列薄膜等之接合時,藉由適當調整黏著劑之折射率來控制光的繞射,可有助於提升亮度及/或視角。The technology disclosed herein can be suitably used for the bonding of optical films such as light-guiding films, diffusion films, fluorescent films, color-adjusting films, prism films, columnar mirror films, and microlens array films. In such applications, from the perspective of miniaturization or high performance of optical components, thinning or improvement of light extraction efficiency is required. The technology disclosed herein can be suitably used as an adhesive optical film having an adhesive that can meet the above requirements. In more detail, for example, when bonding a light-guiding film or a diffusion film, adjusting the refractive index of the adhesive layer serving as the bonding layer (e.g., increasing the refractive index) can help achieve thinning. The bonding of fluorescent films can improve the light extraction efficiency (also regarded as luminous efficiency) by properly adjusting the refractive index difference between the fluorescent light emitter and the adhesive. For the bonding of color-adjusting films, by properly adjusting the refractive index of the adhesive to reduce the refractive index difference with the color-adjusting pigment, the scattering component can be reduced, which helps to improve light transmittance. When bonding prisms, lenticular films, microlens array films, etc., by properly adjusting the refractive index of the adhesive to control the diffraction of light, it can help to improve brightness and/or viewing angle.
在此揭示之黏著型光學薄膜可適宜在貼附於高折射率之被黏著體(可為高折射率之層或構件等)之態樣下使用,而可抑制與上述被黏著體之界面反射。可在所述態樣下使用之黏著型光學薄膜以如上述與被黏著體之折射率差小且在與被黏著體之界面的密著性高為佳。又,由提高外觀之均勻性之觀點來看,黏著劑層之厚度的均質性宜高,例如黏著面之表面平滑性宜高。當高折射率之被黏著體的厚度較小時(例如為5µm以下、4µm以下或2µm以下時),由抑制反射光之干涉造成之著色或顏色不均之觀點來看,抑制在界面之反射一事特別有意義。作為所述使用態樣之一例可舉以下態樣:可在依序具備偏光件、第1相位差層及第2相位差層之附相位差層之偏光板中,用於上述偏光件與上述第1相位差層之接合及/或上述第1相位差層與上述第2相位差層之接合。The adhesive optical film disclosed herein can be suitably used in a state of being attached to an adherend with a high refractive index (which can be a layer or component with a high refractive index, etc.), and can suppress the interface reflection with the above-mentioned adherend. The adhesive optical film that can be used in the above-mentioned state preferably has a small refractive index difference with the adherend as described above and high adhesion at the interface with the adherend. In addition, from the perspective of improving the uniformity of the appearance, the thickness homogeneity of the adhesive layer should be high, for example, the surface smoothness of the adhesive surface should be high. When the thickness of the high refractive index adherend is small (for example, less than 5µm, less than 4µm or less than 2µm), from the perspective of suppressing coloring or color unevenness caused by interference of reflected light, suppressing reflection at the interface is particularly meaningful. As an example of the usage, the following can be cited: in a polarizing plate with a phase difference layer having a polarizer, a first phase difference layer and a second phase difference layer in sequence, it can be used for bonding the polarizer and the first phase difference layer and/or bonding the first phase difference layer and the second phase difference layer.
又,在此揭示之黏著型光學薄膜因適於黏著劑層之高折射率化,故可適宜在貼附於光半導體等之發光層(例如主要為藉由無機材料構成之高折射的發光層)之態樣下來使用。藉由縮小發光層與黏著劑層之折射率差,可抑制在該等界面之反射,提升光擷取效率。可在所述態樣下使用之黏著型光學薄膜宜具備高折射率之黏著劑層。又,由可事先防止水分造成自發光元件劣化之觀點來看,黏著劑層之吸水率宜低。由提升亮度之觀點來看,黏著型光學薄膜宜為低著色。其由抑制黏著型光學薄膜造成之非刻意之著色之觀點來看亦有利。Furthermore, the adhesive optical film disclosed herein is suitable for increasing the refractive index of the adhesive layer, and therefore can be suitably used in a state of being attached to a luminescent layer of an optical semiconductor or the like (for example, a high-refractive luminescent layer mainly composed of inorganic materials). By reducing the refractive index difference between the luminescent layer and the adhesive layer, reflection at the interface can be suppressed, thereby improving light extraction efficiency. The adhesive optical film that can be used in the above state preferably has an adhesive layer with a high refractive index. Furthermore, from the perspective of being able to prevent the self-luminescent element from deteriorating due to moisture in advance, the water absorption rate of the adhesive layer should be low. From the perspective of improving brightness, the adhesive optical film should be low in coloration. It is also advantageous from the perspective of suppressing unintentional coloration caused by the adhesive optical film.
由本說明書揭示之黏著劑在作為相機或發光裝置等構成構件使用之微透鏡及其他透鏡構件(例如構成微透鏡陣列薄膜之微透鏡或相機用微透鏡等透鏡構件)中,可適宜作為覆蓋透鏡面之塗佈層、和與上述透鏡面相對向之構件(例如具有與透鏡面對應之表面形狀的構件)的接合層、充填於上述透鏡面與上述構件之間的充填層等來使用。在此揭示之黏著劑因適於高折射率化,故即使為高折射率之透鏡(例如藉由高折射率樹脂構成之透鏡、或具有高折射率樹脂製之表面層的透鏡),仍可減低與該透鏡之折射率差。此事由上述透鏡及具備有該透鏡之製品的薄型化之觀點來看是有利的,亦可有助於抑制像差或提升阿貝數。在此揭示之黏著劑亦可在例如充填於適當之透明構件之凹部或空隙之形態下,將其本身作為透鏡樹脂來利用。The adhesive disclosed in this specification can be suitably used as a coating layer covering the lens surface, a bonding layer for a component opposite to the lens surface (e.g., a component having a surface shape corresponding to the lens surface), a filling layer filled between the lens surface and the component, etc. in microlenses and other lens components (e.g., microlenses constituting a microlens array film or lens components such as a microlens for a camera) used as components of a camera or a light-emitting device. The adhesive disclosed herein is suitable for increasing the refractive index, so even if it is a lens with a high refractive index (for example, a lens made of a high refractive index resin, or a lens having a surface layer made of a high refractive index resin), the refractive index difference with the lens can be reduced. This is advantageous from the perspective of thinning the above-mentioned lens and the product having the lens, and can also help to suppress aberration or increase the Abbe number. The adhesive disclosed herein can also be used as a lens resin in the form of filling a concave portion or gap of an appropriate transparent component.
在此揭示之黏著型光學薄膜亦可視為黏著型光學構件。又,使用上述機能性薄膜作為在此揭示之黏著型光學薄膜之光透射性構件時,在此揭示之黏著型光學薄膜亦可視為在機能性薄膜之至少單面側具有在此揭示之黏著劑層的「黏著型機能性薄膜」。The adhesive optical film disclosed herein can also be regarded as an adhesive optical component. Furthermore, when the above-mentioned functional film is used as a light-transmitting component of the adhesive optical film disclosed herein, the adhesive optical film disclosed herein can also be regarded as an "adhesive functional film" having the adhesive layer disclosed herein on at least one side of the functional film.
由上述,根據在此揭示之技術,可提供一種具備在此揭示之黏著型光學薄膜的積層體。可貼附黏著型光學薄膜之構件可為具有上述被黏著體材料之折射率者。又,黏著型光學薄膜之折射率與構件之折射率的差(折射率差)可為上述被黏著體與黏著型光學薄膜之折射率差。關於構成積層體之構件,如以上述構件、材料、被黏著體所說明,故不反覆重複說明。From the above, according to the technology disclosed herein, a laminate having the adhesive optical film disclosed herein can be provided. The component to which the adhesive optical film can be attached can be a component having the refractive index of the material of the adherend described above. In addition, the difference between the refractive index of the adhesive optical film and the refractive index of the component (refractive index difference) can be the refractive index difference between the adherend described above and the adhesive optical film. The components constituting the laminate are as described above with respect to the components, materials, and adherend, and therefore will not be described repeatedly.
如從以上說明及以下實施例可理解,藉由本說明書揭示之事項中包含以下事項。 [1]一種黏著片,係包含黏著劑層者;且 其具有藉由上述黏著劑層構成之黏著面; 上述黏著劑層之折射率大於1.570,全光線透射率為86%以上,且霧度值為3.0%以下。 [2]如上述[1]之黏著片,其中上述黏著劑層之厚度為5µm以上。 [3]如上述[1]或[2]之黏著片,其黏著力為3N/25mm以上。 [4]如上述[1]~[3]中任一項之黏著片,其中上述黏著面之算術平均粗度Ra為100nm以下。 [5]如上述[1]~[4]中任一項之黏著片,其中上述黏著劑層之吸水率為1.0%以下。 [6]如上述[1]~[5]中任一項之黏著片,其係以包含上述黏著劑層與光透射性構件之積層體之形式構成。 [7]如上述[6]之黏著片,其中上述光透射性構件為樹脂薄膜。 [8]如上述[1]~[5]中任一項之黏著片,其係由上述黏著劑層構成之雙面接著性黏著片。 [9]一種附剝離襯墊之黏著片,包含: 如上述[1]~[8]中任一項之黏著片;與 配置於上述黏著片之黏著面上的剝離襯墊。 [91]一種黏著型光學薄膜,係包含光透射性構件與積層於該光透射性構件上之黏著劑層者;且 其具有藉由上述黏著劑層構成之黏著面; 上述黏著劑層之折射率大於1.570,全光線透射率為86%以上,且霧度值為3.0%以下。 [92]如上述[91]之黏著型光學薄膜,其中上述黏著劑層之厚度為5µm以上。 [93]如上述[91]或[92]之黏著型光學薄膜,其對玻璃板之剝離強度為3N/25mm以上。 [94]如上述[91]~[93]中任一項之黏著型光學薄膜,其中上述黏著面之算術平均粗度Ra為100nm以下。 [95]如上述[91]~[94]中任一項之黏著型光學薄膜,其中上述黏著劑層之吸水率為1.0%以下。 [96]如上述[91]~[95]中任一項記載之黏著型光學薄膜,其中上述光透射性構件為樹脂薄膜。 [97]如上述[91]~[96]中任一項之黏著型光學薄膜,其中上述光透射性構件係選自於由偏光板、保護薄膜及覆蓋窗構件所構成之群組。 [98]一種附剝離襯墊之黏著型光學薄膜,包含: 如上述[91]~[97]中任一項之黏著型光學薄膜;與 配置於上述黏著型光學薄膜之黏著面上的剝離襯墊。 [10]一種黏著劑組成物,係用以形成如上述[1]~[8]中任一項之黏著片的黏著劑層或如上述[91]~[97]中任一項之黏著型光學薄膜的黏著劑層。As can be understood from the above description and the following embodiments, the matters disclosed in this specification include the following matters. [1] An adhesive sheet comprising an adhesive layer; and It has an adhesive surface formed by the above adhesive layer; The refractive index of the above adhesive layer is greater than 1.570, the total light transmittance is greater than 86%, and the haze value is less than 3.0%. [2] An adhesive sheet as described in [1] above, wherein the thickness of the above adhesive layer is greater than 5µm. [3] An adhesive sheet as described in [1] or [2] above, wherein the adhesive force is greater than 3N/25mm. [4] An adhesive sheet as described in any one of [1] to [3] above, wherein the arithmetic average roughness Ra of the above adhesive surface is less than 100nm. [5] An adhesive sheet as described in any one of [1] to [4] above, wherein the water absorption rate of the adhesive layer is 1.0% or less. [6] An adhesive sheet as described in any one of [1] to [5] above, which is in the form of a laminate comprising the adhesive layer and a light-transmitting member. [7] An adhesive sheet as described in [6] above, wherein the light-transmitting member is a resin film. [8] An adhesive sheet as described in any one of [1] to [5] above, which is a double-sided adhesive sheet composed of the adhesive layer. [9] An adhesive sheet with a peel-off pad, comprising: The adhesive sheet as described in any one of [1] to [8] above; and A peel-off pad disposed on the adhesive surface of the adhesive sheet. [91] An adhesive optical film comprising a light-transmitting member and an adhesive layer laminated on the light-transmitting member; and it has an adhesive surface formed by the adhesive layer; the adhesive layer has a refractive index greater than 1.570, a total light transmittance of greater than 86%, and a haze value of less than 3.0%. [92] The adhesive optical film of [91], wherein the thickness of the adhesive layer is greater than 5µm. [93] The adhesive optical film of [91] or [92], wherein the peeling strength of the adhesive film against a glass plate is greater than 3N/25mm. [94] The adhesive optical film of any one of [91] to [93], wherein the arithmetic mean roughness Ra of the adhesive surface is less than 100nm. [95] An adhesive optical film as described in any one of [91] to [94] above, wherein the water absorption rate of the adhesive layer is less than 1.0%. [96] An adhesive optical film as described in any one of [91] to [95] above, wherein the light-transmitting component is a resin film. [97] An adhesive optical film as described in any one of [91] to [96] above, wherein the light-transmitting component is selected from the group consisting of a polarizing plate, a protective film and a cover window component. [98] An adhesive optical film with a peel-off pad, comprising: An adhesive optical film as described in any one of [91] to [97] above; and A peel-off pad disposed on the adhesive surface of the adhesive optical film. [10] An adhesive composition used to form an adhesive layer of an adhesive sheet as described in any one of [1] to [8] above or an adhesive layer of an adhesive optical film as described in any one of [91] to [97] above.
[11]一種黏著劑組成物,包含: 丙烯酸系聚合物(A),其包含含芳香環單體(m1)作為單體單元;與 添加劑(HRO ),其係折射率較上述丙烯酸系聚合物(A)更高之有機材料。 [12]如上述[11]之黏著劑組成物,其中上述添加劑(HRO )之折射率為1.60以上。 [13]如上述[11]或[12]之黏著劑組成物,其中上述添加劑(HRO )相對於上述丙烯酸系聚合物(A)100重量份之含量大於0重量份且在60重量份以下。 [14]如上述[11]~[13]中任一項之黏著劑組成物,其中上述添加劑(HRO )包含選自於由含芳香環化合物及含雜環化合物所構成群組中之至少1種化合物。 [15]如上述[11]~[14]中任一項之黏著劑組成物,其中上述添加劑(HRO )包含1分子內具有2個以上芳香環之化合物。 [16]如上述[15]之黏著劑組成物,其中上述添加劑(HRO )包含滿足下述至少一項之化合物作為上述1分子內具有2個以上芳香環之化合物: (i)包含2個非縮合芳香環直接化學鍵結之結構;及 (ii)包含2個芳香環已行縮合之結構。 [17]如上述[11]~[16]中任一項之黏著劑組成物,其中構成上述丙烯酸系聚合物(A)之單體成分中,上述含芳香環單體(m1)之含量為50重量%以上。 [18]如上述[11]~[17]中任一項之黏著劑組成物,其中構成上述丙烯酸系聚合物(A)之單體成分中,上述含芳香環單體(m1)之含量大於70重量%且小於100重量%,並且 上述含芳香環單體(m1)中50重量%以上為均聚物之玻璃轉移溫度在10℃以下之單體。 [19]如上述[11]~[18]中任一項之黏著劑組成物,其中構成上述丙烯酸系聚合物(A)之單體成分更含有單體(m2),該單體(m2)具有羥基及羧基中之至少一者。 [20]如上述[11]~[18]中任一項之黏著劑組成物,其係用以形成如上述[1]~[8]中任一項之黏著片的黏著劑層或如上述[91]~[97]中任一項之黏著型光學薄膜的黏著劑層。 [21]一種黏著劑,係由如上述[11]~[20]中任一項之黏著劑組成物形成,且折射率高於1.570。 [22]一種黏著片,包含藉由黏著劑所構成之黏著劑層,且該黏著劑係由如上述[11]~[20]中任一項之黏著劑組成物形成。 [23]如上述[22]之黏著片,其中上述黏著劑層之霧度值為1.0%以下。[11] An adhesive composition comprising: an acrylic polymer (A) comprising an aromatic ring-containing monomer (m1) as a monomer unit; and an additive (H RO ) which is an organic material having a higher refractive index than the acrylic polymer (A). [12] The adhesive composition of [11] above, wherein the refractive index of the additive (H RO ) is greater than 1.60. [13] The adhesive composition of [11] or [12] above, wherein the content of the additive (H RO ) relative to 100 parts by weight of the acrylic polymer (A) is greater than 0 parts by weight and less than 60 parts by weight. [14] The adhesive composition of any one of [11] to [13] above, wherein the additive (H RO ) comprises at least one compound selected from the group consisting of aromatic ring-containing compounds and heterocyclic ring-containing compounds. [15] The adhesive composition of any one of [11] to [14] above, wherein the additive (H RO ) comprises a compound having two or more aromatic rings in one molecule. [16] The adhesive composition of [15] above, wherein the additive (H RO ) comprises a compound satisfying at least one of the following as the compound having two or more aromatic rings in one molecule: (i) a structure comprising two non-condensed aromatic rings directly chemically bonded; and (ii) a structure comprising two condensed aromatic rings. [17] The adhesive composition as described in any one of the above [11] to [16], wherein the content of the above aromatic ring-containing monomer (m1) in the monomer components constituting the above acrylic polymer (A) is 50% by weight or more. [18] The adhesive composition as described in any one of the above [11] to [17], wherein the content of the above aromatic ring-containing monomer (m1) in the monomer components constituting the above acrylic polymer (A) is greater than 70% by weight and less than 100% by weight, and more than 50% by weight of the above aromatic ring-containing monomer (m1) is a monomer having a glass transition temperature of 10°C or less in the homopolymer. [19] An adhesive composition as described in any one of [11] to [18] above, wherein the monomer component constituting the acrylic polymer (A) further comprises a monomer (m2), wherein the monomer (m2) has at least one of a hydroxyl group and a carboxyl group. [20] An adhesive composition as described in any one of [11] to [18] above, which is used to form an adhesive layer of an adhesive sheet as described in any one of [1] to [8] above or an adhesive layer of an adhesive optical film as described in any one of [91] to [97] above. [21] An adhesive formed from an adhesive composition as described in any one of [11] to [20] above, and having a refractive index higher than 1.570. [22] An adhesive sheet comprising an adhesive layer formed by an adhesive, wherein the adhesive is formed by the adhesive composition as described in any one of [11] to [20]. [23] The adhesive sheet as described in [22], wherein the haze value of the adhesive layer is less than 1.0%.
[24]一種層間片,係在光學用途上配置於積層體之層間來使用者;並且 其包含折射率n1 為1.570以上之黏彈性層V1 ,且滿足: 全光線透射率為86%以上; 霧度值為1.0%以下;及 在25℃下之儲存彈性模數G'為30kPa~700kPa。 [25]如上述[24]之層間片,其厚度為5µm以上。 [26]如上述[24]或[25]之層間片,其中上述黏彈性層V1 包含主聚合物與分子量較上述主聚合物更低之塑化材料。 [27]如上述[26]之層間片,其中上述塑化材料之重量平均分子量為30000以下。 [28]如上述[24]~[27]中任一項之層間片,其更包含積層於上述黏彈性層V1 之黏彈性層V2 ,且 上述黏彈性層V2 在25℃下之儲存彈性模數G’V2 低於上述黏彈性層V1 在25℃下之儲存彈性模數G’V1 。 [29]如上述[28]之層間片,其中上述黏彈性層V2 之折射率n2 低於上述黏彈性層V1 之折射率n1 。 [30]如上述[24]~[29]中任一項之層間片,其中上述黏彈性層V1 係由如上述[11]~[18]中任一項之黏著劑組成物形成之層。 [31]如上述[24]~[29]中任一項之層間片,其中上述黏彈性層V1 係如上述[1]~[5]中任一項之黏著片中之黏著劑層。 [32]一種光學積層體,包含: 如上述[24]~[31]中任一項之層間片、與 積層於上述層間片之樹脂薄膜。 [33]一種附剝離襯墊之層間片,包含: 如上述[24]~[31]中任一項之層間片、與 覆蓋上述層間片之至少一表面的剝離襯墊。[24] A spacer for use between layers of a laminate for optical purposes; and comprising a viscoelastic layer V1 having a refractive index n1 of 1.570 or more, and satisfying: a total light transmittance of 86% or more; a haze value of 1.0% or less; and a storage elastic modulus G' of 30 kPa to 700 kPa at 25°C. [25] The spacer of [24], wherein the thickness is 5 µm or more. [26] The spacer of [24] or [25], wherein the viscoelastic layer V1 comprises a main polymer and a plasticizer having a molecular weight lower than that of the main polymer. [27] The spacer of [26], wherein the weight average molecular weight of the plasticizer is 30,000 or less. [28] The interlayer spacer as described in any one of [24] to [27], further comprising a viscoelastic layer V2 laminated on the viscoelastic layer V1 , wherein the storage elastic modulus G'V2 of the viscoelastic layer V2 at 25°C is lower than the storage elastic modulus G'V1 of the viscoelastic layer V1 at 25°C. [ 29 ] The interlayer spacer as described in [28], wherein the refractive index n2 of the viscoelastic layer V2 is lower than the refractive index n1 of the viscoelastic layer V1 . [30] A layer spacer as described in any one of [24] to [29] above, wherein the viscoelastic layer V1 is a layer formed by the adhesive composition as described in any one of [11] to [18] above. [31] A layer spacer as described in any one of [24] to [29] above, wherein the viscoelastic layer V1 is an adhesive layer in the adhesive sheet as described in any one of [1] to [5] above. [32] An optical laminate comprising: a layer spacer as described in any one of [24] to [31] above, and a resin film laminated on the layer spacer. [33] A layer spacer with a peel-off liner, comprising: a layer spacer as described in any one of [24] to [31] above, and a peel-off liner covering at least one surface of the layer spacer.
實施例 以下,說明數個與本發明相關聯之實驗例。此外,以下說明中,表示使用量或含量之「份」及「%」在未特別說明下為重量基準。Examples The following describes several experimental examples related to the present invention. In addition, in the following description, "parts" and "%" indicating the amount or content are based on weight unless otherwise specified.
<例1>
(丙烯酸系聚合物溶液之調製)
於具備攪拌葉片、溫度計、氮氣導入管及冷卻器之四口燒瓶中,饋入作為單體成分之間苯氧基苄基丙烯酸酯(共榮社化學股份公司製,商品名「LIGHT ACRYLATE POB-A」,折射率:1.566,均聚物之Tg:-35℃;以下簡稱為「POB-A」)99份及丙烯酸4-羥丁酯(4HBA)1份、作為聚合引發劑之2,2'-偶氮雙異丁腈(AIBN)0.2份、及作為聚合溶劑之甲苯100份,一邊緩慢地攪拌一邊導入氮氣,並將燒瓶內之液溫保持在60℃附近進行6小時聚合反應,調製出丙烯酸系聚合物A1之溶液(50%)。上述丙烯酸系聚合物A1中,根據上述單體成分之組成的Tg(即TgT
)為-35℃,而根據含芳香環單體之組成的Tg(即Tgm1
)為-35℃。<Example 1> (Preparation of acrylic polymer solution) m-phenoxybenzyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LIGHT ACRYLATE POB-A", refractive index: 1.566, homopolymer Tg: -35°C; hereinafter referred to as "POB-A") 99 parts and 4-hydroxybutyl acrylate (4HBA) 1 part, 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator 0.2 parts, and
(黏著劑組成物之調製) 將上述丙烯酸系聚合物A1之溶液(50%)用乙酸乙酯稀釋成30%,並於該溶液334份(非揮發成分100份)中添加作為交聯劑之六亞甲基二異氰酸酯的三聚異氰酸酯體(Tosoh公司製,商品名「Coronate HX」,3官能異氰酸酯化合物)之1%乙酸乙酯溶液10份(非揮發成分0.1份)、作為交聯延遲劑之乙醯丙酮2份、作為交聯觸媒之乙醯丙酮鐵(III)之1%乙酸乙酯溶液1份(非揮發成分0.01份)並攪拌混合,調製出丙烯酸系黏著劑組成物C1。(Preparation of adhesive composition) The solution (50%) of the acrylic polymer A1 was diluted to 30% with ethyl acetate, and 10 parts (0.1 parts of non-volatile components) of a 1% ethyl acetate solution of a triisocyanate of hexamethylene diisocyanate (manufactured by Tosoh, trade name "Coronate HX", a trifunctional isocyanate compound) as a crosslinking agent, 2 parts of acetylacetone as a crosslinking delay agent, and 1 part (0.01 parts of non-volatile components) of a 1% ethyl acetate solution of iron (III) acetylacetonate as a crosslinking catalyst were added to 334 parts of the solution (100 parts of non-volatile components) and stirred to prepare an acrylic adhesive composition C1.
(黏著片之製作) 將上述調製出之丙烯酸系黏著劑組成物C1塗佈於單面經聚矽氧處理過之聚對苯二甲酸乙二酯(PET)薄膜R1(厚度50µm,聚矽氧處理面的算術平均粗度Ra 21nm,最大高度Rz 233nm)的聚矽氧處理面上,在130℃下加熱2分鐘,形成厚度20µm之黏著劑層。接著,於上述黏著劑層之表面(第1黏著面)貼合單面經聚矽氧處理過之PET薄膜R2(厚度25µm,聚矽氧處理面之算術平均粗度Ra 15nm,最大高度Rz 180nm)的聚矽氧處理面上。依上述方式而獲得由上述黏著劑層構成之無基材之雙面黏著片S1。黏著片S1之兩面受到PET薄膜(剝離襯墊)R1、R2保護。相較於保護第2黏著面之剝離襯墊R1(塗佈黏著劑組成物之剝離襯墊),貼合於第1黏著面之剝離襯墊R2相對上為輕剝離。(Adhesive sheet preparation) The acrylic adhesive composition C1 prepared above was applied to the silicone-treated surface of a single-sided polyethylene terephthalate (PET) film R1 (thickness 50µm, arithmetic average roughness Ra of the silicone-treated surface 21nm, maximum height Rz 233nm), and heated at 130°C for 2 minutes to form an adhesive layer with a thickness of 20µm. Then, a silicone-treated surface of a single-sided PET film R2 (thickness 25µm, arithmetic average roughness Ra of the silicone-treated surface 15nm, maximum height Rz 180nm) was attached to the surface of the adhesive layer (first adhesive surface). According to the above method, a double-sided adhesive sheet S1 without a substrate composed of the above adhesive layer is obtained. Both sides of the adhesive sheet S1 are protected by PET films (peel-off pads) R1 and R2. Compared with the peel-off pad R1 (peel-off pad coated with the adhesive composition) protecting the second adhesive surface, the peel-off pad R2 attached to the first adhesive surface is relatively easy to peel off.
<例2~3、7~8、10~14> 除了將單體成分之組成如表1所示進行變更外,以與例1中之丙烯酸系聚合物溶液之調製相同方式,調製出各例之丙烯酸系聚合物A2~3、7~8、10~14之溶液。 除了分別使用上述各例之丙烯酸系聚合物之溶液來取代丙烯酸系聚合物A1之溶液外,以與例1中之黏著劑組成物之調製相同方式,調製出各例之丙烯酸系黏著劑組成物C2~3、7~8、10~14。 分別使用上述各例之丙烯酸系黏著劑組成物來取代丙烯酸系黏著劑組成物C1,並將黏著劑層之厚度設定成如表1所示,除此之外以與例1中之黏著片之製作相同方式,製作出各例之黏著片(由黏著劑層構成之無基材之雙面黏著片)S2~3、7~8、10~14。 此外,於表1所示單體成分之組成中,「NMT-A」表示丙烯酸1-萘甲酯(共榮社化學股份公司製,商品名「LIGHT ACRYLATE NMT-A」,折射率:1.595,均聚物之Tg:31℃),HEA表示丙烯酸2-羥乙酯,BA表示丙烯酸正丁酯,2EHA表示丙烯酸2-乙基己酯。<Examples 2~3, 7~8, 10~14> Except changing the composition of the monomer components as shown in Table 1, the acrylic polymer solutions A2~3, 7~8, 10~14 of each example were prepared in the same manner as the preparation of the acrylic polymer solution in Example 1. Except using the acrylic polymer solutions of the above examples to replace the acrylic polymer A1 solution, the acrylic adhesive compositions C2~3, 7~8, 10~14 of each example were prepared in the same manner as the preparation of the adhesive composition in Example 1. The acrylic adhesive composition of each example was used to replace the acrylic adhesive composition C1, and the thickness of the adhesive layer was set as shown in Table 1. In addition, the adhesive sheets (double-sided adhesive sheets without substrate composed of adhesive layers) S2~3, 7~8, 10~14 of each example were prepared in the same manner as the adhesive sheet in Example 1. In addition, in the composition of the monomer components shown in Table 1, "NMT-A" represents 1-naphthyl acrylate (produced by Kyoeisha Chemical Co., Ltd., trade name "LIGHT ACRYLATE NMT-A", refractive index: 1.595, homopolymer Tg: 31°C), HEA represents 2-hydroxyethyl acrylate, BA represents n-butyl acrylate, and 2EHA represents 2-ethylhexyl acrylate.
<例4> 將例3調製出之丙烯酸系聚合物A3之溶液(50%)用乙酸乙酯稀釋成30%,並於該溶液334份(非揮發成分100份)中添加作為添加劑(HRO )之6-丙烯醯氧基甲基二萘并噻吩(SUGAI化學工業股份公司製之二萘并噻吩-6-甲基丙烯酸酯體,商品名「6MDNTA」,折射率1.75)5份、作為交聯劑之六亞甲基二異氰酸酯的三聚異氰酸酯體(Tosoh公司製,商品名「Coronate HX」,3官能異氰酸酯化合物)之1%乙酸乙酯溶液10份(非揮發成分0.1份)、作為交聯延遲劑之乙醯丙酮2份、作為交聯觸媒之乙醯丙酮鐵(III)之1%乙酸乙酯溶液1份(非揮發成分0.01份)並攪拌混合,調製出丙烯酸系黏著劑組成物C4。 使用丙烯酸系黏著劑組成物C4來取代丙烯酸系黏著劑組成物C1,並將黏著劑層之厚度設定成25µm,除此之外以與例1中之黏著片之製作相同方式,製作出本例之黏著片(由黏著劑層構成之無基材之雙面黏著片)S4。<Example 4> The solution (50%) of the acrylic polymer A3 prepared in Example 3 was diluted to 30% with ethyl acetate, and 5 parts of 6-acryloyloxymethyl dinaphthothiophene (6-naphthothiophene-6-methylacrylate manufactured by SUGAI Chemical Industry Co., Ltd., trade name "6MDNTA", refractive index 1.75) as an additive (H RO ), 334 parts of the solution (100 parts of non-volatile components) and 10 parts of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "Coronate HX", a trifunctional isocyanate compound) in 1% ethyl acetate solution (0.1 part of non-volatile component), 2 parts of acetylacetone as a crosslinking delayer, and 1 part of 1% ethyl acetate solution of iron (III) acetylacetonate as a crosslinking catalyst (0.01 part of non-volatile component) were stirred and mixed to prepare an acrylic adhesive composition C4. The acrylic adhesive composition C4 was used to replace the acrylic adhesive composition C1, and the thickness of the adhesive layer was set to 25μm. Except that, the adhesive sheet of this example (a double-sided adhesive sheet without a substrate composed of an adhesive layer) S4 was prepared in the same manner as the adhesive sheet in Example 1.
<例5~6> 除了將添加劑((HRO )之種類與相對於丙烯酸系聚合物100份之使用量(phr;per hundred resin)如表1所示進行變更外,以與例4中之丙烯酸系黏著劑組成物C4之調製相同方式,調製出例5、6之丙烯酸系黏著劑組成物C5、C6。在此,表1中之「BPFL」表示9,9-雙(4-羥苯基)茀(Osaka Gas Chemicals Co., Ltd.製,折射率1.68),「BAFL」表示9,9-雙(4-胺基苯基)茀(Osaka Gas Chemicals Co., Ltd.製,折射率1.73)。 除了分別使用丙烯酸系黏著劑組成物C5、C6來取代丙烯酸系黏著劑組成物C4外,以與例4中之黏著片之製作相同方式,製作出例5、6之黏著片(由黏著劑層構成之無基材之雙面黏著片)。<Examples 5-6> Except that the type of additive (H RO ) and the amount used relative to 100 parts of acrylic polymer (phr; per hundred resin) were changed as shown in Table 1, the acrylic adhesive composition C5 and C6 of Examples 5 and 6 were prepared in the same manner as the preparation of the acrylic adhesive composition C4 in Example 4. Here, "BPFL" in Table 1 represents 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Osaka Gas Chemicals Co., Ltd., refractive index 1.68), and "BAFL" represents 9,9-bis(4-aminophenyl)fluorene (manufactured by Osaka Gas Chemicals Co., Ltd., refractive index 1.73). The adhesive sheets of Examples 5 and 6 (double-sided adhesive sheets without a substrate composed of an adhesive layer) were prepared in the same manner as the adhesive sheet of Example 4, except that acrylic adhesive compositions C5 and C6 were used instead of acrylic adhesive composition C4.
<例9> 將例8調製出之丙烯酸系聚合物A8之溶液(50%)用乙酸乙酯稀釋成30%,並於該溶液334份(非揮發成分100份)中添加作為添加劑(HRO )之BPFL 10份、作為交聯劑之六亞甲基二異氰酸酯的三聚異氰酸酯體(Tosoh公司製,商品名「Coronate HX」,3官能異氰酸酯化合物)之1%乙酸乙酯溶液10份(非揮發成分0.1份)、作為交聯延遲劑之乙醯丙酮2份、作為交聯觸媒之乙醯丙酮鐵(III)之1%乙酸乙酯溶液1份(非揮發成分0.01份)並攪拌混合,調製出丙烯酸系黏著劑組成物C9。 除了使用丙烯酸系黏著劑組成物C9來取代丙烯酸系黏著劑組成物C8外,以與例8中之黏著片之製作相同方式,製作出本例之黏著片(由黏著劑層構成之無基材之雙面黏著片)S9。<Example 9> The solution (50%) of the acrylic polymer A8 prepared in Example 8 was diluted to 30% with ethyl acetate, and 10 parts of BPFL as an additive (H RO ), 10 parts of a 1% ethyl acetate solution of a triisocyanate of hexamethylene diisocyanate (manufactured by Tosoh, trade name "Coronate HX", a trifunctional isocyanate compound) as a crosslinking agent (0.1 parts of a non-volatile component), 2 parts of acetylacetone as a crosslinking retarder, and 1 part of a 1% ethyl acetate solution of iron (III) acetylacetonate (0.01 parts of a non-volatile component) as a crosslinking catalyst were added to 334 parts of the solution (100 parts of a non-volatile component) and stirred to prepare an acrylic adhesive composition C9. The adhesive sheet (a double-sided adhesive sheet without a substrate composed of an adhesive layer) S9 of this example was prepared in the same manner as the adhesive sheet in Example 8, except that the acrylic adhesive composition C9 was used instead of the acrylic adhesive composition C8.
<例15>
除了將單體成分之組成進行變更,而將丙烯酸2-乙基己酯(2EHA)變更為90份、將4HBA變更為10份外,以與例1中之丙烯酸系聚合物溶液之調製相同方式,調製出丙烯酸系聚合物A14之溶液(40%)。
將上述丙烯酸系聚合物A14之溶液(40%)用乙酸乙酯稀釋成20%,並於該溶液500份(非揮發成分100份)中添加以固體成分基準計10份之氧化鋯粒子分散液、作為交聯劑之六亞甲基二異氰酸酯的三聚異氰酸酯體(Tosoh公司製,商品名「Coronate HX」,3官能異氰酸酯化合物)之1%乙酸乙酯溶液10份(非揮發成分0.1份)、作為交聯延遲劑之乙醯丙酮2份、作為交聯觸媒之乙醯丙酮鐵(III)之1%乙酸乙酯溶液1份(非揮發成分0.01份)並攪拌混合,調製出丙烯酸系黏著劑組成物C15。上述氧化鋯粒子分散液係使用使已施行表面處理之氧化鋯粒子(平均粒徑20nm,固體成分折射率:1.64,表面處理:羧酸系/磷酸系疏水化處理,共榮社化學股份公司製)分散於丙二醇單甲基醚(PGME)中的表面處理氧化鋯粒子分散液。
除了使用丙烯酸系黏著劑組成物C15來取代丙烯酸系黏著劑組成物C14外,以與例14中之黏著片之製作相同方式,製作出例15之黏著片(由黏著劑層構成之無基材之雙面黏著片)S15。<Example 15>
Except that the composition of the monomer components was changed, 2-ethylhexyl acrylate (2EHA) was changed to 90 parts, and 4HBA was changed to 10 parts, the acrylic polymer A14 solution (40%) was prepared in the same manner as the acrylic polymer solution in Example 1.
The solution (40%) of the acrylic polymer A14 was diluted to 20% with ethyl acetate, and 10 parts of a zirconia particle dispersion based on solid content, 10 parts of a 1% ethyl acetate solution of a triisocyanate of hexamethylene diisocyanate (manufactured by Tosoh, trade name "Coronate HX", a trifunctional isocyanate compound) as a crosslinking agent (0.1 parts of non-volatile components), 2 parts of acetylacetone as a crosslinking retarder, and 1 part of a 1% ethyl acetate solution of iron (III) acetylacetonate as a crosslinking catalyst (0.01 parts of non-volatile components) were added to 500 parts of the solution (100 parts of non-volatile components) and stirred to prepare an acrylic adhesive composition C15. The above-mentioned zirconia particle dispersion is a surface-treated zirconia particle dispersion in which surface-treated zirconia particles (
使所得黏著片充分適應23℃、50%RH之環境後,用於下述測定及評估。The obtained adhesive sheet was fully acclimatized to an environment of 23°C and 50%RH before being used for the following measurements and evaluations.
<測定及評估(1)> (折射率) 針對各例之黏著劑層(無基材之雙面黏著片),使用阿貝折射計(ATAGO CO., LTD.製,型式「DR-M4」)在測定波長589nm、測定溫度25℃之條件下測定折射率。將結果列於表1。<Measurement and evaluation (1)> (Refractive index) For each adhesive layer (double-sided adhesive sheet without substrate), the refractive index was measured using an Abbe refractometer (manufactured by ATAGO CO., LTD., model "DR-M4") at a measurement wavelength of 589 nm and a measurement temperature of 25°C. The results are listed in Table 1.
(全光線透射率及霧度值) 使用已將各例之黏著劑層貼合於無鹼玻璃(厚度0.8~1.0mm,全光線透射率92%,霧度0.4%)上之試驗片,用霧度計(村上色彩技術研究所製,商品名「HAZEMETER HM-150」,在23℃之測定環境下測定上述試驗片之全光線透射率及霧度。將從測定值減去上述無鹼玻璃之全光線透射率及霧度後之值作為黏著劑層之全光線透射率及霧度值。將結果列於表1。(Total light transmittance and haze value) The total light transmittance and haze of the test piece with the adhesive layer of each example bonded to the alkali-free glass (thickness 0.8~1.0mm, total light transmittance 92%, haze 0.4%) were measured using a haze meter (made by Murakami Color Technology Laboratory, trade name "HAZEMETER HM-150") at 23°C. The total light transmittance and haze of the adhesive layer were obtained by subtracting the total light transmittance and haze of the alkali-free glass from the measured values. The results are listed in Table 1.
(吸水率) 藉由上述方法測定各例之黏著劑之吸水率。將結果列於表1。(Water absorption) The water absorption of each adhesive was measured by the above method. The results are listed in Table 1.
此外,以上述方法測定各例之黏著劑層之儲存彈性模數G'(25)後,確認了在例1~14中皆為350kPa以下。另一方面,藉由摻合高折射率之無機粒子來提升折射率之例15的黏著劑層,其儲存彈性模數G'(25)高達750kPa,為缺乏柔軟性及黏著性者。Furthermore, the storage modulus G'(25) of the adhesive layer of each example was measured by the above method, and it was confirmed that the storage modulus G'(25) was less than 350 kPa in Examples 1 to 14. On the other hand, the storage modulus G'(25) of the adhesive layer of Example 15, in which the refractive index was increased by mixing high refractive index inorganic particles, was as high as 750 kPa, which was poor in flexibility and adhesion.
[表1] [Table 1]
<例16> 除了以可形成厚度5µm之黏著劑層之方式調節丙烯酸系黏著劑組成物C3之塗佈量外,以與例3之無基材之雙面黏著片S3之製作相同方式,而獲得本例之無基材之雙面黏著片S16。<Example 16> Except that the coating amount of the acrylic adhesive composition C3 is adjusted in such a way that a 5µm thick adhesive layer can be formed, the substrate-free double-sided adhesive sheet S16 of this example is obtained in the same manner as the substrate-free double-sided adhesive sheet S3 of Example 3.
<測定及評估(2)> 針對數個上述做成之黏著片,進一步進行以下測定及評估。將結果列於表2。<Measurement and evaluation (2)> The following measurements and evaluations were further performed on several of the adhesive sheets prepared above. The results are listed in Table 2.
(黏著面之算術平均粗度(Ra)及最大高度(Rz)) 將各例之無基材之雙面黏著片連同保護第1、第2黏著面之剝離襯墊R1、R2裁切成長度150mm、寬度50mm之尺寸,而製作出測定用試樣。將該測定用試樣之剝離襯墊R1側固定於試驗板,使用拉伸試驗機(裝置名「Autograph AG-IS」,島津製作所製),在23℃、50%RH之氣體環境下,以拉伸速度300mm/分鐘、剝離角度180°之條件,從上述測定用試樣的第1黏著面剝除剝離襯墊R2,使第1黏著面露出。靜置30分鐘後,針對上述第1黏著面,使用3維光學輪廓儀(商品名「NewView7300」,ZYGO公司製),在23℃、50%RH之環境下測定表面形狀。從測得之資料依循JIS B 0601-2001算出算術表面粗度Ra。 又,最大高度(Rz)係針對藉由上述測定所得資料(粗度曲線),求出自該粗度曲線之平均線至上側最高之頂部之高度Rp與自上述平均線至下側最深之谷部之深度Rv的和。測定條件如下。 進行5次Ra及Rz之測定(亦即N=5),並採用該等之平均值。 [測定條件] 測定面積:5.62mm×4.22mm (物鏡:2.5倍,內部透鏡:0.5倍) 解析模式: Remove:Cylinder Data Fill:ON(Max:25) Remove Spikes:ON (xRMS:1) Filter:OFF(Arithmetic mean roughness (Ra) and maximum height (Rz) of adhesive surface) The double-sided adhesive sheet without substrate of each example was cut into a size of 150 mm in length and 50 mm in width together with the peel-off pads R1 and R2 protecting the first and second adhesive surfaces to produce a test sample. The peel-off pad R1 side of the test sample was fixed to the test plate, and the peel-off pad R2 was peeled off from the first adhesive surface of the test sample using a tensile tester (device name "Autograph AG-IS", manufactured by Shimadzu Corporation) in a gas environment of 23°C and 50%RH at a tensile speed of 300 mm/min and a peeling angle of 180° to expose the first adhesive surface. After standing for 30 minutes, the surface shape of the first adhesive surface was measured using a 3D optical profiler (trade name "NewView7300", manufactured by ZYGO) at 23°C and 50% RH. The arithmetic surface roughness Ra was calculated from the measured data in accordance with JIS B 0601-2001. In addition, the maximum height (Rz) is the sum of the height Rp from the average line of the roughness curve to the highest top on the upper side and the depth Rv from the average line to the deepest valley on the lower side for the data obtained by the above measurement (roughness curve). The measurement conditions are as follows. Ra and Rz were measured 5 times (i.e. N=5), and the average value was adopted. [Measurement conditions] Measurement area: 5.62mm×4.22mm (Objective lens: 2.5x, Internal lens: 0.5x) Analysis mode: Remove: Cylinder Data Fill: ON (Max: 25) Remove Spikes: ON (xRMS: 1) Filter: OFF
(光學應變) 準備對素板玻璃以鍍銀製法製作出之市售鏡件(厚度2mm),以肉眼進行確認且使用經確認以鏡件單體利用與後述記載相同之手法使反射像投影至屏幕後無應變者。在無塵室內,將上述鏡件之表面以乾淨的布擦拭去除異物等後,從各例之無基材之雙面黏著片剝除剝離薄膜R2使第1黏著面露出,並以不使異物或氣泡、變形的條痕進入之方式施加適當之張力貼附於上述鏡件之表面,且為了去除微小氣泡之影響,利用加壓脫泡裝置(高壓釜)進行了脫泡處理(處理條件:50℃,0.5MPa、30分鐘)。在室溫下放冷30分鐘以上後,剝除剝離薄膜R1使第2黏著面露出,藉此製作出光學應變評估試樣(由黏著片及鏡件構成之積層體)。使上述評估試樣之黏著片側朝向點光源側,並以使相對於來自上述點光源之光線的角度成為約45度之方式來配置。在光線之前端設置白色屏幕,映入反射之影像。點光源可使用濱松光子學公司製之商品名「氙氣燈C2577」或等效品,而在此次之實驗中係使用上述商品名「氙氣燈C2577」。點光源、評估試樣及螢幕係以使評估試樣與點光源為止之距離、及評估試樣與螢幕為止之距離分別成為約50cm之位置之方式配置。 點亮上述點光源,以肉眼觀察在上述試樣反射而投影至上述螢幕之影像,按以下3個水準來評估有無光學應變及程度。 E:未觀察到光學應變。 A:雖然觀察到些許光學應變,但為實用上可容許之程度。 P:觀察到明顯之光學應變。(Optical strain) A commercially available mirror (2 mm thick) made by silver plating plain glass was prepared, and confirmed with the naked eye and used after the reflected image was projected onto a screen using the same method as described below. In a clean room, the surface of the mirror was wiped with a clean cloth to remove foreign matter, etc., and then the peeling film R2 was peeled off from the double-sided adhesive sheet without a substrate in each example to expose the first adhesive surface, and then the surface of the mirror was attached with appropriate tension in a manner that prevented foreign matter, bubbles, or deformation streaks from entering. In order to remove the influence of micro bubbles, a degassing treatment was performed using a pressurized degassing device (autoclave) (treatment conditions: 50°C, 0.5MPa, 30 minutes). After cooling at room temperature for more than 30 minutes, peel off the release film R1 to expose the second adhesive surface, thereby making an optical strain evaluation sample (a laminate consisting of an adhesive sheet and a mirror). The adhesive sheet side of the above evaluation sample is oriented toward the point light source side, and is configured so that the angle relative to the light from the above point light source is about 45 degrees. A white screen is set in front of the light to reflect the reflected image. The point light source can use the product name "Xenon Lamp C2577" manufactured by Hamamatsu Photonics Co., Ltd. or an equivalent product, and in this experiment, the above product name "Xenon Lamp C2577" is used. The point light source, the evaluation sample, and the screen are arranged so that the distance between the evaluation sample and the point light source and the distance between the evaluation sample and the screen are respectively about 50 cm. The above point light source is lit, and the image reflected by the above sample and projected onto the above screen is observed with the naked eye, and the presence and degree of optical strain are evaluated according to the following three levels. E: No optical strain is observed. A: Although some optical strain is observed, it is to a practically acceptable degree. P: Obvious optical strain is observed.
(對玻璃板剝離強度) 在23℃、50%RH之測定環境下,從黏著片之一面剝離剝離襯墊,並貼合厚度50µm之PET薄膜進行襯底後,裁切成寬度25mm、長度100mm之尺寸做成試驗片。從試驗片剝離另一面之剝離襯墊,使2kg之滾筒於作為被黏著體之鹼玻璃板(松浪硝子工業公司製,厚度1.35mm,青板磨砂品)的表面進行1往復來壓接。將其放置於該環境下30分鐘,接著投入加壓脫泡裝置(高壓釜)中,在溫度50℃、壓力0.5MPa之條件下進行30分鐘高壓釜處理,再於23℃、50%RH之氣體環境下放置24小時後,使用萬能拉伸壓縮試驗機,依循JIS Z 0237:2000,在拉伸速度300mm/分鐘、剝離角度180度之條件下測定剝離強度(黏著力)[N/25mm]。萬能拉伸壓縮試驗機係使用美蓓亞公司製之「拉伸壓縮試驗機,TG-1kN」。(Peel strength on glass plate) Under the test environment of 23℃ and 50%RH, peel off the peeling pad from one side of the adhesive sheet, and after laminating with a 50µm thick PET film as a backing, cut into a test piece with a width of 25mm and a length of 100mm. Peel off the peeling pad on the other side of the test piece, and press the surface of the alkaline glass plate (made by Matsunami Glass Industry Co., Ltd., thickness 1.35mm, blue plate frosted product) as the adherend with a 2kg roller for 1 reciprocating press. It was placed in this environment for 30 minutes, then placed in a pressurized degassing device (autoclave) for 30 minutes at a temperature of 50°C and a pressure of 0.5MPa. After being placed in a gas environment of 23°C and 50%RH for 24 hours, the peel strength (adhesion) [N/25mm] was measured using a universal tensile compression tester in accordance with JIS Z 0237:2000 at a tensile speed of 300mm/min and a peeling angle of 180 degrees. The universal tensile compression tester used was a "tensile compression tester, TG-1kN" manufactured by Minebea Corporation.
[表2] [Table 2]
表1、2中所示例1~13、16之黏著片顯示大於1.570之高折射率且展現高透明性。又,如表2所示,顯示作為黏著劑實用之剝離強度,且表面平滑性亦佳。關於使用相同黏著劑組成物之例3與例16之對比,在例16中獲得了在光學應變之評估中更良好的結果。另,表2中雖未顯示,但例16之吸水率為0.2%。藉由將該等黏著片(無基材之黏著片)貼合於任意光透射性構件,可輕易製作以下黏著型光學薄膜:其於光透射性構件上具有黏著劑層,該黏著劑層之折射率大於1.570,全光線透射率為86%以上,且霧度值為3.0%以下。The adhesive sheets of Examples 1 to 13 and 16 shown in Tables 1 and 2 show a high refractive index greater than 1.570 and exhibit high transparency. Also, as shown in Table 2, they show a peel strength that is practical as an adhesive and also have good surface smoothness. In comparison between Example 3 and Example 16 using the same adhesive composition, Example 16 obtained a better result in the evaluation of optical strain. In addition, although not shown in Table 2, the water absorption rate of Example 16 is 0.2%. By bonding such adhesive sheets (adhesive sheets without a substrate) to any light-transmitting component, the following adhesive optical film can be easily produced: it has an adhesive layer on the light-transmitting component, the refractive index of the adhesive layer is greater than 1.570, the total light transmittance is greater than 86%, and the haze value is less than 3.0%.
另一方面,相較於例1~13,藉由摻混高折射率之無機粒子來提升折射率之例15明顯透明性較差(尤其霧度顯著較高),且如表2所示,表面平滑性亦低,還觀察到明顯之光學應變,且未顯示適於作為黏著劑之實用的黏著性能(剝離強度)。On the other hand, compared with Examples 1 to 13, Example 15, in which the refractive index is increased by mixing high-refractive-index inorganic particles, has significantly poorer transparency (especially significantly higher haze), and as shown in Table 2, the surface smoothness is also low, obvious optical strain is also observed, and practical adhesive properties (peeling strength) suitable for use as an adhesive are not shown.
<例17、18、23> 除了將單體成分之組成設定成如表3所示外,以與例1相同方式,調製出例17、18、23之各例之丙烯酸系聚合物之溶液,而調製出丙烯酸系黏著劑組成物。分別使用各例之丙烯酸系黏著劑組成物來取代丙烯酸系黏著劑組成物C1,並將黏著劑層之厚度設定成25µm,除此之外以與例1中之黏著片之製作相同方式,製作出各例之黏著片。<Examples 17, 18, 23> Except that the monomer components are set as shown in Table 3, the acrylic polymer solutions of Examples 17, 18, and 23 are prepared in the same manner as Example 1 to prepare acrylic adhesive compositions. The acrylic adhesive composition of each example is used to replace the acrylic adhesive composition C1, and the thickness of the adhesive layer is set to 25µm. Other than that, the adhesive sheets of each example are prepared in the same manner as the adhesive sheet in Example 1.
此外,於表3所示單體成分之組成中,「BZA」表示丙烯酸苄酯(大阪有機化學工業股份公司製,商品名「Viscoat #160」,折射率(nD20):1.519,均聚物之Tg:6℃),「PEA」表示丙烯酸苯氧乙酯(大阪有機化學工業股份公司製,商品名「Viscoat #192」,折射率(nD20):1.517,均聚物之Tg:2℃),「P2H-A」表示苯氧基二乙二醇丙烯酸酯(共榮社化學股份公司製,商品名「LIGHT ACRYLATE P2H-A」,折射率:1.510,均聚物之Tg:-35℃),HEMA表示甲基丙烯酸2-羥乙酯,CBA表示乙基卡必醇丙烯酸酯。In addition, in the composition of monomer components shown in Table 3, "BZA" represents benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #160", refractive index (nD20): 1.519, homopolymer Tg: 6°C), "PEA" represents phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #192", refractive index (nD20): 1.517, homopolymer Tg: 2°C), "P2H-A" represents phenoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LIGHT ACRYLATE P2H-A", refractive index: 1.510, homopolymer Tg: -35°C), HEMA represents 2-hydroxyethyl methacrylate, and CBA represents ethyl carbitol acrylate.
<例19> 除了將單體成分之組成設定成如表3所示外,以與例1相同方式,調製出本例之丙烯酸系聚合物A19之溶液。使用丙烯酸系聚合物A19之溶液來取代丙烯酸系聚合物A3之溶液,並使用2,12-二烯丙基氧基二萘并噻吩(SUGAI化學工業股份公司製,縮寫:2,12-DAODNT,折射率:1.729)10phr作為添加劑(HRO ),除此以外以與例4相同方式,調製出本例之丙烯酸系黏著劑組成物,而製作出黏著片。<Example 19> In the same manner as in Example 1, except that the composition of the monomer components was set as shown in Table 3, a solution of acrylic polymer A19 of this example was prepared. The acrylic polymer A19 solution was used instead of the acrylic polymer A3 solution, and 10 phr of 2,12-diallyloxy dinaphthothiophene (manufactured by SUGAI Chemical Industry Co., Ltd., abbreviation: 2,12-DAODNT, refractive index: 1.729) was used as an additive (H RO ), and the acrylic adhesive composition of this example was prepared in the same manner as in Example 4 to produce an adhesive sheet.
<例20~22> 除了將單體成分之組成設定成如表3所示外,以與例1相同方式,調製出例20~22之各例之丙烯酸系聚合物之溶液。使用各例之丙烯酸系聚合物之溶液來取代丙烯酸系聚合物A3之溶液,並使用6-乙基丙烯酸酯-二萘并[2,1-b:1’,2’-d]噻吩(SUGAI化學工業股份公司製之6-丙烯醯氧基乙基二萘并噻吩,縮寫:6EDNTA,折射率:1.722)20phr作為添加劑(HRO ),除此以外以與例4相同方式,調製出本例之丙烯酸系黏著劑組成物,而製作出黏著片。<Examples 20-22> Except that the composition of the monomer components was set as shown in Table 3, the acrylic polymer solution of each example of Examples 20-22 was prepared in the same manner as Example 1. The acrylic polymer solution of each example was used instead of the acrylic polymer A3 solution, and 20 phr of 6-ethylacrylate-dinaphtho[2,1-b:1',2'-d]thiophene (6-acryloyloxyethyldinaphthothiophene manufactured by SUGAI Chemical Industry Co., Ltd., abbreviation: 6EDNTA, refractive index: 1.722) was used as an additive (H RO ), and the acrylic adhesive composition of this example was prepared in the same manner as Example 4 to produce an adhesive sheet.
使藉由例17~23所得黏著片充分適應23℃、50%RH之環境後,與上述之「測定及評估(1)」相同方式進行各項目之測定及評估。將結果列於表3。After the adhesive sheets obtained in Examples 17 to 23 were fully acclimatized to an environment of 23°C and 50% RH, the various items were measured and evaluated in the same manner as in the above-mentioned "Measurement and Evaluation (1)". The results are listed in Table 3.
[表3] [Table 3]
表3中所示例17~23之黏著片皆顯示大於1.570之高折射率且展現高透明性。該等中,相較於例17~22之黏著片,例23之黏著片為較硬之觸感且吸水率亦較高。 從以上可知,例1~14、例16、例17~23之黏著片(由黏著劑層構成之無基材之雙面黏著片)有抑制光學特性之降低且業已高折射率化,因此適於在上述黏著劑層積層於光透射性構件上之黏著型光學薄膜之形態下用於光學構件(例如具有至少1種光之波導、聚光、繞射之功能的光學薄膜)之接合等用途。The adhesive sheets of Examples 17 to 23 shown in Table 3 all show a high refractive index greater than 1.570 and exhibit high transparency. Among them, the adhesive sheet of Example 23 has a harder touch and a higher water absorption rate than the adhesive sheets of Examples 17 to 22. From the above, it can be seen that the adhesive sheets of Examples 1 to 14, Example 16, and Example 17 to 23 (double-sided adhesive sheets without a substrate composed of an adhesive layer) have suppressed the reduction of optical properties and have a high refractive index, so they are suitable for use in the form of an adhesive optical film in which the above-mentioned adhesive layer is laminated on a light-transmitting component for use in optical components (e.g., optical films having at least one function of light waveguide, light focusing, and diffraction) bonding and the like.
以上已詳細說明本發明之具體例,惟該等僅為例示,非限定申請專利範圍者。申請專利範圍中記載之技術包含以上所例示之具體例經各種變形、變更者。The specific examples of the present invention have been described in detail above, but these are only examples and do not limit the scope of the patent application. The technology described in the scope of the patent application includes various modifications and changes of the specific examples described above.
1:黏著型光學薄膜
10:黏著劑層
10A:第1表面(黏著面)
10B:第2表面
20:光透射性構件
20A:第1面(非剝離性表面)
20B:第2面(背面)
30,31,32:剝離襯墊
50:附剝離襯墊之黏著型光學薄膜
70:光學構件(被黏著體)
100:光學積層體1: Adhesive optical film
10:
圖1係示意顯示一實施形態之黏著型光學薄膜之構成的截面圖。 圖2係示意顯示一實施形態之包含黏著型光學薄膜之光學積層體之構成的截面圖。FIG1 is a cross-sectional view schematically showing the structure of an adhesive optical film in an implementation form. FIG2 is a cross-sectional view schematically showing the structure of an optical laminate including an adhesive optical film in an implementation form.
1:黏著型光學薄膜 1: Adhesive optical film
10:黏著劑層 10: Adhesive layer
10A:第1表面(黏著面) 10A: Surface 1 (adhesive surface)
10B:第2表面 10B: Surface 2
20:光透射性構件 20: Light-transmitting component
20A:第1面(非剝離性表面) 20A: Surface 1 (non-peelable surface)
20B:第2面(背面) 20B: Side 2 (back)
30:剝離襯墊 30: Peel off the liner
50:附剝離襯墊之黏著型光學薄膜 50: Adhesive optical film with peel-off pad
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- 2021-03-24 TW TW110110676A patent/TWI881085B/en active
- 2021-03-24 KR KR1020227036353A patent/KR20220156594A/en active Pending
- 2021-03-24 CN CN202180024191.3A patent/CN115315647A/en active Pending
- 2021-03-24 WO PCT/JP2021/012257 patent/WO2021193720A1/en not_active Ceased
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20220156594A (en) | 2022-11-25 |
| TW202144520A (en) | 2021-12-01 |
| WO2021193720A1 (en) | 2021-09-30 |
| CN115315647A (en) | 2022-11-08 |
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