TW202111980A - Laminated optical film and image display device including at least a first optical film and a second optical film that are laminated with an adhesive layer between them - Google Patents
Laminated optical film and image display device including at least a first optical film and a second optical film that are laminated with an adhesive layer between them Download PDFInfo
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- G—PHYSICS
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- G02B5/00—Optical elements other than lenses
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- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G—PHYSICS
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- 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
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- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
Description
發明領域Invention field
本發明涉及隔著接著劑層至少積層有第1光學薄膜及第2光學薄膜的積層光學薄膜。該積層光學薄膜適用於影像顯示裝置、特別是有機EL顯示裝置。The present invention relates to a laminated optical film in which at least a first optical film and a second optical film are laminated via an adhesive layer. The laminated optical film is suitable for image display devices, especially organic EL display devices.
發明背景Background of the invention
為了改善影像顯示裝置的顯示畫面中由外部光反射、背景的映入而導致的視覺辨認性不良，已知有在顯示面板的可視側配置有圓偏光板的顯示裝置。專利文獻1及2中提出了一種偏光薄膜及具備上述偏光薄膜的顯示裝置，該偏光薄膜可減少黑顯示中來自傾斜方向的入射光反射，而實現優異的傾斜方向的反射色相。 先前技術文獻 專利文獻In order to improve the poor visibility of the display screen of the image display device caused by the reflection of external light and the reflection of the background, a display device in which a circular polarizing plate is arranged on the visible side of the display panel is known. Patent Documents 1 and 2 propose a polarizing film and a display device provided with the above-mentioned polarizing film, which can reduce the reflection of incident light from oblique directions in black display, and realize an excellent reflection hue in oblique directions. Prior art literature Patent literature
專利文獻1：日本特開2015-111236號公報 專利文獻2：日本特開2015-210459號公報Patent Document 1: Japanese Patent Application Publication No. 2015-111236 Patent Document 2: Japanese Patent Application Publication No. 2015-210459
發明概要 發明欲解決之問題Summary of the invention The problem that the invention solves
然而，專利文獻1及2中記載的使用了偏光薄膜的顯示裝置，其存在反射光產生不均、視覺辨認性不充分的問題。However, the display devices using the polarizing film described in Patent Documents 1 and 2 have the problems of uneven reflected light and insufficient visibility.
鑒於上述實際情況，本發明的課題在於，提供一種積層光學薄膜及具備該積層光學薄膜的影像顯示裝置、特別是有機EL顯示裝置，其能減少來自外部光的反射率、且視覺辨認性優異。 用以解決問題的方法In view of the above-mentioned actual situation, the subject of the present invention is to provide a laminated optical film and an image display device including the laminated optical film, particularly an organic EL display device, which can reduce the reflectance of external light and is excellent in visibility. Methods to solve the problem
上述問題可以藉由下述構成來解決。即，本發明涉及一種積層光學薄膜，其隔著接著劑層至少積層有第1光學薄膜及第2光學薄膜，上述接著劑層的第1光學薄膜側表面F1的面內折射率RF1 與第2光學薄膜側表面F2的面內折射率RF2 不同，上述RF1 與上述第1光學薄膜的面內平均折射率之差為0.05以內，上述RF2 與上述第2光學薄膜的面內平均折射率之差為0.05以內。The above-mentioned problem can be solved by the following configuration. That is, the present invention relates to a laminated optical film in which at least a first optical film and a second optical film are laminated via an adhesive layer. The in-plane refractive index R F1 of the first optical film side surface F1 of the adhesive layer and the first optical film 2 The in-plane refractive index R F2 of the optical film side surface F2 is different, the difference between the in-plane average refractive index of the above-mentioned R F1 and the above-mentioned first optical film is within 0.05, and the above-mentioned R F2 and the above-mentioned second optical film have the in-plane average refractive index The difference in rates is within 0.05.
優選在上述積層光學薄膜中，上述第1光學薄膜的厚度為30μm以下，上述第2光學薄膜的厚度為20μm以下。Preferably, in the laminated optical film, the thickness of the first optical film is 30 μm or less, and the thickness of the second optical film is 20 μm or less.
優選在上述積層光學薄膜中，上述接著劑層的厚度為5μm以下。Preferably, in the above-mentioned laminated optical film, the thickness of the above-mentioned adhesive layer is 5 μm or less.
優選在上述積層光學薄膜中，上述第1光學薄膜為透明保護薄膜，上述第2光學薄膜為偏光件。Preferably, in the laminated optical film, the first optical film is a transparent protective film, and the second optical film is a polarizer.
另外，本發明涉及具備上述記載的積層光學薄膜的影像顯示裝置、特別是有機EL顯示裝置。 發明的效果In addition, the present invention relates to an image display device, particularly an organic EL display device, provided with the above-described laminated optical film. The effect of the invention
影像顯示裝置具備積層有2片以上光學薄膜的積層光學薄膜，構成上述積層光學薄膜的各光學薄膜通常隔著接著劑層積層在一起。本發明人等進行了深入研究的結果發現，目前存在的積層光學薄膜所具備的接著劑層，其在一光學薄膜側(將其表述為“表面側”)及另一光學薄膜側(將其表述為“背面側”)的折射率相同，至今為止並不存在為了抑制表面側光學薄膜與接著劑層的界面、及背面側光學薄膜與接著劑的界面的反射，而使接著劑層的折射率在表面側與背面側不同的概念。The image display device is provided with a laminated optical film in which two or more optical films are laminated, and each optical film constituting the above-mentioned laminated optical film is usually laminated with an adhesive interposed therebetween. The inventors of the present invention have conducted intensive studies and found that the adhesive layer of the currently existing laminated optical film has one optical film side (denoted as the "surface side") and the other optical film side (which is referred to as "surface side"). Expressed as "back side") the refractive index is the same. So far, there is no way to suppress the reflection of the interface between the optical film on the front side and the adhesive layer and the interface between the optical film on the back side and the adhesive, so that the adhesive layer is refracted. The rate is a different concept on the front side and the back side.
然而，在本發明中，對於隔著接著劑層至少積層有第1光學薄膜及第2光學薄膜的積層光學薄膜而言，為了抑制各光學薄膜與接著劑層的界面的反射，使用表面側與背面側的折射率不同的接著劑層作為上述接著劑層。具體而言，如下所述地進行了設計：使用第1光學薄膜側表面F1的面內折射率RF1 與第2光學薄膜側表面F2的面內折射率RF2 不同的接著劑層，並且RF1 與第1光學薄膜的面內平均折射率之差為0.05以內，RF2 與第2光學薄膜的面內平均折射率之差為0.05以內。由此，可以顯著抑制第1光學薄膜與接著劑層的界面、及第2光學薄膜與接著劑層的界面的反射，因此，可以減少外部光、特別是自然光的反射率，視覺辨認性也提高。此外，在裝入至影像顯示裝置的情況下，也可以提高面板光等內部光的透射率。However, in the present invention, for a laminated optical film in which at least a first optical film and a second optical film are laminated via an adhesive layer, in order to suppress reflection at the interface between each optical film and the adhesive layer, the surface side and The adhesive layer having a different refractive index on the back side is used as the adhesive layer. Specifically, it was designed as follows: an adhesive layer having a different in- plane refractive index R F1 on the first optical film side surface F1 and a second optical film side surface F2 different in-plane refractive index R F2 was used, and R The difference between the in-plane average refractive index of F1 and the first optical film is within 0.05, and the difference between the in-plane average refractive index of R F2 and the second optical film is within 0.05. As a result, reflection at the interface between the first optical film and the adhesive layer and the interface between the second optical film and the adhesive layer can be significantly suppressed. Therefore, the reflectance of external light, especially natural light, can be reduced, and the visibility can also be improved. . In addition, when incorporated in an image display device, the transmittance of internal light such as panel light can also be increased.
一般而言，積層光學薄膜越薄，反射光也容易產生不均，關注上述問題的結果，特別是對於本發明的積層光學薄膜而言，即使第1光學薄膜及第2光學薄膜、以及接著劑層的厚度較薄，也可以減少外部光、特別是自然光的反射率，視覺辨認性也能提高。因此，本發明的積層光學薄膜適用於影像顯示裝置、特別是有機EL顯示裝置。Generally speaking, the thinner the laminated optical film is, the uneven reflected light is likely to occur. The result of paying attention to the above-mentioned problems, especially for the laminated optical film of the present invention, even if the first optical film and the second optical film, and the adhesive The thickness of the layer is thin, and the reflectance of external light, especially natural light, can be reduced, and the visibility can also be improved. Therefore, the laminated optical film of the present invention is suitable for image display devices, particularly organic EL display devices.
用以實施發明之形態The form used to implement the invention
在本發明中，積層光學薄膜隔著接著劑層至少積層有第1光學薄膜及第2光學薄膜，其特徵在於，為了抑制各光學薄膜與接著劑層的界面的反射，使用表面側與背面側的折射率不同的接著劑層作為上述接著劑層。關於上述特徵，其與具備現有的積層光學薄膜的影像顯示裝置進行對比，並在以下進行說明。In the present invention, the laminated optical film has at least the first optical film and the second optical film laminated with the adhesive layer interposed therebetween. It is characterized in that in order to suppress reflection at the interface between each optical film and the adhesive layer, the front side and the back side are used. Adhesive layers with different refractive indices are used as the above-mentioned adhesive layer. Regarding the above-mentioned characteristics, it is compared with an image display device provided with a conventional laminated optical film, and is described below.
圖1是示出具備目前存在的積層光學薄膜的影像顯示裝置中來自外部光(自然光)L的反射光LR
的一例的圖。圖1所示的影像顯示裝置M是具備有機發光二極體7的有機EL影像顯示裝置，該影像顯示裝置M具備隔著第1接著劑層2積層有第1光學薄膜(透明保護薄膜)1及第2光學薄膜(偏光件)3的積層光學薄膜10。在圖1所示的現有構成的情況下，由於第1接著劑層2在表面側及背面側的折射率相同，透明保護薄膜1的折射率與第1接著劑層2的折射率的不同、以及第1接著劑層2與偏光件3的折射率的不同的原因，外部光(自然光)L在透明保護薄膜1與第1接著劑層2的界面、以及在第1接著劑層2與偏光件3的界面發生反射，因此，反射光產生不均，視覺辨認性變得不充分。1 is a diagram showing an example of the external apparatus from the reflected light (natural light) L light L R is shown comprising an optical film laminate existing video display. The image display device M shown in FIG. 1 is an organic EL image display device including an organic light-
圖2是示出具備本發明的積層光學薄膜的影像顯示裝置的一例的圖。圖2所示的影像顯示裝置M是具備有機發光二極體7的有機EL影像顯示裝置，該影像顯示裝置M具備隔著接著劑層2積層有第1光學薄膜(透明保護薄膜)1及第2光學薄膜(偏光件)3的積層光學薄膜10。此外，在本發明中，積層光學薄膜只要至少從外側面(可視側面)向內側面具備第1光學薄膜→接著劑層→第2光學薄膜，則也可以由3片以上的光學薄膜構成，在圖2(a)所示的實施方式中，影像顯示裝置M從最外側面向有機發光二極體7依次具備透明保護薄膜(第1光學薄膜)1→第1接著劑層2→偏光件(第2光學薄膜)3→第2接著劑層4→相位差薄膜(第3光學薄膜)5→黏著劑層6。如圖2(b)所示，將本發明的積層光學薄膜10所具備的第1接著劑層2如下所述地設計：透明保護薄膜(第1光學薄膜)1側表面F1的面內折射率RF1
與偏光件(第2光學薄膜)3側F2的面內折射率RF2
不同，並且RF1
與透明保護薄膜的面內平均折射率之差為0.05以內，RF2
與偏光件的面內平均折射率之差為0.05以內。由此，在本發明的積層光學薄膜10中，外部光(自然光)L在透明保護薄膜1與接著劑層2的界面、以及在接著劑層2與偏光件3的界面的反射率會降低，視覺辨認性優異。FIG. 2 is a diagram showing an example of an image display device provided with the laminated optical film of the present invention. The image display device M shown in FIG. 2 is an organic EL image display device provided with an organic light-
＜第1接著劑層＞ 以下，對本發明的積層光學薄膜所具備的接著劑層進行說明。在本發明中，優選接著劑層的厚度薄的情況，具體而言，接著劑層的厚度優選為5μm以下、更優選為0.5~3μm。＜The first adhesive layer＞ Hereinafter, the adhesive layer included in the laminated optical film of the present invention will be described. In the present invention, the thickness of the adhesive layer is preferably thin. Specifically, the thickness of the adhesive layer is preferably 5 μm or less, more preferably 0.5 to 3 μm.
本發明的積層光學薄膜所具備的接著劑層的特徵在於，折射率在表面側與背面側不同。具體而言，第1光學薄膜側表面F1的面內折射率RF1 與第2光學薄膜側表面F2的面內折射率RF2 不同，RF1 與第1光學薄膜的面內平均折射率之差為0.05以內，RF2 與第2光學薄膜的面內平均折射率之差為0.05以內。為了進一步抑制第1光學薄膜與接著劑層的界面、及第2光學薄膜與接著劑層的界面的反射，更優選將RF1 與第1光學薄膜的面內平均折射率之差設為0.03以內，更優選將RF2 與第2光學薄膜的面內平均折射率之差設為0.03以內。The adhesive layer included in the laminated optical film of the present invention is characterized in that the refractive index is different on the front side and the back side. Specifically, the in-plane refractive index R F1 of the first optical film side surface F1 is different from the in-plane refractive index R F2 of the second optical film side surface F2, and the difference between R F1 and the in-plane average refractive index of the first optical film It is within 0.05, and the difference between R F2 and the average in-plane refractive index of the second optical film is within 0.05. In order to further suppress reflection at the interface between the first optical film and the adhesive layer, and the interface between the second optical film and the adhesive layer, it is more preferable to set the difference between the in-plane average refractive index of R F1 and the first optical film to be within 0.03 It is more preferable that the difference between the in-plane average refractive index of R F2 and the second optical film is within 0.03.
此外，在本發明中，對於接著劑層的第1光學薄膜側表面F1(或第2光學薄膜側表面F2)中的“面內折射率”而言，使用稜鏡耦合器SPA-4000(Cylon technology公司製)來測定接著劑層的各表面側的面內的折射率。測定溫度設為23℃、測定波長設為532nm。In addition, in the present invention, for the "in-plane refractive index" in the first optical film side surface F1 (or the second optical film side surface F2) of the adhesive layer, a 騜鏡 coupler SPA-4000 (Cylon Technology Corporation) to measure the in-plane refractive index on each surface side of the adhesive layer. The measurement temperature was set to 23°C, and the measurement wavelength was set to 532 nm.
在本發明中，接著劑層只要滿足上述特徵，則可以為任意的材料設計，特別優選為活性能量射線硬化型接著劑組成物經活性能量射線照射後而得到硬化物層來形成者。此外，關於面內折射率在表面側和背面側不同的接著劑層的製造方法的一例，在後面進行敘述。活性能量射線硬化型接著劑組成物可以大致區分為電子束硬化型、紫外線硬化型、可見光硬化型等。進而，紫外線硬化型、可見光硬化型接著劑可以大致區分為自由基聚合硬化型接著劑和陽離子聚合型接著劑。在本發明中，可將波長範圍10nm~380nm的活性能量射線記載為紫外線、將波長範圍380nm~800nm的活性能量射線記載為可見光。In the present invention, the adhesive layer may be of any material design as long as it satisfies the above-mentioned characteristics, and is particularly preferably formed by an active energy ray-curable adhesive composition that is irradiated with an active energy ray to obtain a cured layer. In addition, an example of a method of manufacturing an adhesive layer in which the in-plane refractive index is different on the front side and the back side will be described later. Active energy ray-curable adhesive compositions can be roughly classified into electron beam curing type, ultraviolet curing type, visible light curing type, and the like. Furthermore, ultraviolet curing type and visible light curing type adhesives can be roughly classified into radical polymerization curing type adhesives and cationic polymerization type adhesives. In the present invention, the active energy rays in the wavelength range of 10 nm to 380 nm can be described as ultraviolet rays, and the active energy rays in the wavelength range of 380 nm to 800 nm can be described as visible light.
作為構成自由基聚合硬化型接著劑的化合物，可列舉自由基聚合性化合物。自由基聚合性化合物可列舉具有(甲基)丙烯醯基、乙烯基等碳-碳雙鍵的自由基聚合性官能基的化合物。這些硬化性成分可以使用單官能自由基聚合性化合物或二官能以上的多官能自由基聚合性化合物中的任一種。另外，這些自由基聚合性化合物可以單獨使用1種，或者組合使用2種以上。作為這些自由基聚合性化合物，優選例如具有(甲基)丙烯醯基的化合物。本發明中使用的活性能量射線硬化型接著劑組成物優選含有具有(甲基)丙烯醯基的化合物作為主成分，具體而言，將活性能量射線硬化型接著劑組成物的總量設為100重量%時，優選含有50重量%以上的具有(甲基)丙烯醯基的化合物、更優選含有80重量%以上。此外，在本發明中，(甲基)丙烯醯基是指丙烯醯基及/或甲基丙烯醯基，“(甲基)”在以下是相同的含義。Examples of the compound constituting the radical polymerization curable adhesive include radical polymerizable compounds. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group having carbon-carbon double bonds such as a (meth)acryloyl group and a vinyl group. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds may be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, compounds having a (meth)acryloyl group are preferable. The active energy ray-curable adhesive composition used in the present invention preferably contains a compound having a (meth)acryloyl group as a main component. Specifically, the total amount of the active energy ray-curable adhesive composition is 100 In the case of weight %, it is preferable to contain 50 weight% or more of the compound which has a (meth)acryloyl group, and it is more preferable to contain 80 weight% or more. In addition, in the present invention, the (meth)acryloyl group means an acryloyl group and/or a methacryloyl group, and "(meth)" has the same meaning in the following.
作為單官能自由基聚合性化合物，可列舉例如具有(甲基)丙烯醯胺基的(甲基)丙烯醯胺衍生物。(甲基)丙烯醯胺衍生物在確保與偏光件、各種透明保護薄膜的接著性方面、以及聚合速度快、生產性優異的方面是優選的。作為(甲基)丙烯醯胺衍生物的具體例，可列舉例如：N-甲基(甲基)丙烯醯胺、N, N-二甲基(甲基)丙烯醯胺、N, N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺等含N-烷基(甲基)丙烯醯胺衍生物；N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺、N-羥甲基-N-丙基(甲基)丙烯醯胺等含N-羥基烷基(甲基)丙烯醯胺衍生物；氨基甲基(甲基)丙烯醯胺、氨基乙基(甲基)丙烯醯胺等含N-氨基烷基(甲基)丙烯醯胺衍生物；N-甲氧基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺等含N-烷氧基(甲基)丙烯醯胺衍生物；巰基甲基(甲基)丙烯醯胺、巰基乙基(甲基)丙烯醯胺等含N-巰基烷基(甲基)丙烯醯胺衍生物；等等。另外，作為(甲基)丙烯醯胺基的氮原子形成了雜環的含雜環(甲基)丙烯醯胺衍生物，可列舉例如：N-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯烷等。As a monofunctional radical polymerizable compound, the (meth)acrylamide derivative which has a (meth)acrylamide group is mentioned, for example. The (meth)acrylamide derivative is preferable in terms of ensuring adhesion to polarizers and various transparent protective films, and in terms of high polymerization speed and excellent productivity. As specific examples of (meth)acrylamide derivatives, for example, N-methyl(meth)acrylamide, N, N-dimethyl(meth)acrylamide, N, N-di Ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc. Containing N-alkane (Meth)acrylamide derivatives; N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxymethyl-N-propyl(methyl) ) Acrylamide and other N-hydroxyalkyl (meth)acrylamide derivatives; aminomethyl (meth)acrylamide, aminoethyl (meth)acrylamide, etc. containing N-aminoalkyl ( (Meth)acrylamide derivatives; N-alkoxy (meth)acrylamide derivatives such as N-methoxymethacrylamide, N-ethoxymethacrylamide, etc.; mercaptomethyl (Meth)acrylamide, mercaptoethyl (meth)acrylamide and other N-mercaptoalkyl (meth)acrylamide derivatives; etc. In addition, as a heterocyclic ring-containing (meth)acrylamide derivative in which the nitrogen atom of the (meth)acrylamido group forms a heterocyclic ring, for example, N-acryloylmorpholine, N-acryloylpiper Pyridine, N-methacryloylpiperidine, N-acryloylpyrrolidine, etc.
在上述(甲基)丙烯醯胺衍生物中，從與偏光件、各種透明保護薄膜的接著性的觀點來看，優選含N-羥基烷基(甲基)丙烯醯胺衍生物，另外，作為單官能自由基聚合性化合物，可列舉例如具有(甲基)丙烯醯氧基的各種(甲基)丙烯酸衍生物。具體而言，可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-甲基-2-硝基丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸叔戊酯、(甲基)丙烯酸3-戊酯、(甲基)丙烯酸2, 2-二甲基丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸4-甲基-2-丙基戊酯、(甲基)丙烯酸正十八烷基酯等(甲基)丙烯酸(碳原子數1-20)烷基酯類。Among the above-mentioned (meth)acrylamide derivatives, from the viewpoint of adhesion to polarizers and various transparent protective films, N-hydroxyalkyl (meth)acrylamide derivatives are preferred. In addition, as Examples of the monofunctional radical polymerizable compound include various (meth)acrylic acid derivatives having a (meth)acryloyloxy group. Specifically, examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl (meth)acrylate 2-nitropropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid N-pentyl ester, tert-amyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, (meth) Cetyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid (1-20 carbon atoms) alkyl esters such as n-octadecyl ester.
另外，作為上述(甲基)丙烯酸衍生物，可列舉例如：(甲基)丙烯酸環己酯、(甲基)丙烯酸酯環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸2-異冰片酯、(甲基)丙烯酸2-降冰片基甲酯、(甲基)丙烯酸5-降冰片烯-2-基甲酯、(甲基)丙烯酸3-甲基-2-降冰片基甲酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯等多環式(甲基)丙烯酸酯；(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基甲氧基乙酯、(甲基)丙烯酸3-甲氧基丁酯、(甲基)丙烯酸乙基卡必醇酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸烷基苯氧基聚乙二醇酯等含烷氧基或苯氧基的(甲基)丙烯酸酯；等等。In addition, examples of the above-mentioned (meth)acrylic acid derivatives include (meth)acrylic acid cycloalkyl esters such as cyclohexyl (meth)acrylate and cyclopentyl (meth)acrylate; (meth)acrylic acid Aralkyl (meth)acrylate such as benzyl ester; 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornene-2-(meth)acrylate Methyl ester, 3-methyl-2-norbornyl methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (methyl) ) Polycyclic (meth)acrylates such as dicyclopentyl acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(meth)acrylate Methoxymethoxyethyl, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylic acid Alkylphenoxy polyethylene glycol esters and other alkoxy or phenoxy-containing (meth)acrylates; etc.
另外，作為上述(甲基)丙烯酸衍生物，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯等(甲基)丙烯酸羥基烷基酯、 [4-(羥基甲基)環己基]甲基丙烯酸酯、環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯等含羥基(甲基)丙烯酸酯；(甲基)丙烯酸縮水甘油酯、4-羥基丁基(甲基)丙烯酸酯縮水甘油醚等含環氧基(甲基)丙烯酸酯；(甲基)丙烯酸2, 2, 2-三氟乙酯、(甲基)丙烯酸2, 2, 2-三氟乙基乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸十七氟癸酯、(甲基)丙烯酸3-氯-2-羥基丙酯等含鹵素(甲基)丙烯酸酯；(甲基)丙烯酸二甲基氨基乙酯等(甲基)丙烯酸烷基氨基烷基酯；(甲基)丙烯酸3-氧雜環丁烷基甲酯、(甲基)丙烯酸3-甲基氧雜環丁烷基甲酯、(甲基)丙烯酸3-乙基氧雜環丁烷基甲酯、(甲基)丙烯酸3-丁基氧雜環丁烷基甲酯、(甲基)丙烯酸3-己基氧雜環丁烷基甲酯等含氧雜環丁烷基(甲基)丙烯酸酯；(甲基)丙烯酸四氫糠酯、丁內酯(甲基)丙烯酸酯等具有雜環的(甲基)丙烯酸酯、羥基特戊酸新戊二醇(甲基)丙烯酸加成物、對苯基苯酚(甲基)丙烯酸酯等。In addition, examples of the above-mentioned (meth)acrylic acid derivatives include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid derivatives. Base) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxyl (meth)acrylate Decyl ester, 12-hydroxylauryl (meth)acrylate and other hydroxyalkyl (meth)acrylates, [4-(hydroxymethyl)cyclohexyl]methacrylate, cyclohexanedimethanol mono(methyl) Acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and other hydroxy-containing (meth)acrylates; glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate shrinkage Glyceryl ether and other epoxy-containing (meth)acrylates; 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 2-trifluoroethyl ethyl (meth) acrylate, (meth) Base) tetrafluoropropyl acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, 3-chloro-2-(meth)acrylate Halogen-containing (meth)acrylates such as hydroxypropyl ester; Alkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate; 3-oxetanyl (meth)acrylate Methyl ester, 3-methyloxetanyl methyl (meth)acrylate, 3-ethyloxetanyl methyl (meth)acrylate, 3-butyloxa (meth)acrylate Oxetanyl (meth)acrylates such as cyclobutanyl methyl ester, 3-hexyl oxetanyl methyl (meth)acrylate, etc.; tetrahydrofurfuryl (meth)acrylate, butane (Meth)acrylates having a heterocycle such as ester (meth)acrylate, neopentyl glycol hydroxypivalate (meth)acrylic acid adduct, p-phenylphenol (meth)acrylate, and the like.
另外，作為單官能自由基聚合性化合物，可列舉出：(甲基)丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸、異巴豆酸等含羧基單體。In addition, examples of monofunctional radical polymerizable compounds include (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, etc. Carboxyl-containing monomers.
另外，作為單官能自由基聚合性化合物，例如可列舉出：N-乙烯基吡咯烷酮、N-乙烯基-ε-己內醯胺、甲基乙烯基吡咯烷酮等內醯胺類乙烯基單體；乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌嗪、乙烯基吡嗪、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基嗎啉等具有含氮雜環的乙烯基類單體等。In addition, examples of monofunctional radical polymerizable compounds include endoamine-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and methyl vinylpyrrolidone; ethylene Vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine and other vinyls with nitrogen-containing heterocycles Monomers and so on.
另外，作為單官能自由基聚合性化合物，可以使用具有活性亞甲基的自由基聚合性化合物。具有活性亞甲基的自由基聚合性化合物為末端或分子中具有(甲基)丙烯酸基等活性雙鍵基團、且具有活性亞甲基的化合物。作為活性亞甲基，可列舉例如：乙醯乙醯基、烷氧基丙二醯基、或氰基乙醯基等。上述活性亞甲基優選為乙醯乙醯基。作為具有活性亞甲基的自由基聚合性化合物的具體例，可列舉例如：(甲基)丙烯酸2-乙醯乙醯氧基乙酯、(甲基)丙烯酸2-乙醯乙醯氧基乙基丙酯、(甲基)丙烯酸2-乙醯乙醯氧基乙基-1-甲基乙酯等(甲基)丙烯酸乙醯乙醯氧基乙基烷基酯；(甲基)丙烯酸2-乙氧基丙二醯氧基乙酯、(甲基)丙烯酸2-氰基乙醯氧基乙酯、N-(2-氰基乙醯氧基乙基)丙烯醯胺、N-(2-丙醯基乙醯氧基丁基)丙烯醯胺、N-(4-乙醯乙醯氧基乙基甲基苄基)丙烯醯胺、N-(2-乙醯乙醯基氨基乙基)丙烯醯胺等。具有活性亞甲基的自由基聚合性化合物優選為(甲基)丙烯酸乙醯乙醯氧基乙基烷基酯。In addition, as the monofunctional radical polymerizable compound, a radical polymerizable compound having an active methylene group can be used. The radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acrylic group in the terminal or in the molecule, and having an active methylene group. As the active methylene group, for example, acetylacetoxy, alkoxypropanedioxin, cyanoacetoxy, and the like can be mentioned. The above-mentioned active methylene group is preferably an acetylacetonyl group. Specific examples of radical polymerizable compounds having active methylene groups include, for example, 2-acetylacetoxyethyl (meth)acrylate, 2-acetylacetoxyethyl (meth)acrylate Acetyl propyl ester, (meth) acrylate 2-acetyl acetoxy ethyl-1-methyl ethyl (meth) acrylate, etc. Acetyl acetoxy ethyl alkyl ester; (meth) acrylic acid 2 -Ethoxypropanedioxyethyl, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N-(2 -Propylacetoxybutyl)acrylamide, N-(4-acetylacetoxyethylmethylbenzyl)acrylamide, N-(2-acetylacetoxyaminoethyl) ) Acrylamide and so on. The radically polymerizable compound having an active methylene group is preferably acetoxyethyl alkyl (meth)acrylate.
另外，作為二官能以上的多官能自由基聚合性化合物，可列舉例如：三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1, 6-己二醇二(甲基)丙烯酸酯、1, 9-壬二醇二(甲基)丙烯酸酯、1, 10-癸二醇二丙烯酸酯、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、雙酚A環氧乙烷加成物二(甲基)丙烯酸酯、雙酚A環氧丙烷加成物二(甲基)丙烯酸酯、雙酚A二縮水甘油醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、環狀三羥甲基丙烷甲縮醛(甲基)丙烯酸酯(cyclic trimethylolpropane formal(meth)Acrylate)、二 噁烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、EO改性二甘油四(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇的酯化物、9, 9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]芴。作為具體例，可列舉ARONIX M-220(東亞合成股份有限公司製)、LIGHT ACRYLATE 1,9ND-A(共榮社化學股份有限公司製)、LIGHT ACRYLATE DGE-4A(共榮社化學股份有限公司製)、LIGHT ACRYLATE DCP-A(共榮社化學股份有限公司製)、SR-531(Sartomer公司製)、CD-536(Sartomer公司製)等。另外，根據需要，可列舉出：各種環氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、各種(甲基)丙烯酸酯類單體等。In addition, examples of polyfunctional radical polymerizable compounds having two or more functions include tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Meth) acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, Bisphenol A di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A di Glycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclic trimethylolpropane methylal (methyl) )Acrylate (cyclic trimethylolpropane formal(meth)Acrylate), dioxanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol four (Meth) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO modified diglycerol tetra(meth)acrylate, etc.(meth)acrylic acid and polyol ester Compound, 9, 9-bis[4-(2-(meth)propenyloxyethoxy)phenyl]fluorene. Specific examples include ARONIX M-220 (manufactured by Toagosei Co., Ltd.), LIGHT ACRYLATE 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), and LIGHT ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.) System), LIGHT ACRYLATE DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer), CD-536 (manufactured by Sartomer), etc. In addition, if necessary, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, various (meth)acrylate monomers, etc. can be cited .
對於活性能量射線硬化型接著劑組成物而言，在活性能量射線使用電子束等的情況下，該活性能量射線硬化型接著劑組成物不需要含有光聚合引發劑，但在活性能量射線使用紫外線或可見光的情況下，優選含有光聚合引發劑。For the active energy ray-curable adhesive composition, when an electron beam is used for the active energy ray, the active energy ray-curable adhesive composition does not need to contain a photopolymerization initiator, but ultraviolet rays are used for the active energy ray. Or in the case of visible light, it is preferable to contain a photopolymerization initiator.
使用自由基聚合性化合物的情況下的光聚合引發劑，可根據活性能量射線而適宜選擇。在藉由紫外線或可見光來硬化的情況下，可使用紫外線或可見光裂解的光聚合引發劑。上述光聚合引發劑可以單獨使用，但在混合多種光聚合引發劑而使用的情況下，可以調整硬化速度、硬化性，因而優選。作為上述光聚合引發劑，可列舉例如：苯偶醯、二苯甲酮、苯甲醯苯甲酸、3, 3′-二甲基-4-甲氧基二苯甲酮等二苯甲酮類化合物；4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α, α′-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基丙醯基)苄基]苯基}-2-甲基丙烷-1-酮等芳香族酮化合物；甲氧基苯乙酮、2, 2-二甲氧基-2-苯基苯乙酮、2, 2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮等苯乙酮類化合物；苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻丁基醚、茴香偶姻甲基醚等苯偶姻醚類化合物；苯偶醯二甲基縮酮等芳香族縮酮類化合物；2-萘磺醯氯等芳香族磺醯氯類化合物；1-苯基-1, 1-丙二酮-2-(鄰乙氧基羰基)肟等光活性肟類化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2, 4-二甲基噻噸酮、異丙基噻噸酮、2, 4-二氯噻噸酮、2 ,4-二乙基噻噸酮、2, 4-二異丙基噻噸酮、十二烷基噻噸酮等噻噸酮類化合物；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸酯等。The photopolymerization initiator in the case of using a radically polymerizable compound can be appropriately selected according to active energy rays. In the case of curing by ultraviolet or visible light, a photopolymerization initiator that is cleaved by ultraviolet or visible light can be used. The above-mentioned photopolymerization initiator may be used alone, but when a plurality of photopolymerization initiators are mixed and used, the curing speed and curability can be adjusted, which is preferable. Examples of the photopolymerization initiator include benzophenones such as benzil, benzophenone, benzophenone benzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone. Compound; 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxyl Propiophenone, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy- 1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl]phenyl}-2-methylpropane-1-one and other aromatic ketone compounds; methoxyacetophenone, 2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholinopropane-1-one and other acetophenone compounds; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisole methyl ether Benzoin ether compounds; Aromatic ketal compounds such as benzil dimethyl ketal; Aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenyl-1, 1-propane Ketone-2-(o-ethoxycarbonyl) oxime and other photoactive oxime compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, iso Propyl thioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and other thioxanthones Compounds; camphorquinone; halogenated ketones; acyl phosphine oxide; acyl phosphonates, etc.
將活性能量射線硬化型接著劑組成物的總量設為100重量%時，上述光聚合引發劑的摻合量為20重量%以下。光聚合引發劑的摻合量優選為0.01~20重量%、更優選為0.05~10重量%、進一步優選為0.1~5重量%。When the total amount of the active energy ray-curable adhesive composition is 100% by weight, the blending amount of the photopolymerization initiator is 20% by weight or less. The blending amount of the photopolymerization initiator is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and even more preferably 0.1 to 5% by weight.
另外，本發明之積層光學薄膜用硬化型接著劑，於使用含有自由基聚合性化合物作為硬化性成分之可見光線硬化型時，特別優選使用對380nm以上的光為高靈敏度的光聚合引發劑。關於對380nm以上的光為高靈敏度的光聚合引發劑，後面進行敘述。In addition, when the curable adhesive for laminated optical films of the present invention uses a visible light curable type containing a radical polymerizable compound as a curable component, it is particularly preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more. The photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
作為上述光聚合引發劑，優選單獨使用下述通式(1)所示的化合物；或者組合使用通式(1)所示的化合物和後面敘述的對380nm以上的光高靈敏度的光聚合引發劑。As the above-mentioned photopolymerization initiator, it is preferable to use a compound represented by the following general formula (1) alone; or a combination of a compound represented by the general formula (1) and a photopolymerization initiator with high sensitivity to light of 380 nm or more described later .
[化學式1]
另外，優選根據需要添加聚合引發助劑。作為聚合引發助劑，可列舉出：三乙胺、二乙胺、N-甲基二乙醇胺、乙醇胺、4-二甲基氨基苯甲酸、4-二甲基氨基苯甲酸甲酯、4-二甲基氨基苯甲酸乙酯、4-二甲基氨基苯甲酸異戊酯等，特別優選4-二甲基氨基苯甲酸乙酯。使用聚合引發助劑的情況下，其添加量相對於硬化性成分的總量100重量份通常為0~5重量份，優選為0~4重量份，最優選為0~3重量份。In addition, it is preferable to add a polymerization initiation assistant as necessary. Examples of the polymerization initiation aids include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-diethylamine Ethyl methylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc., ethyl 4-dimethylaminobenzoate is particularly preferred. In the case of using a polymerization initiation assistant, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight with respect to 100 parts by weight of the total amount of curable components.
另外，根據需要，可以組合使用公知的光聚合引發劑。具有UV吸收能力的透明保護薄膜由於不透過380nm以下的光，因此作為光聚合引發劑，優選使用對380nm以上的光為高靈敏度的光聚合引發劑。具體而言，可列舉出：2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-嗎啉代苯基)-1-丁酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、2, 4, 6-三甲基苯甲醯基二苯基氧化膦、雙(2, 4, 6-三甲基苯甲醯基)苯基氧化膦、雙(η5-2, 4-環戊二烯-1-基)雙(2, 6-二氟-3-(1H-吡咯-1-基)苯基)鈦等。In addition, if necessary, a known photopolymerization initiator can be used in combination. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, it can include: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) )Phenyl)-1-butanone, 2, 4, 6-trimethylbenzyl diphenyl phosphine oxide, bis(2, 4, 6-trimethylbenzyl) phenyl phosphine oxide, Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
特別地，作為光聚合引發劑，除通式(1)的光聚合引發劑以外，優選進一步使用下述通式(2)所示的化合物，In particular, as the photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (1), it is preferable to further use a compound represented by the following general formula (2),
[化學式2]
在本發明中，在上述光聚合引發劑中，優選使用含羥基光聚合引發劑。當活性能量射線硬化型接著劑組成物含有含羥基光聚合引發劑作為聚合引發劑時，對於偏光件側的A成分濃度高的接著劑層的溶解性會提高，接著劑層的硬化性亦會提高。作為具有羥基的光聚合引發劑，可列舉例如：2-甲基-2-羥基苯丙酮(商品名“DAROCUR1173”、IGMresins公司製)、1-羥基環己基苯基酮(商品名“Omnirad184”、IGMresins公司製)、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮(商品名“Omnirad2959”、IGMresins公司製)、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮(商品名“Omnirad127”、IGMresins公司製)等。特別是1-羥基環己基苯基酮，其對於A成分濃度高的接著劑層的溶解性特別優異，因而更優選。In the present invention, among the above-mentioned photopolymerization initiators, a hydroxyl group-containing photopolymerization initiator is preferably used. When the active energy ray-curable adhesive composition contains a hydroxyl-containing photopolymerization initiator as the polymerization initiator, the solubility of the adhesive layer with a high concentration of component A on the polarizer side will increase, and the curing property of the adhesive layer will also be improved. improve. Examples of photopolymerization initiators having a hydroxyl group include 2-methyl-2-hydroxypropiophenone (trade name "DAROCUR1173", manufactured by IGMresins), 1-hydroxycyclohexyl phenyl ketone (trade name "Omnirad 184", (Manufactured by IGMresins), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (trade name "Omnirad 2959", manufactured by IGMresins) , 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propane-1-one (trade name "Omnirad127 ", made by IGMresins), etc. In particular, 1-hydroxycyclohexyl phenyl ketone has particularly excellent solubility in an adhesive layer with a high A component concentration, and therefore is more preferable.
本發明中使用的活性能量射線硬化型接著劑組成物中，除上述自由基聚合性化合物的硬化性成分以外，還可以含有使(甲基)丙烯酸單體聚合而成的丙烯酸類寡聚物。藉由在活性能量射線硬化型接著劑組成物中含有丙烯酸類寡聚物成分，可降低對該組成物照射活性能量射線並使其硬化時的硬化收縮，並減少接著劑與偏光件及透明保護薄膜等被黏附物的界面應力。其結果，可抑制接著劑層與被黏附物的接著性降低。為了充分抑制硬化物層(接著劑層)的硬化收縮，將活性能量射線硬化型接著劑組成物的總量設為100重量%時，優選將丙烯酸類寡聚物的含量設為5~30重量%、更優選設為10~20重量%。The active energy ray-curable adhesive composition used in the present invention may contain an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer in addition to the curable component of the radical polymerizable compound. By containing the acrylic oligomer component in the active energy ray-curable adhesive composition, the curing shrinkage when the composition is irradiated with active energy rays and hardened can be reduced, and the adhesive and polarizers and transparent protection can be reduced. The interfacial stress of adherends such as films. As a result, it is possible to suppress the deterioration of the adhesiveness between the adhesive layer and the adherend. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), when the total amount of the active energy ray-curable adhesive composition is 100% by weight, the content of the acrylic oligomer is preferably 5 to 30% by weight %, more preferably 10 to 20% by weight.
在考慮塗敷時的作業性、均勻性的情況下，優選活性能量射線硬化型接著劑組成物為低黏度，因此，將(甲基)丙烯酸單體聚合而成的丙烯酸類寡聚物也優選為低黏度。作為低黏度的丙烯酸類寡聚物，其重均分子量(Mw)優選為15000以下、更優選為10000以下、特別優選為5000以下。另一方面，為了使夾在偏光件及透明保護薄膜間的接著劑組成物的成分更加集中存在，丙烯酸類寡聚物(A)的重均分子量(Mw)優選為500以上、更優選為1000以上、特別優選為1500以上。作為構成丙烯酸類寡聚物(A)的(甲基)丙烯酸類單體，具體可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-甲基-2-硝基丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸叔戊酯、(甲基)丙烯酸3-戊酯、(甲基)丙烯酸2, 2-二甲基丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸4-甲基-2-丙基戊酯、(甲基)丙烯酸正十八烷基酯等(甲基)丙烯酸(碳原子數1-20)烷基酯類、以及例如：(甲基)丙烯酸環烷基酯(例如(甲基)丙烯酸環己酯、(甲基)丙烯酸酯環戊酯等)、(甲基)丙烯酸芳烷基酯(例如(甲基)丙烯酸苄酯等)、多環式(甲基)丙烯酸酯(例如(甲基)丙烯酸2-異冰片酯、(甲基)丙烯酸-2-降冰片基甲酯、(甲基)丙烯酸5-降冰片烯-2-基甲酯、(甲基)丙烯酸3-甲基-2-降冰片基甲酯等)、含羥基(甲基)丙烯酸酯類(例如(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸2, 3-二羥基丙基甲基丁酯等)、含烷氧基或苯氧基(甲基)丙烯酸酯類((甲基)丙烯酸-2-甲氧基乙酯、(甲基)丙烯酸-2-乙氧基乙酯、(甲基)丙烯酸-2-甲氧基甲氧基乙酯、(甲基)丙烯酸-3-甲氧基丁酯、(甲基)丙烯酸乙基卡必醇酯、(甲基)丙烯酸苯氧基乙酯等)、含環氧基(甲基)丙烯酸酯類(例如(甲基)丙烯酸縮水甘油酯等)、含鹵素(甲基)丙烯酸酯類(例如(甲基)丙烯酸2, 2, 2-三氟乙酯、(甲基)丙烯酸2, 2, 2-三氟乙基乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸十七氟癸酯等)、(甲基)丙烯酸烷基氨基烷基酯(例如，(甲基)丙烯酸二甲基氨基乙酯等)等。這些(甲基)丙烯酸酯可以單獨使用或組合使用2種以上。作為丙烯酸類寡聚物(A)的具體例，可列舉東亞合成股份有限公司製“ARUFON”、綜研化學股份有限公司製“ACTFLOW”、IGMresins Japan Ltd.製“JONCRYL”等。In consideration of workability and uniformity during coating, it is preferable that the active energy ray-curable adhesive composition has a low viscosity. Therefore, acrylic oligomers formed by polymerizing (meth)acrylic monomers are also preferable It is low viscosity. As a low-viscosity acrylic oligomer, the weight average molecular weight (Mw) is preferably 15,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less. On the other hand, in order to make the components of the adhesive composition sandwiched between the polarizer and the transparent protective film more concentrated, the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, more preferably 1000 Above, 1500 or above is particularly preferable. Specific examples of the (meth)acrylic monomer constituting the acrylic oligomer (A) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary (meth)acrylate Butyl ester, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, tert-pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-di (meth)acrylate Methyl butyl ester, n-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-(meth)acrylate (Meth)acrylic acid (1-20 carbon atoms) alkyl esters such as methyl-2-propylpentyl ester and n-octadecyl (meth)acrylate, and for example: (meth)acrylic acid cycloalkane Base ester (e.g. cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, etc.), aralkyl (meth)acrylate (e.g. benzyl (meth)acrylate, etc.), polycyclic ( Meth) acrylate (e.g. 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornen-2-yl methyl (meth)acrylate, ( (Meth) acrylate 3-methyl-2-norbornyl methyl ester, etc.), hydroxyl-containing (meth)acrylates (e.g. hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate) , (Meth)acrylate 2,3-dihydroxypropyl methyl butyl ester, etc.), alkoxy or phenoxy (meth)acrylates ((meth)acrylate-2-methoxyethyl) , 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, (meth) Ethyl carbitol acrylate, phenoxyethyl (meth)acrylate, etc.), epoxy-containing (meth)acrylates (such as glycidyl (meth)acrylate, etc.), halogen-containing (methyl) ) Acrylic esters (e.g. 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 2-trifluoroethyl ethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, Hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylate (for example, (methyl) ) Dimethylaminoethyl acrylate, etc.) and so on. These (meth)acrylates can be used individually or in combination of 2 or more types. Specific examples of the acrylic oligomer (A) include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Soken Chemical Co., Ltd., "JONCRYL" manufactured by IGMresins Japan Ltd., and the like.
當丙烯酸類寡聚物為液體時，因不需考慮對於接著劑組成物的溶解性，因而可適宜使用。丙烯酸類寡聚物在玻璃轉移溫度(Tg)為小於25℃時，通常為液體。另外，為了兼顧與接著劑組成物的相容性和成分在接著劑層中的集中存在，優選丙烯酸類寡聚物含有極性官能基。作為極性官能基，可列舉羥基、環氧基、羧基、烷氧基甲矽烷基等。具體而言，可列舉例如：“ARUFONUH系列”、“ARUFON UC系列”、“ARUFON UF系列”、“ARUFON UG系列”、“ARUFON US系列”(均為東亞合成股份有限公司製)等。其中，由於可以實現由與偏光件的相互作用帶來的接著性的提高，優選含有環氧基。具體而言，可列舉例如：“ARUFON UG-4000”、“ARUFON UG-4010”(均為東亞合成股份有限公司製)。When the acrylic oligomer is a liquid, it is not necessary to consider the solubility to the adhesive composition, so it can be suitably used. Acrylic oligomers are usually liquid when the glass transition temperature (Tg) is less than 25°C. In addition, in order to balance compatibility with the adhesive composition and concentrated presence of components in the adhesive layer, it is preferable that the acrylic oligomer contains a polar functional group. Examples of the polar functional group include a hydroxyl group, an epoxy group, a carboxyl group, and an alkoxysilyl group. Specifically, for example, "ARUFONUH series", "ARUFON UC series", "ARUFON UF series", "ARUFON UG series", "ARUFON US series" (all manufactured by Toagosei Co., Ltd.), etc. can be mentioned. Among them, it is preferable to contain an epoxy group because the adhesiveness can be improved by the interaction with the polarizer. Specifically, for example, "ARUFON UG-4000" and "ARUFON UG-4010" (both are manufactured by Toagosei Co., Ltd.) can be cited.
＜第1光學薄膜＞ 在本發明中，作為第1光學薄膜，可以適宜使用透明保護薄膜。優選透明保護薄膜的厚度薄的情況，具體而言，優選為30μm以下、更優選為1~20μm。作為透明保護薄膜，優選為透明性、機械強度、熱穩定性、水分阻隔性、各向同性等優異者。例如可列舉：聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯類聚合物、二乙酸纖維素、三乙酸纖維素等纖維素類聚合物、聚甲基丙烯酸甲酯等丙烯酸類聚合物、聚苯乙烯、丙烯腈-苯乙烯共聚物(AS樹脂)等苯乙烯類聚合物、聚碳酸酯類聚合物等。另外，聚乙烯、聚丙烯、具有環類或降冰片烯結構的聚烯烴、乙烯-丙烯共聚物這樣的聚烯烴類聚合物、氯乙烯類聚合物、尼龍、芳香族聚醯胺等醯胺類聚合物、醯亞胺類聚合物、碸類聚合物、聚醚碸類聚合物、聚醚醚酮類聚合物、聚苯硫醚類聚合物、乙烯醇類聚合物、偏氯乙烯類聚合物、乙烯基縮丁醛類聚合物、聚芳酯類聚合物、聚甲醛類聚合物、環氧類聚合物、或上述聚合物的混合物等也可以作為形成上述透明保護薄膜的聚合物的實例而列舉出。透明保護薄膜中可以含有1種以上任意適當的添加劑。作為添加劑，例如可列舉：紫外線吸收劑、抗氧劑、潤滑劑、增塑劑、脫模劑、防著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護薄膜中的上述熱塑性樹脂的含量優選為50~100重量%、更優選為50~99重量%、進一步優選為60~98重量%、特別優選為70~97重量%。透明保護薄膜中的上述熱塑性樹脂的含量為50重量%以下的情況下，恐有不能充分表現出熱塑性樹脂本來具有的高透明性等之虞。＜The first optical film＞ In the present invention, as the first optical film, a transparent protective film can be suitably used. The thickness of the transparent protective film is preferably thin, and specifically, it is preferably 30 μm or less, and more preferably 1 to 20 μm. As a transparent protective film, those excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. are preferable. Examples include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulosic polymers such as cellulose diacetate and cellulose triacetate, and polymethylmethacrylate Acrylic polymers such as esters, styrene polymers such as polystyrene, acrylonitrile-styrene copolymer (AS resin), polycarbonate polymers, etc. In addition, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, polyolefin polymers such as ethylene-propylene copolymers, vinyl chloride polymers, nylons, aromatic polyamides and other amides Polymers, imine polymers, turbid polymers, polyether turbid polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers , Vinyl butyral polymers, polyarylate polymers, polyoxymethylene polymers, epoxy polymers, or mixtures of the above-mentioned polymers, etc. can also be used as examples of polymers forming the above-mentioned transparent protective film. Enumerate. One or more arbitrary suitable additives may be contained in the transparent protective film. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, there is a possibility that the high transparency inherent in the thermoplastic resin may not be sufficiently expressed.
另外，作為透明保護薄膜，可列舉日本特開2001-343529號公報(WO01/37007)中記載的聚合物膜，例如(A)含有側鏈具有取代及/或未取代醯亞胺基的熱塑性樹脂和側鏈具有取代及/或未取代苯基及腈基的熱塑性樹脂的樹脂組成物。作為具體例，可列舉含有由異丁烯與N-甲基馬來醯亞胺形成的交替共聚物和丙烯腈-苯乙烯共聚物的樹脂組成物的薄膜。薄膜可以使用由樹脂組成物的混合擠出品等形成的膜。這些膜的相位差小、光彈性係數小，因此能夠消除由偏光薄膜的應變導致的不均等不良情況，另外，透濕度小，因此加濕耐久性優異。In addition, examples of the transparent protective film include polymer films described in Japanese Patent Application Laid-Open No. 2001-343529 (WO01/37007), such as (A) a thermoplastic resin containing a substituted and/or unsubstituted imidine group on the side chain And a resin composition of a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in the side chain. As a specific example, a film containing a resin composition of an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be cited. As the film, a film formed of a mixed extruded product of a resin composition or the like can be used. These films have a small retardation and a small photoelastic coefficient, and therefore can eliminate problems such as unevenness caused by the strain of the polarizing film. In addition, the moisture permeability is small, and therefore, the humidification durability is excellent.
此外，在本發明中，透明保護薄膜的“面內平均折射率”使用稜鏡耦合器SPA-4000(Cylon technology製)，測定透明保護膜的面內折射率中的快軸方向的折射率及慢軸方向的折射率，將它們的平均值作為面內平均折射率。測定溫度設為23℃、測定波長設為532nm。In addition, in the present invention, the "in-plane average refractive index" of the transparent protective film is measured using the SPA-4000 (manufactured by Cylon Technology) coupler in the fast-axis direction of the in-plane refractive index of the transparent protective film. Regarding the refractive index in the slow axis direction, the average value thereof is regarded as the in-plane average refractive index. The measurement temperature was set to 23°C, and the measurement wavelength was set to 532 nm.
＜第2光學薄膜＞ 本發明中，作為第2光學薄膜，可以適宜使用偏光件。偏光件沒有特殊限制，可以使用各種偏光件。作為偏光件，例如可列舉：在聚乙烯醇類膜、部分甲縮醛化聚乙烯醇類膜、乙烯-乙酸乙烯酯共聚物類部分皂化膜等親水性高分子膜上吸附碘、二色性染料等二色性材料且進行了單向拉伸而成的薄膜、聚乙烯醇的脫水處理物、聚氯乙烯的脫鹽酸處理物等多烯類配向薄膜等。這些當中，由聚乙烯醇類膜和碘等二色性物質形成的偏光件是適宜的。＜Second optical film＞ In the present invention, a polarizer can be suitably used as the second optical film. The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include: adsorption of iodine on hydrophilic polymer films such as polyvinyl alcohol films, partially methylalized polyvinyl alcohol films, ethylene-vinyl acetate copolymer partially saponified films, and dichroic properties. Uniaxially stretched films made of dichroic materials such as dyes, polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrated polyvinyl chloride. Among these, a polarizer formed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is suitable.
此外，在本發明中，對於偏光件的“面內平均折射率”而言，使用稜鏡耦合器SPA-4000(Cylon technology製)，測定偏光件的面內折射率中的透射軸方向的折射率及吸收軸方向的折射率，將它們的平均值作為偏光件的面內平均折射率。測定波長設為23℃、測定波長設為532nm。In addition, in the present invention, for the "in-plane average refractive index" of the polarizing element, the SPA-4000 (manufactured by Cylon technology) is used to measure the refraction in the transmission axis direction in the in-plane refractive index of the polarizing element. The average value of the refractive index and the refractive index in the direction of the absorption axis is taken as the in-plane average refractive index of the polarizer. The measurement wavelength was set to 23°C, and the measurement wavelength was set to 532 nm.
偏光件的厚度一般為1~30μm，但如上所述，積層光學薄膜越薄，反射光越容易產生不均，在本發明中，偏光件特別優選為薄型偏光件，具體而言，厚度優選為20μm以下、更優選為1~12μm。The thickness of the polarizer is generally 1 to 30 μm, but as mentioned above, the thinner the laminated optical film, the more likely to be uneven in reflected light. In the present invention, the polarizer is particularly preferably a thin polarizer. Specifically, the thickness is preferably 20 μm or less, more preferably 1 to 12 μm.
作為薄型的偏光件，代表性的可以舉出：日本特開昭51-069644號公報、日本特開2000-338329號公報、WO2010/100917號小冊子、PCT/JP2010/001460的說明書、或日本特願2010-269002號說明書、日本特願2010-263692號說明書中記載的薄型偏光膜。這些薄型偏光膜可以藉由包括將聚乙烯醇類樹脂(以下，也稱為PVA類樹脂)層與拉伸用樹脂基材，以積層體的狀態進行拉伸步驟和進行染色步驟的製法來獲得。如果是該製法，則即使PVA類樹脂層薄，也能夠藉由被拉伸用樹脂基材支撐來進行拉伸而不發生由拉伸導致的斷裂等不良情況。As thin polarizers, representative examples include: Japanese Patent Application Publication No. 51-069644, Japanese Patent Application Publication No. 2000-338329, pamphlet WO2010/100917, specification of PCT/JP2010/001460, or Japanese Patent Application The thin polarizing film described in the specification No. 2010-269002 and Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a manufacturing method including a polyvinyl alcohol-based resin (hereinafter, also referred to as PVA-based resin) layer and a resin substrate for stretching, in the state of a laminate, performing a stretching step and performing a dyeing step . According to this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched by being supported by the resin base material for stretching without causing problems such as breakage due to stretching.
作為上述薄型偏光膜，在包括以積層體的狀態進行拉伸步驟和進行染色步驟的製法中，從能夠以高倍率進行拉伸、能夠提高偏光性能的方面來看，優選藉由WO2010/100917號小冊子、PCT/JP2010/001460的說明書、或日本特願2010-269002號說明書、日本特願2010-263692號說明書中記載的那樣的、包括在硼酸水溶液中進行拉伸的步驟的製法來獲得，特別優選藉由日本特願2010-269002號說明書、日本特願2010-263692號說明書中記載的、包括在硼酸水溶液中進行拉伸之前輔助地進行空中拉伸的步驟的製法來獲得。As the above-mentioned thin polarizing film, in a manufacturing method that includes a stretching step and a dyeing step in the state of a laminate, it is preferable to use WO2010/100917 from the viewpoint that it can be stretched at a high magnification and can improve the polarization performance. Brochure, PCT/JP2010/001460 specification, or Japanese Patent Application No. 2010-269002 specification, Japanese Patent Application No. 2010-263692 specification, which includes a step of stretching in a boric acid aqueous solution, is obtained by a manufacturing method, especially Preferably, it is obtained by a manufacturing method described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, which includes a step of auxiliary air stretching before stretching in a boric acid aqueous solution.
本發明的積層光學薄膜的特徵在於，面內折射率在接著劑層的表面側和背面側不同。具備上述接著劑層的積層光學薄膜，例如可以藉由下述製造方法來製造。 一種積層光學薄膜的製造方法，該積層光學薄膜隔著接著劑層至少積層有第1光學薄膜及第2光學薄膜，接著劑層包含第1接著劑組成物的第1硬化物層及第2接著劑組成物的第2硬化物層，上述第1接著劑組成物與上述第2接著劑組成物含有至少一部分不同的成分，該方法包括：在上述第1光學薄膜的貼合面塗敷上述第1接著劑組成物的第1步驟；在上述第2光學薄膜的貼合面塗敷上述第2接著劑組成物的第2步驟；使上述第1光學薄膜的上述第1接著劑組成物塗敷面及上述第2光學薄膜的上述第2接著劑組成物塗敷面貼合的第3步驟；以及從上述第1光學薄膜面側或上述第2光學薄膜面側照射活性能量射線，使上述第1光學薄膜與上述第2光學薄膜接著的第4步驟。The laminated optical film of the present invention is characterized in that the in-plane refractive index is different between the front side and the back side of the adhesive layer. The laminated optical film provided with the said adhesive layer can be manufactured by the following manufacturing method, for example. A method for manufacturing a laminated optical film, in which at least a first optical film and a second optical film are laminated via an adhesive layer, and the adhesive layer includes a first cured layer and a second adhesive of the first adhesive composition The second cured layer of the agent composition, wherein the first adhesive composition and the second adhesive composition contain at least a part of different components, and the method includes: coating the first optical film on the bonding surface of the first optical film. 1. The first step of the adhesive composition; the second step of applying the second adhesive composition to the bonding surface of the second optical film; applying the first adhesive composition of the first optical film The third step of bonding the second adhesive composition coating surface of the second optical film to the second optical film; and irradiating active energy rays from the first optical film surface side or the second optical film surface side to make the second optical film surface 1 The fourth step of bonding the optical film to the above-mentioned second optical film.
在上述製造方法中，接著劑層包含第1接著劑組成物的第1硬化物層及第2接著劑組成物的第2硬化物層，且第1接著劑組成物與第2接著劑組成物含有至少一部分不同的成分，因此，可形成一接著劑層其在第1光學薄膜側表面F1的面內折射率RF1 與第2光學薄膜側表面F2的面內折射率RF2 不同。在此，第1光學薄膜的面內平均折射率及第2光學薄膜的面內平均折射率可以預先測定，第1接著劑組成物的第1硬化物層的第1光學薄膜側表面F1的面內折射率RF1 及第2光學薄膜側表面F2的面內折射率RF2 也可以藉由分別進行最佳的配合設計而設計成任意的值。因此，在上述製造方法中，可以製造具備下述接著劑層的積層光學薄膜，該接著劑層的RF1 與第1光學薄膜的面內平均折射率之差為0.05以內、RF2 與第2光學薄膜的面內平均折射率之差為0.05以內。In the above manufacturing method, the adhesive layer includes the first cured layer of the first adhesive composition and the second cured layer of the second adhesive composition, and the first adhesive composition and the second adhesive composition Containing at least a part of different components, it is possible to form an adhesive layer in which the in-plane refractive index R F1 of the first optical film side surface F1 is different from the in-plane refractive index R F2 of the second optical film side surface F2. Here, the in-plane average refractive index of the first optical film and the in-plane average refractive index of the second optical film can be measured in advance. The first optical film side surface F1 of the first cured layer of the first adhesive composition The internal refractive index R F1 and the in-plane refractive index R F2 of the second optical film side surface F2 can also be designed to arbitrary values by performing optimal matching design, respectively. Therefore, in the above-mentioned manufacturing method, it is possible to manufacture a laminated optical film having an adhesive layer whose R F1 and the first optical film have an in-plane average refractive index difference within 0.05, R F2 and the second optical film. The difference in the average in-plane refractive index of the optical film is within 0.05.
此外，在上述第1步驟中，可以從上述第1光學薄膜面側或上述第1光學薄膜的上述第1接著劑組成物塗敷面側，對塗敷後的上述第1接著劑組成物照射活性能量射線，使上述第1接著劑組成物硬化，預先形成上述第1硬化物層，也可以藉由將塗敷後的上述第1接著劑組成物風乾，進而在塗敷後的上述第1接著劑組成物含有溶劑的情況下，將溶劑除去，從而預先形成未硬化的第1接著劑組成物的塗敷層。In the first step, the coated first adhesive composition may be irradiated from the first optical film surface side or the first adhesive composition application surface side of the first optical film. Active energy rays harden the first adhesive composition to form the first cured layer in advance. Alternatively, the coated first adhesive composition may be dried by air, and then the first adhesive composition after application may be dried. When the adhesive composition contains a solvent, the solvent is removed to form an uncured coating layer of the first adhesive composition in advance.
在本發明的積層光學薄膜中，在第1光學薄膜為透明保護薄膜、第2光學薄膜為偏光件的情況下，可以在上述第1步驟及/或第二塗敷步驟(塗敷步驟)前進行表面改性處理。作為具體的處理，可列舉基於電暈處理、電漿處理、皂化處理的處理等。In the laminated optical film of the present invention, in the case where the first optical film is a transparent protective film and the second optical film is a polarizer, it may be before the first step and/or the second coating step (coating step). Carry out surface modification treatment. Specific treatments include corona treatment, plasma treatment, saponification treatment, and the like.
另外，在上述第1步驟及/或第二塗敷步驟(塗敷步驟)中，活性能量射線硬化型接著劑組成物的塗敷方式可根據組成物的黏度、目標厚度適宜選擇。作為塗敷方式的例子，可列舉例如：逆向塗布器、凹版塗布器(直接、反向、或膠版)、棒式逆向塗布器、輥塗機、模塗機、繞線棒塗布器、棒塗機等。此外，塗敷時可以適宜使用浸漬方式等方式。In addition, in the above-mentioned first step and/or second coating step (coating step), the coating method of the active energy ray-curable adhesive composition can be appropriately selected according to the viscosity and target thickness of the composition. Examples of coating methods include reverse coaters, gravure coaters (direct, reverse, or offset), bar reverse coaters, roll coaters, die coaters, wire-wound coaters, and bar coaters. Machine waiting. In addition, a method such as a dipping method can be suitably used for coating.
在上述第3步驟(貼合步驟)中，隔著塗敷後的活性能量射線硬化型接著劑組成物貼合2種不同的光學薄膜。光學薄膜的貼合可以藉由例如輥式層壓機等來進行。In the above-mentioned third step (bonding step), two different optical films are bonded via the applied active energy ray-curable adhesive composition. The bonding of the optical film can be performed by, for example, a roll laminator.
在上述第4步驟(接著步驟)中，活性能量射線硬化型接著劑組成物可以以電子束硬化型、紫外線硬化型、可見光硬化型的方式使用。作為活性能量射線硬化型接著劑組成物，從生產性的觀點考慮，優選可見光硬化型接著劑組成物。In the above-mentioned fourth step (following step), the active energy ray curable adhesive composition can be used in an electron beam curable type, an ultraviolet curable type, or a visible light curable type. As the active energy ray-curable adhesive composition, a visible light-curable adhesive composition is preferable from the viewpoint of productivity.
對於活性能量射線硬化型接著劑組成物而言，例如將偏光件和透明保護薄膜貼合後，照射活性能量射線(電子束、紫外線、可見光等)，使活性能量射線硬化型接著劑組成物硬化，從而形成接著劑層。在上述第4步驟(接著步驟)中，活性能量射線(電子束、紫外線、可見光等)的照射方向可從任意適當的方向照射。優選從透明保護薄膜側照射。如果從偏光件側照射，則恐有偏光件因活性能量射線(電子束、紫外線、可見光等)而劣化之虞。For the active energy ray hardening adhesive composition, for example, after bonding a polarizer and a transparent protective film, active energy rays (electron beam, ultraviolet, visible light, etc.) are irradiated to harden the active energy ray hardening adhesive composition , Thereby forming an adhesive layer. In the above-mentioned fourth step (following step), the irradiation direction of the active energy rays (electron beam, ultraviolet light, visible light, etc.) can be irradiated from any appropriate direction. It is preferable to irradiate from the side of the transparent protective film. If it is irradiated from the polarizer side, the polarizer may be degraded by active energy rays (electron beam, ultraviolet light, visible light, etc.).
在電子束硬化型中，電子束的照射條件只要是能使上述活性能量射線硬化型接著劑組成物硬化的條件即可，可以採用任意適當的條件。例如，電子束照射的加速電壓優選為5kV~300kV、進一步優選為10kV~250kV。加速電壓小於5kV時，恐有電子束不能達到接著劑、變得硬化不充分之虞，如果加速電壓大於300kV，則恐有穿過試樣的浸透力過強而對透明保護薄膜、偏光件帶來損傷之虞。作為照射線量，為5~100kGy、進一步優選為10~75kGy。照射線量小於5kGy時，接著劑的硬化不充分，如果大於100kGy，則對透明保護薄膜、偏光件帶來損傷，發生機械強度的降低、黃變，無法得到給定的光學特性。In the electron beam hardening type, the irradiation conditions of the electron beam may be conditions that can harden the above-mentioned active energy ray hardening adhesive composition, and any appropriate conditions can be adopted. For example, the acceleration voltage of electron beam irradiation is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. When the accelerating voltage is less than 5kV, there is a risk that the electron beam cannot reach the adhesive and the curing will be insufficient. If the accelerating voltage is greater than 300kV, the penetration force through the sample may be too strong, which may affect the transparent protective film and the polarizer. The danger of injury. The radiation dose is 5 to 100 kGy, and more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the curing of the adhesive is insufficient, and if it is more than 100 kGy, it damages the transparent protective film and polarizer, reduces the mechanical strength, yellows, and cannot obtain the given optical properties.
電子束照射通常在非活性氣體中進行照射，可以根據需要在大氣中、少量導入了氧的條件下進行。根據透明保護薄膜的材料的不同，適宜導入氧，與最初電子束接觸的透明保護薄膜面接觸，發生氧阻礙，可防止對透明保護薄膜的損傷，可以僅對接著劑高效地照射電子束。The electron beam irradiation is usually carried out in an inert gas, and can be carried out in the atmosphere with a small amount of oxygen introduced as needed. Depending on the material of the transparent protective film, oxygen is appropriately introduced, and the surface of the transparent protective film that is in contact with the first electron beam is blocked by oxygen. This prevents damage to the transparent protective film, and can efficiently irradiate only the adhesive with electron beams.
製造本發明的積層光學薄膜時，作為活性能量射線，優選使用包含波長範圍380nm~450nm的可見光的活性能量射線、特別是波長範圍380nm~450nm的可見光的照射量最多的活性能量射線。在紫外線硬化型、可見光硬化型中，在使用賦予了紫外線吸收能力的透明保護薄膜(紫外線不透射型透明保護薄膜)的情況下，吸收大約比380nm短波長的光，因此，比380nm短波長的光不會到達活性能量射線硬化型接著劑，對其聚合反應沒有貢獻。此外，由透明保護薄膜吸收的比380nm短波長的光會轉變成熱，透明保護薄膜自身會發熱，而成為積層光學薄膜捲曲/褶皺等不良的原因。因此，在本發明中，採用紫外線硬化型、可見光硬化型的情況下，優選使用不發出比380nm短波長的光的裝置作為活性能量射線產生裝置，更具體而言，波長範圍380~440nm的累積照度與波長範圍250~370nm的累積照度之比優選為100:0~100:50、更優選為100:0~100:40。作為本發明的活性能量射線，優選封入有鎵的金屬鹵化物燈、發出波長範圍380~440nm的光的LED光源。或者可以使用低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、白熾燈、氙燈、鹵素燈、碳弧燈、金屬鹵化物燈、螢光燈、鎢燈、鎵燈、準分子雷射或太陽光等包含紫外線和可見光的光源，也可以用帶通濾波器將比380nm短的波長的紫外線阻斷後使用。為了提高偏光件與透明保護薄膜之間的接著劑層的接著性能，並防止積層光學薄膜的捲曲，優選使用封入有鎵的金屬鹵化物燈，且使用藉由可阻斷比380nm短波長的光的帶通濾波器得到的活性能量射線、或使用LED光源得到的波長405nm的活性能量射線。When manufacturing the laminated optical film of the present invention, as the active energy ray, it is preferable to use an active energy ray containing visible light having a wavelength range of 380 nm to 450 nm, particularly an active energy ray having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm. In the ultraviolet curable type and visible light curable type, when a transparent protective film (UV non-transmissive transparent protective film) imparted with ultraviolet absorbing ability is used, it absorbs light with a wavelength shorter than 380nm, so it is shorter than 380nm. Light does not reach the active energy ray-curable adhesive and does not contribute to its polymerization reaction. In addition, light with a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkles of the laminated optical film. Therefore, in the present invention, when the ultraviolet curing type and the visible light curing type are used, it is preferable to use a device that does not emit light with a wavelength shorter than 380 nm as the active energy ray generating device, more specifically, the cumulative wavelength range of 380 to 440 nm. The ratio of the illuminance to the cumulative illuminance in the wavelength range of 250 to 370 nm is preferably 100:0 to 100:50, more preferably 100:0 to 100:40. As the active energy ray of the present invention, a metal halide lamp encapsulated with gallium and an LED light source emitting light in the wavelength range of 380 to 440 nm are preferable. Or you can use low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer Light sources containing ultraviolet and visible light, such as lasers or sunlight, can also be used after blocking ultraviolet rays with a wavelength shorter than 380 nm with a band-pass filter. In order to improve the bonding performance of the adhesive layer between the polarizer and the transparent protective film, and prevent curling of the laminated optical film, it is preferable to use a metal halide lamp encapsulated with gallium, and it is preferable to use a metal halide lamp that can block light with a wavelength shorter than 380nm. The active energy rays obtained by the band-pass filter or the active energy rays with a wavelength of 405 nm obtained by using an LED light source.
在紫外線硬化型或可見光硬化型中，也優選在照射紫外線或可見光後對活性能量射線硬化型接著劑進行加熱(照射後加熱)，該情況下，優選加熱至40℃以上、更優選加熱至50℃以上。In the ultraviolet curable or visible light curable type, it is also preferable to heat the active energy ray curable adhesive after irradiating ultraviolet or visible light (heating after irradiation). In this case, it is preferably heated to 40°C or higher, more preferably to 50°C. ℃ above.
本發明中使用的活性能量射線硬化型接著劑，特別可適用在形成下述接著劑層時，該接著劑層會將偏光件與波長365nm的透光率小於5%的透明保護薄膜接著。此處，本發明的活性能量射線硬化型接著劑藉由含有上述的通式(1)的光聚合引發劑，能夠隔著具有UV吸收能力的透明保護薄膜照射紫外線而硬化形成接著劑層。因此，即使對於在偏光件的兩面積層有具有UV吸收能力的透明保護薄膜的積層光學薄膜，也能夠使接著劑層硬化。但是，當然，對於積層有不具有UV吸收能力的透明保護薄膜的積層光學薄膜，也能夠使接著劑層硬化。此外，具有UV吸收能力的透明保護薄膜是指對380nm的光的透射率小於10%的透明保護薄膜。The active energy ray-curable adhesive used in the present invention is particularly suitable for forming the following adhesive layer, which will bond the polarizer to a transparent protective film with a light transmittance of less than 5% at a wavelength of 365 nm. Here, the active energy ray-curable adhesive of the present invention contains the photopolymerization initiator of the above-mentioned general formula (1), and can be cured by irradiating ultraviolet rays through a transparent protective film having UV absorbing ability to form an adhesive layer. Therefore, even for a laminated optical film in which a transparent protective film having UV absorption capability is layered on both areas of the polarizer, the adhesive layer can be cured. However, of course, it is also possible to harden the adhesive layer for a laminated optical film in which a transparent protective film having no UV absorbing ability is laminated. In addition, a transparent protective film with UV absorption capability refers to a transparent protective film with a transmittance of less than 10% to 380nm light.
作為對透明保護薄膜賦予UV吸收能力的方法，可列舉：使透明保護薄膜中含有紫外線吸收劑的方法、在透明保護薄膜表面積層含有紫外線吸收劑的表面處理層的方法。As a method of imparting UV absorbing ability to a transparent protective film, a method of containing an ultraviolet absorber in the transparent protective film, and a method of containing a surface treatment layer of an ultraviolet absorber in the surface area of the transparent protective film can be cited.
作為紫外線吸收劑的具體例，例如可列舉：以往公知的氧基二苯甲酮類化合物、苯並***類化合物、水楊酸酯類化合物、二苯甲酮類化合物、氰基丙烯酸酯類化合物、鎳絡鹽類化合物、三嗪類化合物等。Specific examples of ultraviolet absorbers include, for example, conventionally known oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, and cyanoacrylates. Compounds, nickel complex salt compounds, triazine compounds, etc.
＜第2接著劑層＞ 在圖2所示的實施方式中，第2接著劑層4可以與上述第1接著劑層同樣地設計。然而，在圖2所示的實施方式中，入射至第2接著劑層4的光L透過偏光件(第2光學薄膜)3而入射，因此，會成為偏光件3透射軸方向的偏光。因此，為了抑制在偏光件3與第2接著劑層4的界面、以及在相位差薄膜5與第2接著劑層4的界面的反射，優選第2接著劑層4的偏光件3側表面F3的偏光件3透射軸方向的折射率RF3 與相位差薄膜5側表面F4的偏光件3透射軸方向的折射率RF4 不同，RF3 與偏光件3的透射軸方向的折射率之差為0.05以內，RF4 與相位差薄膜5的偏光件3的透射軸方向的折射率之差為0.05以內。該情況下，影像顯示裝置M整體的反射率會降低，視覺辨認性會顯著提高。<Second Adhesive Layer> In the embodiment shown in FIG. 2, the second adhesive layer 4 can be designed in the same manner as the first adhesive layer described above. However, in the embodiment shown in FIG. 2, the light L incident on the second adhesive layer 4 passes through the polarizer (second optical film) 3 and enters, and therefore becomes polarized light in the direction of the transmission axis of the polarizer 3. Therefore, in order to suppress reflection at the interface between the polarizer 3 and the second adhesive layer 4 and at the interface between the retardation film 5 and the second adhesive layer 4, it is preferable that the surface F3 of the second adhesive layer 4 on the side of the polarizer 3 The refractive index R F3 in the transmission axis direction of the polarizer 3 is different from the refractive index R F4 in the transmission axis direction of the polarizer 3 on the side surface F4 of the retardation film 5, and the difference between the refractive index in the transmission axis direction of R F3 and the polarizer 3 is Within 0.05, the difference between the refractive index of the RF4 and the transmission axis direction of the polarizer 3 of the retardation film 5 is within 0.05. In this case, the reflectance of the entire image display device M will decrease, and the visibility will be significantly improved.
＜第3光學薄膜＞ 第3光學薄膜沒有特別限定，可以使用例如反射薄膜、半透射薄膜、相位差薄膜(包括1/2、1/4等波片)、視覺補償薄膜等會在影像顯示裝置等的形成時使用的光學層。在本發明中，優選第3光學薄膜的厚度薄的情況，具體而言，優選為20μm以下、更優選為1~10μm。＜The third optical film＞ The third optical film is not particularly limited. For example, reflective films, semi-transmissive films, retardation films (including 1/2 and 1/4 wave plates), visual compensation films, etc. can be used in the formation of image display devices. Optical layer. In the present invention, the thickness of the third optical film is preferably thin. Specifically, it is preferably 20 μm or less, and more preferably 1 to 10 μm.
＜黏著劑層＞
在圖2所示的實施方式中，將上述的具備透明保護薄膜(第1光學薄膜)1、第1接著劑層2、偏光件(第2光學薄膜)3、第2接著劑層4及相位差薄膜(第3光學薄膜)5的積層光學薄膜隔著黏著劑層6積層於有機發光二極體7。形成黏著層的黏著劑沒有特殊限制，可以適宜地選擇將例如丙烯酸類聚合物、矽氧類聚合物、聚酯、聚氨酯、聚醯胺、聚醚、氟類、橡膠類等聚合物作為基礎聚合物的黏著劑來使用。可以特別優選使用丙烯酸類黏著劑那樣的光學透明性優異、顯示出適度的潤濕性、聚集性和接著性這種黏著特性，耐候性、耐熱性等優異的黏著劑。＜Adhesive layer＞
In the embodiment shown in FIG. 2, the above-mentioned transparent protective film (first optical film) 1, the first adhesive layer 2, the polarizer (the second optical film) 3, the second adhesive layer 4, and the phase The laminated optical film of the difference film (third optical film) 5 is laminated on the organic
黏著層可以以不同的組成或種類等的層作成重疊層而設置於偏光薄膜、光學薄膜的單面或兩面上。另外，設置於兩面時，也可以在偏光薄膜、光學薄膜的表面和背面上形成不同的組成、種類、厚度等的黏著層。黏著層的厚度可以根據使用目的、接著力等來適宜決定，通常為1~500μm、優選為1~200μm、特別優選為1~100μm。The adhesive layer can be formed as an overlapping layer with layers of different compositions or types, etc., and arranged on one side or both sides of a polarizing film or an optical film. In addition, when it is installed on both sides, adhesive layers of different compositions, types, thicknesses, etc. can also be formed on the front and back surfaces of the polarizing film and the optical film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use, adhesive strength, etc., and is usually 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.
黏著層的露出面在直到供於實際使用為止的期間，出於防止其污染等目的，暫時接著分隔件將其覆蓋。由此，能夠防止在通常的處理狀態下與黏著層接觸。作為分隔件，可以使用除了上述厚度條件以外，根據需要以矽氧類、長鏈烷基類、氟類、硫化鉬等適宜的剝離劑，對下述列舉各者進行塗布處理而成的分隔件等依以往規定的適宜分隔件，例如：塑膠膜、橡膠片、紙、布、無紡布、網、發泡片、金屬箔、其等的層壓體等適宜的薄層體。The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination and the like until it is put into actual use. This can prevent contact with the adhesive layer in a normal processing state. As the separator, in addition to the above-mentioned thickness conditions, a separator obtained by applying suitable release agents such as silicones, long-chain alkyls, fluorines, molybdenum sulfide, etc., to each of the following can be used as required. Suitable separators according to previous regulations, such as plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets, metal foils, laminates of these, and other suitable thin layers.
＜影像顯示裝置＞ 本發明的積層光學薄膜可以優選用於有機EL圖像裝置、液晶顯示裝置等各種影像顯示裝置的形成等。影像顯示裝置的形成可以根據以往的方式來進行。即，影像顯示裝置通常藉由將有機發光二極體、液晶單元與積層光學薄膜、及根據需要使用的照明系統等構成部件適宜組裝並將驅動電路裝入等來形成，在本發明中，除了使用本發明的積層光學薄膜這一點以外，沒有特別限定，可以根據以往的方式來進行。＜Video display device＞ The laminated optical film of the present invention can be preferably used for the formation of various image display devices such as organic EL image devices and liquid crystal display devices. The formation of the image display device can be performed according to the conventional method. That is, the image display device is generally formed by appropriately assembling constituent parts such as an organic light-emitting diode, a liquid crystal cell, a laminated optical film, and an illumination system used as needed, and incorporating a driving circuit, etc., in the present invention, except It is not particularly limited except for the use of the laminated optical film of the present invention, and it can be performed according to a conventional method.
將本發明的積層光學薄膜用於液晶顯示裝置時，可以形成在液晶單元的單側或兩側配置有積層光學薄膜的液晶顯示裝置、在照明系統中使用了背光燈或反射板的液晶顯示裝置等適宜的液晶顯示裝置。在這種情況下，本發明的積層光學薄膜可以設置在液晶單元的單側或兩側。在兩側設置積層光學薄膜的情況下，它們可以相同，也可以不同。進而，在液晶顯示裝置的形成時，可以在適宜的位置配置1層或2層以上的例如擴散板、防眩層、防反射膜、保護板、稜鏡陣列、透鏡陣列片、光擴散板、背光燈等適宜的部件。 實施例When the laminated optical film of the present invention is used in a liquid crystal display device, it can be formed in a liquid crystal display device with a laminated optical film arranged on one side or both sides of a liquid crystal cell, and a liquid crystal display device using a backlight or a reflective plate in an illumination system And other suitable liquid crystal display devices. In this case, the laminated optical film of the present invention may be provided on one side or both sides of the liquid crystal cell. When the laminated optical film is provided on both sides, they may be the same or different. Furthermore, when the liquid crystal display device is formed, one layer or two or more layers such as diffuser, anti-glare layer, anti-reflection film, protective plate, lens array, lens array sheet, light diffuser, etc. can be arranged at a suitable position. Suitable parts such as backlights. Example
在以下示出的實施例1~3及比較例1中，藉由模擬來對積層光學薄膜進行模型設計。模擬時，使用市售液晶模擬器的“LCD Mater(Shintech公司製)”。另外，將光學計算演算法設為4×4瓊斯矩陣法。此外，使用380nm~780nm的光來作為從第1光學薄膜側至積層光學薄膜的入射光(隨機光)。In Examples 1 to 3 and Comparative Example 1 shown below, the model design of the laminated optical film was performed by simulation. For the simulation, "LCD Mater (manufactured by Shintech Corporation)" of a commercially available liquid crystal simulator was used. In addition, the optical calculation algorithm is set to the 4×4 Jones matrix method. In addition, light of 380 nm to 780 nm was used as incident light (random light) from the side of the first optical film to the laminated optical film.
(第1光學薄膜(透明保護薄膜)) 作為第1光學薄膜，使用了550nm的面內平均折射率為1.6的QL膜(厚度1.5μm、富士薄膜股份有限公司製)。(First optical film (transparent protective film)) As the first optical film, a QL film (thickness 1.5 μm, manufactured by Fuji Film Co., Ltd.) having a 550 nm in-plane average refractive index of 1.6 was used.
(第2光學薄膜(偏光件)) 作為第2光學薄膜，使用了550nm的面內平均折射率為1.555的偏光件(厚度5μm)的光學薄膜。(Second optical film (polarizer)) As the second optical film, an optical film of a polarizer (thickness 5 μm) with a 550 nm in-plane average refractive index of 1.555 was used.
實施例1~3 使用LCD Mater，設計第1光學薄膜側表面F1的面內折射率RF1 及第2光學薄膜側表面F2的面內折射率RF2 成為表1所載之值的接著劑層，並設計隔著上述接著劑層積層有第1光學薄膜及第2光學薄膜的積層光學薄膜，計算出從第1光學薄膜側向積層光學薄膜照射隨機光時的反射率，將結果示於表1。Examples 1 to 3 Using LCD Mater, an adhesive layer was designed such that the in-plane refractive index R F1 of the first optical film side surface F1 and the in-plane refractive index R F2 of the second optical film side surface F2 became the values listed in Table 1. , And design a laminated optical film in which the first optical film and the second optical film are laminated via the above-mentioned adhesive layer, and calculate the reflectance when random light is irradiated from the side of the first optical film to the laminated optical film. The results are shown in the table 1.
比較例1 使用LCD Mater，設計在厚度方向上面內折射率恒定的接著劑層(單層的接著劑層)，並設計隔著上述接著劑層積層有第1光學薄膜及第2光學薄膜的積層光學薄膜，計算出其反射率，將結果示於表1。Comparative example 1 Using LCD Mater, design an adhesive layer (single-layer adhesive layer) with a constant refractive index on the upper surface in the thickness direction, and design a laminated optical film in which a first optical film and a second optical film are laminated via the above-mentioned adhesive layer, The reflectance was calculated, and the results are shown in Table 1.
表1
根據表1的結果可知，對於實施例1~3的積層光學薄膜而言，由於將｜R(a) -RF1 ｜及｜R(b) -RF2 ｜設計為0.05以內，因此，外部光(隨機光)入射至積層光學薄膜時的反射率低，視覺辨認性優異。另一方面，對於相當於現有積層光學薄膜的比較例的積層光學薄膜而言，可知｜R(a) -RF1 ｜及｜R(b) -RF2 ｜均超過0.05，因此，反射率大，視覺辨認性差。According to the results in Table 1, for the laminated optical films of Examples 1 to 3, since |R (a) -R F1 | and |R (b) -R F2 | are designed to be within 0.05, the external light (Random light) The reflectance when incident on the laminated optical film is low, and the visibility is excellent. On the other hand, for the laminated optical film corresponding to the comparative example of the conventional laminated optical film, it can be seen that both |R (a) -R F1 | and |R (b) -R F2 | , Poor visual recognition.
1:第1光學薄膜,透明保護薄膜 2:第1接著劑層,接著劑層 3:第2光學薄膜,偏光件 4:第2接著劑層 5:第3光學薄膜,相位差薄膜 6:黏著劑層 7:有機發光二極體 10:積層光學薄膜 F1,F2:側表面 L:外部光,自然光 LR:反射光 M:影像顯示裝置1: The first optical film, transparent protective film 2: the first adhesive layer, the adhesive layer 3: the second optical film, the polarizer 4: the second adhesive layer 5: the third optical film, the retardation film 6: the adhesion Agent layer 7: organic light-emitting diode 10: laminated optical film F1, F2: side surface L: external light, natural light L R : reflected light M: image display device
圖1是示出具備目前存在的積層光學薄膜的影像顯示裝置中來自外部光的反射的一例的圖。 圖2(a)~(b)是示出具備本發明的積層光學薄膜的影像顯示裝置的一例的圖。FIG. 1 is a diagram showing an example of reflection of external light in an image display device provided with a conventional laminated optical film. 2(a) to (b) are diagrams showing an example of an image display device provided with the laminated optical film of the present invention.
1:第1光學薄膜，透明保護薄膜 1: The first optical film, transparent protective film
2:第1接著劑層，接著劑層 2: The first adhesive layer, adhesive layer
3:第2光學薄膜，偏光件 3: The second optical film, polarizer
4:第2接著劑層 4: The second adhesive layer
5:第3光學薄膜，相位差薄膜 5: The third optical film, retardation film
6:黏著劑層 6: Adhesive layer
7:有機發光二極體 7: Organic light-emitting diode
10:積層光學薄膜 10: Laminated optical film
F1,F2:側表面 F1, F2: side surface
L:外部光，自然光 L: External light, natural light
M:影像顯示裝置 M: Video display device
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