TW202138851A - Circular polarizing sheet and optical laminate - Google Patents
Circular polarizing sheet and optical laminate Download PDFInfo
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- TW202138851A TW202138851A TW110108606A TW110108606A TW202138851A TW 202138851 A TW202138851 A TW 202138851A TW 110108606 A TW110108606 A TW 110108606A TW 110108606 A TW110108606 A TW 110108606A TW 202138851 A TW202138851 A TW 202138851A
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- layer
- polarizing plate
- retardation
- adhesive
- liquid crystal
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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
- H10K59/80—Constructional details
- H10K59/8793—Arrangements for polarized light emission
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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
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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- 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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- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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Abstract
Description
本發明是有關於一種圓偏光板、光學積層體及顯示裝置。The invention relates to a circular polarizing plate, an optical laminate and a display device.
在有機電致發光（electroluminescence，EL）顯示裝置為代表的顯示裝置中，已知有使用具有可撓性的材料而能夠實現顯示裝置的彎曲等的撓性顯示器（例如專利文獻1、專利文獻2）。已知在有機EL顯示裝置中，為了抑制因外部光的反射而導致的視認性的降低，使用圓偏光板等來提高防反射性能。圓偏光板可將直線偏光板及相位差層積層而獲得，有時使用聚合性液晶化合物的硬化物層作為相位差層。
[現有技術文獻]
[專利文獻]Among display devices typified by organic electroluminescence (EL) display devices, there are known flexible displays that can achieve bending of the display device by using flexible materials (for example,
[專利文獻1]日本專利特開2019-91021號公報 [專利文獻2]日本專利特開2019-91091號公報[Patent Document 1] Japanese Patent Laid-Open No. 2019-91021 [Patent Document 2] Japanese Patent Laid-Open No. 2019-91091
[發明所欲解決之課題][The problem to be solved by the invention]
如上所述，包括聚合性液晶化合物的硬化物層的相位差層的圓偏光板作為與構成顯示裝置的最表面的前表面板等貼合的光學積層體，組裝在撓性顯示器中，有時以圓偏光板的直線偏光層側成為外側的方式反覆彎曲。在歷經此種彎曲的撓性顯示器中，與自正面觀察時的反射光的色相（色澤）相比，自傾斜方向觀察時的反射光的色相有時不同。As described above, the circularly polarizing plate including the retardation layer of the cured layer of the polymerizable liquid crystal compound is assembled in a flexible display as an optical laminate bonded to the front surface plate or the like constituting the outermost surface of the display device. The circular polarizing plate is repeatedly bent so that the linear polarizing layer side of the circular polarizing plate becomes the outer side. In a flexible display that undergoes such bending, the hue of reflected light when viewed from an oblique direction may be different from the hue (color) of reflected light when viewed from the front.
本發明的目的在於提供一種即使在撓性顯示器等顯示裝置等中歷經彎曲後，亦可抑制自傾斜方向觀察時的反射光的色相較自正面觀察時不同的圓偏光板、包括其的光學積層體及顯示裝置。 [解決課題之手段]The object of the present invention is to provide a circular polarizing plate that can suppress the color of reflected light when viewed from an oblique direction is different from that when viewed from the front, and an optical laminate including the same even after bending in a display device such as a flexible display. Body and display device. [Means to solve the problem]
本發明提供以下的圓偏光板、光學積層體、及顯示裝置。 〔1〕一種圓偏光板，依次包括至少包含直線偏光層的光學層、第一貼合層、第一相位差層、第二貼合層、及第二相位差層，所述圓偏光板中， 所述第一相位差層包括作為聚合性液晶化合物的硬化物層的第一液晶層， 當所述第一貼合層及所述第二貼合層的溫度25℃下的彈性係數分別為G'1[kPa]及G'2[kPa]，所述第一貼合層及所述第二貼合層的厚度分別為d1[μm]及d2[μm]時，滿足下述式（1）的關係： G'1/d1≧G'2/d2 （1）。 〔2〕如〔1〕所述的圓偏光板，所述第一相位差層的厚度為t[μm]，且 在彎曲試驗後的所述圓偏光板的彎曲部分的剖面中，所述第一相位差層的所述第一貼合層側的表面中的最接近所述光學層側的位置與距所述光學層側最遠的位置之間的厚度方向上的距離為ΔS[μm]時，滿足下述式（2）的關係： ΔS≦2t （2）。 〔3〕如〔1〕或〔2〕所述的圓偏光板，其中，所述第二相位差層包括作為聚合性液晶化合物的硬化物層的第二液晶層。 〔4〕如〔1〕至〔3〕中任一項所述的圓偏光板，其中，所述第一相位差層的厚度為5 μm以下。 〔5〕如〔1〕至〔4〕中任一項所述的圓偏光板，其中，所述直線偏光層包含聚合性液晶化合物的硬化物及二色性色素。 〔6〕如〔1〕至〔5〕中任一項所述的圓偏光板，其中，所述光學層為於所述直線偏光層的單面或兩面具有保護層的偏光板。 〔7〕如〔1〕至〔6〕中任一項所述的圓偏光板，其中，所述第一相位差層及所述第二相位差層滿足下述[a]或[b]的關係： [a]所述第一相位差層為1/2波長板，所述第二相位差層為1/4波長板； [b]所述第一相位差層及所述第二相位差層中的一者為逆波長分散性的1/4波長板，另一者為正C板。 〔8〕如〔1〕至〔7〕中任一項所述的圓偏光板，其中，所述第一相位差層是逆波長分散性的1/4波長板， 所述第二相位差層是正C板。 〔9〕一種光學積層體，包括：如〔1〕至〔8〕中任一項所述的圓偏光板；以及前表面板，積層在所述圓偏光板的所述光學層側。 〔10〕一種顯示裝置，包括如〔9〕所述的光學積層體。 [發明的效果]The present invention provides the following circular polarizing plate, optical laminate, and display device. [1] A circularly polarizing plate comprising an optical layer including at least a linearly polarizing layer, a first bonding layer, a first retardation layer, a second bonding layer, and a second retardation layer in this order, in the circular polarizing plate , The first retardation layer includes a first liquid crystal layer as a cured layer of a polymerizable liquid crystal compound, When the elastic coefficients of the first bonding layer and the second bonding layer at a temperature of 25°C are G'1 [kPa] and G'2 [kPa], respectively, the first bonding layer and the When the thickness of the second bonding layer is d1 [μm] and d2 [μm], the relationship of the following formula (1) is satisfied: G'1/d1≧G'2/d2 (1). [2] The circular polarizing plate as described in [1], the thickness of the first retardation layer is t [μm], and In the cross section of the curved portion of the circularly polarizing plate after the bending test, the position closest to the optical layer side of the surface of the first retardation layer on the first bonding layer side and the distance from the When the distance in the thickness direction between the farthest positions on the optical layer side is ΔS [μm], the relationship of the following formula (2) is satisfied: ΔS≦2t (2). [3] The circularly polarizing plate according to [1] or [2], wherein the second retardation layer includes a second liquid crystal layer as a cured layer of a polymerizable liquid crystal compound. [4] The circularly polarizing plate according to any one of [1] to [3], wherein the thickness of the first retardation layer is 5 μm or less. [5] The circularly polarizing plate according to any one of [1] to [4], wherein the linearly polarizing layer includes a cured product of a polymerizable liquid crystal compound and a dichroic dye. [6] The circular polarizing plate according to any one of [1] to [5], wherein the optical layer is a polarizing plate having a protective layer on one or both sides of the linear polarizing layer. [7] The circularly polarizing plate according to any one of [1] to [6], wherein the first retardation layer and the second retardation layer satisfy the following [a] or [b] relation: [a] The first retardation layer is a half-wavelength plate, and the second retardation layer is a quarter-wavelength plate; [b] One of the first retardation layer and the second retardation layer is a reverse wavelength dispersion quarter-wave plate, and the other is a positive C plate. [8] The circularly polarizing plate according to any one of [1] to [7], wherein the first retardation layer is a quarter-wave plate with reverse wavelength dispersion, The second retardation layer is a positive C plate. [9] An optical laminate, comprising: the circular polarizing plate according to any one of [1] to [8]; and a front surface plate laminated on the optical layer side of the circular polarizing plate. [10] A display device comprising the optical laminate as described in [9]. [Effects of the invention]
根據本發明，可提供一種即使在撓性顯示器等顯示裝置等中歷經彎曲後，亦可抑制自傾斜方向觀察時的反射光的色相較自正面觀察時不同的圓偏光板。According to the present invention, it is possible to provide a circular polarizing plate that can suppress the color of reflected light when viewed from an oblique direction from being different when viewed from the front even after bending in a display device such as a flexible display.
以下，參照圖式說明本發明的實施方式，但本發明並不限定於以下的實施方式。以下所有圖式是為了幫助理解本發明而示出，圖式中所示的各構成要素的尺寸或形狀未必與實際的構成要素的尺寸或形狀一致。Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. All the following drawings are shown to help understand the present invention, and the size or shape of each component shown in the drawings may not be consistent with the size or shape of the actual component.
（圓偏光板）
圖1是示意性表示本實施方式的圓偏光板的一例的概略剖面圖。圖2是用於說明在圓偏光板的彎曲試驗之後使彎曲狀態返回的情況的一例的概略剖面圖。如圖1所示，圓偏光板1依次包括至少含有直線偏光層31的光學層30、第一貼合層21、第一相位差層11、第二貼合層22、及第二相位差層12。第一相位差層11包括作為聚合性液晶化合物的硬化物層的第一液晶層。(Circular Polarizing Plate)
FIG. 1 is a schematic cross-sectional view schematically showing an example of the circularly polarizing plate of this embodiment. Fig. 2 is a schematic cross-sectional view for explaining an example of a case where the bent state is returned after a bending test of a circularly polarizing plate. As shown in FIG. 1, the circularly
圓偏光板1滿足下述所示的＜i＞及＜ii＞中的至少一者。圓偏光板1可僅滿足＜i＞及＜ii＞中的一者，但較佳為至少滿足＜i＞，更佳為滿足＜i＞及＜ii＞兩者。The circularly
＜i＞當第一貼合層21的溫度25℃下的彈性係數為G'1[kPa]，第二貼合層22的溫度25℃下的彈性係數為G'2[kPa]，第一貼合層21的厚度為d1[μm]，第二貼合層22的厚度為d2[μm]時，圓偏光板1滿足下述式（1）的關係：
G'1/d1≧G'2/d2 （1）。
圓偏光板1較佳為滿足下述式（1'）的關係：
G'1/d1＞G'2/d2 （1'）。<i> When the elastic coefficient of the
＜ii＞圓偏光板1的第一相位差層11的厚度為t[μm]，且
在彎曲試驗後的所述圓偏光板的彎曲部分的剖面中，第一相位差層11的第一貼合層21側的表面中的最接近光學層30側的位置與距光學層30側最遠的位置之間的厚度方向上的距離為ΔS[μm]時，圓偏光板1滿足下述式（2）的關係：
ΔS≦2t （2）。<ii> The thickness of the
光學層30只要至少包括直線偏光層31即可，可包括在直線偏光層31的單面或兩面具有保護層的偏光板，亦可為偏光板本身。直線偏光層31可含有聚乙烯醇系樹脂膜，亦可含有聚合性液晶化合物的硬化物及二色性色素。圖1所示的圓偏光板1中，以光學層30為在直線偏光層31的兩面具有保護層32、保護層33的偏光板的情況為例來示出。The
第一貼合層21是用於貼合光學層30與第一相位差層11的層，可與光學層30及第一相位差層11直接接觸。第一貼合層21是黏著劑層或接著劑硬化層，較佳為接著劑硬化層。The
第一貼合層21的溫度25℃下的彈性係數G'1例如可為50 kPa以上，亦可為70 kPa以上，亦可為90 kPa以上，亦可為100 kPa以上，亦可為300 kPa以上，亦可為500 kPa以上。彈性係數G'1例如可為5×106
kPa以下，亦可為4×106
kPa以下，亦可為3×106
kPa以下，亦可為2.5×106
kPa以下，亦可為1×105
kPa以下，亦可為1×104
kPa以下，亦可為5×103
kPa以下，亦可為3×103
kPa以下，亦可為2×103
kPa以下，亦可為1×103
kPa以下，亦可為800 kPa以下。彈性係數G'1可藉由後述實施例中記載的方法來測定。The elastic coefficient G'1 of the
於第一貼合層21是黏著劑層的情況下，所述彈性係數G'1例如可為50 kPa以上，亦可為70 kPa以上，亦可為90 kPa以上，另外，亦可為5×103
kPa以下，亦可為3×103
kPa以下，亦可為2×103
kPa以下，亦可為1×103
kPa以下，亦可為800 kPa以下。於第一貼合層21是接著劑硬化層的情況下，所述彈性係數G'1例如可為8×105
kPa以上，亦可為1×106
kPa以上，另外，亦可為5×106
kPa以下，亦可為3×106
kPa以下，亦可為1×105
kPa以下。In the case where the
於第一貼合層21為黏著劑層的情況下，第一貼合層21的厚度d1例如可為1 μm以上，亦可為5 μm以上，亦可為10 μm以上，亦可為15 μm以上，另外，例如可為50 μm以下，亦可為40 μm以下，亦可為30 μm以下，亦可為25 μm以下。於第一貼合層21為接著劑硬化層的情況下，第一貼合層21的厚度d1例如可為0.01 μm以上，亦可為0.1 μm以上，亦可為0.5 μm以上，亦可為1 μm以上，另外，例如可為20 μm以下，亦可為15 μm以下，亦可為10 μm以下，亦可為5 μm以下。When the
如上所述，第一相位差層11包含作為聚合性液晶化合物的硬化物層的第一液晶層。第一相位差層11可為第一液晶層本身，亦可為第一液晶層與第一配向層的積層體。在第一相位差層11包括第一配向層的情況下，第一配向層可設置在第一液晶層的光學層30側，亦可設置在第一液晶層的第二貼合層22側。As described above, the
第一相位差層11的厚度t例如可為0.01 μm以上，亦可為0.05 μm以上，亦可為0.1 μm以上，亦可為0.5 μm以上，亦可為1 μm以上。厚度t較佳為5 μm以下，可為4 μm以下，亦可為3 μm以下。The thickness t of the
第二貼合層22是用於貼合第一相位差層11與第二相位差層12的層，可與第一相位差層11及第二相位差層12直接接觸。第二貼合層22是黏著劑層或接著劑硬化層，較佳為黏著劑層。The
第二貼合層22的溫度25℃下的彈性係數G'2例如可為10 kPa以上，亦可為20 kPa以上，亦可為30 kPa以上。彈性係數G'2例如可為3×106
kPa以下，亦可為2×106
kPa以下，亦可為1×106
kPa以下，亦可為5×105
kPa以下，亦可為1×105
kPa以下，亦可為1×104
kPa以下，亦可為5×103
kPa以下，亦可為3×103
kPa以下，亦可為2×103
kPa以下，亦可為1×103
kPa以下，亦可為800 kPa以下。彈性係數G'2可藉由後述實施例中記載的方法來測定。The elastic coefficient G'2 at the temperature of the
於第二貼合層22是黏著劑層的情況下，所述彈性係數G'2例如可為10 kPa以上，亦可為20 kPa以上，亦可為30 kPa以上，另外，亦可為5×103
kPa以下，亦可為3×103
kPa以下，亦可為2×103
kPa以下，亦可為1×103
kPa以下，亦可為800 kPa以下。於第二貼合層22是接著劑硬化層的情況下，所述彈性係數G'2例如可為1×105
kPa以上，亦可為5×105
kPa以上，另外，亦可為3×106
kPa以下，亦可為2×106
kPa以下，亦可為1×106
kPa以下。When the
於第二貼合層22為黏著劑層的情況下，第二貼合層22的厚度d2例如可為3 μm以上，亦可為5 μm以上，亦可為10 μm以上，另外，例如可為50 μm以下，亦可為40 μm以下，亦可為30 μm以下，亦可為25 μm以下。於第二貼合層22為接著劑硬化層的情況下，第二貼合層22的厚度d2例如可為0.01 μm以上，亦可為0.1 μm以上，亦可為0.5 μm以上，亦可為1 μm以上，另外，例如可為20 μm以下，亦可為15 μm以下，亦可為10 μm以下，亦可為5 μm以下。When the
第二相位差層12可為將樹脂膜拉伸而成的拉伸膜，亦可包括作為聚合性液晶化合物的硬化物層的第二液晶層。在第二相位差層12包括第二液晶層的情況下，第二相位差層12可為第二液晶層本身，亦可為第二液晶層與第二配向層的積層體。在第二相位差層12包括第二配向層的情況下，第二配向層通常設置在第二液晶層的與第二貼合層22側相反的一側。The
第二相位差層12的厚度例如可為0.01 μm以上，亦可為5 μm以上，另外，亦可為20 μm以下，亦可為15 μm以下。在第二相位差層12包括第二液晶層的情況下，第二相位差層的厚度例如可為0.01 μm以上，亦可為0.05 μm以上，亦可為0.1 μm以上，亦可為0.5 μm以上，亦可為1 μm以上，另外，可為5 μm以下，亦可為4 μm以下，亦可為3 μm以下。The thickness of the
圓偏光板被組裝在撓性顯示器等中，有時會以光學層30側成為外側的方式（第二相位差層側成為內側的方式）彎曲。在此種情況下，例如如圖2所示，第一相位差層11中有時會發生起伏。第一相位差層11中產生的起伏可能會成為使觀察圓偏光板時的第一相位差層11的相位差特性不均勻的原因。因此，認為例如會產生如下現象：在圓偏光板1的光學層30側，自傾斜方向觀察圓偏光板1時的反射光的色相（色澤）較自正面觀察圓偏光板1時不同。The circular polarizing plate is incorporated in a flexible display or the like, and may be bent so that the
本實施方式的圓偏光板1中，滿足所述＜i＞記載的式（1）的關係、及/或所述＜ii＞記載的式（2）的關係。因此，認為即使在以光學層30側成為外側的方式使圓偏光板1彎曲之後，使彎曲狀態返回為平坦的狀態的情況下，亦抑制了在第一相位差層11中產生的起伏。藉此，如上所述，認為可抑制反射光的色相根據觀察方向而不同。In the circularly
在滿足式（1）關係的圓偏光板1中可抑制第一相位差層11的所述起伏的理由推測如下。當以光學層30側成為外側的方式使圓偏光板1彎曲時，第二貼合層22被壓縮，藉此第二貼合層22欲向第一相位差層11膨脹。可認為，當第二貼合層22膨脹時，與第二貼合層22鄰接配置的第一相位差層11受其影響而變形，即使圓偏光板1返回到彎曲前的狀態，第一相位差層11亦不會返回到彎曲前的狀態，而會產生所述的起伏。The reason why the above-mentioned undulation of the
第一貼合層21及第二貼合層22中，彈性係數G'1及彈性係數G'2越大，越容易膨脹，而有越容易變硬的傾向。因此，藉由使第二貼合層22的彈性係數G'2相對變小（例如，G'1＞G'2），抑制因圓偏光板1的彎曲而使第二貼合層22膨脹的變形，而容易抑制伴隨著第二貼合層22的膨脹的第一相位差層11的變形。另外，藉由使第一貼合層21的彈性係數G'1相對變大（例如，G'1＞G'2），使第一貼合層21變硬，容易抑制第一相位差層11追隨隨著圓偏光板1的彎曲的第二貼合層22的膨脹而變形。In the
另一方面，第一貼合層21及第二貼合層22中，厚度d1及厚度d2越大，即，厚度d1及厚度d2的倒數的值越小，應力緩和性越高。因此，藉由相對地增大第二貼合層22的厚度d2（例如，d1＜d2）而使厚度d2的倒數的值相對地減小，迅速緩和第二貼合層22伴隨著圓偏光板1的彎曲而受到的應力，而容易降低傳遞到第一相位差層11的應力。另外，藉由相對地減小第一貼合層21的厚度d1（例如，d1＜d2）而使厚度d1的倒數的值相對地增大，不易緩和第一貼合層21所受到的應力，而容易抑制第一相位差層11因伴隨著圓偏光板1的彎曲的第二貼合層22的膨脹而變形。On the other hand, in the
如此，認為藉由將第一貼合層21及第二貼合層22的彈性係數G'1及G'2以及厚度d1及d2調整為滿足式（1）的關係，在以光學層30側成為外側的方式使圓偏光板1彎曲的情況下，可抑制第一相位差層11變形，從而抑制所述起伏的產生。In this way, it is considered that by adjusting the elastic coefficients G'1 and G'2 and the thicknesses d1 and d2 of the
認為在圓偏光板1滿足所述＜ii＞中記載的式（2）的關係的情況下，在彎曲試驗後的圓偏光板1中，處於第一相位差層11的第一貼合層21側的表面的起伏得到抑制的狀態。藉此，推測可抑制在圓偏光板1的光學層30側，自傾斜方向觀察圓偏光板1時的反射光的色相（色澤）較自正面觀察圓偏光板1時不同。It is considered that when the circularly
在彎曲試驗後的圓偏光板1的彎曲部分的剖面中，如圖2所示，式（2）中的ΔS為第一相位差層11的第一貼合層21側的表面中的最接近光學層30側的位置與距光學層30側最遠的位置之間的厚度方向上的距離。厚度方向是與圓偏光板1的平面正交的方向（圓偏光板1的積層方向）。彎曲部分的剖面設為在彎曲前的圓偏光板1的平面中平行於與彎曲試驗中的旋轉軸（擺動軸）正交的方向的剖面，詳細而言，是說明後述的實施例中的彎曲試驗的圖4的（a）中與紙面平行的剖面。彎曲部分是後述實施例的彎曲試驗的兩個台之間的間隙C1的範圍。In the cross section of the curved portion of the circular
ΔS的大小與所述第一相位差層11的起伏的大小對應，認為ΔS越小，起伏越得到抑制，因此在ΔS滿足式（2）的情況下，可認為在彎曲試驗後的圓偏光板1中第一相位差層11的起伏得到抑制。如後述的實施例記載般，ΔS可基於利用掃描型電子顯微鏡觀察彎曲試驗後的圓偏光板1的彎曲部分而得的顯微鏡圖像來決定。The magnitude of ΔS corresponds to the magnitude of the undulation of the
在式（2）中，ΔS例如可為2.1t以下，亦可為2.0t以下，亦可為1.7t以下，亦可為1.5t以下，亦可為1.3t以下，亦可為1.2t以下。ΔS例如可為0.1t以上，亦可為0.5t以上，亦可為t以上，亦可超過t。In the formula (2), ΔS may be 2.1 t or less, or 2.0 t or less, or 1.7 t or less, 1.5 t or less, 1.3 t or less, or 1.2 t or less, for example. ΔS may be, for example, 0.1t or more, 0.5t or more, t or more, or more than t.
圓偏光板1中，第一相位差層11及第二相位差層12較佳為滿足下述[a]或[b]的關係：
[a]第一相位差層11為1/2波長板，第二相位差層12為1/4波長板；
[b]第一相位差層11及第二相位差層12中的一者是逆波長分散性的1/4波長板，另一者是正C板。
在所述[b]的情況下，較佳為第一相位差層11為逆波長分散性的1/4波長板，第二相位差層12為正C板。In the
圓偏光板1較佳為能夠彎曲。能夠彎曲是指可在構成圓偏光板1的層（例如第一相位差層11等）上不產生裂紋地彎曲。圓偏光板1較佳為能夠向以光學層30側為外側的方向彎曲。The circularly
圓偏光板1的厚度通常為5 μm以上，亦可為10 μm以上，亦可為15 μm以上，另外，較佳為80 μm以下，更佳為60 μm以下。The thickness of the circular
（光學積層體）
圖3是示意性表示本實施方式的光學積層體的一例的概略剖面圖。如圖3所示，光學積層體5包括圓偏光板1、及在圓偏光板1的光學層30側經由第三貼合層23而積層的前表面板40。光學積層體5較佳為能夠向圓偏光板1側成為外側的方向彎曲。(Optical laminate)
FIG. 3 is a schematic cross-sectional view schematically showing an example of the optical layered body of the present embodiment. As shown in FIG. 3, the optical
前表面板40可作為用於保護顯示裝置的顯示元件等的層發揮功能，並且是能夠透射光的板狀體。為了使光學積層體5能夠彎曲，板狀體較佳為具有樹脂膜或玻璃膜。板狀體亦可為樹脂膜與玻璃膜的積層體。前表面板40可配置在顯示裝置的最表面。The
第三貼合層23可與前表面板40及圓偏光板1的光學層30直接接觸。第三貼合層23是黏著劑層或接著劑硬化層。The
光學積層體5亦可在圓偏光板1側（第二相位差層側）具有用於貼合在後述的顯示裝置的顯示元件等上的第四貼合層。第四貼合層是黏著劑層或接著劑硬化層。The optical
光學積層體5亦可包括觸控感測器面板等。觸控感測器面板可配置在前表面板40與圓偏光板1之間，亦可配置在光學積層體5的圓偏光板1側（第二相位差層側）。The
（顯示裝置）
光學積層體5可組裝在有機EL顯示裝置等顯示裝置中。顯示裝置例如可藉由將光學積層體5積層在包含顯示元件等的顯示積層體上來獲得。顯示積層體除了顯示元件以外，亦可包括觸控感測器面板等。(Display device)
The
顯示裝置可為智慧型手機、輸入板等移動終端，亦可為電視機、數碼相框、電子廣告牌、測量器或計量儀器類、辦公用設備、醫療設備、電算設備等。顯示裝置較佳為撓性顯示器。The display device can be a mobile terminal such as a smart phone, an input board, and can also be a television, a digital photo frame, an electronic billboard, a measuring instrument or a measuring instrument, office equipment, medical equipment, computer equipment, etc. The display device is preferably a flexible display.
以下，對圓偏光板及光學積層體的各層進行詳細說明。 （光學層） 光學層至少包括直線偏光層。光學層除了直線偏光層以外，亦可具有保護直線偏光層的單面或兩面的保護層、反射膜、半透射型反射膜、亮度提高膜、光學補償膜、帶防眩功能的膜等。Hereinafter, each layer of the circularly polarizing plate and the optical laminate will be described in detail. (Optical layer) The optical layer includes at least a linearly polarizing layer. In addition to the linear polarizing layer, the optical layer may have a protective layer that protects one or both sides of the linear polarizing layer, a reflective film, a semi-transmissive reflective film, a brightness enhancement film, an optical compensation film, a film with an anti-glare function, and the like.
（直線偏光層） 直線偏光層是具有從自然光等非偏光的光線選擇性地透過某一方向的直線偏光的功能者。直線偏光層可列舉：吸附有二色性色素的拉伸膜、或者含有聚合性液晶化合物的硬化物及二色性色素、且二色性色素分散於聚合性液晶化合物的硬化物中並進行配向的液晶層等。二色性色素是指具有分子的長軸方向的吸光度與短軸方向的吸光度不同的性質的色素。(Linear polarizing layer) The linearly polarizing layer has a function of selectively transmitting linearly polarized light in a certain direction from non-polarized light such as natural light. Examples of linear polarizing layers include: stretched films with dichroic pigments adsorbed, or cured products containing polymerizable liquid crystal compounds and dichroic pigments, and the dichroic pigments are dispersed and aligned in the cured product of polymerizable liquid crystal compounds The liquid crystal layer and so on. The dichroic dye refers to a dye having a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction of the molecule.
（使用了拉伸膜的直線偏光層） 吸附有二色性色素的拉伸膜通常經由如下步驟而製造：將聚乙烯醇系樹脂膜單軸拉伸的步驟；藉由利用碘等二色性色素對聚乙烯醇系樹脂膜進行染色來吸附該二色性色素的步驟；利用硼酸水溶液對吸附有二色性色素的聚乙烯醇系樹脂膜進行處理的步驟；以及在利用硼酸水溶液進行處理後進行水洗的步驟。吸附有二色性色素的拉伸膜亦可經由如下步驟來製造：將含有聚乙烯醇系樹脂的塗佈液塗佈在基材膜上而獲得積層膜的步驟、將獲得的積層膜單軸拉伸的步驟、使單軸拉伸後的積層膜的聚乙烯醇系樹脂層吸附二色性色素的步驟、利用硼酸水溶液處理吸附有二色性色素的聚乙烯醇系樹脂層的步驟、以及利用硼酸水溶液處理後進行水洗的步驟。可將所獲得的膜直接用作直線偏光層，亦可用作在其單面或兩面形成有保護層的直線偏光板。如此獲得的直線偏光層的厚度較佳為2 μm～40 μm。(Using the linear polarizing layer of the stretched film) Stretched films adsorbing dichroic pigments are usually produced through the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; by dyeing the polyvinyl alcohol-based resin film with dichroic pigments such as iodine The step of adsorbing the dichroic dye; the step of treating the polyvinyl alcohol resin film on which the dichroic dye is adsorbed with an aqueous solution of boric acid; and the step of washing with water after the treatment with the aqueous solution of boric acid. The stretched film adsorbing the dichroic dye can also be manufactured through the following steps: a step of applying a coating liquid containing a polyvinyl alcohol-based resin on a base film to obtain a laminated film, and uniaxially applying the obtained laminated film The step of stretching, the step of adsorbing the dichroic pigment on the polyvinyl alcohol-based resin layer of the uniaxially stretched laminate film, the step of treating the polyvinyl alcohol-based resin layer with the dichroic pigment adsorbed with an aqueous solution of boric acid, and A step of washing with water is performed after treatment with an aqueous solution of boric acid. The obtained film can be used directly as a linear polarizing layer, and can also be used as a linear polarizing plate having a protective layer formed on one or both sides. The thickness of the linear polarizing layer thus obtained is preferably 2 μm to 40 μm.
聚乙烯醇系樹脂是藉由將聚乙酸乙烯酯系樹脂皂化而獲得。作為聚乙酸乙烯酯系樹脂，除了作為乙酸乙烯酯的均聚物的聚乙酸乙烯酯以外，亦可使用乙酸乙烯酯與能夠與其共聚合的其他單量體的共聚物。作為能夠與乙酸乙烯酯共聚合的其他單量體，例如可列舉不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類、具有銨基的(甲基)丙烯醯胺類等。The polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers that can be copolymerized therewith can also be used. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylamides having an ammonium group.
聚乙烯醇系樹脂的皂化度通常為85莫耳%～100莫耳%左右，較佳為98莫耳%以上。聚乙烯醇系樹脂可被改質，例如亦可使用經醛類改質的聚乙烯醇縮甲醛或聚乙烯縮醛。聚乙烯醇系樹脂的聚合度通常為1,000～10,000左右，較佳為1,500～5,000的範圍。The degree of saponification of the polyvinyl alcohol-based resin is generally about 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000 or so, preferably in the range of 1,500 to 5,000.
將此種聚乙烯醇系樹脂製成的膜作為直線偏光層的原材膜使用。對聚乙烯醇系樹脂進行製膜的方法並無特別限定，可採用公知的方法來製膜。聚乙烯醇系原材膜的膜厚例如可為10 μm～150 μm左右。A film made of such a polyvinyl alcohol-based resin is used as the original film of the linear polarizing layer. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be used for forming a film. The film thickness of the polyvinyl alcohol-based raw material film can be, for example, about 10 μm to 150 μm.
聚乙烯醇系樹脂膜的單軸拉伸可在利用二色性色素的染色之前、染色的同時或染色之後進行。在染色之後進行單軸拉伸的情況下，該單軸拉伸既可在硼酸處理之前進行，亦可在硼酸處理中進行。另外，亦可在所述的多個階段進行單軸拉伸。在單軸拉伸時，可在圓周速度不同的輥間進行單軸拉伸、亦可使用熱輥進行單軸拉伸。另外，單軸拉伸既可為乾式拉伸，亦可為濕式拉伸，其中乾式拉伸在大氣中進行拉伸，濕式拉伸在使用溶劑使聚乙烯醇系樹脂膜溶脹的狀態下進行拉伸。拉伸倍率通常為3～8倍左右。The uniaxial stretching of the polyvinyl alcohol-based resin film can be carried out before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. When uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before the boric acid treatment or may be performed during the boric acid treatment. In addition, it is also possible to perform uniaxial stretching in the multiple stages described above. In the case of uniaxial stretching, uniaxial stretching can be performed between rolls with different peripheral speeds, or a heated roll can be used for uniaxial stretching. In addition, the uniaxial stretching can be either dry stretching or wet stretching. The dry stretching is stretched in the atmosphere, and the wet stretching is in a state where the polyvinyl alcohol resin film is swelled with a solvent. Stretch. The stretching ratio is usually about 3 to 8 times.
將拉伸膜作為直線偏光層、且在其單面或兩面包括保護層的直線偏光板的厚度例如可為1 μm以上且100 μm以下，亦可為5 μm以上，亦可為7 μm以上，另外，可為70 μm以下，亦可為50 μm以下，亦可為20 μm以下，亦可為10 μm以下。The thickness of a linear polarizing plate having a stretched film as a linear polarizing layer and including a protective layer on one or both sides thereof may be, for example, 1 μm or more and 100 μm or less, may be 5 μm or more, or may be 7 μm or more, In addition, it may be 70 μm or less, 50 μm or less, 20 μm or less, or 10 μm or less.
作為在直線偏光層的單面或兩面設置的保護層的材料，並無特別限定，例如可列舉環狀聚烯烴系樹脂；包含三乙醯纖維素（Triacetyl Cellulose，TAC）、二乙醯纖維素之類的樹脂的乙酸纖維素系樹脂；包含聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯之類的樹脂的聚酯系樹脂；聚碳酸酯系樹脂；(甲基)丙烯酸系樹脂；聚丙烯系樹脂等本領域公知的樹脂。就薄型化的觀點而言，保護層的厚度通常為300 μm以下，較佳為200 μm以下，更佳為100 μm以下，另外，通常為5 μm以上，較佳為20 μm以上。保護層可為膜，作為膜的保護層可具有相位差。在保護層為膜的情況下，直線偏光層與保護層可經由黏著劑層或接著劑硬化層進行積層。黏著劑層或接著劑硬化層可使用後述的黏著劑組成物或接著劑組成物來形成。The material of the protective layer provided on one or both sides of the linear polarizing layer is not particularly limited. Examples include cyclic polyolefin resins; including triacetyl cellulose (Triacetyl Cellulose, TAC) and diacetyl cellulose Cellulose acetate resins such as resins; polyester resins containing resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; Polycarbonate resins; (meth)acrylic resins; polypropylene resins and other resins known in the art. From the viewpoint of thinning, the thickness of the protective layer is usually 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and usually 5 μm or more, preferably 20 μm or more. The protective layer may be a film, and the protective layer as the film may have a phase difference. When the protective layer is a film, the linear polarizing layer and the protective layer may be laminated via an adhesive layer or an adhesive hardening layer. The adhesive layer or the adhesive hardened layer can be formed using the adhesive composition or the adhesive composition described later.
（使用了液晶層的直線偏光層） 用於形成液晶層的聚合性液晶化合物是具有聚合性反應基且顯示液晶性的化合物。聚合性反應基是參與聚合反應的基，較佳為光聚合性反應基。光聚合性反應基是指藉由自光聚合引發劑產生的活性自由基或酸等而能夠參與聚合反應的基。作為光聚合性官能基，可列舉乙烯基、乙烯基氧基、1-氯乙烯基、異丙烯基、4-乙烯基苯基、丙烯醯基氧基、甲基丙烯醯基氧基、氧雜環丙烷基、氧雜環丁烷基等。其中，較佳為丙烯醯基氧基、甲基丙烯醯基氧基、乙烯基氧基、氧雜環丙烷基及氧雜環丁烷基，更佳為丙烯醯基氧基。聚合性液晶化合物的種類並無特別限定，可使用棒狀液晶化合物、圓盤狀液晶化合物、及該些的混合物。聚合性液晶化合物的液晶性可為熱致（thermotropic）性液晶亦可為溶致（lyotropic）性液晶，作為相序結構可為向列液晶亦可為層列液晶。(Linear polarizing layer using liquid crystal layer) The polymerizable liquid crystal compound used for forming the liquid crystal layer is a compound having a polymerizable reactive group and exhibiting liquid crystallinity. The polymerizable reactive group is a group that participates in the polymerization reaction, and is preferably a photopolymerizable reactive group. The photopolymerizable reactive group refers to a group that can participate in a polymerization reaction by a living radical or acid generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, and oxa Cyclopropanyl, oxetanyl, etc. Among them, propyleneoxy, methacryloxy, vinyloxy, oxetanyl, and oxetanyl are preferred, and propyleneoxy is more preferred. The type of the polymerizable liquid crystal compound is not particularly limited, and rod-shaped liquid crystal compounds, discotic liquid crystal compounds, and mixtures thereof can be used. The liquid crystal properties of the polymerizable liquid crystal compound may be thermotropic liquid crystal or lyotropic liquid crystal, and may be nematic liquid crystal or smectic liquid crystal as a phase sequence structure.
作為用於使用了液晶層的直線偏光層的二色性色素，較佳為在300 nm～700 nm的範圍具有吸收極大波長（λMAX）者。作為此種二色性色素，例如可列舉吖啶色素、噁嗪色素、花青色素、萘色素、偶氮色素、及蒽醌色素等，其中較佳為偶氮色素。作為偶氮色素，可列舉單偶氮色素、雙偶氮色素、三偶氮色素、四偶氮色素及二苯乙烯偶氮色素等，較佳為雙偶氮色素及三偶氮色素。二色性色素可為單獨，亦可組合兩種以上，較佳為組合三種以上。尤其更佳為組合三種以上的偶氮化合物。二色性色素的一部分可具有反應性基，另外亦可具有液晶性。As the dichroic dye used in the linear polarizing layer using the liquid crystal layer, one having an absorption maximum wavelength (λMAX) in the range of 300 nm to 700 nm is preferable. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes. Among them, azo dyes are preferred. Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrasazo dyes, and stilbene azo dyes, and bisazo dyes and trisazo dyes are preferred. The dichroic dye may be singly or in combination of two or more, preferably three or more in combination. In particular, it is more preferable to combine three or more azo compounds. A part of the dichroic dye may have a reactive group, and may also have liquid crystallinity.
使用了液晶層的直線偏光層例如可藉由在形成於基材上的配向層上塗佈含有聚合性液晶化合物及二色性色素的偏光層形成用組成物，並將聚合性液晶化合物聚合使其硬化而形成。或者，亦可在基材上塗佈偏光層形成用組成物而形成塗膜，並將該塗膜與基材層一起拉伸，藉此形成直線偏光層。用於形成直線偏光層的基材亦可作為直線偏光層的保護層使用。作為基材，可列舉樹脂膜，例如可列舉使用形成所述保護層的材料而成形的膜。The linear polarizing layer using the liquid crystal layer can be formed by, for example, coating a polarizing layer forming composition containing a polymerizable liquid crystal compound and a dichroic dye on an alignment layer formed on a substrate, and polymerizing the polymerizable liquid crystal compound to make It hardens to form. Alternatively, the composition for forming a polarizing layer may be coated on a substrate to form a coating film, and the coating film may be stretched together with the substrate layer to form a linear polarizing layer. The base material used to form the linearly polarizing layer can also be used as a protective layer for the linearly polarizing layer. As the base material, a resin film is exemplified, for example, a film molded using the material forming the protective layer is exemplified.
作為含有聚合性液晶化合物及二色性色素的偏光層形成用組成物、及使用該組成物的直線偏光層的製造方法，可例示日本專利特開2013-37353號公報、日本專利特開2013-33249號公報、日本專利特開2017-83843號公報等中記載者。除了聚合性液晶化合物及二色性色素以外，偏光層形成用組成物可更含有溶媒、聚合引發劑、交聯劑、調平劑、抗氧化劑、塑化劑、增感劑等添加劑。該些成分分別可僅使用一種，亦可組合使用兩種以上。As a composition for forming a polarizing layer containing a polymerizable liquid crystal compound and a dichroic dye, and a method for producing a linear polarizing layer using the composition, Japanese Patent Laid-Open No. 2013-37353 and Japanese Patent Laid-Open 2013- It is described in No. 33249, Japanese Patent Laid-Open No. 2017-83843, etc. In addition to the polymerizable liquid crystal compound and the dichroic dye, the composition for forming a polarizing layer may further contain additives such as a solvent, a polymerization initiator, a crosslinking agent, a leveling agent, an antioxidant, a plasticizer, and a sensitizer. Only one kind of these components may be used, respectively, or two or more kinds may be used in combination.
偏光層形成用組成物可含有的聚合引發劑是可引發聚合性液晶化合物的聚合反應的化合物，就可在更低溫條件下引發聚合反應的方面而言，較佳為光聚合性引發劑。具體而言，可列舉藉由光的作用而可產生活性自由基或酸的光聚合引發劑，其中，較佳為藉由光的作用而產生自由基的光聚合引發劑。相對於聚合性液晶化合物的總量100質量份，聚合引發劑的含量較佳為1質量份～10質量份，更佳為3質量份～8質量份。若為該範圍內，則聚合性基的反應充分進行，且容易使液晶化合物的配向狀態穩定化。The polymerization initiator that may be contained in the composition for forming a polarizing layer is a compound that can initiate a polymerization reaction of a polymerizable liquid crystal compound, and a photopolymerizable initiator is preferred in terms of being capable of initiating a polymerization reaction under lower temperature conditions. Specifically, photopolymerization initiators that can generate active radicals or acids by the action of light are exemplified. Among them, photopolymerization initiators that can generate free radicals by the action of light are preferred. The content of the polymerization initiator is preferably 1 part by mass to 10 parts by mass, and more preferably 3 parts by mass to 8 parts by mass relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound. If it is within this range, the reaction of the polymerizable group proceeds sufficiently, and it is easy to stabilize the alignment state of the liquid crystal compound.
使用了液晶層的直線偏光層的厚度並無特別限定，較佳為20 μm以下，更佳為10 μm以下，進而佳為5 μm以下。The thickness of the linear polarizing layer using the liquid crystal layer is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less.
使用了液晶層的直線偏光層亦可在直線偏光層的單面或兩面具有作為保護層的外塗層。外塗層可以保護直線偏光層等為目的而設置。外塗層較佳為耐溶劑性、透明性、機械強度、熱穩定性、遮蔽性及各向同性等優異者。外塗層例如可藉由在直線偏光層上塗佈用於形成外塗層的材料（組成物）而形成。作為構成外塗層的材料，例如可列舉光硬化性樹脂或水溶性聚合物等，可使用(甲基)丙烯酸系樹脂、聚乙烯醇系樹脂、聚醯胺環氧樹脂等。The linear polarizing layer using the liquid crystal layer may have an overcoat as a protective layer on one side or both sides of the linear polarizing layer. The overcoat can be provided for the purpose of protecting the linear polarizing layer. The overcoat layer is preferably one that is excellent in solvent resistance, transparency, mechanical strength, thermal stability, shielding properties, and isotropy. The overcoat layer can be formed, for example, by coating a material (composition) for forming the overcoat layer on the linear polarizing layer. Examples of the material constituting the overcoat layer include photocurable resins, water-soluble polymers, and the like, and (meth)acrylic resins, polyvinyl alcohol-based resins, polyamide epoxy resins, and the like can be used.
外塗層的厚度並無特別限定，較佳為20 μm以下，更佳為15 μm以下，進而佳為10 μm以下，亦可為5 μm以下，另外為0.05 μm以上，亦可為0.5 μm以上。The thickness of the overcoat layer is not particularly limited, but is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, may be 5 μm or less, and may be 0.05 μm or more, or may be 0.5 μm or more .
（第一相位差層、第二相位差層） 第一相位差層包括作為聚合性液晶化合物的硬化物層的第一液晶層。作為聚合性液晶化合物，例如可使用以上所說明的化合物。在第二相位差層包含作為聚合性液晶化合物的硬化物層的第二液晶層的情況下，作為聚合性液晶化合物，例如可使用以上所說明的化合物。形成直線偏光層的聚合性液晶化合物、形成第一相位差層的聚合性液晶化合物、及形成第二相位差層的聚合性液晶化合物可相互相同，亦可僅一部分相同，亦可全部不同。(First retardation layer, second retardation layer) The first retardation layer includes a first liquid crystal layer as a cured layer of a polymerizable liquid crystal compound. As the polymerizable liquid crystal compound, for example, the compounds described above can be used. When the second retardation layer includes a second liquid crystal layer as a cured layer of a polymerizable liquid crystal compound, as the polymerizable liquid crystal compound, for example, the compounds described above can be used. The polymerizable liquid crystal compound forming the linear polarizing layer, the polymerizable liquid crystal compound forming the first retardation layer, and the polymerizable liquid crystal compound forming the second retardation layer may be the same as each other, may be the same in only a part, or all may be different.
在第二相位差層為將樹脂膜拉伸而成的拉伸膜的情況下，作為樹脂膜，可列舉出所述保護層中例示的樹脂膜。When the second retardation layer is a stretched film obtained by stretching a resin film, examples of the resin film include the resin films exemplified in the protective layer.
第一相位差層及第二相位差層（以下，有時將兩者統稱為「相位差層」）例如可藉由在基材層上塗佈含有聚合性液晶化合物的相位差層形成用組成物，並將聚合性液晶化合物聚合使其硬化而形成。用於形成相位差層的基材層亦可包含在圓偏光板中。作為基材層，例如可使用在所述保護層中說明的樹脂膜。The first retardation layer and the second retardation layer (hereinafter, the two may be collectively referred to as the "retardation layer"), for example, can be formed by coating a substrate layer containing a polymerizable liquid crystal compound for forming a retardation layer It is formed by polymerizing a polymerizable liquid crystal compound to harden it. The substrate layer for forming the retardation layer may also be included in the circular polarizing plate. As the base layer, for example, the resin film described in the protective layer can be used.
第一相位差層如上所述可為第一液晶層與第一配向層的積層體。在第二相位差層包括第二液晶層的情況下，第二相位差層如上所述可為第二液晶層與第二配向層的積層體。As described above, the first retardation layer may be a laminate of the first liquid crystal layer and the first alignment layer. In the case where the second retardation layer includes the second liquid crystal layer, the second retardation layer may be a laminate of the second liquid crystal layer and the second alignment layer as described above.
（第一配向層、第二配向層） 第一配向層及第二配向層（以下，有時將兩者統稱為「配向層」）具有使聚合性液晶化合物在所期望的方向上液晶配向的配向限制力。作為配向層，可列舉包含配向性聚合物的配向性聚合物層、包含光配向聚合物的光配向性聚合物層、在層表面具有凹凸圖案或多個溝槽（groove）（槽）的溝槽配向層。配向層的厚度通常為10 nm～500 nm，較佳為10 nm～200 nm。(First alignment layer, second alignment layer) The first alignment layer and the second alignment layer (hereinafter, both may be collectively referred to as the “alignment layer”) have an alignment restricting force for aligning the polymerizable liquid crystal compound in a desired direction. Examples of the alignment layer include an alignment polymer layer containing an alignment polymer, a photoalignment polymer layer containing a photoalignment polymer, and a groove having a concave-convex pattern or a plurality of grooves (grooves) on the surface of the layer. Slot alignment layer. The thickness of the alignment layer is usually 10 nm to 500 nm, preferably 10 nm to 200 nm.
（第一貼合層、第二貼合層、第三貼合層、第四貼合層） 第一貼合層～第四貼合層是黏著劑層或接著劑硬化層。黏著劑層可使用公知的黏著劑組成物形成。接著劑硬化層可使用公知的接著劑組成物形成。(The first bonding layer, the second bonding layer, the third bonding layer, the fourth bonding layer) The first bonding layer to the fourth bonding layer are an adhesive layer or an adhesive hardened layer. The adhesive layer can be formed using a known adhesive composition. The adhesive hardening layer can be formed using a known adhesive composition.
作為黏著劑組成物，可列舉以(甲基)丙烯酸系、橡膠系、胺基甲酸酯系、酯系、矽酮系、聚乙烯醚系之類的樹脂為主要成分的黏著劑組成物。其中，較佳為以透明性、耐候性、耐熱性等優異的(甲基)丙烯酸系樹脂為原料聚合物的黏著劑組成物。黏著劑組成物可為活性能量線硬化型、熱硬化型。Examples of the adhesive composition include adhesive compositions containing resins such as (meth)acrylic, rubber, urethane, ester, silicone, and polyvinyl ether resins as main components. Among them, an adhesive composition using a (meth)acrylic resin excellent in transparency, weather resistance, heat resistance, etc., as a base polymer is preferred. The adhesive composition can be an active energy ray hardening type or a heat hardening type.
作為黏著劑組成物中使用的(甲基)丙烯酸系樹脂（原料聚合物），例如可較佳地使用將(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯之類的(甲基)丙烯酸酯的1種或2種以上作為單體的聚合物或共聚物。基礎聚合物中較佳為使極性單體共聚合。作為極性單體，例如可列舉(甲基)丙烯酸、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯醯胺、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸縮水甘油酯之類的具有羧基、羥基、醯胺基、胺基、環氧基等的單體。As the (meth)acrylic resin (raw polymer) used in the adhesive composition, for example, butyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate can be preferably used. One or two or more of (meth)acrylates such as octyl ester and 2-ethylhexyl (meth)acrylate are polymers or copolymers as monomers. In the base polymer, it is preferable to copolymerize a polar monomer. Examples of polar monomers include (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, (meth)acrylic acid N, N -A monomer having a carboxyl group, a hydroxyl group, an amine group, an amino group, an epoxy group, etc., such as dimethylaminoethyl and glycidyl (meth)acrylate.
黏著劑組成物可僅含有所述原料聚合物，但通常更含有交聯劑。作為交聯劑，可例示：為2價以上的金屬離子，且與羧基之間形成羧酸金屬鹽者；為多胺化合物，且與羧基之間形成醯胺鍵者；為聚環氧化合物或多元醇，且與羧基之間形成酯鍵者；為聚異氰酸酯化合物，且與羧基之間形成醯胺鍵者。其中，較佳為聚異氰酸酯化合物。The adhesive composition may only contain the base polymer, but usually contains a crosslinking agent. Examples of the crosslinking agent include: a metal ion having a valence of 2 or higher and forming a metal carboxylate with a carboxyl group; a polyamine compound forming an amide bond with a carboxyl group; a polyepoxy compound or Polyols, which form ester bonds with carboxyl groups; polyisocyanate compounds, which form amide bonds with carboxyl groups. Among them, polyisocyanate compounds are preferred.
所謂活性能量線硬化型黏著劑組成物是指如下的黏著劑組成物：具有受到紫外線或電子線之類的活性能量線的照射而硬化的性質，從而具有在活性能量線照射前仍具有黏著性而可與膜等被黏物密著，且藉由活性能量線的照射而硬化，可調整密著力的性質。活性能量線硬化型黏著劑組成物較佳為紫外線硬化型。活性能量線硬化型黏著劑組成物除了原料聚合物、交聯劑以外，更含有活性能量線聚合性化合物。此外，根據需要，亦含有光聚合引發劑或光敏劑等。The so-called active energy ray curable adhesive composition refers to the following adhesive composition: it has the property of being cured by the irradiation of active energy rays such as ultraviolet rays or electron rays, and thus has adhesiveness before the active energy rays are irradiated It can be closely adhered to adherends such as films, and is cured by the irradiation of active energy rays, and the properties of adhesion can be adjusted. The active energy ray curable adhesive composition is preferably an ultraviolet curable adhesive composition. The active energy ray curable adhesive composition contains an active energy ray polymerizable compound in addition to the raw material polymer and the crosslinking agent. In addition, if necessary, a photopolymerization initiator, photosensitizer, etc. are also contained.
黏著劑組成物可含有用於賦予光散射性的微粒子、珠（樹脂珠、玻璃珠等）、玻璃纖維、原料聚合物以外的樹脂、增黏劑、填充劑（金屬粉或其他無機粉末等）、抗氧化劑、紫外線吸收劑、染料、顏料、著色劑、消泡劑、防腐蝕劑、光聚合引發劑等添加劑。The adhesive composition may contain fine particles, beads (resin beads, glass beads, etc.), glass fibers, resins other than raw polymers, tackifiers, fillers (metal powder or other inorganic powders, etc.) for imparting light scattering properties. , Antioxidants, UV absorbers, dyes, pigments, colorants, defoamers, corrosion inhibitors, photopolymerization initiators and other additives.
黏著劑層可藉由將所述黏著劑組成物的有機溶劑稀釋液塗佈於基材上並使其乾燥而形成。使用活性能量線硬化型黏著劑組成物時，藉由對所形成的黏著劑層照射活性能量線，可製成具有所期望的硬化度的硬化物。The adhesive layer can be formed by applying an organic solvent diluent of the adhesive composition on a substrate and drying it. When an active energy ray curable adhesive composition is used, by irradiating the formed adhesive layer with active energy rays, a cured product having a desired degree of curing can be obtained.
作為接著劑組成物，例如可列舉：水系接著劑、活性能量線硬化型接著劑、天然橡膠接著劑、α-烯烴系接著劑、胺基甲酸酯樹脂系接著劑、乙烯-乙酸乙烯酯樹脂乳液接著劑、乙烯-乙酸乙烯酯樹脂系熱熔接著劑、環氧樹脂系接著劑、氯乙烯樹脂溶劑系接著劑、氯丁二烯橡膠系接著劑、氰基丙烯酸酯系接著劑、矽酮系接著劑、苯乙烯-丁二烯橡膠溶劑系接著劑、腈橡膠系接著劑、硝化纖維素系接著劑、反應性熱熔接著劑、酚樹脂系接著劑、改質矽酮系接著劑、聚酯系熱熔接著劑、聚醯胺樹脂熱熔接著劑、聚醯亞胺系接著劑、聚胺基甲酸酯樹脂熱熔接著劑、聚烯烴樹脂熱熔接著劑、聚乙酸乙烯酯樹脂溶劑系接著劑、聚苯乙烯樹脂溶劑系接著劑、聚乙烯醇系接著劑、聚乙烯吡咯啶酮樹脂系接著劑、聚乙烯縮丁醛系接著劑、聚苯並咪唑接著劑、聚甲基丙烯酸酯樹脂溶劑系接著劑、三聚氰胺樹脂系接著劑、脲樹脂系接著劑、間苯二酚系接著劑等。此種接著劑可單獨使用一種或混合使用兩種以上。Examples of the adhesive composition include: water-based adhesives, active energy ray-curable adhesives, natural rubber adhesives, α-olefin-based adhesives, urethane resin-based adhesives, and ethylene-vinyl acetate resins. Emulsion adhesive, ethylene-vinyl acetate resin hot melt adhesive, epoxy resin adhesive, vinyl chloride resin solvent adhesive, chloroprene rubber adhesive, cyanoacrylate adhesive, silicone Adhesives, styrene-butadiene rubber solvent-based adhesives, nitrile rubber-based adhesives, nitrocellulose-based adhesives, reactive hot melt adhesives, phenol resin-based adhesives, modified silicone-based adhesives, Polyester hot melt adhesive, polyamide resin hot melt adhesive, polyimide resin hot melt adhesive, polyurethane resin hot melt adhesive, polyolefin resin hot melt adhesive, polyvinyl acetate resin Solvent adhesive, polystyrene resin solvent adhesive, polyvinyl alcohol adhesive, polyvinylpyrrolidone resin adhesive, polyvinyl butyral adhesive, polybenzimidazole adhesive, polymethyl Acrylic resin solvent-based adhesives, melamine resin-based adhesives, urea resin-based adhesives, resorcinol-based adhesives, etc. Such an adhesive can be used individually by 1 type or in mixture of 2 or more types.
作為水系接著劑，例如可列舉聚乙烯醇系樹脂水溶液、水系二液型胺基甲酸酯系乳液接著劑等。作為活性能量線硬化型接著劑，是藉由照射紫外線等活性能量線而硬化的接著劑，例如可列舉含有聚合性化合物及光聚合性引發劑者、含有光反應性樹脂者、含有黏著劑樹脂及光反應***聯劑者等。作為所述聚合性化合物，可列舉光硬化性環氧系單體、光硬化性(甲基)丙烯酸系單體、光硬化性胺基甲酸酯系單體等光聚合性單體、或源自該些單體的寡聚物等。作為所述光聚合引發劑，可列舉含有照射紫外線等活性能量線而產生中性自由基、陰離子自由基、陽離子自由基等活性種的物質者。As the water-based adhesive, for example, a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane-based emulsion adhesive, and the like can be cited. The active energy ray curable adhesive is an adhesive that is cured by irradiating active energy rays such as ultraviolet rays. Examples include those containing polymerizable compounds and photopolymerizable initiators, those containing photoreactive resins, and resins containing adhesives. And photo-reactive cross-linking agents, etc. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth)acrylic monomers, and photocurable urethane monomers, or sources. Oligomers from these monomers, etc. Examples of the photopolymerization initiator include those containing active species such as neutral radicals, anionic radicals, and cationic radicals by irradiating active energy rays such as ultraviolet rays.
（前表面板） 前表面板只要是能夠透過光的板狀體，則材料及厚度並無限定。前表面板可僅包含一層，亦可包含兩層以上。作為前表面板，可列舉樹脂製的板狀體（例如樹脂板、樹脂片、樹脂膜等）、玻璃製的板狀體（例如玻璃板、玻璃膜等）。前表面板可構成顯示裝置的最表面。另外，前表面板可為樹脂膜、或在樹脂膜的至少一面設置硬塗層而進一步提高了硬度的帶硬塗層的樹脂膜。在使用帶硬塗層的樹脂膜的情況下，硬塗層較佳為設置成配置在顯示裝置的最表面。另外，前表面板可具有藍光隔斷功能、視角調整功能等。(Front panel) As long as the front surface plate is a plate-shaped body that can transmit light, the material and thickness are not limited. The front surface plate may include only one layer, or may include two or more layers. As the front surface plate, a resin-made plate-shaped body (for example, a resin plate, a resin sheet, a resin film, etc.) and a glass-made plate-shaped body (for example, a glass plate, a glass film, etc.) can be mentioned. The front surface plate may constitute the outermost surface of the display device. In addition, the front surface plate may be a resin film or a hard coat resin film with a hard coat layer provided on at least one surface of the resin film to further increase the hardness. In the case of using a resin film with a hard coat layer, the hard coat layer is preferably provided so as to be arranged on the outermost surface of the display device. In addition, the front surface panel may have a blue light blocking function, a viewing angle adjustment function, and the like.
在前表面板含有樹脂膜的情況下，光學積層體的第三貼合層較佳為與樹脂膜相接觸地設置。例如，在前表面板包含在樹脂膜的一個面上具有硬塗層的帶硬塗層的樹脂膜的情況下，光學積層體中的第三貼合層較佳為與前表面板的樹脂膜相接觸地設置。When the front surface plate contains a resin film, the third bonding layer of the optical laminate is preferably provided in contact with the resin film. For example, in the case where the front surface plate includes a hard coat resin film having a hard coat layer on one surface of the resin film, the third bonding layer in the optical laminate is preferably the resin film of the front surface plate. Set in contact.
作為形成前表面板的樹脂膜，只要為能夠透射光的樹脂膜，則不進行限定。例如可列舉包含如下高分子的膜：三乙醯纖維素、乙醯纖維素丁酸酯、乙烯-乙酸乙烯酯共聚物、丙醯纖維素、丁醯纖維素、乙醯丙醯纖維素、聚酯、聚苯乙烯、聚醯胺、聚醚醯亞胺、聚(甲基)丙烯酸、聚醯亞胺、聚醚碸、聚碸、聚乙烯、聚丙烯、聚甲基戊烯、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、聚乙烯縮醛、聚醚酮、聚醚醚酮、聚醚碸、聚(甲基)丙烯酸甲酯、聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚碳酸酯、聚醯胺醯亞胺等。該些高分子可單獨使用或混合兩種以上使用。在顯示裝置是撓性顯示器的情況下，較佳地使用由聚醯亞胺、聚醯胺、聚醯胺醯亞胺等高分子形成的樹脂膜，該樹脂膜能夠構成為具有優異的可撓性、並且具有高強度及高透明性。The resin film forming the front surface plate is not limited as long as it is a resin film capable of transmitting light. For example, a film containing the following polymers can be cited: triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propylene cellulose, butyl cellulose, acetyl cellulose, poly Ester, polystyrene, polyamide, polyetherimide, poly(meth)acrylic acid, polyimide, polyether turpentine, polysulfide, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride , Polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether ether, poly(methyl)acrylate, polyethylene terephthalate, poly Butylene phthalate, polyethylene naphthalate, polycarbonate, polyamide imide, etc. These polymers can be used alone or in combination of two or more. When the display device is a flexible display, it is preferable to use a resin film formed of a polymer such as polyimide, polyimide, polyimide imide, etc., and the resin film can be configured to have excellent flexibility. It has high strength and high transparency.
就硬度的觀點而言，前表面板可為包括硬塗層的樹脂膜。硬塗層可形成於樹脂膜的其中一面，亦可形成於兩面。藉由設置硬塗層，可提高硬度及耐劃痕性。硬塗層例如為紫外線硬化型樹脂的硬化層。作為紫外線硬化型樹脂，例如可列舉單官能(甲基)丙烯酸系樹脂、多官能(甲基)丙烯酸系樹脂、具有樹枝狀聚合物結構的多官能(甲基)丙烯酸系樹脂等(甲基)丙烯酸系樹脂等(甲基)丙烯酸系樹脂；矽酮系樹脂；聚酯系樹脂；胺基甲酸酯系樹脂；醯胺系樹脂；環氧系樹脂等。為了提高強度，硬塗層亦可含有添加劑。添加劑並無特別限定，可列舉無機系微粒、有機系微粒、或者該些的混合物。在樹脂膜的兩面具有硬塗層的情況下，各硬塗層的組成、厚度可彼此相同，亦可彼此不同。From the viewpoint of hardness, the front surface plate may be a resin film including a hard coat layer. The hard coat layer can be formed on one side of the resin film or on both sides. By providing a hard coat, the hardness and scratch resistance can be improved. The hard coat layer is, for example, a cured layer of ultraviolet curable resin. Examples of ultraviolet curable resins include monofunctional (meth)acrylic resins, polyfunctional (meth)acrylic resins, and polyfunctional (meth)acrylic resins having a dendritic polymer structure (meth). (Meth)acrylic resins such as acrylic resins; silicone resins; polyester resins; urethane resins; amide resins; epoxy resins, etc. In order to increase the strength, the hard coat layer may also contain additives. The additives are not particularly limited, and examples include inorganic fine particles, organic fine particles, or mixtures of these. When the resin film has hard coat layers on both sides, the composition and thickness of each hard coat layer may be the same or different from each other.
當前表面板為玻璃板時，玻璃板較佳地使用顯示用強化玻璃。藉由使用玻璃板，可構成具有優異的機械強度及表面硬度的前表面板。When the front surface plate is a glass plate, it is preferable to use tempered glass for display as the glass plate. By using a glass plate, a front surface plate with excellent mechanical strength and surface hardness can be constructed.
前表面板的厚度例如可為10 μm以上且300 μm以下，較佳為20 μm以上且200 μm以下，更佳可為30 μm以上且100 μm以下。The thickness of the front surface plate may be, for example, 10 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less, and more preferably 30 μm or more and 100 μm or less.
（觸控感測器面板） 觸控感測器面板是能夠檢測被觸控的位置的感測器。觸控感測器面板的檢測方式不受限定，可例示：電阻膜方式、靜電電容耦合方式、光學感測器方式、超音波方式、電磁感應耦合方式、表面聲波方式等的觸控感測器面板，就低成本方面而言，該些中較佳使用電阻膜方式、靜電電容耦合方式的觸控感測器面板。 [實施例](Touch sensor panel) The touch sensor panel is a sensor that can detect the position being touched. The detection method of the touch sensor panel is not limited. Examples include: resistive film method, electrostatic capacitance coupling method, optical sensor method, ultrasonic method, electromagnetic induction coupling method, surface acoustic wave method, etc. For the panel, in terms of low cost, it is preferable to use a touch sensor panel of a resistive film method or an electrostatic capacitance coupling method. [Example]
以下，藉由實施例更詳細地說明本發明，但本發明並不受該些例子限定。實施例、比較例中的「%」及「份」只要並無特別說明，為質量%及質量份。Hereinafter, the present invention will be explained in more detail with examples, but the present invention is not limited by these examples. The "%" and "parts" in the examples and comparative examples are mass% and parts by mass unless otherwise specified.
[厚度的測定] 直線偏光層、各配向層、及各相位差層的厚度使用雷射顯微鏡（奧林巴斯（Olympus）股份有限公司製、OLS3000）進行測定。所述以外的厚度使用接觸式膜厚測定裝置（尼康（Nikon）股份有限公司製、MS-5C）測定。[Measurement of thickness] The thickness of the linear polarizing layer, each alignment layer, and each retardation layer was measured using a laser microscope (manufactured by Olympus Co., Ltd., OLS3000). Thicknesses other than the above are measured using a contact-type film thickness measuring device (manufactured by Nikon Co., Ltd., MS-5C).
[彈性係數的測定] （黏著劑層的彈性係數的測定） 第一貼合層及第二貼合層為黏著劑層時的溫度25℃下的彈性係數按以下程序進行。將包括作為第一貼合層或第二貼合層的黏著劑層的黏著劑片裁斷為寬30 mm×長30 mm後，剝離輕分離膜（輕SP（Separate）膜），以厚度為150 μm的方式積層多個黏著劑層。將積層的黏著劑層貼合在玻璃板上。使用黏彈性測定裝置（安東帕（Anton Paar）公司、MCR-301）在將所積層的黏著劑層與測定晶片接合的狀態下，在-20℃至100℃的溫度區域，在頻率1.0 Hz、變形量1%、升溫速度5℃/分鐘的條件下進行測定，將溫度25℃下、相對濕度50%下的儲存彈性係數確定為彈性係數。[Measurement of Elastic Coefficient] (Measurement of the coefficient of elasticity of the adhesive layer) When the first bonding layer and the second bonding layer are adhesive layers, the coefficient of elasticity at a temperature of 25° C. is performed according to the following procedure. After cutting the adhesive sheet including the adhesive layer as the first bonding layer or the second bonding layer to a width of 30 mm × a length of 30 mm, peel off the light separation film (light SP (Separate) film) to a thickness of 150 Laminate multiple adhesive layers in μm. Laminate the laminated adhesive layer on the glass plate. Using a viscoelasticity measuring device (Anton Paar, MCR-301) in the state where the laminated adhesive layer is bonded to the measuring wafer, in the temperature range of -20°C to 100°C, at a frequency of 1.0 Hz, The measurement is performed under the conditions of a deformation amount of 1% and a heating rate of 5°C/min, and the storage elastic coefficient at a temperature of 25°C and a relative humidity of 50% is determined as the elastic coefficient.
（接著劑硬化層的彈性係數的測定） 第一貼合層及第二貼合層為接著劑硬化層時的溫度25℃下的彈性係數按照以下程序進行。在將用於形成作為第一貼合層或第二貼合層的接著劑硬化層的接著劑組成物塗佈在玻璃（厚度1.0 mm）上而獲得的塗膜上，積層環烯烴聚合物（Cyclo Olefin Polymer，COP）膜（日本瑞翁（ZEON）股份有限公司製、厚度50 μm）。其後，使用紫外線照射裝置（輻深紫外線系統（Fusion UV Systems）公司製造、包括無電極紫外線燈的H閥的裝置）以光照射強度為400 mW/cm2 、波長280 nm～320 nm下的累計光量為1500 mJ/cm2 的方式對塗膜照射紫外線，使接著劑組成物硬化，從而獲得具有玻璃/接著劑硬化層（厚度2 μm）/COP膜的層結構的積層結構體。自積層結構體剝離COP膜後，使用奈米壓痕儀（Nano Indenter）（HM-500，菲希爾儀器（FISCHER INSTRUMENTS）公司製），在溫度25℃、相對濕度50%、壓力1 mN的條件下對露出的接著劑硬化層進行壓縮彈性係數的測定，並將其作為彈性係數。壓頭使用伯克維奇（Berkovich）三角錘壓頭。(Measurement of the coefficient of elasticity of the adhesive hardened layer) The elastic coefficient at a temperature of 25° C. when the first adhesive layer and the second adhesive layer are the adhesive hardened layer was performed according to the following procedure. On a coating film obtained by coating the adhesive composition for forming the adhesive hardening layer as the first bonding layer or the second bonding layer on glass (thickness 1.0 mm), the cycloolefin polymer ( Cyclo Olefin Polymer, COP) film (manufactured by ZEON Co., Ltd., thickness 50 μm). After that, an ultraviolet irradiation device (a device made by Fusion UV Systems, which includes an H valve of an electrodeless ultraviolet lamp) was used to irradiate light with an intensity of 400 mW/cm 2 and a wavelength of 280 nm to 320 nm. The coating film was irradiated with ultraviolet rays so that the cumulative light amount was 1500 mJ/cm 2 to harden the adhesive composition, thereby obtaining a laminated structure having a glass/adhesive hardened layer (thickness 2 μm)/COP film layer structure. After peeling off the COP film from the laminated structure, use a Nano Indenter (HM-500, manufactured by FISCHER INSTRUMENTS) at a temperature of 25°C, a relative humidity of 50%, and a pressure of 1 mN. Under the conditions, the exposed adhesive hardened layer was subjected to the measurement of the coefficient of compressive elasticity, and it was taken as the coefficient of elasticity. The indenter uses a Berkovich (Berkovich) triangle hammer indenter.
[彎曲性的評價]
對自各實施例及比較例中獲得的光學積層體剝離圓偏光板側的重分離膜（重SP膜）而露出的黏著劑層、以及假設顯示裝置的顯示積層體的厚度100 μm的聚對苯二甲酸乙二醇酯（Polyethylene Terephthalate，PET）膜的表面進行電暈處理（輸出0.3 kW、處理速度3 m/分）後，將電暈處理面彼此貼合而獲得試驗片100。使用該試驗片100，如以下般進行了彎曲試驗。圖4的（a）及圖4的（b）是示意性表示彎曲試驗的方法的圖。準備具有兩個台501、502的彎曲裝置（科學城（Science Town）公司製造，STS-VRT-500）。在台501、台502上以前表面板側朝下的方式載置試驗片100（圖4的（a））。以間隙C1配置兩個台501、502，以寬度方向的中心位於間隙C1的中心的方式固定配置試驗片100（圖4的（a））。該台501、台502能夠擺動，初期兩個台501、502構成同一平面。將使兩個台501、502以位置P1及位置P2為旋轉軸的中心向上方旋轉90度而以相向的試驗片100彼此的間隔C2為5 mm的方式（在該狀態下彎曲的部分的半徑大致為2.5R）關閉兩個台501、502（圖4的（b）），並且再次打開台501、台502的動作定義為一次彎曲。反覆進行該動作，對試驗片100上最初產生裂紋為止的彎曲次數進行計數來評價彎曲性。評價的基準如下。
A：產生裂紋之前的彎曲次數為30萬次以上
B：產生裂紋之前的彎曲次數為20萬次以上且小於30萬次
C：產生裂紋之前的彎曲次數為10萬次以上且小於20萬次
D：產生裂紋之前的彎曲次數為5萬次以上且小於10萬次[Evaluation of Flexibility]
The adhesive layer exposed by peeling off the re-separation film (heavy SP film) on the side of the circular polarizing plate of the optical laminate obtained in each of the Examples and Comparative Examples, and the 100 μm-thickness polyparaphenylene of the display laminate of the assumed display device After corona treatment was performed on the surface of the polyethylene terephthalate (PET) film (output 0.3 kW, treatment speed 3 m/min), the corona treatment surfaces were bonded to each other to obtain a
[ΔS的測定]
按照所述彎曲性的評價程序由各實施例及比較例中獲得的光學積層體製作試驗片100，並按照所述彎曲性的評價程序對該試驗片100實施了進行20萬次彎曲操作的彎曲試驗。利用掃描型電子顯微鏡觀察彎曲試驗後的試驗片100中的圓偏光板的彎曲部分（所述兩個台的間隙C1的範圍）的剖面。彎曲部分的剖面設為在彎曲前的圓偏光板的平面中平行於與彎曲試驗中的旋轉軸（擺動軸）正交的方向的剖面（圖4的（a）中與紙面平行的剖面）。在彎曲試驗後的試驗片剖面的顯微鏡圖像中，對於圓偏光板的彎曲部分，將第一相位差層的第一貼合層側的表面中的最接近光學層（偏光板）側的位置與距光學層（偏光板）側最遠的位置間的圓偏光板的厚度（積層）方向（與圓偏光板的平面正交的方向）上的距離作為ΔS來測定。[Measurement of ΔS]
A
[目視評價]
使按照所述的ΔS的測定程序進行了彎曲試驗的試驗片100（進行了20萬次的彎曲操作的試驗片）成為彎曲前的狀態（如圖4的（a）所示的平坦的狀態），在試驗片100的前表面板側，目視確認自正面觀察時的反射光的色相（色澤）與自相對於試驗片100的平面成角度40°的傾斜方向（將正面的方向設為0°時為角度50°的方向）觀察時的反射光的色相（色調），並對比兩者進行評價。
a：對比的結果，未發現反射光的色相的差異。
b：對比的結果，發現反射光的色相有少許差異。
c：對比的結果，發現反射光的色相不同。
d：在第一相位差層中產生裂紋。[Visual Evaluation]
The test piece 100 (test piece subjected to 200,000 bending operations) subjected to the bending test according to the above-mentioned ΔS measurement procedure is brought into the state before bending (the flat state as shown in Fig. 4(a)) , On the front plate side of the
各實施例及比較例中使用的材料按照以下順序準備。 [偏光板（1）的準備] （保護層形成用組成物的製作） 用於形成作為保護層的外塗（overcoat，OC）層的保護層形成用組成物是將水100份、聚乙烯醇樹脂粉末（KL-318，可樂麗（Kuraray）（股）製造，平均聚合度18000）3份、作為交聯劑的聚醯胺環氧樹脂（SR650（30），住化化科（Sumika Chemtex）（股）製造）1.5份混合而製備。The materials used in the respective examples and comparative examples were prepared in the following procedure. [Preparation of Polarizing Plate (1)] (Production of composition for forming protective layer) The protective layer forming composition used to form the overcoat (OC) layer as the protective layer is made of 100 parts of water, polyvinyl alcohol resin powder (KL-318, Kuraray (stock), average polymerization It was prepared by mixing 3 parts of polyamide epoxy resin (SR650 (30), manufactured by Sumika Chemtex (stock)) as a crosslinking agent in 3 parts.
（偏光板（1）的製作） 在作為保護層的厚度25 μm的三乙醯纖維素（TAC）膜上塗佈配向層形成用組成物形成塗膜。對該塗膜照射偏光UV而形成厚度為100 nm的配向層（光配向層）。在配向層（與TAC膜側相反的一側）上塗佈含有聚合性液晶化合物及偶氮色素的偏光層形成用組成物而形成塗膜。使該塗膜乾燥後，照射紫外線而形成厚度1.8 μm的直線偏光層（1）。在直線偏光層（1）（與TAC膜側相反的一側）上塗佈保護層形成用組成物並使其乾燥而形成作為保護層的厚度1.0 μm的OC層，從而獲得作為光學層的偏光板（1）。偏光板（1）由TAC膜、配向層、直線偏光層（1）、OC層依次積層而成。(Production of polarizing plate (1)) The composition for forming an alignment layer was coated on a 25 μm-thick triacetyl cellulose (TAC) film as a protective layer to form a coating film. The coating film was irradiated with polarized light UV to form an alignment layer (photoalignment layer) with a thickness of 100 nm. On the alignment layer (the side opposite to the TAC film side), a composition for forming a polarizing layer containing a polymerizable liquid crystal compound and an azo dye is applied to form a coating film. After drying the coating film, ultraviolet rays were irradiated to form a linearly polarizing layer (1) having a thickness of 1.8 μm. The composition for forming a protective layer was coated on the linear polarizing layer (1) (the side opposite to the TAC film side) and dried to form an OC layer with a thickness of 1.0 μm as a protective layer, thereby obtaining polarized light as an optical layer Board (1). The polarizing plate (1) is formed by stacking a TAC film, an alignment layer, a linear polarizing layer (1), and an OC layer in sequence.
[偏光板（2）的準備] （直線偏光層（2）的製作） 將厚度30 μm的長條狀的聚乙烯醇（PVA）原材膜（平均聚合度2400，皂化度99.9莫耳%以上）浸漬在包含純水的膨潤浴中（膨潤步驟）後，浸漬在含碘的染色浴中（染色步驟），並浸漬在含碘化鉀及硼酸的交聯浴中（交聯步驟）。在染色步驟及交聯步驟中，藉由浴中的輥間拉伸進行縱向單軸拉伸。以原材膜為基準的總拉伸倍率為5.4倍。接著，將自交聯浴拉出的膜浸漬在包含純水的清洗浴中（清洗步驟）後，導入能夠調節濕度的加熱爐，藉此進行高溫高濕處理（高溫高濕處理步驟），而獲得厚度12.1 μm的直線偏光層（2）。[Preparation of Polarizing Plate (2)] (Production of linear polarizing layer (2)) A long strip of polyvinyl alcohol (PVA) raw material film (average degree of polymerization of 2400, saponification degree of 99.9 mol% or more) with a thickness of 30 μm is immersed in a swelling bath containing pure water (swelling step), and then immersed in a swelling bath containing pure water (swelling step). In a dyeing bath with iodine (dyeing step), and immersed in a cross-linking bath containing potassium iodide and boric acid (cross-linking step). In the dyeing step and the cross-linking step, longitudinal uniaxial stretching is performed by stretching between rolls in a bath. The total stretch magnification based on the original film is 5.4 times. Next, the film drawn from the crosslinking bath is immersed in a clean bath containing pure water (washing step), and then introduced into a heating furnace capable of adjusting humidity, thereby performing high temperature and high humidity treatment (high temperature and high humidity treatment step), and A linear polarizing layer (2) with a thickness of 12.1 μm was obtained.
（偏光板（2）的製作） 對作為保護層的厚度23 μm的環狀聚烯烴（COP）膜及直線偏光層（2）分別進行了電暈處理（輸出為0.3 kW，處理速度為3 m/分）。使用在所述[偏光板（1）的準備]中製作的保護層形成用組成物作為接著劑組成物，將COP膜的電暈處理面與直線偏光層（2）的電暈處理面貼合，並在溫度60°C下乾燥2分鐘，而獲得作為光學層的偏光板（2）。偏光板（2）由COP膜、接著劑硬化層、直線偏光層（2）依次積層而成。(Production of polarizing plate (2)) The cyclic polyolefin (COP) film with a thickness of 23 μm as the protective layer and the linear polarizing layer (2) were respectively subjected to corona treatment (output 0.3 kW, processing speed 3 m/min). Using the composition for forming a protective layer prepared in the aforementioned [Preparation of Polarizing Plate (1)] as an adhesive composition, the corona treated surface of the COP film and the corona treated surface of the linear polarizing layer (2) were bonded together , And dried at a temperature of 60°C for 2 minutes to obtain a polarizing plate (2) as an optical layer. The polarizing plate (2) is formed by laminating a COP film, an adhesive hardening layer, and a linear polarizing layer (2) in this order.
[第一相位差層的準備] （第一配向層形成用組成物） 用於形成第一配向層的第一配向層形成用組成物藉由將具有以下結構式所表示的光反應性基的聚合物以5%的濃度溶解在環戊酮中來製備。[Preparation of the first retardation layer] (Composition for forming the first alignment layer) The first alignment layer forming composition for forming the first alignment layer is prepared by dissolving a polymer having a photoreactive group represented by the following structural formula in cyclopentanone at a concentration of 5%.
[化1]
（第一液晶層形成用組成物） 用於形成第一液晶層的第一液晶層形成用組成物藉由將以下所示的各成分混合，並將所得的混合物在80℃下攪拌1小時來製備。 ･由下述結構式表示的化合物：80份(Composition for forming the first liquid crystal layer) The composition for forming the first liquid crystal layer for forming the first liquid crystal layer is prepared by mixing the components shown below, and stirring the resulting mixture at 80°C for 1 hour. ･Compound represented by the following structural formula: 80 parts
[化2]
[化3]
（帶基材層的第一相位差層的製作） 在作為基材層的厚度100 μm的聚對苯二甲酸乙二醇酯膜（PET）上，藉由棒塗法塗佈第一配向層形成用組成物，在80℃的乾燥烘箱中加熱乾燥1分鐘。以累計光量 100 mJ/cm2 （365 nm基準）對得到的乾燥被膜實施偏光UV照射處理（「SPOT CURE SP-9」、牛尾（Ushio）電機股份有限公司製），而形成第一配向層。以偏光UV的偏光方向相對於直線偏光層的吸收軸為45°的方式進行。(Production of the first retardation layer with a base layer) The first alignment layer was coated by a bar coating method on a polyethylene terephthalate film (PET) with a thickness of 100 μm as the base layer The composition for formation was heated and dried in a drying oven at 80°C for 1 minute. The obtained dry film was subjected to a polarization UV irradiation treatment ("SPOT CURE SP-9", manufactured by Ushio Electric Co., Ltd.) at a cumulative light amount of 100 mJ/cm 2 (365 nm standard) to form a first alignment layer. It is performed so that the polarization direction of the polarized light UV is 45° with respect to the absorption axis of the linear polarizing layer.
藉由棒塗法在第一配向層（與PET膜側相反的一側）上塗佈第一液晶層形成用組成物，在120℃的乾燥烘箱中加熱乾燥1分鐘後，冷卻至室溫。對所獲得的乾燥被膜照射累計光量1000 mJ/cm2 （365 nm基準）的紫外線，藉此形成厚度2.0 μm的第一液晶層。第一液晶層是在面內方向顯示λ/4相位差值的λ/4板，且具有逆波長分散性。藉此，獲得了依次積層PET膜、第一相位差層（第一配向層、第一液晶層）而成的帶基材層的第一相位差層。The first alignment layer (the side opposite to the PET film side) was coated with the first liquid crystal layer forming composition by a bar coating method, heated and dried in a drying oven at 120° C. for 1 minute, and then cooled to room temperature. The obtained dry film was irradiated with ultraviolet rays having a cumulative light quantity of 1000 mJ/cm 2 (based on 365 nm) to form a first liquid crystal layer with a thickness of 2.0 μm. The first liquid crystal layer is a λ/4 plate exhibiting a λ/4 retardation value in the in-plane direction, and has reverse wavelength dispersion. In this way, a first retardation layer with a base material layer in which a PET film and a first retardation layer (first alignment layer, first liquid crystal layer) were laminated in this order was obtained.
[第二相位差層的準備] （第二配向層形成用組成物） 用於形成第二配向層的第二配向層形成用組成物是藉由將丙烯酸2-苯氧乙酯、丙烯酸四氫糠酯、二季戊四醇三丙烯酸酯、及雙(2-乙烯基氧基乙基)醚以質量比計為1：1：4：5的比例混合，並向該混合物中以4%的比例添加露西林蒂珀（LUCIRIN TPO）作為聚合引發劑而製備。[Preparation of the second retardation layer] (Composition for forming the second alignment layer) The composition for forming the second alignment layer for forming the second alignment layer is obtained by combining 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, dipentaerythritol triacrylate, and bis(2-vinyloxyethyl) The base) ether is mixed in a ratio of 1:1:4:5 in a mass ratio, and LUCIRIN TPO is added as a polymerization initiator to the mixture in a ratio of 4% to prepare it.
（第二液晶層形成用組成物） 用於形成第二液晶層的第二液晶層形成用組成物是將光聚合性向列液晶化合物（默克（Merck）公司製、RMM28B）及溶媒製備成固體成分為1 g～1.5 g而得。溶媒使用將甲基乙基酮（methyl ethyl ketone，MEK）、甲基異丁基酮（methyl isobutyl ketone，MIBK）和環己酮（cyclo hexanone，CHN）以質量比（MEK：MIBK：CHN）計為35：30：35的比例混合而成的混合溶媒。(Composition for forming the second liquid crystal layer) The composition for forming the second liquid crystal layer for forming the second liquid crystal layer is obtained by preparing a photopolymerizable nematic liquid crystal compound (manufactured by Merck, RMM28B) and a solvent to have a solid content of 1 g to 1.5 g. The solvent used is based on the mass ratio of methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone (CHN) (MEK: MIBK: CHN) It is a mixed solvent with a ratio of 35:30:35.
（帶基材層的第二相位差層的製作） 以厚度為3 μm的方式在作為基材層的厚度38 μm的聚對苯二甲酸乙二醇酯（PET）膜上塗佈第二配向層形成用組成物，並照射200 mJ/cm2 的紫外線，而形成作為垂直配向層的第二配向層。(Production of the second retardation layer with a base layer) The second alignment was applied to a 38 μm thick polyethylene terephthalate (PET) film as a base layer in a thickness of 3 μm The composition for layer formation was irradiated with 200 mJ/cm 2 of ultraviolet rays to form a second alignment layer as a vertical alignment layer.
在第二配向層（與PET膜側相反的一側）上，藉由模塗佈以4 g～5 g（濕（wet））的塗敷量塗敷第二液晶層形成用組成物，形成塗膜。將乾燥溫度設為75℃、乾燥時間設為120秒鐘，使塗膜乾燥後，照射紫外線，形成厚度3 μm的第二液晶層。第二液晶層為正C板。藉此，獲得依次積層PET膜、第二相位差層（第二配向層、第二液晶層）而成的帶基材層的第二相位差層。On the second alignment layer (the side opposite to the PET film side), the composition for forming the second liquid crystal layer is coated by die coating in a coating amount of 4 g to 5 g (wet) to form涂膜。 Coating. The drying temperature was set to 75° C. and the drying time was set to 120 seconds. After the coating film was dried, ultraviolet rays were irradiated to form a second liquid crystal layer with a thickness of 3 μm. The second liquid crystal layer is a positive C plate. Thereby, a second retardation layer with a base material layer in which a PET film and a second retardation layer (second alignment layer, second liquid crystal layer) are laminated in this order is obtained.
[黏著劑層的準備] 準備下述黏著劑組成物A～黏著劑組成物D，使用該黏著劑準備黏著劑層A～黏著劑層C、黏著劑層D1及黏著劑層D2。[Preparation of Adhesive Layer] The following adhesive composition A to adhesive composition D are prepared, and the adhesive layer A to adhesive layer C, the adhesive layer D1, and the adhesive layer D2 are prepared using the adhesive.
使丙烯酸正丁酯70份、丙烯酸甲酯20份、丙烯酸1.0份共聚合，製備丙烯酸系聚合物（A）。測定丙烯酸系聚合物（A）的分子量，結果重量平均分子量Mw為150萬。70 parts of n-butyl acrylate, 20 parts of methyl acrylate, and 1.0 part of acrylic acid were copolymerized to prepare an acrylic polymer (A). The molecular weight of the acrylic polymer (A) was measured, and as a result, the weight average molecular weight Mw was 1.5 million.
在丙烯酸系聚合物（A）100份中混合0.3份交聯劑（日本聚胺基甲酸酯工業（Nippon Polyurethane Industry）（股）「科羅奈特（Coronate）L」）、0.5份矽烷偶合劑（信越化學工業股份有限公司製「X-12-981」），以使整體固體成分濃度為10%的方式添加乙酸乙酯，獲得黏著劑組成物A。利用塗敷器，以乾燥後的厚度為25 μm的方式將所得的黏著劑組成物A塗佈於經脫模處理的聚對苯二甲酸乙二醇酯膜（重分離膜（重SP膜）、厚度38 μm）的脫模處理面。將塗佈層在100℃下乾燥1分鐘，形成黏著劑層A。其後，在黏著劑層A的露出面上貼合經脫模處理的另一聚對苯二甲酸乙二醇酯膜（輕分離膜（輕SP膜）、厚度38 μm）。然後，在溫度23℃、相對濕度50%RH條件下養護7天。藉此，製作了包含重SP膜/黏著劑層A/輕SP膜的黏著劑片A。測定黏著劑片A所具有的黏著劑層A的25℃下的彈性係數。將結果示於表1中。In 100 parts of acrylic polymer (A), 0.3 part of crosslinking agent (Nippon Polyurethane Industry (stock) "Coronate L"), 0.5 part of silane coupling For the mixture ("X-12-981" manufactured by Shin-Etsu Chemical Co., Ltd.), ethyl acetate was added so that the overall solid content concentration was 10%, and adhesive composition A was obtained. Using an applicator, apply the resulting adhesive composition A to a release-treated polyethylene terephthalate film (heavy separation film (heavy SP film) so that the thickness after drying is 25 μm) , 38 μm thickness) demoulding surface. The coating layer was dried at 100°C for 1 minute to form an adhesive layer A. After that, another polyethylene terephthalate film (light separation film (light SP film), thickness 38 μm) that was subjected to mold release treatment was stuck on the exposed surface of the adhesive layer A. Then, it was cured for 7 days at a temperature of 23° C. and a relative humidity of 50% RH. In this way, an adhesive sheet A including a heavy SP film/adhesive layer A/light SP film was produced. The elastic modulus at 25°C of the adhesive layer A of the adhesive sheet A was measured. The results are shown in Table 1.
（黏著劑組成物B及黏著劑片B的製作） 使丙烯酸正丁酯98.9份、丙烯酸1.1份共聚合，製備丙烯酸系聚合物（B）。測定丙烯酸系聚合物（B）的分子量，結果重量平均分子量Mw為136萬。(Production of adhesive composition B and adhesive sheet B) 98.9 parts of n-butyl acrylate and 1.1 parts of acrylic acid were copolymerized to prepare an acrylic polymer (B). The molecular weight of the acrylic polymer (B) was measured, and as a result, the weight average molecular weight Mw was 1.36 million.
在丙烯酸系聚合物（B）100份中混合2份第一交聯劑（日本聚胺基甲酸酯工業（Nippon Polyurethane Industry）（股）的「科羅奈特（Coronate）L」）、0.02份第二交聯劑（相互藥工（股）的「TAZM」）、0.5份矽烷偶合劑（信越化學工業股份有限公司製「KBM403」），以使整體固體成分濃度為10%的方式添加乙酸乙酯，得到黏著劑組成物B。除了使用黏著劑組成物B以外，按照與黏著劑片A的製作相同的程序，製作了包含重SP膜/黏著劑層B/輕SP膜的黏著劑片B。測定黏著劑片B所具有的黏著劑層B的25℃下的彈性係數。將結果示於表1中。Mix 2 parts of the first crosslinking agent ("Coronate L" from Nippon Polyurethane Industry (stock)) in 100 parts of acrylic polymer (B), 0.02 Part of the second crosslinking agent ("TAZM" of Mutual Pharmaceutical Co., Ltd.), 0.5 part of silane coupling agent ("KBM403" made by Shin-Etsu Chemical Co., Ltd.), and adding acetic acid so that the overall solid content concentration is 10% Ethyl ester, the adhesive composition B was obtained. Except for using the adhesive composition B, an adhesive sheet B including a heavy SP film/adhesive layer B/light SP film was produced according to the same procedure as the production of the adhesive sheet A. The elastic modulus at 25°C of the adhesive layer B of the adhesive sheet B was measured. The results are shown in Table 1.
（黏著劑組成物C及黏著劑片C的製作） 使丙烯酸正丁酯70.4份、丙烯酸2-乙基己酯45份、丙烯酸4-羥基丁酯1份共聚合，製備丙烯酸系聚合物（C）。測定丙烯酸系聚合物（C）的分子量，結果重量平均分子量Mw為80萬。(Production of adhesive composition C and adhesive sheet C) 70.4 parts of n-butyl acrylate, 45 parts of 2-ethylhexyl acrylate, and 1 part of 4-hydroxybutyl acrylate were copolymerized to prepare an acrylic polymer (C). The molecular weight of the acrylic polymer (C) was measured, and as a result, the weight average molecular weight Mw was 800,000.
在丙烯酸系聚合物（C）100份中混合0.4份交聯劑（日本聚胺基甲酸酯工業（Nippon Polyurethane Industry）（股）「科羅奈特（Coronate）L」）、0.5份矽烷偶合劑（信越化學工業股份有限公司製「KBM403」），以使整體固體成分濃度為10%的方式添加乙酸乙酯，得到黏著劑組成物C。除了使用黏著劑組成物C以外，按照與黏著劑片A的製作相同的程序，製作了包含重SP膜/黏著劑層C/輕SP膜的黏著劑片C。測定黏著劑片C所具有的黏著劑層C的25℃下的彈性係數。將結果示於表1中。In 100 parts of acrylic polymer (C), 0.4 part of crosslinking agent (Nippon Polyurethane Industry (stock) "Coronate L"), 0.5 part of silane coupling For the mixture ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.), ethyl acetate was added so that the overall solid content concentration was 10%, and an adhesive composition C was obtained. Except for using the adhesive composition C, an adhesive sheet C including a heavy SP film/adhesive layer C/light SP film was produced in accordance with the same procedure as the production of the adhesive sheet A. The elastic modulus at 25°C of the adhesive layer C of the adhesive sheet C was measured. The results are shown in Table 1.
（黏著劑組成物D、以及黏著劑片D1及黏著劑片D2的製作） 使丙烯酸正丁酯68份、丙烯酸甲酯30份及丙烯酸2-羥基乙酯1份、丙烯酸1份共聚合，製備丙烯酸系聚合物（D）。測定丙烯酸系聚合物（D）的分子量，結果重量平均分子量Mw為135萬。(Production of adhesive composition D, adhesive sheet D1 and adhesive sheet D2) 68 parts of n-butyl acrylate, 30 parts of methyl acrylate, 1 part of 2-hydroxyethyl acrylate, and 1 part of acrylic acid were copolymerized to prepare an acrylic polymer (D). The molecular weight of the acrylic polymer (D) was measured, and as a result, the weight average molecular weight Mw was 1.35 million.
在丙烯酸系聚合物（D）100份中混合3份交聯劑（日本聚胺基甲酸酯工業（Nippon Polyurethane Industry）（股）「科羅奈特（Coronate）L」）、0.5份矽烷偶合劑（信越化學工業股份有限公司製「KBM403」），以使整體固體成分濃度為10%的方式添加乙酸乙酯，得到黏著劑組成物D。Mix 3 parts of crosslinking agent (Nippon Polyurethane Industry (stock) "Coronate L") in 100 parts of acrylic polymer (D), 0.5 part of silane coupling For the mixture ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.), ethyl acetate was added so that the overall solid content concentration was 10%, and an adhesive composition D was obtained.
除了使用黏著劑組成物D，以乾燥後的厚度為15 μm的方式塗佈黏著劑組成物D以外，按照與黏著劑片A的製作相同的程序，製作了包含重SP膜/黏著劑層D1/輕SP膜的黏著劑片D1。另外，除了使用黏著劑組成物D，以乾燥後的厚度為5 μm的方式塗佈黏著劑組成物D以外，按照與黏著劑片A的製作同樣的順序，製作了包含重SP膜/黏著劑層D2/輕SP膜的黏著劑片D2。測定黏著劑片D1及黏著劑片D2分別具有的黏著劑層D1及黏著劑層D2的25℃下的彈性係數。將結果示於表1中。Except that the adhesive composition D was used and the adhesive composition D was applied to a thickness of 15 μm after drying, the same procedure as the production of the adhesive sheet A was followed to produce a heavy SP film/adhesive layer D1 / Adhesive sheet D1 of light SP film. In addition, except that the adhesive composition D was used and the adhesive composition D was applied to a thickness of 5 μm after drying, the same procedure as the production of the adhesive sheet A was followed to produce a heavy SP film/adhesive Adhesive sheet D2 of layer D2/light SP film. The elastic modulus at 25° C. of the adhesive layer D1 and the adhesive layer D2 of the adhesive sheet D1 and the adhesive sheet D2, respectively, was measured. The results are shown in Table 1.
[接著劑組成物的準備]
混合作為硬化性成分的商品名「CEL2021P」（大賽璐（Daicel）公司製造）50份及商品名「OXT-221」（東亞合成公司製造）50份、作為光聚合引發劑的商品名「CPI-100」（桑洛普（San-apro）公司製造）2.25份、作為增感劑的1,4-二乙氧基萘2份來製作接著劑組成物。[Preparation of Adhesive Composition]
50 parts of the brand name "CEL2021P" (manufactured by Daicel) and 50 parts of the brand name "OXT-221" (manufactured by Toagosei Co., Ltd.) as the curable component, and the brand name "CPI-" as the
[前表面板的準備] 作為前表面板，使用了在厚度50 μm的聚醯亞胺（PI）系樹脂膜的單面形成有厚度10 μm的硬塗層（hardcoat，HC）層的帶HC層的膜。HC層是由包含末端具有多官能丙烯酸基的樹枝狀聚合物化合物的組成物形成的層。[Preparation of the front panel] As the front surface plate, a film with an HC layer in which a hardcoat (HC) layer with a thickness of 10 μm was formed on one side of a polyimide (PI)-based resin film with a thickness of 50 μm was used. The HC layer is a layer formed of a composition containing a dendritic polymer compound having a multifunctional acrylic group at the terminal.
〔實施例1〕 （相位差積層體（1）的製作） 對所述準備的帶基材層的第一相位差層的第一相位差層側、及所述準備的黏著劑片A的剝離輕SP膜而露出的黏著劑層A進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘）後，將電暈處理面彼此貼合。接著，對黏著劑片A的剝離重SP膜而露出的黏著劑層A、以及所述準備的帶基材層的第二相位差層的第二相位差層側進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘），然後將電暈處理面彼此貼合，將該黏著劑層A作為第二貼合層，從而獲得相位差積層體（1）。相位差積層體（1）是依次積層PET膜、第一相位差層（第一配向層、第一液晶層）、第二貼合層（黏著劑層A）、第二相位差層（第二液晶層、第二配向層）、PET膜而成。[Example 1] (Production of retardation laminate (1)) Corona treatment was performed on the first retardation layer side of the first retardation layer with the base layer and the adhesive layer A exposed by peeling off the light SP film of the prepared adhesive sheet A (output After 0.3 kW, processing speed 3 m/min), the corona treated surfaces are attached to each other. Next, corona treatment was performed on the second retardation layer side of the second retardation layer of the second retardation layer prepared by peeling off the heavy SP film of the adhesive sheet A and the second retardation layer prepared as described above (output 0.3 kW , Processing speed 3 m/min), and then the corona-treated surfaces are bonded to each other, and the adhesive layer A is used as the second bonding layer to obtain a retardation laminate (1). The retardation laminate (1) is a layered PET film, a first retardation layer (first alignment layer, first liquid crystal layer), a second bonding layer (adhesive layer A), a second retardation layer (second Liquid crystal layer, second alignment layer), PET film.
（圓偏光板（1）的製作） 對相位差積層體（1）的剝離第一相位差層側的PET膜而露出的表面、以及所述準備的偏光板（1）的OC層進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘）。在第一相位差層側的電暈處理面上，塗佈所述準備的接著劑組成物，與偏光板（1）的電暈處理面貼合。使用紫外線照射裝置（紫外線燈使用輻深紫外線系統（Fusion UV Systems）公司製造的「H閥」），以使光照射強度為400 mW/cm2 、波長280 nm～320 nm下的累計光量為800 mJ/cm2 的方式照射紫外線，使接著劑組成物硬化，從而形成作為第一貼合層的厚度2 μm的接著劑硬化層而獲得圓偏光板（1）。圓偏光板（1）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（接著劑硬化層）、第一相位差層、第二貼合層（黏著劑層A）、第二相位差層而成。(Production of circular polarizing plate (1)) The surface of the retardation laminate (1) exposed by peeling off the PET film on the side of the first retardation layer and the OC layer of the polarizing plate (1) prepared as described above were corona. Processing (output 0.3 kW, processing speed 3 m/min). On the corona-treated surface on the side of the first retardation layer, the prepared adhesive composition was applied and bonded to the corona-treated surface of the polarizing plate (1). Use an ultraviolet irradiation device (the ultraviolet lamp uses the "H valve" manufactured by Fusion UV Systems) so that the light irradiation intensity is 400 mW/cm 2 and the cumulative light intensity at the wavelength of 280 nm to 320 nm is 800 Ultraviolet rays were irradiated at mJ/cm 2 to cure the adhesive composition to form a 2 μm-thick adhesive cured layer as the first bonding layer to obtain a circular polarizing plate (1). The circular polarizing plate (1) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive hardening layer), first retardation layer, The second bonding layer (adhesive layer A) and the second retardation layer are formed.
再者，由於有時第一配向層亦會隨著第一基材層的剝離而剝離，同樣地，有時第二基材層亦會隨著第二基材層的剝離而剝離，因此圓偏光板（1）中的第一相位差層及第二相位差層的層結構未必與相位差積層體（1）中的第一相位差層及第二相位差層的層結構一致。在以下的實施例及比較例中亦同樣。Furthermore, because sometimes the first alignment layer will also peel off with the peeling of the first base layer, similarly, sometimes the second base layer will also peel off with the peeling of the second base layer, so the circle The layer structure of the first retardation layer and the second retardation layer in the polarizing plate (1) does not necessarily match the layer structure of the first retardation layer and the second retardation layer in the retardation laminate (1). The same applies to the following Examples and Comparative Examples.
（光學積層體（1）的製作） 對圓偏光板（1）的第二相位差層側、及所述準備的黏著劑片A的剝離輕SP膜而露出的黏著劑層A進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘）後，將電暈處理面彼此貼合，從而獲得帶黏著劑層的圓偏光板（1）。(Production of optical laminate (1)) The second retardation layer side of the circular polarizing plate (1) and the adhesive layer A exposed by peeling off the light SP film of the prepared adhesive sheet A were corona treated (output 0.3 kW, processing speed 3 m/ Minutes) later, the corona treated surfaces are attached to each other to obtain a circular polarizing plate (1) with an adhesive layer.
對所述準備的前表面板的PI系樹脂膜側、及所述準備的黏著劑片A的剝離輕SP膜而露出的黏著劑層A進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘），然後將電暈處理面彼此貼合，而獲得帶黏著劑層的前表面板。Corona treatment was performed on the PI-based resin film side of the prepared front surface plate and the adhesive layer A exposed by peeling off the light SP film of the prepared adhesive sheet A (output 0.3 kW, processing speed 3 m/ Minutes), and then the corona treated surfaces are attached to each other to obtain a front surface plate with an adhesive layer.
接著，對帶黏著劑層的前表面板的剝離重SP膜而露出的黏著劑層A、及帶黏著劑層的圓偏光板（1）的偏光板（1）側進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘），然後將電暈處理面彼此貼合而獲得光學積層體（1）。光學積層體（1）是將前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（1）、黏著劑層A、重SP膜依次積層而成。Next, corona treatment was performed on the adhesive layer A exposed by peeling off the heavy SP film of the front surface plate with the adhesive layer, and the polarizing plate (1) side of the circular polarizing plate (1) with the adhesive layer (output 0.3 kW, processing speed 3 m/min), and then the corona-treated surfaces are bonded to each other to obtain an optical laminate (1). The optical laminate (1) is formed by laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (1), adhesive layer A, and heavy SP film in this order.
使用所獲得的光學積層體（1）進行彎曲性的評價、ΔS的測定、目視評價。將結果示於表1中。Using the obtained optical layered body (1), evaluation of flexibility, measurement of ΔS, and visual evaluation were performed. The results are shown in Table 1.
〔實施例2〕 （相位差積層體（2）的製作） 除了使用所述準備的黏著劑片D1代替黏著劑片A以外，藉由與相位差積層體（1）的製作同樣的程序獲得相位差積層體（2）。相位差積層體（2）是依次積層PET膜、第一相位差層（第一配向層、第一液晶層）、第二貼合層（黏著劑層D1）、第二相位差層（第二液晶層、第二配向層）、PET膜而成。[Example 2] (Production of retardation laminate (2)) Except that the prepared adhesive sheet D1 was used instead of the adhesive sheet A, the retardation layered body (2) was obtained by the same procedure as the production of the retardation layered body (1). The retardation laminate (2) is a layered PET film, a first retardation layer (first alignment layer, first liquid crystal layer), a second bonding layer (adhesive layer D1), a second retardation layer (second Liquid crystal layer, second alignment layer), PET film.
（圓偏光板（2）的製作） 對所述準備的黏著劑片D2的剝離輕SP膜而露出的黏著劑層D2、以及所述準備的偏光板（1）的OC層進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘）後，將電暈處理面彼此貼合。接著，對黏著劑片D2的剝離重SP膜而露出的黏著劑層D2、以及相位差積層體（2）的剝離第一相位差層側的PET膜而露出的表面進行電暈處理（輸出0.3 kW、處理速度3 m/分鐘），然後將電暈處理面彼此貼合，將該黏著劑層D2作為第一貼合層。然後剝離第二相位差層側的PET膜而獲得圓偏光板（2）。圓偏光板（2）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（黏著劑層D2）、第一相位差層、第二貼合層（黏著劑層D1）、第二相位差層而成。(Production of circular polarizing plate (2)) The adhesive layer D2 exposed by peeling off the light SP film of the prepared adhesive sheet D2 and the OC layer of the prepared polarizing plate (1) were subjected to corona treatment (output 0.3 kW, processing speed 3 m/min) ) After that, the corona treated surfaces are attached to each other. Next, corona treatment was performed on the exposed surface of the adhesive sheet D2 by peeling off the heavy SP film and exposing the adhesive layer D2 and the retardation laminate (2) on the exposed surface of the PET film on the side of the first retardation layer (output 0.3 kW, processing speed 3 m/min), and then the corona-treated surfaces are bonded to each other, and the adhesive layer D2 is used as the first bonding layer. Then, the PET film on the side of the second retardation layer was peeled off to obtain a circular polarizing plate (2). The circular polarizing plate (2) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive layer D2), first retardation layer, The second bonding layer (adhesive layer D1) and the second retardation layer are formed.
（光學積層體（3）的製作） 除了使用圓偏光板（2）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（2）。光學積層體（2）是將前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（2）、黏著劑層A、重SP膜依次積層而成。使用所獲得的光學積層體（2）進行彎曲性的評價、ΔS的測定、目視評價。將結果示於表1中。(Production of optical laminate (3)) Except that the circular polarizing plate (2) was used instead of the circular polarizing plate (1), the optical laminate (2) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (2) is formed by laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (2), adhesive layer A, and heavy SP film in sequence. Using the obtained optical layered product (2), evaluation of flexibility, measurement of ΔS, and visual evaluation were performed. The results are shown in Table 1.
〔實施例3〕 （相位差積層體（3）的製作） 除了使用所述準備的黏著劑片B代替黏著劑片A以外，按照與相位差積層體（1）的製作相同的程序獲得相位差積層體（3）。相位差積層體（3）是依次積層PET膜、第一相位差層（第一配向層、第一液晶層）、第二貼合層（黏著劑層B）、第二相位差層（第二液晶層、第二配向層）、PET膜而成。[Example 3] (Production of retardation laminate (3)) Except that the prepared adhesive sheet B was used instead of the adhesive sheet A, the retardation layered body (3) was obtained according to the same procedure as the production of the retardation layered body (1). The retardation laminate (3) is a layered PET film, a first retardation layer (first alignment layer, first liquid crystal layer), a second bonding layer (adhesive layer B), a second retardation layer (second Liquid crystal layer, second alignment layer), PET film.
（圓偏光板（3）的製作） 除了使用所述準備的黏著劑片C代替黏著劑片D2，使用相位差積層體（3）代替相位差積層體（2）以外，按照與圓偏光板（2）的製作同樣的程序獲得圓偏光板（3）。圓偏光板（3）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（黏著劑層C）、第一相位差層、第二貼合層（黏著劑層B）、第二相位差層而成。(Production of circular polarizing plate (3)) Except that the prepared adhesive sheet C was used instead of the adhesive sheet D2, and the retardation laminate (3) was used instead of the retardation laminate (2), circularly polarized light was obtained according to the same procedure as the production of the circular polarizing plate (2) Board (3). The circular polarizing plate (3) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive layer C), first retardation layer, The second bonding layer (adhesive layer B) and the second retardation layer are formed.
（光學積層體（3）的製作） 除了使用圓偏光板（3）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（3）。光學積層體（3）是將前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（3）、黏著劑層A、重SP膜依次積層而成。使用所獲得的光學積層體（3）進行彎曲性的評價、ΔS的測定、目視評價。將結果示於表1中。(Production of optical laminate (3)) Except that the circular polarizing plate (3) was used instead of the circular polarizing plate (1), the optical laminate (3) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (3) is formed by laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (3), adhesive layer A, and heavy SP film in sequence. Using the obtained optical layered product (3), evaluation of flexibility, measurement of ΔS, and visual evaluation were performed. The results are shown in Table 1.
〔實施例4〕 （圓偏光板（4）的製作） 使用所述準備的偏光板（2）代替偏光板（1），對偏光板（2）的直線偏光層（2）及作為第一貼合層的黏著劑層D2進行電暈處理（輸出0.3 kW，處理速度3 m/分鐘）而貼合，除此以外，按照與圓偏光板（2）的製作同樣的程序獲得圓偏光板（4）。圓偏光板（4）是將偏光板（2）（COP膜、接著劑硬化層、直線偏光層（2）（COP膜、接著劑層、直線偏光層（2）））、第一貼合層（黏著劑層D2）、第一相位差層、第二貼合層（黏著劑層D1）、第二相位差層依次積層而成。[Example 4] (Production of circular polarizing plate (4)) Using the prepared polarizing plate (2) instead of the polarizing plate (1), corona treatment was performed on the linear polarizing layer (2) of the polarizing plate (2) and the adhesive layer D2 as the first bonding layer (output 0.3 kW) , Processing speed 3 m/min) and bonding, except for this, the circular polarizing plate (4) was obtained according to the same procedure as the production of the circular polarizing plate (2). The circular polarizing plate (4) is a combination of the polarizing plate (2) (COP film, adhesive hardened layer, linear polarizing layer (2) (COP film, adhesive layer, linear polarizing layer (2))), the first bonding layer (Adhesive layer D2), the first retardation layer, the second bonding layer (adhesive layer D1), and the second retardation layer are laminated in this order.
（光學積層體（4）的製作） 除了使用圓偏光板（4）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（4）。光學積層體（4）是將前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（4）、黏著劑層A、重SP膜依次積層而成。使用所獲得的光學積層體（4）進行彎曲性的評價、ΔS的測定、目視評價。將結果示於表1中。(Production of optical laminate (4)) Except that the circular polarizing plate (4) was used instead of the circular polarizing plate (1), the optical laminate (4) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (4) is formed by sequentially laminating a front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (4), adhesive layer A, and heavy SP film. Using the obtained optical layered body (4), evaluation of flexibility, measurement of ΔS, and visual evaluation were performed. The results are shown in Table 1.
〔實施例5〕 （相位差積層體（5）的製作） 除了使用所述準備的黏著劑片D2代替黏著劑片A以外，按照與相位差積層體（1）的製作同樣的程序獲得相位差積層體（5）。相位差積層體（5）是依次積層PET膜、第一相位差層（第一配向層、第一液晶層）、第二貼合層（黏著劑層D2）、第二相位差層（第二液晶層、第二配向層）、PET膜而成。[Example 5] (Production of retardation laminate (5)) Except that the prepared adhesive sheet D2 was used instead of the adhesive sheet A, the retardation layered body (5) was obtained according to the same procedure as the production of the retardation layered body (1). The retardation laminate (5) is a layered PET film, a first retardation layer (first alignment layer, first liquid crystal layer), a second bonding layer (adhesive layer D2), and a second retardation layer (second Liquid crystal layer, second alignment layer), PET film.
（圓偏光板（5）的製作） 除了使用相位差積層體（5）代替相位差積層體（2）以外，按照與圓偏光板（2）的製作同樣的程序獲得圓偏光板（5）。圓偏光板（5）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（黏著劑層D2）、第一相位差層、第二貼合層（黏著劑層D2）、第二相位差層而成。(Production of circular polarizing plate (5)) Except for using the retardation layered body (5) instead of the retardation layered body (2), the circularly polarizing plate (5) was obtained according to the same procedure as the production of the circularly polarizing plate (2). The circular polarizing plate (5) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive layer D2), first retardation layer, The second bonding layer (adhesive layer D2) and the second retardation layer are formed.
（光學積層體（5）的製作） 除了使用圓偏光板（5）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（5）。光學積層體（5）是將前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（5）、黏著劑層A、重SP膜依次積層而成。使用所獲得的光學積層體（5）進行彎曲性的評價、ΔS的測定、目視評價。將結果示於表1中。(Production of optical laminate (5)) Except that the circular polarizing plate (5) was used instead of the circular polarizing plate (1), the optical laminate (5) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (5) is formed by laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (5), adhesive layer A, and heavy SP film in sequence. Using the obtained optical layered product (5), evaluation of flexibility, measurement of ΔS, and visual evaluation were performed. The results are shown in Table 1.
〔比較例1〕 （相位差積層體（C1）的製作） 除了使用所述準備的黏著劑片C代替黏著劑片A以外，按照與相位差積層體（1）的製作相同的程序獲得相位差積層體（C1）。相位差積層體（C1）是依次積層PET膜、第一相位差層（第一配向層、第一液晶層），第二貼合層（黏著劑層C）、第二相位差層（第二液晶層、第二配向層）、PET膜而成。[Comparative Example 1] (Production of retardation laminate (C1)) Except that the prepared adhesive sheet C was used instead of the adhesive sheet A, the retardation layered body (C1) was obtained according to the same procedure as the production of the retardation layered body (1). The retardation laminate (C1) is a layered PET film, a first retardation layer (first alignment layer, first liquid crystal layer), a second bonding layer (adhesive layer C), a second retardation layer (second Liquid crystal layer, second alignment layer), PET film.
（圓偏光板（C1）的製作） 除了使用所述準備的黏著劑片B代替黏著劑片D2，使用相位差積層體（C1）代替相位差積層體（2）以外，按照與圓偏光板（2）的製作同樣的程序獲得圓偏光板（C1）。圓偏光板（C1）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（黏著劑層B）、第一相位差層、第二貼合層（黏著劑層C）、第二相位差層而成。(Production of circular polarizing plate (C1)) Except that the prepared adhesive sheet B was used instead of the adhesive sheet D2, and the retardation laminate (C1) was used instead of the retardation laminate (2), circularly polarized light was obtained according to the same procedure as the production of the circular polarizer (2) Plate (C1). The circular polarizing plate (C1) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive layer B), first retardation layer, The second bonding layer (adhesive layer C) and the second retardation layer are formed.
（光學積層體（C1）的製作） 除了使用圓偏光板（C1）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（C1）。光學積層體（C1）是將前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（C1）、黏著劑層A、重SP膜依次積層而成。使用所獲得的光學積層體（C1）進行彎曲性的評價、ΔS的測定、目視評價。將結果示於表1中。(Production of optical laminate (C1)) Except that the circular polarizing plate (C1) was used instead of the circular polarizing plate (1), the optical laminate (C1) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (C1) is formed by laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (C1), adhesive layer A, and heavy SP film in this order. Using the obtained optical layered body (C1), evaluation of flexibility, measurement of ΔS, and visual evaluation were performed. The results are shown in Table 1.
〔比較例2〕 （圓偏光板（C2）的製作） 除了使用所述準備的黏著劑片D1代替黏著劑片D2，使用相位差積層體（5）代替相位差積層體（2）以外，按照與圓偏光板（2）的製作同樣的程序獲得圓偏光板（C2）。圓偏光板（C2）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（黏著劑層D1）、第一相位差層、第二貼合層（黏著劑層D2）、第二相位差層而成。[Comparative Example 2] (Production of circular polarizing plate (C2)) Except that the prepared adhesive sheet D1 was used instead of the adhesive sheet D2, and the retardation laminate (5) was used instead of the retardation laminate (2), circularly polarized light was obtained according to the same procedure as the production of the circular polarizer (2) Board (C2). The circular polarizing plate (C2) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive layer D1), first retardation layer, The second bonding layer (adhesive layer D2) and the second retardation layer are formed.
（光學積層體（C2）的製作） 除了使用圓偏光板（C2）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（C2）。光學積層體（C2）是依次積層前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（C2）、黏著劑層A、重SP膜而成。使用所獲得的光學積層體（C2）進行彎曲性的評價、目視評價。由於藉由彎曲試驗產生了裂紋，故未進行ΔS的測定。將結果示於表1中。(Production of optical laminate (C2)) Except that the circular polarizing plate (C2) was used instead of the circular polarizing plate (1), the optical laminate (C2) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (C2) is formed by sequentially laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (C2), adhesive layer A, and heavy SP film. The obtained optical laminate (C2) was used for evaluation of flexibility and visual evaluation. Since cracks were generated by the bending test, the ΔS measurement was not performed. The results are shown in Table 1.
〔比較例3〕 （相位差積層體（C3）的製作） 對所述準備的帶基材層的第一相位差層的第一相位差層側、以及所述準備的帶基材層的第二相位差層的第二相位差層側進行了電暈處理（輸出0.3 kW、處理速度3 m/分鐘）。在帶基材層的第一相位差層的電暈處理面上，塗佈所述準備的接著劑組成物，與帶基材層的第二相位差層的電暈處理面貼合。使用紫外線照射裝置（紫外線燈使用輻深紫外線系統（Fusion UV Systems）公司製造的「H閥」），以使光照射強度為400 mW/cm2 、波長280 nm～320 nm下的累計光量為400 mJ/cm2 的方式照射紫外線，使接著劑組成物硬化，從而形成作為第二貼合層的厚度2 μm的接著劑硬化層。藉此，獲得依次積層PET膜、第一相位差層（第一配向層、第一液晶層）、第二貼合層（接著劑硬化層）、第二相位差層（第二液晶層、第二配向層）、PET膜而成的相位差積層體（C3）。[Comparative Example 3] (Preparation of Retardation Laminated Body (C3)) The first retardation layer side of the first retardation layer with a base layer prepared as described above, and the first retardation layer side of the prepared first retardation layer with a base layer The second retardation layer side of the two retardation layer is corona treated (output 0.3 kW, processing speed 3 m/min). On the corona-treated surface of the first retardation layer with a base material layer, the prepared adhesive composition is applied and bonded to the corona-treated surface of the second retardation layer with a base material layer. Use an ultraviolet irradiation device (the ultraviolet lamp uses the "H valve" manufactured by Fusion UV Systems) so that the light irradiation intensity is 400 mW/cm 2 and the cumulative light intensity at a wavelength of 280 nm to 320 nm is 400 Ultraviolet rays were irradiated at mJ/cm 2 to cure the adhesive composition to form a 2 μm thick adhesive cured layer as the second bonding layer. Thereby, a PET film, a first retardation layer (first alignment layer, first liquid crystal layer), a second bonding layer (adhesive hardening layer), and a second retardation layer (second liquid crystal layer, first Two-alignment layer) and a retardation laminate (C3) made of PET film.
（圓偏光板（C3）的製作） 除了使用所述準備的黏著劑片A代替黏著劑片D2，使用相位差積層體（C3）代替相位差積層體（2）以外，按照與圓偏光板（2）的製作同樣的程序獲得圓偏光板（C3）。圓偏光板（C3）是依次積層偏光板（1）（TAC膜、配向層、直線偏光層（1）、OC層）、第一貼合層（黏著劑層A）、第一相位差層、第二貼合層（接著劑硬化層）、第二相位差層而成。(Production of circular polarizing plate (C3)) Except that the prepared adhesive sheet A was used instead of the adhesive sheet D2 and the retardation laminate (C3) was used instead of the retardation laminate (2), circularly polarized light was obtained in the same procedure as the production of the circular polarizer (2) Board (C3). The circular polarizing plate (C3) is a layered polarizing plate (1) (TAC film, alignment layer, linear polarizing layer (1), OC layer), first bonding layer (adhesive layer A), first retardation layer, The second bonding layer (adhesive curing layer) and the second retardation layer are formed.
（光學積層體（C3）的製作） 除了使用圓偏光板（C3）代替圓偏光板（1）以外，按照與光學積層體（1）的製作同樣的程序獲得光學積層體（C3）。光學積層體（C3）是依次積層前表面板（HC層、PI系樹脂膜）、黏著劑層A、圓偏光板（C3）、黏著劑層A、重SP膜而成。使用所獲得的光學積層體（C3）進行彎曲性的評價、目視評價。由於藉由彎曲試驗產生了裂紋，故未進行ΔS的測定。將結果示於表1中。(Production of optical laminate (C3)) Except that the circular polarizing plate (C3) was used instead of the circular polarizing plate (1), the optical laminate (C3) was obtained according to the same procedure as the production of the optical laminate (1). The optical laminate (C3) is formed by sequentially laminating the front surface plate (HC layer, PI-based resin film), adhesive layer A, circular polarizing plate (C3), adhesive layer A, and heavy SP film. The obtained optical laminate (C3) was used for evaluation of flexibility and visual evaluation. Since cracks were generated by the bending test, the ΔS measurement was not performed. The results are shown in Table 1.
[表1]
1:圓偏光板
5:光學積層體
11:第一相位差層
12:第二相位差層
21:第一貼合層
22:第二貼合層
23:第三貼合層
30:光學層
31:直線偏光層
32、33:保護層
40:前表面板
100:試驗片
501、502:台
C1:間隙
C2:間隔
P1、P2:位置1: Circular polarizing plate
5: Optical laminate
11: The first phase difference layer
12: The second phase difference layer
21: The first bonding layer
22: The second bonding layer
23: The third bonding layer
30: Optical layer
31:
圖1是示意性表示本發明的圓偏光板的一例的概略剖面圖。 圖2是用於說明在圓偏光板的彎曲試驗之後使彎曲狀態返回的情況的一例的概略剖面圖。 圖3是示意性表示本發明的光學積層體的一例的概略剖面圖。 圖4的（a）及圖4的（b）是用以說明彎曲試驗的方法的概略圖。FIG. 1 is a schematic cross-sectional view schematically showing an example of the circularly polarizing plate of the present invention. Fig. 2 is a schematic cross-sectional view for explaining an example of a case where the bent state is returned after a bending test of a circularly polarizing plate. Fig. 3 is a schematic cross-sectional view schematically showing an example of the optical laminate of the present invention. 4(a) and 4(b) are schematic diagrams for explaining the method of the bending test.
Claims (10)
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| CN110959307B (en) * | 2017-07-26 | 2022-08-23 | 富士胶片株式会社 | Organic electroluminescent display device |
| WO2019093474A1 (en) * | 2017-11-10 | 2019-05-16 | 住友化学株式会社 | Circularly polarizing plate and display device |
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| JP2019091029A (en) * | 2017-11-10 | 2019-06-13 | 住友化学株式会社 | Composite retardation plate, optical laminate, and image display device |
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| JP7390101B2 (en) * | 2018-05-10 | 2023-12-01 | 住友化学株式会社 | Optical laminates and display devices |
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