TW202306212A - Laminate - Google Patents
Laminate Download PDFInfo
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- TW202306212A TW202306212A TW111120080A TW111120080A TW202306212A TW 202306212 A TW202306212 A TW 202306212A TW 111120080 A TW111120080 A TW 111120080A TW 111120080 A TW111120080 A TW 111120080A TW 202306212 A TW202306212 A TW 202306212A
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- Prior art keywords
- layer
- adhesive layer
- liquid crystal
- adhesive
- film
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
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- G06F1/16—Constructional details or arrangements
- G06F1/1613—Constructional details or arrangements for portable computers
- G06F1/1633—Constructional details or arrangements of portable computers not specific to the type of enclosures covered by groups G06F1/1615 - G06F1/1626
- G06F1/1637—Details related to the display arrangement, including those related to the mounting of the display in the housing
- G06F1/1641—Details related to the display arrangement, including those related to the mounting of the display in the housing the display being formed by a plurality of foldable display components
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
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- G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
- G06F1/16—Constructional details or arrangements
- G06F1/1613—Constructional details or arrangements for portable computers
- G06F1/1633—Constructional details or arrangements of portable computers not specific to the type of enclosures covered by groups G06F1/1615 - G06F1/1626
- G06F1/1637—Details related to the display arrangement, including those related to the mounting of the display in the housing
- G06F1/1652—Details related to the display arrangement, including those related to the mounting of the display in the housing the display being flexible, e.g. mimicking a sheet of paper, or rollable
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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Abstract
Description
本發明係關於一種積層體及圖像顯示裝置。 The present invention relates to a laminated body and an image display device.
於專利文獻1中揭示一種積層體，其係依序具備第1保護層、第1黏著劑層、中間塗佈層、第2黏著劑層，為了抑制在將第1保護層設為內側而彎曲時於中間塗佈層產生之龜裂，提出將第1黏著劑層及第2黏著劑層於溫度25℃下之儲存模數與厚度之比設為一定範圍。 Patent Document 1 discloses a laminate that sequentially includes a first protective layer, a first adhesive layer, an intermediate coating layer, and a second adhesive layer in order to prevent warpage when the first protective layer is set inside. When cracks occur in the middle coating layer, it is proposed to set the storage modulus-thickness ratio of the first adhesive layer and the second adhesive layer at a temperature of 25°C to a certain range.
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Document]
[專利文獻1]日本特開2020-157577號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2020-157577
作為可彎曲之圖像顯示裝置，係使用可將視認側之面朝內側彎曲之可撓性顯示器、或可將視認側之面朝外側彎曲之可撓性顯示器、可將視認側之 面朝外側或朝內側彎曲之可撓性顯示器。因此，要求可撓性顯示器所使用之積層體無論於將視認側之面設為內側或設為外側之情形時，均可於兩種情形時彎曲。 As a flexible image display device, a flexible display that can bend the face of the viewing side toward the inside, or a flexible display that can bend the face of the viewing side toward the outside, or a flexible display that can bend the face of the viewing side Flexible displays that face outward or bend inward. Therefore, it is required that the laminate used in the flexible display can be bent in both cases regardless of whether the viewing side surface is set to the inside or the outside.
本發明提供一種積層體及使其對齊之顯示裝置，該積層體係依序積層直線偏光層、第1黏著層、液晶塗佈層、及第2黏著層，在以直線偏光層側為內側進行反覆彎曲之情形及以直線偏光層側為外側進行反覆彎曲之情形的任一情形時均不易產生龜裂。 The present invention provides a laminated body and a display device for aligning it. The laminated system sequentially laminates a linear polarizing layer, a first adhesive layer, a liquid crystal coating layer, and a second adhesive layer, and repeats the process on the inner side of the linear polarizing layer. Cracks are less likely to occur in either of the case of bending and the case of repeated bending with the linear polarizing layer side as the outside.
本發明提供以下之積層體及圖像顯示裝置。 The present invention provides the following laminate and image display device.
[1]一種積層體，係依序積層直線偏光層、第1黏著層、液晶塗佈層及第2黏著層， [1] A laminate comprising a linear polarizing layer, a first adhesive layer, a liquid crystal coating layer and a second adhesive layer sequentially laminated,
將上述第1黏著層於溫度25℃下之儲存模數設為G'1[kPa]，將上述第2黏著層於溫度25℃下之儲存模數設為G'2[kPa]時，滿足下述條件(1)或(2)。 When the storage modulus of the above-mentioned first adhesive layer at a temperature of 25°C is set as G'1 [kPa], and the storage modulus of the above-mentioned second adhesive layer at a temperature of 25°C is set as G'2 [kPa], it satisfies The following conditions (1) or (2).
(1)G'1≧1000kPa且G'2≦50kPa (1) G'1≧1000kPa and G'2≦50kPa
(2)G'1≦50kPa且G'2≧1000kPa (2) G'1≦50kPa and G'2≧1000kPa
[2]如[1]所述之積層體，其中上述直線偏光層包含：含有聚合性液晶化合物與1種或複數種偶氮系色素之組成物的硬化物、與配向膜。 [2] The laminate according to [1], wherein the linear polarizing layer includes a cured product of a composition containing a polymerizable liquid crystal compound and one or more azo dyes, and an alignment film.
[3]如[1]或[2]所述之積層體，其中，上述液晶塗佈層係由1層或複數層所構成。 [3] The laminate according to [1] or [2], wherein the liquid crystal coating layer is composed of one layer or a plurality of layers.
[4]如請求項[1]至[3]中任一項所述之積層體，其中於上述直線偏光層之與上述第1黏著層的相反側具備選自由熱塑性樹脂薄膜及硬化樹脂層所成群組中之至少1者的保護層。 [4] The laminate according to any one of claims [1] to [3], wherein the linear polarizing layer is provided with a material selected from a thermoplastic resin film and a cured resin layer on the side opposite to the first adhesive layer. A protective layer for at least one of the groups.
[5]如[4]所述之積層體，其中於上述直線偏光層之與上述第1黏著層相反側之最外表面隔著第3黏著層具備前面板。 [5] The laminate according to [4], wherein a front plate is provided on the outermost surface of the linear polarizing layer opposite to the first adhesive layer via a third adhesive layer.
[6]如[5]所述之積層體，其中上述前面板於溫度23℃下的拉伸模數為4.0GPa以上。 [6] The laminate according to [5], wherein the tensile modulus of the front sheet at a temperature of 23° C. is 4.0 GPa or more.
[7]如[5]或[6]所述之積層體，其中上述第3黏著層於溫度25℃下之儲存模數為50KPa以下。 [7] The laminate described in [5] or [6], wherein the storage modulus of the third adhesive layer at a temperature of 25° C. is 50 KPa or less.
[8]如請求項[1]至[7]中任一項所述之積層體，其中於上述第2黏著層之與上述液晶塗佈層相反側具備有機EL面板。 [8] The laminate according to any one of claims [1] to [7], wherein an organic EL panel is provided on the side opposite to the liquid crystal coating layer of the second adhesive layer.
[9]如請求項[1]至[8]中任一項所述之積層體，其中上述有機EL面板於溫度23℃下之拉伸模數為4.0GPa以上。 [9] The laminate according to any one of claims [1] to [8], wherein the organic EL panel has a tensile modulus of 4.0 GPa or more at a temperature of 23°C.
[10]一種圖像顯示裝置，其包含如[1]至[9]中任一項所述之積層體。 [10] An image display device comprising the laminate according to any one of [1] to [9].
根據本發明，可提供一種積層體，其依序積層直線偏光層、第1黏著層、液晶塗佈層、及第2黏著層，以直線偏光層側為內側進行反覆彎曲之情形及以直線偏光層側為外側進行反覆彎曲之情形的任一情形時均不易產生龜裂。 According to the present invention, it is possible to provide a laminate in which a linear polarizing layer, a first adhesive layer, a liquid crystal coating layer, and a second adhesive layer are laminated in this order, and the case where the linear polarizing layer is bent repeatedly and the linear polarizing layer In any case where the side of the layer is repeatedly bent on the outside, cracks are less likely to occur.
10,30,51:直線偏光層 10,30,51: linear polarizing layer
11,24,44:第1黏著層 11,24,44: 1st adhesive layer
12,25,45:液晶塗佈層 12,25,45: Liquid crystal coating layer
13,26,46:第2黏著層 13,26,46: 2nd adhesive layer
21,41:前面板 21,41: front panel
22,42:第3黏著層 22,42: 3rd adhesive layer
23,43:直線偏光板 23,43: linear polarizer
27,47:有機EL面板 27,47: Organic EL panel
28,48:基材膜 28,48: Substrate film
49:保護層(HC層) 49: Protective layer (HC layer)
29,50:配向膜 29,50: Alignment film
31,52:保護層(OC層) 31,52: protective layer (OC layer)
100,200,300:積層體 100,200,300: laminated body
500:測定用樣品 500: Determination of samples
501,502:治具 501,502: Jigs
圖1呈示本發明之積層體的層構成之一例的概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of the layer configuration of the laminate of the present invention.
圖2呈示本發明之積層體的層構成之另一例的概略剖視圖。 Fig. 2 is a schematic cross-sectional view showing another example of the layer configuration of the laminate of the present invention.
圖3呈示本發明之積層體的層構成之另一例的概略剖視圖。 Fig. 3 is a schematic cross-sectional view showing another example of the layer constitution of the laminate of the present invention.
圖4係說明彎曲性試驗之方法的概略圖。 Fig. 4 is a schematic diagram illustrating a method of a bendability test.
以下，一面參照圖式一面對本發明之實施形態進行說明，但本發明並不限定於以下之實施形態。以下之所有圖式中，為了容易理解各構成要素而適當調整比例尺來表示，圖式所示之各構成要素之比例尺與實際構成要素之比例尺未必一致。 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. In all the drawings below, the scales of the components shown in the drawings are appropriately adjusted for easy understanding of the components, and the scales of the components shown in the drawings do not necessarily match the scales of the actual components.
<積層體> <laminate>
本發明之一態樣之積層體係依序積層直線偏光層、第1黏著層、液晶塗佈層、及第2黏著層，將第1黏著層於溫度25℃下之儲存模數設為G'1[kPa]，將第2黏著層於溫度25℃下之儲存模數設為G'2[kPa]時，滿足下述條件(1)或(2)。 The lamination system of one aspect of the present invention laminates the linear polarizing layer, the first adhesive layer, the liquid crystal coating layer, and the second adhesive layer sequentially, and sets the storage modulus of the first adhesive layer at a temperature of 25°C as G' 1 [kPa], when the storage modulus of the second adhesive layer at a temperature of 25°C is G'2 [kPa], the following conditions (1) or (2) are satisfied.
(1)G'1≧1000kPa且G'2≦50kPa (1) G'1≧1000kPa and G'2≦50kPa
(2)G'1≦50kPa且G'2≧1000kPa (2) G'1≦50kPa and G'2≧1000kPa
圖1呈示本發明之一態樣之積層體之概略剖視圖。圖1所示之積層體100係依序積層直線偏光層10、第1黏著層11、液晶塗佈層12、及第2黏著層13。第1黏著層11及第2黏著層13均與液晶塗佈層12相接而配置。直線偏光層10與第1黏著層11可相互接觸地配置。液晶塗佈層12中不含包含屬於直線偏光層10之一形態的聚合性液晶化合物之硬化物的偏光片。積層體100除了上述層以外，例如可進一步包含保護層、前面板、第3黏著層、貼合層、有機EL面板、觸控感測器等其他層。
Fig. 1 shows a schematic cross-sectional view of a laminate according to an aspect of the present invention. In the laminated
積層體100可對於彎曲軸以直線偏光層10側為內側而彎曲(以下，亦稱為內摺)。積層體100可相對於彎曲軸以直線偏光層10側為外側而彎曲(以
下，亦稱為外摺)。所謂可彎曲，意指可於液晶塗佈層及偏光片層不產生龜裂之情況下使積層體彎曲。彎曲包含於彎曲部分形成曲面之彎折之形態。於彎折之形態中，彎折之內面之彎曲半徑並無特別限定。又，彎曲包含內面之折射角大於0°且小於180。之折射形態、及內面之彎曲半徑接近零、或內面之折射角為0°之折疊形態。由於本發明之積層體可彎曲，故而適於可撓性顯示器。
The laminated
積層體100於後述內摺試驗中進行反覆彎曲之情形時亦不易產生龜裂之彎曲半徑例如可為4mm，較佳為2mm。積層體100於內摺試驗中以彎曲半徑為2mm進行反覆彎曲時，最初產生龜裂之彎曲次數較佳為20萬次以上，更佳為30萬次以上，又更佳為40萬次以上，特佳為50萬次以上。
The bending radius of the
積層體100於下述外摺試驗中進行反覆彎曲之情形時亦不易產生龜裂之彎曲半徑例如可為4mm，較佳為2mm。積層體100於外摺試驗中以彎曲半徑為2mm進行反覆彎曲時，最初產生龜裂之彎曲次數較佳為20萬次以上，更佳為30萬次以上，又更佳為40萬次以上，特佳為50萬次以上。
The bending radius of the
積層體100之厚度根據積層體所要求之功能及積層體之用途等而不同，因此並無特別限定，例如為30μm以上4000μm以下，較佳為2000μm以下，更佳為1000μm以下。於本說明書中，積層體及各層之厚度可依據下述實施例中所說明之厚度測定方法進行測定。 The thickness of the laminate 100 varies depending on the required function of the laminate and the use of the laminate, so it is not particularly limited, for example, it is 30 μm to 4000 μm , preferably 2000 μm or less, and more preferably 1000 μm. µm or less. In this specification, the thickness of the laminate and each layer can be measured in accordance with the thickness measurement method described in the following examples.
積層體100之俯視形狀例如可為方形形狀，較佳為具有長邊與短邊之方形形狀，更佳為長方形。於積層體100之面方向之形狀為長方形之情形時，長邊之長度例如可為10mm以上1400mm以下，較佳為600mm以下。短邊之長度例如為5mm以上且800mm以下，較佳為500mm以下，更佳為300mm以
下。構成積層體之各層亦可對角部進行R加工、或對端部進行缺口加工、或進行開孔加工。
The plan view shape of the
[黏著層於溫度25℃下之儲存模數] [Storage modulus of the adhesive layer at a temperature of 25°C]
積層體100滿足上述條件(1)或(2)。歷來，包含液晶塗佈層之積層體雖然於內摺時可反覆彎曲，但於外摺時會有無法反覆彎曲之情形。本發明者發現，藉由將液晶塗佈層配置於溫度25℃下之儲存模數為1000kPa以上之相對較硬之黏著層與溫度25℃下之儲存模數為50kPa以下之相對較軟之黏著層之間，不僅能夠利用內摺進行反覆彎曲，而且即便外摺亦能夠進行反覆彎曲。溫度25℃下之儲存模數可依據下述實施例之欄中所說明之方法進行測定。
The
第1黏著層11在溫度25℃下之儲存模數G'1[kPa]及第2黏著層13在溫度25℃下之儲存模數G'2[kPa]之一者較佳為1100kPa以上，更佳為1200kPa以上，又更佳為1300kPa以上，特佳為1400kPa以上，另一者較佳為48kPa以下，更佳為45kPa以下，又更佳為43kPa以下，特佳為41kPa以下。
One of the storage modulus G'1 [kPa] of the first
第1黏著層11及第2黏著層13係由後述黏著劑組成物所形成。第1黏著層11在溫度25℃下之儲存模數G'1[kPa]及第2黏著層13在溫度25℃下之儲存模數G'2[kPa]例如可藉由選擇黏著劑組成物中所含之構成(甲基)丙烯酸系聚合物之單體之種類、或調節(甲基)丙烯酸系聚合物之分子量、或根據交聯劑之添加量調整交聯密度、或調節黏著層之厚度之方法、及該等之組合之方法等進行調節。亦可自市售之黏著劑中選擇使用具有所需之儲存模數者。
The first
[積層體之用途] [Use of laminated body]
積層體100例如可用於圖像顯示裝置等。圖像顯示裝置並無特別限定，例如可列舉：有機電致發光(有機EL)顯示裝置、無機電致發光(無機EL)顯示裝置、
液晶顯示裝置、場致發光顯示裝置等。圖像顯示裝置可具有觸控面板功能。圖像顯示裝置較佳為可撓性顯示器。積層體100可以直線偏光層10側成為視認側之方式配置於圖像顯示裝置。
The
[直線偏光層] [Linear Polarizing Layer]
作為直線偏光層10，可列舉吸附有二色性色素之延伸膜或延伸層、塗佈二色性色素並使其硬化而成之偏光片層等。塗佈二色性色素並使之硬化而成之偏光片層與吸附有具有吸收各向異性之色素之延伸膜或延伸層相比，彎曲方向並無限制，故而較佳。
Examples of the linear
作為二色性色素，具體上係可使用碘或二色性有機染料。作為二色性有機染料，例如可列舉偶氮系色素等。偶氮系色素包含例如由C.I.直接紅39等雙偶氮化合物所構成之二色性直接染料、由三偶氮、四偶氮等化合物所構成之二色性直接染料。 Specifically, iodine or a dichroic organic dye can be used as the dichroic dye. As a dichroic organic dye, an azo dye etc. are mentioned, for example. Azo pigments include, for example, dichroic direct dyes composed of disazo compounds such as C.I. Direct Red 39, and dichroic direct dyes composed of compounds such as trisazo and tetrasazo.
(吸附有二色性色素之延伸膜或延伸層) (Extended film or extended layer with dichroic pigment adsorbed)
吸附有二色性色素之延伸膜通常可經由如下步驟而製造：對聚乙烯醇系樹脂膜進行單軸延伸之步驟；藉由利用二色性色素對聚乙烯醇系樹脂膜進行染色而使吸附該二色性色素之步驟；利用硼酸水溶液對吸附有二色性色素之聚乙烯醇系樹脂膜進行處理之步驟；及於利用硼酸水溶液之處理後進行水洗之步驟。 The stretched film adsorbed with a dichroic dye can generally be manufactured through the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; dyeing the polyvinyl alcohol-based resin film with a dichroic dye The step of the dichroic dye; the step of treating the polyvinyl alcohol-based 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 an aqueous solution of boric acid.
吸附有二色性色素之延伸膜之厚度例如可為2μm以上40μm以下，可為5μm以上，亦可為20μm以下，更可為15μm以下，又更可為10μm以下。 The thickness of the stretched film on which the dichroic dye is adsorbed may be, for example, 2 μm to 40 μm , 5 μm to 20 μm , 15 μm to 15 μm , or 10 μm or less.
聚乙烯醇系樹脂係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，除了屬於乙酸乙烯酯之均聚物之聚乙酸乙烯酯以外，亦可使用乙酸乙烯酯與可與其共聚合之其他單體之共聚物。作為可與乙酸乙烯酯共 聚合之其他單體，例如可列舉：不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基之(甲基)丙烯醯胺類等。 The polyvinyl alcohol-based resin is obtained by saponifying polyvinyl acetate-based resin. As the polyvinyl acetate resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith can also be used. As compatible with vinyl acetate Other monomers to be polymerized include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth)acrylamides having ammonium groups, and the like.
聚乙烯醇系樹脂之皂化度通常為85莫耳%以上100莫耳%以下左右，較佳為98莫耳%以上。聚乙烯醇系樹脂可經改質，例如亦可使用經醛類改質之聚乙烯甲醛或聚乙烯縮醛。聚乙烯醇系樹脂之聚合度通常為1000以上10000以下，較佳為1500以上5000以下。 The degree of saponification of the polyvinyl alcohol-based resin is usually not less than 85 mol % and not more than 100 mol %, preferably not less than 98 mol %. The polyvinyl alcohol-based resin can be modified, for example, polyvinyl formaldehyde or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually not less than 1,000 and not more than 10,000, preferably not less than 1,500 and not more than 5,000.
吸附有二色性色素之延伸層通常包括如下步驟：將含有上述聚乙烯醇系樹脂之塗佈液塗佈於基材膜上之步驟；對所獲得之積層膜進行單軸延伸之步驟；藉由利用二色性色素對經單軸延伸之積層膜之聚乙烯醇系樹脂層進行染色，使吸附該二色性色素而製成偏光片層之步驟；利用硼酸水溶液對吸附有二色性色素之膜進行處理之步驟，及以硼酸水溶液處理後經過水洗步驟而製造。 The stretching layer adsorbed with a dichroic pigment generally includes the following steps: a step of applying a coating solution containing the above-mentioned polyvinyl alcohol-based resin on the base film; a step of uniaxially stretching the obtained laminated film; The step of dyeing the polyvinyl alcohol-based resin layer of the uniaxially stretched laminated film with a dichroic dye to absorb the dichroic dye to form a polarizer layer; using boric acid aqueous solution to absorb the dichroic dye The film is processed by the step of treating it with an aqueous solution of boric acid and then washing it with water.
視需要，亦可將基材膜自吸附有二色性色素之延伸層剝離去除。基材膜之材料及厚度可與下述熱塑性樹脂膜之材料及厚度相同。 If necessary, the substrate film may also be peeled off from the extension layer on which the dichroic dye is adsorbed. The material and thickness of the base film may be the same as those of the thermoplastic resin film described below.
(塗佈二色性色素並使其硬化而成之偏光片層) (Polarizer layer coated with dichroic pigment and hardened)
作為塗佈二色性色素並使其硬化而成之偏光片層，可列舉：包含具有液晶性之聚合性二色性色素之組成物或包含聚合性液晶化合物與二色性色素之組成物塗佈於基材膜並使其硬化而獲得之層等包含聚合性液晶化合物之硬化物之偏光片層。可於基材膜之一面設置配向膜。就提高彎曲性之觀點而言，直線偏光層10較佳為包含含有聚合性液晶化合物與1種或複數種偶氮系色素之組成物的硬化物、與配向膜之層。配向膜之厚度例如可為5nm以上1μm以下。
Examples of the polarizer layer coated with a dichroic dye and hardened include: a composition containing a polymerizable dichroic dye having liquid crystallinity or a composition containing a polymerizable liquid crystal compound and a dichroic dye. A polarizer layer including a cured product of a polymerizable liquid crystal compound, such as a layer obtained by laying on a base film and curing it. An alignment film may be provided on one side of the base film. From the viewpoint of improving flexibility, the linear
直線偏光層可與基材膜一併組入至積層體中，亦可將基材膜自塗佈二色性色素並使硬化而成之偏光片層剝離去除而組入至積層體中。基材膜之 材料及厚度可與下述熱塑性樹脂膜之材料及厚度相同。基材膜亦可於至少一面形成硬塗層(HC層)作為下述保護層。 The linear polarizing layer can be incorporated into the laminate together with the base film, or the base film can be incorporated into the laminate by peeling off the polarizer layer formed by applying a dichroic pigment and hardening it. base film The material and thickness may be the same as those of the thermoplastic resin film described below. The base film may form a hard coat layer (HC layer) on at least one surface as a protective layer described below.
塗布二色性色素並使其硬化而成之偏光片層的厚度，通常為10μm以下，較佳為8μm以下，更佳為5μm以下。 The thickness of the polarizer layer formed by applying a dichroic dye and curing it is usually not more than 10 μm , preferably not more than 8 μm , more preferably not more than 5 μm .
[保護層] [The protective layer]
保護層可配置於直線偏光層10之單側或兩側，具有保護直線偏光層10之表面之功能。於本說明書中，有時將積層有保護層之直線偏光層稱為直線偏光板。
The protective layer can be disposed on one side or both sides of the linear
保護層可為有機物層或無機物層。有機物層或無機物層可為藉由塗佈而形成之層。有機物層可為保護層形成用組成物，例如(甲基)丙烯酸系樹脂組成物、環氧系樹脂組成物、聚醯亞胺系樹脂組成物等硬化樹脂層。保護層形成用組成物可為活性能量線硬化型，亦可為熱硬化型。無機物層例如可由矽氧化物等形成。保護層為有機物層之情形時，保護層可稱為硬塗層(HC層)或外塗層(OC)層者。保護層可直接形成於上述基材膜上，亦可直接形成於直線偏光層上。 The protection layer can be an organic layer or an inorganic layer. An organic layer or an inorganic layer may be a layer formed by coating. The organic layer may be a composition for forming a protective layer, such as a hardened resin layer such as (meth)acrylic resin composition, epoxy resin composition, polyimide resin composition, or the like. The composition for forming a protective layer may be an active energy ray curing type or a thermosetting type. The inorganic layer can be formed of, for example, silicon oxide. When the protective layer is an organic layer, the protective layer may be called a hard coat layer (HC layer) or an overcoat layer (OC) layer. The protective layer may be directly formed on the above-mentioned base film, or may be directly formed on the linear polarizing layer.
保護層為有機物層之情形時，例如可藉由將活性能量線硬化型之保護層形成用組成物塗佈於基材膜上，照射活性能量使其硬化而製作保護層。基材膜適用上述基材膜之說明。保護層可於基材膜被剝離並去除之狀態下組入至積層體。作為塗佈保護層形成用組成物之方法，例如可列舉旋轉塗佈法等。保護層為無機物層之情形時，例如可藉由濺鍍法、蒸鍍法等形成保護層。保護層為有機物層或無機物層的情況下，保護層的厚度例如可為0.1μm以上10μm以下，較佳為5μm以下。 When the protective layer is an organic layer, the protective layer can be produced by, for example, applying an active energy ray-curable composition for forming a protective layer on a substrate film, and irradiating active energy to harden it. Base film The description of the above-mentioned base film applies. The protective layer can be incorporated into the laminate in a state where the base film is peeled and removed. As a method of applying the composition for protective layer formation, a spin coating method etc. are mentioned, for example. When the protective layer is an inorganic layer, the protective layer can be formed by, for example, a sputtering method, a vapor deposition method, or the like. When the protective layer is an organic layer or an inorganic layer, the thickness of the protective layer may be, for example, not less than 0.1 μm and not more than 10 μm , preferably not more than 5 μm .
作為保護層，例如亦可使用透明性、機械強度、熱穩定性、水分阻隔性、各向同性、延伸性等優異之熱塑性樹脂膜。作為此種熱塑性樹脂之具體例，可列舉：三乙醯纖維素等纖維素樹脂；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯樹脂；聚醚碸樹脂；聚碸樹脂；聚碳酸酯樹脂；尼龍或芳香族聚醯胺等聚醯胺樹脂；聚醯亞胺樹脂；聚乙烯、聚丙烯、乙烯/丙烯共聚物等聚烯烴樹脂；具有環系及降莰烯結構之環狀聚烯烴樹脂(亦稱為降莰烯系樹脂)；(甲基)丙烯酸樹脂；聚芳酯樹脂；聚苯乙烯樹脂；聚乙烯醇樹脂、以及該等之混合物。直線偏光層10之兩面積層有保護層之情形時，兩個保護層可為同種，亦可為不同種。就薄型化之觀點而言，熱塑性樹脂膜之厚度通常為300μm以下，較佳為200μm以下，更佳為100μm以下，又更佳為50μm以下，再更佳為30μm以下，又，通常為1μm以上，例如可為5μm以上或20μm以上。
As the protective layer, for example, a thermoplastic resin film excellent in transparency, mechanical strength, heat stability, moisture barrier property, isotropy, extensibility and the like can also be used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyether resins; polyethylene Resin; polycarbonate resin; polyamide resin such as nylon or aromatic polyamide; polyimide resin; polyolefin resin such as polyethylene, polypropylene, ethylene/propylene copolymer; with ring system and norcamphene structure Cyclic polyolefin resins (also known as norcamphene resins); (meth)acrylic resins; polyarylate resins; polystyrene resins; polyvinyl alcohol resins, and mixtures thereof. When there are protective layers on both surface layers of the linear
保護層為熱塑性樹脂膜之情形時，熱塑性樹脂膜可介由下述貼合層貼合於直線偏光層10。作為將熱塑性樹脂膜貼合於直線偏光層10之貼合層，較佳為接著劑層。或者，可在上述保護層上形成直線偏光層。積層體100較佳為於直線偏光層10之與第1黏著層11相反側具備選自由熱塑性樹脂膜及硬化樹脂層所成群組中之至少1層保護層。
When the protective layer is a thermoplastic resin film, the thermoplastic resin film can be bonded to the linear
[第1黏著層及第2黏著層] [1st adhesive layer and 2nd adhesive layer]
第1黏著層11可為介於直線偏光層10與液晶塗佈層12之間以接合該等之層。第2黏著層13可為於積層體100之液晶塗佈層12側貼合例如觸控感測器面板或有機EL面板等之層。以下，作為第1黏著層11及第2黏著層13的總稱，有時稱為黏著層。第1黏著層及第2黏著層係以滿足上述式(1)或(2)之方式組合使用。
The first
黏著層例如可為由黏著劑所構成之層或對該層實施某種處理而成之層。所謂黏著劑，亦被稱為壓敏接著劑。於本說明書中，所謂「接著劑」係指黏著劑(壓敏接著劑)以外之接著劑，與黏著劑明確區別。黏著層可為1層，亦可為包含2層以上者，較佳為1層。黏著層可由黏著劑組成物形成。用於第1黏著層11及第2黏著層13之黏著劑之種類可彼此相同，亦可不同。
The adhesive layer may be, for example, a layer composed of an adhesive or a layer obtained by subjecting the layer to some kind of treatment. The so-called adhesive is also called pressure-sensitive adhesive. In this specification, an "adhesive" refers to an adhesive other than an adhesive (pressure-sensitive adhesive), and is clearly distinguished from an adhesive. The adhesive layer may be one layer, or may include two or more layers, and is preferably one layer. The adhesive layer can be formed of an adhesive composition. The types of adhesives used for the first
黏著層可由以如(甲基)丙烯酸系、橡膠系、胺基甲酸乙酯系、酯系、聚矽氧系、聚乙烯醚系之樹脂為主成分之黏著劑組成物所構成。其中，較佳為以透明性、耐候性、耐熱性等優異之(甲基)丙烯酸系樹脂作為基礎聚合物之黏著劑組成物。黏著劑組成物可為活性能量線硬化型、熱硬化型。 The adhesive layer can be composed of an adhesive composition mainly composed of (meth)acrylic, rubber, urethane, ester, polysiloxane, polyvinyl ether resins. Among them, an adhesive composition using a (meth)acrylic resin excellent in transparency, weather resistance, heat resistance, etc. as a base polymer is preferable. The adhesive composition may be an active energy ray curing type or a thermosetting type.
作為黏著劑組成物中所使用之(甲基)丙烯酸系樹脂(基礎聚合物)，例如可較佳地使用將如(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(甲基)丙烯酸酯之1種或2種以上作為單體之聚合物或共聚物。於基礎聚合物中，較佳為使極性單體共聚合。作為極性單體，例如可列舉：如(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)丙烯酸環氧丙酯之具有羧基、羥基、醯胺基、胺基、環氧基等之單體。 As the (meth)acrylic resin (base polymer) used in the adhesive composition, for example, butyl (meth)acrylate, ethyl (meth)acrylate, (meth) Polymer or copolymer of one or more (meth)acrylates of isooctyl acrylate and 2-ethylhexyl (meth)acrylate as monomers. In the base polymer, it is preferred to copolymerize polar monomers. Examples of polar monomers include (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, (meth)acrylic acid N , N-dimethylaminoethyl ester, glycidyl (meth)acrylate monomers with carboxyl, hydroxyl, amido, amino, epoxy, etc.
黏著劑組成物可為僅含有上述基礎聚合物者，但通常進而含有交聯劑。作為交聯劑係例示：為2價以上之金屬離子，與羧基之間形成羧酸金屬鹽者；為多胺化合物，與羧基之間形成醯胺鍵者；為聚環氧化合物或多元醇，與羧基之間形成酯鍵者；為聚異氰酸酯化合物，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 contain only the above-mentioned base polymer, but usually further contains a crosslinking agent. Examples of the cross-linking agent are: metal ions with a valence of more than 2, which form a metal carboxylate salt with a carboxyl group; polyamine compounds, which form an amide bond with a carboxyl group; polyepoxides or polyols, Those that form ester bonds with carboxyl groups; those that form amide bonds with carboxyl groups for polyisocyanate compounds. Among them, polyisocyanate compounds are preferred.
所謂活性能量線硬化型黏著劑組成物，係具有受到如紫外線或電子束之活性能量線之照射而硬化，即便於活性能量線照射前可具有黏著性而密接於膜等被黏著體之性質，且具有可藉由活性能量線之照射而硬化並調整密接力之性質的黏著劑組成物。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基礎聚合物、交聯劑以外，進而含有活性能量線聚合性化合物。進而，視需要亦可含有光聚合起始劑或光敏劑等。 The so-called active energy ray-curable adhesive composition has the property of being hardened by irradiation of active energy rays such as ultraviolet rays or electron beams, and can be adhesively adhered to an adherend such as a film even before the irradiation of active energy rays. And it is an adhesive composition which can be cured by irradiation of active energy rays and can adjust the adhesive force. The active energy ray-curable adhesive composition is preferably an ultraviolet-curable adhesive composition. The active energy ray-curable adhesive composition further contains an active energy ray polymerizable compound in addition to the base polymer and the crosslinking agent. Furthermore, a photopolymerization initiator, a photosensitizer, etc. may be contained as needed.
黏著劑組成物可包含用以賦予光散射性之微粒子、珠粒(樹脂珠粒、玻璃珠粒等)、玻璃纖維、基礎聚合物以外之樹脂、黏著性賦予劑、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、抗靜電劑、光聚合起始劑等添加劑。 The adhesive composition may contain microparticles, beads (resin beads, glass beads, etc.), glass fibers, resins other than base polymers, adhesiveness imparting agents, fillers (metal powder or other) to impart light scattering properties. Inorganic powder, etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, defoamers, anti-corrosion agents, antistatic agents, photopolymerization initiators and other additives.
黏著層可藉由將上述黏著劑組成物之有機溶劑稀釋液塗佈於基材上並使其乾燥而形成。於使用活性能量線硬化型黏著劑組成物之情形時，可藉由對所形成之黏著層照射活性能量線而製成具有所需之硬化度之硬化物。 The adhesive layer can be formed by applying an organic solvent dilution of the above-mentioned adhesive composition on a substrate and drying it. In the case of using an active energy ray-curable adhesive composition, a cured product having a desired degree of hardening can be produced by irradiating the formed adhesive layer with active energy rays.
第1黏著層11及第2黏著層13亦可以滿足上述條件(1)或(2)之方式自市售品中選擇使用。
The first
黏著層的厚度例如較佳為1μm以上100μm以下，更佳為50μm以下，亦可為20μm以上。第1黏著層11及第2黏著層13之厚度可彼此相同亦可不同。
The thickness of the adhesive layer is, for example, preferably not less than 1 μm and not more than 100 μm , more preferably not more than 50 μm , and may be not less than 20 μm . The thicknesses of the first
[液晶塗佈層] [LCD Coating Layer]
液晶塗佈層12介於第1黏著層11與第2黏著層13之間，且與第1黏著層11及第2黏著層13相接而積層。液晶塗佈層12可為聚合性液晶化合物之硬化
層。液晶塗佈層係由1層或複數層所構成。於液晶塗佈層包含複數層之情形時，層彼此可隔著下述貼合層而積層，較佳為隔著下述接著劑層而積層。
The liquid
液晶塗佈層12可為聚合性液晶化合物之硬化層。聚合性液晶化合物之硬化層可藉由將包含聚合性液晶化合物之相位差層形成用組成物塗佈於基材膜並使其硬化而形成。作為塗佈方法，例如可列舉塗佈法、印刷法等。作為塗佈法，可列舉：棒式塗佈法、刮刀塗佈法、刮板塗佈法、模塗佈法、直接凹版塗佈法、反向凹版塗佈法、輥式塗佈法、CAP塗佈法、旋轉塗佈法、噴霧塗佈法、網版塗佈法、狹縫塗佈法、浸漬塗佈法等。作為印刷法，可列舉：平版印刷法、凹版印刷法、網版印刷法、噴墨印刷法等。
The liquid
聚合性液晶化合物之硬化層可為相位差層。相位差層可由1層或2層以上所構成。相位差層可為λ/4板、λ/2板等正A板、及正C板。液晶塗佈層12僅包含1層聚合性液晶化合物之硬化層之情形時，相位差層較佳為λ/4板。液晶塗佈層12包含2層聚合性液晶化合物之硬化層之情形時，相位差層可為包含第1液晶硬化相位差層與第2液晶硬化相位差層之相位差層積層體。第1液晶硬化相位差層與第2液晶硬化相位差層可隔著下述貼合層而積層，較佳為隔著接著劑層而積層。作為第1液晶硬化相位差層及第2液晶硬化相位差層之組合，較佳為第1液晶硬化相位差層為λ/4板且第2液晶硬化相位差層為λ/2板之組合、及第1液晶硬化相位差層為λ/4板且第2液晶硬化相位差層為正C板之組合。於本說明書中，有時將積層有相位差層之直線偏光板稱為圓偏光板。
The cured layer of the polymerizable liquid crystal compound may be a retardation layer. The retardation layer may be composed of one layer or two or more layers. The retardation layer may be a positive A plate such as a λ/4 plate or a λ/2 plate, and a positive C plate. When the liquid
相位差層之厚度例如為0.1μm以上10μm以下，較佳為8μm以下，更佳為6μm以下。 The thickness of the retardation layer is, for example, not less than 0.1 μm and not more than 10 μm , preferably not more than 8 μm , more preferably not more than 6 μm .
亦可於基材膜與聚合性液晶化合物之硬化層之間形成配向層。基材膜之材料及厚度可與上述熱塑性樹脂膜之材料及厚度相同。將聚合性液晶化合物硬化而成之相位差層可與配向層及基材膜中之任一者或兩者一併組入至積層體100。配向層之厚度例如可為5nm以上且1μm以下。 An alignment layer may also be formed between the base film and the cured layer of the polymerizable liquid crystal compound. The material and thickness of the base film may be the same as those of the aforementioned thermoplastic resin film. The retardation layer formed by hardening a polymerizable liquid crystal compound can be incorporated into the laminate 100 together with either or both of the alignment layer and the base film. The thickness of the alignment layer may be, for example, not less than 5 nm and not more than 1 μm .
液晶塗佈層12之厚度例如可為0.1μm以上10μm以下，較佳為8μm以下，更佳為6μm以下。
The thickness of the liquid
[前面板] [front panel]
前面板係構成圖像顯示裝置之視認側之最表面，可具有保護圖像顯示裝置之前表面(畫面)之功能。前面板可稱為窗膜。前面板只要為可透過光之板狀體，則材料及厚度並無限定，又，可僅由1層構成，亦可由2層以上構成。作為其例，可列舉：樹脂製之板狀體(例如樹脂板、樹脂片、樹脂膜等)、玻璃製之板狀體(例如玻璃板、玻璃膜等)、下述觸控感測器面板。積層體100具有前面板的情況下，前面板可配置於積層體100的視認側。積層體100可於直線偏光層10之與第1黏著層11為相反側之最外表面隔著下述第3黏著層而具備前面板。具有前面板之積層體100能夠以前面板構成圖像顯示裝置之最表面之方式配置於圖像顯示裝置。
The front panel is the outermost surface of the viewing side of the image display device, and can have the function of protecting the front surface (screen) of the image display device. The front panel may be referred to as a window film. The material and thickness of the front panel are not limited as long as it is a light-permeable plate-shaped body, and may be composed of only one layer or may be composed of two or more layers. Examples thereof include resin-made plate-shaped objects (such as resin plates, resin sheets, resin films, etc.), glass-made plate-shaped objects (such as glass plates, glass films, etc.), the following touch sensor panels . When the
前面板的厚度例如可為30μm以上500μm以下，較佳為200μm以下，更佳為100μm以下。 The thickness of the front panel may be, for example, not less than 30 μm and not more than 500 μm , preferably not more than 200 μm , more preferably not more than 100 μm .
於前面板為樹脂製之板狀體之情形時，樹脂製之板狀體只要為可透過光者，則並無限定。作為構成樹脂膜等樹脂製之板狀體之樹脂，可列舉由例如三乙醯纖維素、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、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚醯胺醯亞胺等高分子所形成的膜。該等高分子可單獨使用或混合2種以上使用。就提高強度及透明性之觀點而言，較佳為由聚醯亞胺、聚醯胺、聚醯胺醯亞胺等高分子形成之樹脂膜。 When the front panel is a resin-made plate-shaped body, the resin-made plate-shaped body is not limited as long as it can transmit light. As the resin constituting a resin plate-shaped body such as a resin film, for example, triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, acryl cellulose, butyryl cellulose, Acetyl Acryl Cellulose, Polyester, Polystyrene, Polyamide, Polyetherimide, Poly(formaldehyde) base) acrylic, polyimide, polyether sulfide, polyethene, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone , polyether ether ketone, polyether ketone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide A film formed by a polymer such as imide. These polymers can be used individually or in mixture of 2 or more types. From the viewpoint of improving strength and transparency, resin films formed of polymers such as polyimide, polyamide, and polyamideimide are preferable.
就硬度之觀點而言，前面板較佳為於基材膜之至少一面設置有硬塗層(HC層)之膜。作為基材膜，可使用由上述樹脂所成之膜。硬塗層可形成於基材膜之一面，亦可形成於兩面。藉由設置硬塗層，可製成使硬度及耐刮傷性提高之樹脂膜。硬塗層例如為紫外線硬化型樹脂之硬化層。作為紫外線硬化型樹脂，例如可列舉：丙烯酸系樹脂、聚矽氧系樹脂、聚酯系樹脂、胺基甲酸乙酯系樹脂、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。添加劑並無限定，可列舉無機系微粒子、有機系微粒子、或該等之混合物。 From the viewpoint of hardness, the front panel is preferably a film in which a hard coat layer (HC layer) is provided on at least one surface of a base film. As a base film, the film which consists of the said resin can be used. A hard-coat layer may be formed in one surface of a base film, and may be formed in both surfaces. By providing a hard coat layer, a resin film with improved hardness and scratch resistance can be produced. The hard coat layer is, for example, a hardened layer of ultraviolet curable resin. Examples of ultraviolet curable resins include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. In order to increase strength, the hard coat layer may also contain additives. The additive is not limited, and examples thereof include inorganic fine particles, organic fine particles, or mixtures thereof.
於前面板為玻璃板的情況下，玻璃板較佳係使用顯示器用強化玻璃。玻璃板之厚度例如可為50μm以上1000μm以下。藉由使用玻璃板，可構成具有優異之機械強度及表面硬度之前面板。 When the front panel is a glass plate, it is preferable to use tempered glass for displays as the glass plate. The thickness of the glass plate may be, for example, not less than 50 μm and not more than 1000 μm . By using a glass plate, it is possible to constitute a front panel having excellent mechanical strength and surface hardness.
積層體100用於圖像顯示裝置之情形時，前面板不僅具有保護上述圖像顯示裝置之正面(畫面)之功能，亦可為具有作為觸控感測器之功能、藍光截止功能、視角調整功能等者。 When the laminate 100 is used in an image display device, the front panel not only has the function of protecting the front (screen) of the above-mentioned image display device, but also has a function as a touch sensor, blue light cut-off function, and viewing angle adjustment. functions etc.
就容易構成具有優異彎曲性的積層體100之觀點而言，前面板於溫度23℃下之拉伸模數較佳為4.0GPa以上，更佳為5.0GPa以上，又更佳為6.0GPa以上。就容易構成具有優異彎曲性的積層體之觀點而言，前面板較佳為 溫度23℃下之拉伸模數為20GPa以下，更佳為15GPa以下。溫度23℃下之拉伸模數可藉由下述實施例之欄中所記載之試驗方法進行測定。積層體100即便於具備溫度23℃下之拉伸模數為6.0GPa之前面板之情形時，亦可進行內摺及外摺下之反覆彎曲。 The tensile modulus of the front sheet at a temperature of 23° C. is preferably 4.0 GPa or higher, more preferably 5.0 GPa or higher, and still more preferably 6.0 GPa or higher, from the viewpoint of easy formation of the laminate 100 having excellent flexibility. From the viewpoint of being easy to form a laminate having excellent flexibility, the front panel is preferably The tensile modulus at a temperature of 23°C is not more than 20 GPa, more preferably not more than 15 GPa. The tensile modulus at a temperature of 23° C. can be measured by the test method described in the column of the following examples. Even when the laminate 100 has a front panel with a tensile modulus of 6.0 GPa at a temperature of 23° C., repeated bending under inward folding and outward folding can be performed.
構成前面板之基材膜例如可由樹脂膜所構成，較佳為可由透明樹脂膜所構成。作為構成樹脂膜之樹脂，可列舉例如：聚乙烯、聚丙烯、降莰烯系聚合物、環狀烯烴系樹脂等聚烯烴；聚乙烯醇；聚對苯二甲酸乙二酯；聚甲基丙烯酸酯；聚丙烯酸酯；三乙醯纖維素、二乙醯纖維素及纖維素乙酸酯丙酸酯等纖維素酯；聚萘二甲酸乙二酯；聚碳酸酯；聚碸；聚醚碸；聚醚酮；聚苯硫醚；聚苯醚；聚醯胺；聚醯亞胺；聚醯胺醯亞胺等塑膠。其中又以環狀烯烴系樹脂、纖維素酯及聚醯亞胺為佳。 The base film constituting the front panel can be composed of, for example, a resin film, preferably a transparent resin film. Examples of the resin constituting the resin film include polyolefins such as polyethylene, polypropylene, norbornene-based polymers, and cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid Esters; Polyacrylates; Cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polymer; Polyether cellulose; Polyether ketone; polyphenylene sulfide; polyphenylene ether; polyamide; polyimide; polyamide imide and other plastics. Among them, cyclic olefin-based resins, cellulose esters, and polyimides are preferable.
就積層體100之薄膜化之觀點而言，樹脂膜之厚度係以薄者為佳，過薄時，則有難以確保耐衝擊性之傾向。樹脂膜之厚度例如可為10μm以上200μm以下，較佳為15μm以上，更佳為20μm以上。
From the viewpoint of thinning the
基材膜可於至少一表面具有硬塗層、抗反射層、或抗靜電層。 The base film may have a hard coat layer, an antireflection layer, or an antistatic layer on at least one surface.
[第3黏著層] [3rd adhesive layer]
第3黏著層可具有將前面板接合於積層體100的功能。第3黏著層可由黏著劑形成。構成第3黏著層之黏著劑可為與關於構成黏著層之黏著劑組成物所例示者相同之劑，亦可為其他黏著劑，例如(甲基)丙烯酸系黏著劑、苯乙烯系黏著劑、聚矽氧系黏著劑、橡膠系黏著劑、胺基甲酸乙酯系黏著劑、聚酯系黏著劑、環氧系共聚物黏著劑等。就彎曲時液晶塗佈層不易產生龜裂之觀點而言，第3黏
著層於溫度25℃下之儲存模數較佳為50kPa以下，更佳為45kPa以下，又更佳為41kPa以下。
The third adhesive layer may have a function of bonding the front panel to the
[貼合層] [Adhesive layer]
貼合層係由黏著劑或接著劑所構成之層。貼合層例如可為貼合前面板與觸控感測器面板之層、貼合積層體與觸控感測器面板之層、接合直線偏光層與保護層之層、接合第1液晶硬化相位差層與第2液晶硬化相位差層之層等。構成貼合層之黏著劑可為與關於構成上述黏著層之黏著劑組成物所例示者相同之劑，亦可為其他黏著劑，例如(甲基)丙烯酸系黏著劑、苯乙烯系黏著劑、聚矽氧系黏著劑、橡膠系黏著劑、胺基甲酸乙酯系黏著劑、聚酯系黏著劑、環氧系共聚物黏著劑等。積層體100可具備1層貼合層，亦可具備2層以上。積層體100具備多個貼合層的情況下，多個貼合層可彼此相同，亦可不同。
The bonding layer is a layer composed of an adhesive or an adhesive. The bonding layer can be, for example, a layer bonding the front panel and the touch sensor panel, a layer bonding the laminate and the touch sensor panel, a layer bonding the linear polarizing layer and the protective layer, bonding the first liquid crystal curing phase The difference layer and the second liquid crystal harden the layer of the retardation layer, etc. The adhesive constituting the bonding layer may be the same as that exemplified for the adhesive composition constituting the above adhesive layer, or may be other adhesives such as (meth)acrylic adhesives, styrene adhesives, Silicone-based adhesives, rubber-based adhesives, urethane-based adhesives, polyester-based adhesives, epoxy-based copolymer adhesives, etc. The laminate 100 may include one bonding layer, or may include two or more layers. When the
作為構成貼合層之接著劑，例如可將水系接著劑、活性能量線硬化型接著劑、黏著劑等中之1種或2種以上組合而形成。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乙酯系乳液接著劑等。作為活性能量線硬化型接著劑，係藉由照射紫外線等活性能量線而硬化之接著劑，可列舉例如：含有聚合性化合物及光聚合性起始劑者、含有光反應性樹脂者、含有黏合劑樹脂及光反應***聯劑者等。作為上述聚合性化合物，可列舉：光硬化性環氧系單體、光硬化性丙烯酸系單體、光硬化性胺基甲酸乙酯系單體等光聚合性單體、或源自該等單體之低聚物等。作為上述光聚合起始劑，可列舉包含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之物質者。 As an adhesive constituting the bonding layer, for example, one or two or more of water-based adhesives, active energy ray-curable adhesives, adhesives, and the like can be used in combination. Examples of the water-based adhesive include a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, and the like. Active energy ray-curable adhesives are adhesives that are cured by irradiating active energy rays such as ultraviolet rays, and include, for example, those containing a polymerizable compound and a photopolymerizable initiator, those containing a photoreactive resin, those containing an adhesive agent resin and photoreactive crosslinking agent, etc. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, or compounds derived from these monomers. Body oligomers, etc. Examples of the above-mentioned photopolymerization initiator include substances that generate active species such as neutral radicals, anion radicals, and cationic radicals by irradiating active energy rays such as ultraviolet rays.
使用黏著劑層作為貼合層之情形時，較佳為1μm以上，可為5μm以上，通常為200μm以下，例如可為150μm以下或100μm以下。使用接著劑層作為貼合層的情況下，貼合層的厚度較佳為0.1μm以上，可為0.5μm以上，較佳為10μm以下，亦可為5μm以下。 When using the adhesive layer as the bonding layer, it is preferably 1 μm or more, may be 5 μm or more, usually 200 μm or less, for example, may be 150 μm or less or 100 μm or less. When using an adhesive layer as the bonding layer, the thickness of the bonding layer is preferably at least 0.1 μm , may be at least 0.5 μm , is preferably at most 10 μm , and may be at most 5 μm .
(有機EL面板) (Organic EL panel)
有機EL面板可使用公知之有機EL面板。積層體100可於第2黏著層13之與液晶塗佈層12相反之側具備有機EL面板。就容易構成具有優異彎曲性的積層體之觀點而言，有機EL面板於溫度23℃下之拉伸模數較佳為4.0GPa以上，更佳為5.0GPa以上，又更佳為6.0GPa以上。就容易構成具有優異彎曲性的積層體之觀點而言，有機EL面板較佳為溫度23℃下之拉伸模數為20GPa以下，更佳為15GPa以下。積層體100即便於具備溫度23℃下之拉伸模數為6.0GPa之有機EL面板之情形時，亦可藉由內摺及外摺而反覆彎曲。
As the organic EL panel, known organic EL panels can be used. The
(觸控感測器面板) (Touch Sensor Panel)
觸控感測器面板只要為可檢測被觸控之位置之感測器，則檢測方式並無限定，可例示電阻膜方式、電容方式、光感測器方式、超音波方式、電磁感應耦合方式、表面聲波方式等之觸控感測器面板。其中，就低成本、較快之反應速度、薄膜化之方面而言，可較佳地使用電容方式之觸控感測器面板。觸控感測器面板可於透明導電層與支撐其之基材膜之間具備接著層、分離層、保護層等。作為接著層，可列舉接著劑層、黏著劑層。作為支撐透明導電層之基材膜，可列舉：於一表面蒸鍍形成有透明導電層之基材膜、隔著接著層而轉印透明導電層之基材膜等。 As long as the touch sensor panel is a sensor that can detect the touched position, the detection method is not limited, and examples include resistive film method, capacitive method, optical sensor method, ultrasonic method, and electromagnetic induction coupling method , surface acoustic wave method, etc. touch sensor panel. Among them, in terms of low cost, faster response speed, and thinner film, a capacitive touch sensor panel can be preferably used. The touch sensor panel may have an adhesive layer, a separation layer, a protective layer, etc. between the transparent conductive layer and the base film supporting it. As an adhesive layer, an adhesive layer and an adhesive layer are mentioned. As a base film which supports a transparent conductive layer, the base film which vapor-deposited and formed the transparent conductive layer on one surface, the base film which transferred the transparent conductive layer via the adhesive layer, etc. are mentioned.
電容方式之觸控感測器面板之一例係由基材膜、設置於基材膜之表面之位置檢測用之透明導電層、及觸控位置檢測電路所構成。於設置有具有電容方式之觸控感測器面板之積層體之圖像顯示裝置中，若前面板之表面被觸控，則透明導電層於被觸控之點隔著人體之電容而接地。觸控位置檢測電路檢測透明導電層之接地，檢測被觸控之位置。藉由具有相互隔開之複數個透明導電層，可進行更詳細之位置之檢測。 An example of a capacitive touch sensor panel is composed of a base film, a transparent conductive layer for position detection provided on the surface of the base film, and a touch position detection circuit. In an image display device provided with a laminate having a capacitive touch sensor panel, when the surface of the front panel is touched, the transparent conductive layer is grounded at the touched point via the capacitance of the human body. The touch position detection circuit detects the grounding of the transparent conductive layer, and detects the touched position. By having a plurality of transparent conductive layers separated from each other, more detailed position detection can be performed.
透明導電層可為包含ITO等金屬氧化物之透明導電層，亦可為包含鋁、銅、銀、金、或該等之合金等金屬之金屬層。透明電極層係藉由濺鍍法、印刷法、蒸鍍法等塗佈法而形成。於透明電極層上形成感光性抗蝕劑，其後，藉由光微影而形成電極圖案層。感光性抗蝕劑係使用負型感光性抗蝕劑或正型感光性抗蝕劑，於圖案化後可殘存感光性抗蝕劑，亦可去除感光性抗蝕劑。藉由濺鍍法進行製膜之情形時，亦可配置具有電極圖案形狀之遮罩，進行濺鍍而形成電極圖案層。 The transparent conductive layer may be a transparent conductive layer containing metal oxides such as ITO, or may be a metal layer containing metals such as aluminum, copper, silver, gold, or alloys thereof. The transparent electrode layer is formed by coating methods such as sputtering, printing, and vapor deposition. A photosensitive resist is formed on the transparent electrode layer, and then an electrode pattern layer is formed by photolithography. The photosensitive resist is a negative photosensitive resist or a positive photosensitive resist, and the photosensitive resist may remain or be removed after patterning. When forming a film by a sputtering method, a mask having an electrode pattern shape may be arranged, and sputtering may be performed to form an electrode pattern layer.
分離層可為形成於玻璃等基板上，用以將形成於分離層上之透明導電層與分離層一同自基板分離之層。分離層較佳為無機物層或有機物層。作為形成無機物層之材料，可列舉例如矽氧化物。作為形成有機物層的材料，例如可使用(甲基)丙烯酸系樹脂組成物、環氧系樹脂組成物、聚醯亞胺系樹脂組成物等。分離層可藉由公知之塗佈法塗佈，藉由熱硬化或UV硬化或該等之組合之方法使其硬化而形成。 The separation layer may be formed on a substrate such as glass to separate the transparent conductive layer formed on the separation layer from the substrate together with the separation layer. The separation layer is preferably an inorganic layer or an organic layer. Examples of materials for forming the inorganic layer include silicon oxide. As a material for forming the organic layer, for example, a (meth)acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. can be used. The separation layer can be formed by applying a known coating method, curing by heat curing, UV curing, or a combination thereof.
保護層可為了與透明導電層接觸而保護導電層而設置。保護層包含有機絕緣膜及無機絕緣膜中之至少一者，該等膜可藉由旋塗法、濺鍍法、蒸鍍法等塗佈法而形成。 The protective layer may be provided in order to be in contact with the transparent conductive layer to protect the conductive layer. The protective layer includes at least one of an organic insulating film and an inorganic insulating film, and these films can be formed by coating methods such as spin coating, sputtering, and vapor deposition.
絕緣層例如可由矽氧化物等無機絕緣物質、丙烯酸系樹脂等透明有機物質所形成。絕緣層可藉由公知之塗佈法塗佈後，藉由熱硬化、UV硬化、熱乾燥、真空乾燥等而形成。 The insulating layer can be formed, for example, of inorganic insulating substances such as silicon oxide, or transparent organic substances such as acrylic resins. The insulating layer can be formed by heat curing, UV curing, heat drying, vacuum drying, etc. after being coated by a known coating method.
作為觸控感測器面板之基材膜，可列舉：三乙醯纖維素、聚對苯二甲酸乙二酯、環烯烴聚合物、聚萘二甲酸乙二酯、聚烯烴、聚環烯烴、聚碳酸酯、聚醚碸、聚芳酯、聚醯亞胺、聚醯胺、聚苯乙烯、聚降莰烯等樹脂膜。就容易構成具有所需之韌度之基材膜之觀點而言，較佳係使用聚對苯二甲酸乙二酯。 As the base film of the touch sensor panel, triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polyethylene naphthalate, polyolefin, polycycloolefin, Polycarbonate, polyether sulfide, polyarylate, polyimide, polyamide, polystyrene, polynorbornene and other resin films. It is preferable to use polyethylene terephthalate from the viewpoint of easy formation of a base film having desired toughness.
就容易構成具有優異耐彎曲性的積層體之觀點而言，觸控感測器面板之基材膜之厚度較佳為50μm以下，更佳為30μm以下。觸控感測器面板之基材膜之厚度例如可為5μm以上。 The thickness of the base film of the touch sensor panel is preferably 50 μm or less, more preferably 30 μm or less, from the viewpoint of easy formation of a laminate having excellent bending resistance. The thickness of the base film of the touch sensor panel may be, for example, more than 5 μm .
觸控感測器面板例如可以如下方式製造。於第1方法中，首先隔著接著層將基材膜積層於基板。於基材膜上形成藉由光微影而圖案化之透明導電層。藉由施加熱，將基板與基材膜分離，而獲得包含透明導電層與基材膜之觸控感測器面板。基板只要為維持平坦性且具有耐熱性之基板，則並無特別限定，較佳為玻璃基板。 The touch sensor panel can be manufactured, for example, as follows. In the first method, first, a base film is laminated on a substrate through an adhesive layer. A transparent conductive layer patterned by photolithography is formed on the base film. By applying heat, the substrate and the base film are separated to obtain a touch sensor panel including the transparent conductive layer and the base film. The substrate is not particularly limited as long as it maintains flatness and has heat resistance, but is preferably a glass substrate.
第2方法中，首先在基板上塗佈形成分離層的材料以形成分離層。視需要，於分離層上藉由塗佈而形成保護層。保護層可形成為使得保護層不形成於其中形成焊墊圖案層的部分中。於分離層(或保護層)上，藉由光微影法形成圖案化之透明導電層。於透明導電層上，以填埋電極圖案層之方式形成絕緣層。藉由可剝離之黏著劑將保護膜積層於絕緣層上，自絕緣層轉印至分離層，而將基板分離。藉由剝離可剝離之保護膜，可獲得依序具有絕緣層/透明導電層/(保護層)/分離層之觸控感測器面板。 In the second method, first, a material for forming a separation layer is applied on a substrate to form a separation layer. If necessary, a protective layer is formed on the separation layer by coating. The protective layer may be formed such that the protective layer is not formed in a portion where the pad pattern layer is formed. On the separation layer (or protective layer), a patterned transparent conductive layer is formed by photolithography. On the transparent conductive layer, an insulating layer is formed by filling the electrode pattern layer. The protective film is laminated on the insulating layer by a peelable adhesive, and is transferred from the insulating layer to the separation layer to separate the substrate. By peeling off the peelable protective film, a touch sensor panel having an insulating layer/transparent conductive layer/(protective layer)/separation layer in this order can be obtained.
包含基材膜時，觸控感測器面板之厚度例如可為5μm以上2000μm以下，亦可為5μm以上100μm以下。 When the base film is included, the thickness of the touch sensor panel may be, for example, not less than 5 μm and not more than 2000 μm , or may be not less than 5 μm and not more than 100 μm .
不含基材膜時，觸控感測器面板之厚度例如為0.5μm以上10μm以下，較佳為5μm以下。 When the substrate film is not included, the thickness of the touch sensor panel is, for example, not less than 0.5 μm and not more than 10 μm , preferably not more than 5 μm .
於積層體具備有機EL面板、觸控感測器面板及前面板之情形時，作為積層體之層構成，可列舉例如：前面板/積層體/觸控感測器面板/有機EL面板、前面板/觸控感測器面板/積層體/有機EL面板等。 When the laminate includes an organic EL panel, a touch sensor panel, and a front panel, examples of the layer configuration of the laminate include: front panel/laminate/touch sensor panel/organic EL panel, front Panel/touch sensor panel/laminate/organic EL panel, etc.
[積層體之層構成] [Layer composition of laminated body]
圖2所示之積層體200自視認側起依序積層有前面板21、第3黏著層22、直線偏光板23、第1黏著層24、液晶塗佈層25、第2黏著層26、有機EL面板27。直線偏光板23自視認側起依序配置有基材膜28、配向膜29、直線偏光層30、保護層(OC層)31。
The
圖3所示之積層體300自視認側起依序積層有前面板41、第3黏著層42、直線偏光板43、第1黏著層44、液晶塗佈層45、第2黏著層46、有機EL面板47。直線偏光板43自視認側起依序配置有基材膜48、保護層(HC層)49、配向膜50、直線偏光層51、保護層(OC層)52。
The
[積層體之製造方法] [Manufacturing method of laminated body]
積層體可藉由包含將黏著劑層、或進而隔著接著劑層將構成積層體100之層彼此貼合之步驟之方法而製造。隔著黏著劑層或接著劑層將層彼此貼合之情形時，為了提高密接性，較佳為對貼合面之一者或兩者實施例如電暈處理等表面活化處理。
The laminated body can be manufactured by a method including the step of attaching the adhesive layer, or further, the layers constituting the
直線偏光層為吸附有具有吸收各向異性之色素的延伸膜或延伸層之情形時，直線偏光層之製造方法可如上述吸附有具有吸收各向異性之色素的延伸膜或延伸層之說明中所述般製造。 In the case where the linear polarizing layer is a stretched film or a stretched layer on which a pigment with anisotropic absorption is adsorbed, the manufacturing method of the linear polarizing layer can be as described above for the stretched film or stretched layer with an anisotropic absorption of pigment Manufactured as described.
直線偏光層為塗佈具有上述吸收各向異性之色素並使其硬化而成之膜之情形時，直線偏光層可隔著配向膜而形成於基材上。直線偏光層可藉由塗佈包含二色性色素及聚合性液晶化合物之直線偏光層形成用組成物並使其硬化而形成。直線偏光層形成用組成物除了上述二色性色素及聚合性液晶化合物以外，較佳為進而包含聚合起始劑、調平劑、溶劑，更進而包含光敏劑、聚合抑制劑、調平劑等。 When the linear polarizing layer is a film obtained by coating and curing the dye having the above-mentioned absorption anisotropy, the linear polarizing layer can be formed on the substrate via an alignment film. The linear polarizing layer can be formed by applying and curing a composition for forming a linear polarizing layer including a dichroic dye and a polymerizable liquid crystal compound. The composition for forming a linearly polarizing layer preferably further contains a polymerization initiator, a leveling agent, a solvent, and further contains a photosensitizer, a polymerization inhibitor, a leveling agent, etc. in addition to the above-mentioned dichroic dye and polymerizable liquid crystal compound. .
液晶塗佈層可藉由於基材及存在之情形時於配向膜上塗佈包含聚合性液晶化合物之液晶塗佈層形成用組成物，使聚合性液晶化合物聚合而製造。液晶塗佈層形成用組成物可進而包含溶劑、聚合起始劑，更進而包含光敏劑、聚合抑制劑、調平劑等。基材及配向膜可併入液晶塗佈層中，或可自液晶塗佈層剝離以不成為積層體之構成要素。 The liquid crystal coating layer can be produced by coating a composition for forming a liquid crystal coating layer containing a polymerizable liquid crystal compound on an alignment film depending on the substrate and the presence of the situation, and polymerizing the polymerizable liquid crystal compound. The composition for forming a liquid crystal coating layer may further include a solvent, a polymerization initiator, and may further include a photosensitizer, a polymerization inhibitor, a leveling agent, and the like. The substrate and the alignment film may be incorporated into the liquid crystal coating layer, or may be peeled off from the liquid crystal coating layer so as not to become constituent elements of the laminate.
直線偏光層形成用組成物及液晶塗佈層形成用組成物之塗佈、乾燥及聚合性液晶化合物之聚合可藉由先前公知之塗佈方法、乾燥方法及聚合方法而進行。 Coating and drying of the composition for forming a linear polarizing layer and the composition for forming a liquid crystal coating layer, and polymerization of a polymerizable liquid crystal compound can be performed by conventionally known coating methods, drying methods, and polymerization methods.
例如，作為直線偏光層形成用組成物及液晶塗佈層形成用組成物之塗佈方法，可採用線棒塗佈法、擠出塗佈法、直接凹版塗佈法、反向凹版塗佈法、及模塗佈法等。 For example, as the coating method of the composition for forming a linear polarizing layer and the composition for forming a liquid crystal coating layer, a wire bar coating method, an extrusion coating method, a direct gravure coating method, and a reverse gravure coating method can be used. , And die coating method, etc.
聚合性液晶化合物之聚合方法可根據聚合性液晶化合物之聚合性基之種類進行選擇。聚合性基如為光聚合性基，則可藉由光聚合法進行聚合。 聚合基如為熱聚合性基，則可藉由熱聚合法進行聚合。本實施形態之液晶塗佈層之製造方法中，較佳為光聚合法。光聚合法未必需要將透明基材加熱至高溫，因此可使用耐熱性低的透明基材。光聚合法係藉由對由包含聚合性液晶化合物之直線偏光層形成用組成物或液晶塗佈層形成用組成物所構成之膜照射可見光、或紫外光而進行。就操作容易之方面而言，較佳為紫外光。 The polymerization method of the polymerizable liquid crystal compound can be selected according to the type of the polymerizable group of the polymerizable liquid crystal compound. If the polymerizable group is a photopolymerizable group, it can be polymerized by a photopolymerization method. If the polymeric group is a thermally polymerizable group, it can be polymerized by a thermal polymerization method. In the manufacturing method of the liquid crystal coating layer of this embodiment, photopolymerization method is preferable. In the photopolymerization method, it is not necessary to heat the transparent substrate to a high temperature, so a transparent substrate with low heat resistance can be used. The photopolymerization method is carried out by irradiating visible light or ultraviolet light to a film composed of a composition for forming a linearly polarizing layer or a composition for forming a liquid crystal coating layer containing a polymerizable liquid crystal compound. In terms of ease of handling, ultraviolet light is preferred.
黏著層可作為黏著劑片而準備。黏著劑片例如可藉由如下方式等而製作：使黏著劑組成物溶解或分散於甲苯或乙酸乙酯等有機溶劑中而調製黏著劑液，將此經實施脫模處理的剝離膜上先將包含黏著劑的層形成為片狀，於該黏著層上進而貼合其他剝離膜。可藉由將剝離一剝離膜之黏著片貼合於一層，繼而剝離另一剝離膜，貼合另一層之方法貼合各層。 The adhesive layer can be prepared as an adhesive sheet. The adhesive sheet can be produced, for example, by dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare an adhesive liquid, and first applying The layer containing the adhesive is formed into a sheet, and another peeling film is bonded to the adhesive layer. Each layer can be attached by attaching an adhesive sheet peeling off one peeling film to one layer, then peeling off the other peeling film, and attaching the other layer.
作為將黏著劑液塗佈於剝離膜上之方法，係只要採用使用模塗佈機、缺角輪塗佈機、逆輥塗佈機、凹版塗佈機、棒式塗佈機、線棒塗佈機、刮刀塗佈機、氣動刮刀塗佈機等之一般的塗佈技術即可。 As the method of coating the adhesive liquid on the release film, it is only necessary to use a die coater, a chip coater, a reverse roll coater, a gravure coater, a bar coater, a wire bar coater, etc. General coating techniques such as cloth machine, knife coater, pneumatic knife coater, etc. are sufficient.
剝離膜較佳為由塑膠膜與剝離層所構成者。作為塑膠膜，可列舉：聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、及聚萘二甲酸乙二酯膜等聚酯膜、或聚丙烯膜等聚烯烴膜。又，剝離層例如可由剝離層形成用組成物所形成。作為構成剝離層形成用組成物之主要成分(樹脂)，並無特別限定，可列舉聚矽氧樹脂、醇酸樹脂、丙烯酸樹脂、及長鏈烷基樹脂等。 The release film is preferably composed of a plastic film and a release layer. Examples of the plastic film include polyester films such as polyethylene terephthalate films, polybutylene terephthalate films, and polyethylene naphthalate films, and polyolefin films such as polypropylene films. Also, the release layer can be formed, for example, from a composition for forming a release layer. It does not specifically limit as a main component (resin) which comprises the composition for peeling layer formation, Silicone resin, an alkyd resin, an acrylic resin, and a long-chain alkyl resin etc. are mentioned.
接著劑層之厚度可分別根據黏著劑液之塗佈條件進行調節。為了使黏著劑層之厚度變薄，減小塗佈厚度較為有效。 The thickness of the adhesive layer can be adjusted according to the coating conditions of the adhesive liquid. In order to reduce the thickness of the adhesive layer, it is effective to reduce the coating thickness.
積層體係可藉由自直線偏光層與液晶塗佈層隔著黏著層貼合而成之長條狀之膜裁切成特定尺寸而製造。又，積層體亦可藉由利用黏著層將預先裁切為特定尺寸之直線偏光層與液晶塗佈層貼合而製造。 The laminated system can be manufactured by cutting a strip-shaped film of a linear polarizing layer and a liquid crystal coating layer through an adhesive layer and cutting it to a specific size. Moreover, the laminated body can also be manufactured by bonding the linear polarizing layer and liquid crystal coating layer which were preliminarily cut to a specific size using an adhesive layer.
<圖像顯示裝置> <Image display device>
本發明之另一態樣之圖像顯示裝置係包含上述積層體。顯示裝置並無特別限定，可列舉例如：有機EL顯示裝置、無機EL顯示裝置、液晶顯示裝置、場致發光顯示裝置等圖像顯示裝置。圖像顯示裝置可具有觸控面板功能。積層體適合於具有能夠彎曲或折疊等的可撓性之撓性顯示器。 An image display device according to another aspect of the present invention includes the above-mentioned laminate. The display device is not particularly limited, and examples thereof include image display devices such as organic EL display devices, inorganic EL display devices, liquid crystal display devices, and electroluminescence display devices. The image display device may have a touch panel function. The laminate is suitable for a flexible display having flexibility such as bending and folding.
於圖像顯示裝置中，積層體係將前面板朝向外側(與顯示元件側為相反側，即視認側)配置於圖像顯示裝置所具有之顯示元件之視認側。 In the image display device, the laminated system arranges the front panel toward the outside (the side opposite to the display element side, that is, the viewing side) on the viewing side of the display element included in the image display device.
圖像顯示裝置可用作智慧型手機、平板電腦等行動機器、電視、數位相框、電子看板、測定器或儀器類、辦公室用機器、醫療機器、電算機器等。圖像顯示裝置由於抑制了映入至前面板表面的反射像的失真，因此畫面的視認性優異。 Image display devices can be used as mobile devices such as smartphones and tablet PCs, TVs, digital photo frames, electronic signage, measuring instruments or instruments, office equipment, medical equipment, computer equipment, etc. Since the image display device suppresses the distortion of the reflected image reflected on the front panel surface, the visibility of the screen is excellent.
[實施例] [Example]
以下，藉由實施例更詳細地說明本發明。例中之「%」及「份」只要無特別記載，則為質量%及質量份。 Hereinafter, the present invention will be described in more detail by means of examples. "%" and "parts" in the examples are % by mass and parts by mass unless otherwise specified.
[溫度25℃下之儲存模數之測定方法] [Measurement method of storage modulus at 25°C]
黏著層於溫度25℃下之儲存模數係藉由以下方法進行測定。以厚度成為0.2mm之方式積層複數片實施例及比較例中所使用之黏著層。自所獲得之黏著層沖裁直徑8mm之圓柱體，將其作為溫度25℃下之儲存模數之測定用樣品。針 對上述樣品，依據JIS K7244-6，使用黏彈性測定裝置(Physica公司製造，MCR300)，藉由扭轉剪力法，於以下之條件下測定溫度25℃下之儲存模數(Pa)。 The storage modulus of the adhesive layer at a temperature of 25°C was measured by the following method. A plurality of adhesive layers used in Examples and Comparative Examples were laminated so as to have a thickness of 0.2 mm. A cylinder having a diameter of 8 mm was punched out from the obtained adhesive layer, and this was used as a sample for measurement of the storage modulus at a temperature of 25°C. Needle The storage modulus (Pa) at a temperature of 25° C. was measured on the above sample by the torsional shear force method using a viscoelasticity measuring device (manufactured by Physica, MCR300) under the following conditions in accordance with JIS K7244-6.
(測定條件) (measurement conditions)
法向力FN：1N Normal force FN: 1N
應變γ：1% Strain γ: 1%
頻率：1Hz Frequency: 1Hz
溫度：25℃ Temperature: 25°C
[層厚度] [layer thickness]
黏著層之厚度係使用接觸式膜厚測定裝置(Nikon股份有限公司製造之「MS-5C」)進行測定。其中，關於偏光片層及配向膜，係使用雷射顯微鏡(Olympus股份有限公司製造之「OLS4100」)進行測定。 The thickness of the adhesive layer was measured using a contact film thickness measuring device (“MS-5C” manufactured by Nikon Corporation). However, the polarizer layer and the alignment film were measured using a laser microscope ("OLS4100" by Olympus Co., Ltd.).
[溫度23℃下之拉伸模數之測定方法] [Measuring method of tensile modulus at 23°C]
溫度23℃下之拉伸模數係以如下方式進行測定。使用超切割器自前面板或聚醯亞胺膜(相當於有機EL面板之代用品)切出長邊110mm×短邊10mm之長方形之小片。繼而，利用拉伸試驗機(島津製作所股份有限公司製造，Autograph AG-Xplus試驗機)的上下夾具，以夾具的間隔成為5cm的方式夾持上述測定用樣品的長邊方向兩端，於溫度23℃、相對濕度55%的環境下，以拉伸速度4mm/min將測定用樣品於測定用樣品的長度方向上拉伸，根據所獲得的應力-應變曲線中的20MPa至40MPa間的直線的斜率，算出溫度23℃、相對濕度55%下的拉伸模數。此時，用以算出應力之厚度係藉由上述記載之方法進行測定。 The tensile modulus at a temperature of 23°C was measured in the following manner. Use a supercutter to cut out rectangular pieces with a length of 110 mm x a short side of 10 mm from the front panel or polyimide film (equivalent to a substitute for an organic EL panel). Then, using the upper and lower grips of a tensile testing machine (manufactured by Shimadzu Corporation, Autograph AG-Xplus testing machine), the two ends of the longitudinal direction of the above-mentioned measurement sample were clamped so that the distance between the grips became 5 cm, and the sample was heated at a temperature of 23 Under the environment of ℃ and relative humidity of 55%, the sample for measurement is stretched in the longitudinal direction of the sample for measurement at a tensile speed of 4mm/min. According to the slope of the straight line between 20MPa and 40MPa in the obtained stress-strain curve , Calculate the tensile modulus at a temperature of 23°C and a relative humidity of 55%. At this time, the thickness for calculating the stress was measured by the method described above.
[彎曲性之評價] [Evaluation of bendability]
於溫度25℃、相對濕度55%RH下，按照以下所示之順序進行內摺試驗及外摺試驗。 At a temperature of 25°C and a relative humidity of 55%RH, the inner and outer fold tests were carried out in the following order.
(內摺測試) (inward fold test)
使用超級切割器自積層體切出長邊110mm×短邊10mm之長方形之小片。繼而，如圖4(a)所示，於具有可個別移動之兩個治具501、502之彎曲試驗機上，將測定用樣品500以前面板側為內側且以與短邊方向平行之方向為彎曲軸而彎曲，將測定用樣品500之長邊側之端部分別利用黏著帶固定於治具501、502，以治具501、502之間隔D成為70mm之方式調節治具501、502之位置。其後，如圖4(b)所示，以間隔D成為4.0mm(彎曲半徑2R)之方式使治具501向箭頭A之方向運轉而使測定用樣品500彎曲，其後，使治具501向箭頭B之方向運轉而將間隔D設為70mm而開放彎曲，將該一連串之動作設為1次計數，連續反覆20萬次。治具501之移動速度為1.32m/秒，反覆20萬次所需之時間為55.6小時。反覆20萬次後，將測定用樣品自彎曲試驗機取出，藉由光學顯微鏡利用透過光進行觀察，確認有無龜裂之產生。
Use a super cutter to cut out rectangular pieces with a length of 110 mm x a short side of 10 mm from the laminate. Next, as shown in FIG. 4(a), on a bending tester having two
○：有龜裂之產生。 ○: Cracks occur.
×：無龜裂之產生。 ×: No occurrence of cracks.
(外摺試驗) (outward bending test)
於上述內摺試驗中，將前面板側設為外側，將與短邊方向平行之方向設為彎曲軸進行彎曲而配置測定用樣品，除此以外，以與上述內摺試驗相同之方式進行試驗。 In the above-mentioned infolding test, the test was performed in the same manner as the above-mentioned inward-folding test except that the front panel side was set to the outside, and the direction parallel to the short-side direction was set as the bending axis, and the sample for measurement was placed. .
[前面板] [front panel]
作為前面板之窗膜，準備聚醯亞胺膜(PI膜，整體之厚度：40μm，拉伸模數6.8GPa)。 As the window film of the front panel, a polyimide film (PI film, overall thickness: 40 μm , tensile modulus: 6.8 GPa) was prepared.
[第3黏著層] [3rd adhesive layer]
使用對基材膜的單面進行了脫模處理的兩片脫模膜(重Sp、輕Sp)各自的脫模處理面，準備夾著厚度為50μm的第3黏著層的市售的第3黏著劑片(美國3M公司製造的「CEF3501」)。第3黏著層於溫度25℃下之儲存模數為41kPa。 Using the release-treated surfaces of two release films (heavy Sp, light Sp) that had been subjected to release treatment on one side of the base film, a commercially available film with a third adhesive layer of 50 μm in thickness was prepared. The 3rd adhesive agent sheet ("CEF3501" by the 3M company of the United States). The storage modulus of the third adhesive layer at a temperature of 25° C. is 41 kPa.
[直線偏光板A] [Linear polarizer A]
(基材膜) (substrate film)
作為基材膜，準備三乙醯纖維素(TAC)膜(柯尼卡美能達(Konica Minolta)股份有限公司製造，厚度25μm)。
As a base film, a triacetyl cellulose (TAC) film (manufactured by Konica Minolta Co., Ltd.,
(配向膜形成用組成物) (composition for forming an alignment film)
聚合物1係具有包含以下結構單元之光反應性基之聚合物。 Polymer 1 is a polymer having a photoreactive group comprising the following structural units.
藉由GPC測定，所得聚合物1之分子量為數平均分子量28200，Mw/Mn1.82，單體含量為0.5%。 As determined by GPC, the molecular weight of the obtained polymer 1 was number average molecular weight 28200, Mw/Mn 1.82, and the monomer content was 0.5%.
將聚合物1以濃度5質量%溶解於環戊酮之溶液作為配向膜形成用組成物使用。 A solution in which polymer 1 was dissolved in cyclopentanone at a concentration of 5% by mass was used as a composition for forming an alignment film.
(聚合性液晶化合物) (polymerizable liquid crystal compound)
聚合性液晶化合物係使用式(1-6)所表示之聚合性液晶化合物[以下亦稱為化合物(1-6)]與式(1-7)所表示之聚合性液晶化合物[以下亦稱為化合物(1-7)]。 The polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by formula (1-6) [hereinafter also referred to as compound (1-6)] and a polymerizable liquid crystal compound represented by formula (1-7) [hereinafter also referred to as Compound (1-7)].
化合物(1-6)及化合物(1-7)是藉由Lub et al.Recl.Trav.Chim.Pays-Bas、115、321-328(1996)中記載的方法來合成。 Compound (1-6) and compound (1-7) were synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).
(二色性色素) (Dichroic Pigment)
二色性色素係使用下述式(2-1a)、式(2-1b)、式(2-3a)所表示的日本特開2013-101328號公報的實施例中所記載的偶氮色素。 As the dichroic dye, the azo dye described in the Examples of JP 2013-101328 A represented by the following formula (2-1a), formula (2-1b), and formula (2-3a) was used.
(直線偏光層形成用組成物) (Composition for forming linear polarizing layer)
直線偏光層形成用組成物係將化合物(1-6)75質量份、化合物(1-7)25質量份、作為二色性染料之上述式(2-1a)、(2-1b)、(2-3a)所示之偶氮色素各2.5質量份、作為聚合起始劑之2-二甲基胺基-2-苄基-1-(4-嗎啉基苯基)丁烷-1-酮(Irgacure 369、BASF Japan公司製)6質量份、及作為調平劑之聚丙烯酸酯化合物(BYK-361N、 BYK-Chemie公司製)1.2質量份混合於溶劑之甲苯400質量份中，將所獲得之混合物於80℃下攪拌1小時，藉此而調製。 The composition for forming the linear polarizing layer is 75 parts by mass of compound (1-6), 25 parts by mass of compound (1-7), and the above-mentioned formula (2-1a), (2-1b), ( 2.5 parts by mass of each of the azo dyes shown in 2-3a), 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1- as a polymerization initiator Ketone (Irgacure 369, manufactured by BASF Japan Co., Ltd.) 6 parts by mass, and a polyacrylate compound (BYK-361N, BYK-Chemie company) 1.2 mass parts were mixed with 400 mass parts of toluene as a solvent, and the obtained mixture was stirred at 80 degreeC for 1 hour, and it prepared.
(保護層(OC層)用組成物) (Composition for protective layer (OC layer))
保護層用組成物係相對於水100質量份，混合聚乙烯醇樹脂粉末(Kuraray股份有限公司製、平均聚合度18000、商品名：KL-318)3質量份、與聚醯胺環氧樹脂(交聯劑，住化ChemteX股份有限公司製，商品名：SR650(30))1.5質量份而調製。 The composition for the protective layer was mixed with 100 parts by mass of water, 3 parts by mass of polyvinyl alcohol resin powder (manufactured by Kuraray Co., Ltd., average degree of polymerization: 18000, trade name: KL-318), and polyamide epoxy resin ( The crosslinking agent, manufactured by Sumika ChemteX Co., Ltd., brand name: SR650 (30)) was prepared by 1.5 parts by mass.
(直線偏光板A之製作) (Production of Linear Polarizer A)
對基材膜實施電暈處理。電暈處理的條件為輸出0.3kW、處理速度3m/分鐘。其後，藉由棒式塗佈法將配向膜形成用組成物塗佈於基材膜上，於80℃之乾燥烘箱中加熱乾燥1分鐘。對所獲得之乾燥覆膜實施偏光UV照射處理而形成配向膜。偏光UV處理係由UV照射裝置(SPOT CURE SP-7；使自USHIO電機股份有限公司製造)照射之光透過線柵(UIS-27132##，USHIO電機股份有限公司製造)，於波長365nm下測定之累積光量為100mJ/cm2之條件下進行。配向膜之厚度為100nm。 Corona treatment is performed on the base film. The conditions of the corona treatment were an output of 0.3 kW and a treatment speed of 3 m/min. Thereafter, the composition for forming an alignment film was coated on the substrate film by a bar coating method, and heated and dried in a drying oven at 80° C. for 1 minute. The obtained dried film was irradiated with polarized light to form an alignment film. Polarized UV treatment is made by a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Electric Co., Ltd.) through a wire grid (UIS-27132##, manufactured by USHIO Electric Co., Ltd.), and measured at a wavelength of 365nm The cumulative light intensity was 100mJ/cm 2 . The thickness of the alignment film is 100 nm.
藉由棒式塗佈法將直線偏光層形成用組成物塗佈於所形成之配向膜上，於120℃之乾燥烘箱中加熱乾燥1分鐘後，冷卻至室溫。使用上述UV照射裝置，以累積光量1200mJ/cm2(365nm基準)對乾燥覆膜照射紫外線，藉此形成直線偏光層。藉由雷射顯微鏡(Olympus股份有限公司製OLS3000)測定所得之直線偏光層的厚度，結果為1.8μm。如此，獲得由「基材膜/配向膜/直線偏光層」所構成之積層體。 The composition for forming a linear polarizing layer was coated on the formed alignment film by a bar coating method, heated and dried in a drying oven at 120° C. for 1 minute, and then cooled to room temperature. Using the above-mentioned UV irradiation apparatus, ultraviolet rays were irradiated to the dry film at a cumulative light intensity of 1200 mJ/cm 2 (based on 365 nm), thereby forming a linear polarizing layer. The thickness of the obtained linear polarizing layer was measured with a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.), and found to be 1.8 μm . In this way, a laminate composed of "substrate film/alignment film/linear polarizing layer" is obtained.
藉由棒式塗佈法將保護層(OC層)用組成物塗佈於所形成之直線偏光層上，以乾燥後之厚度成為1.0μm之方式進行塗佈，於溫度80℃下乾燥3分鐘。如此，得到由「基材膜/配向膜/直線偏光層/保護層(OC層)」所構成之直線偏光板A。 The composition for the protective layer (OC layer) was coated on the formed linear polarizing layer by a bar coating method, and the coating was applied so that the thickness after drying became 1.0 μm , and dried at a temperature of 80° C. for 3 minute. In this way, linear polarizing plate A composed of "substrate film/alignment film/linear polarizing layer/protective layer (OC layer)" was obtained.
[直線偏光板B] [Linear polarizer B]
(基材膜) (substrate film)
作為基材膜，係準備聚對苯二甲酸乙二酯(PET)薄膜(厚度100μm)。 As the base film, a polyethylene terephthalate (PET) film (100 μm in thickness) was prepared.
(保護層(HC層)用組成物) (Composition for protective layer (HC layer))
將具有18官能的丙烯酸基的樹枝狀聚合物丙烯酸酯(Miramer SP1106，Miwon)2.8質量份、具有6官能的丙烯酸基的胺基甲酸乙酯丙烯酸酯(Miramer PU-620D，Miwon)6.6質量份、光聚合起始劑(Irgacure-184，BASF)0.5質量份、調平劑(BYK-3530，BYK)0.1質量份、及甲基乙基酮(MEK)90質量份混合，而調製成保護層(HC層)用組成物。 2.8 parts by mass of dendrimer acrylate (Miramer SP1106, Miwon) with 18 functional acrylic groups, 6.6 parts by mass of urethane acrylate (Miramer PU-620D, Miwon) with 6 functional acrylic groups, 0.5 parts by mass of a photopolymerization initiator (Irgacure-184, BASF), 0.1 parts by mass of a leveling agent (BYK-3530, BYK), and 90 parts by mass of methyl ethyl ketone (MEK) were mixed to form a protective layer ( HC layer) composition.
配向膜形成用組成物、直線偏光層形成用組成物及保護層(OC層)用組成物分別使用上述[直線偏光板A]之項中記載之組成物。 The composition for forming an alignment film, the composition for forming a linear polarizing layer, and the composition for a protective layer (OC layer) were the compositions described in the section of [Linear Polarizing Plate A] above, respectively.
(直線偏光板B之製作) (Production of Linear Polarizer B)
藉由棒塗法將保護層(HC層)用組成物塗佈於基材膜上，於80℃的乾燥烘箱中加熱乾燥3分鐘。使用UV照射裝置(SPOT CURE SP-7，USHIO電機股份有限公司製造)，對所獲得之乾燥覆膜照射曝光量500mJ/cm2(365nm基準)之UV光而形成保護層(HC層)。藉由雷射顯微鏡(Olympus股份有限公司製造之OLS3000)測定保護層(HC層)之厚度，結果為2.0μm。如此，獲得由「基材膜/保護層(HC層)」所構成之積層體。 The composition for the protective layer (HC layer) was coated on the substrate film by a bar coating method, and heated and dried in a drying oven at 80° C. for 3 minutes. Using a UV irradiation device (SPOT CURE SP-7, manufactured by USHIO Electric Co., Ltd.), the obtained dried film was irradiated with UV light at an exposure dose of 500 mJ/cm 2 (based on 365 nm) to form a protective layer (HC layer). When the thickness of the protective layer (HC layer) was measured with a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.), it was 2.0 μm. In this way, a laminate composed of "substrate film/protective layer (HC layer)" was obtained.
於由「基材膜/保護層(HC層)」所構成之積層體的保護層(HC層)側實施1次電暈處理。電暈處理的條件為輸出0.3kW、處理速度3m/分鐘。其後，藉由棒式塗佈法將配向膜形成用組成物塗佈於保護層(HC層)上，於80℃之乾燥烘箱中加熱乾燥1分鐘。對所獲得之乾燥覆膜實施偏光UV照射處理而形成第1配向膜。偏光UV處理係使自UV照射裝置(SPOT CURE SP-7；USHIO電機股份有限公司製造)照射之光透過線柵(UIS-27132##，USHIO電機股份有限公司製造)，於波長365nm下測定之累積光量為100mJ/cm2之條件下進行。配向膜之厚度為100nm。 Corona treatment was performed once on the protective layer (HC layer) side of the laminate consisting of "substrate film/protective layer (HC layer)". The conditions of the corona treatment were an output of 0.3 kW and a treatment speed of 3 m/min. Thereafter, the composition for forming an alignment film was coated on the protective layer (HC layer) by a bar coating method, and heated and dried in a drying oven at 80° C. for 1 minute. The obtained dried film was irradiated with polarized light UV to form a first alignment film. Polarized UV treatment is to make the light irradiated from the UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Electric Co., Ltd.) pass through the wire grid (UIS-27132##, manufactured by USHIO Electric Co., Ltd.), and measure at a wavelength of 365nm It was carried out under the condition that the accumulated light intensity was 100mJ/cm 2 . The thickness of the alignment film is 100 nm.
藉由棒式塗佈法將直線偏光層形成用組成物塗佈於所形成之配向膜上，於120℃之乾燥烘箱中加熱乾燥1分鐘後，冷卻至室溫。使用上述UV照射裝置，以累積光量1200mJ/cm2(365nm基準)對乾燥覆膜照射紫外線，藉此形成直線偏光層。藉由雷射顯微鏡(Olympus股份有限公司製OLS3000)測定所得之直線偏光層的厚度，結果為1.8μm。如此，獲得由「基材膜/保護層(HC層)/配向膜/直線偏光層」所構成之積層體。 The composition for forming a linear polarizing layer was coated on the formed alignment film by a bar coating method, heated and dried in a drying oven at 120° C. for 1 minute, and then cooled to room temperature. Using the above-mentioned UV irradiation apparatus, ultraviolet rays were irradiated to the dry film at a cumulative light intensity of 1200 mJ/cm 2 (based on 365 nm), thereby forming a linear polarizing layer. The thickness of the obtained linear polarizing layer was measured with a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.), and found to be 1.8 μm . In this way, a laminate composed of "substrate film/protective layer (HC layer)/alignment film/linear polarizing layer" is obtained.
藉由棒式塗佈法將保護層(OC層)用組成物塗佈於所形成之偏光層層上，以乾燥後之厚度成為1.0μm之方式進行塗佈，於溫度80℃下乾燥3分鐘。如此，獲得由「基材膜/保護層(HC層)/配向膜/直線偏光層/保護層(OC層)」所構成之積層體。剝離即將使用之基材膜，獲得由「保護層(HC層)/配向膜/直線偏光層/保護層(OC層)」所構成之直線偏光板B。 Apply the composition for the protective layer (OC layer) on the formed polarizing layer by the bar coating method, apply so that the thickness after drying becomes 1.0 μm, and dry at 80°C for 3 minutes . In this way, a laminate composed of "substrate film/protective layer (HC layer)/alignment film/linear polarizing layer/protective layer (OC layer)" is obtained. The substrate film to be used is peeled off to obtain a linear polarizing plate B consisting of "protective layer (HC layer)/alignment film/linear polarizing layer/protective layer (OC layer)".
[黏著層A] [Adhesive Layer A]
作為具有黏著層A之黏著片A，使用於厚度38μm之聚對苯二甲酸乙二酯膜(基材膜)之單面實施有脫模處理之剝離膜2片(重隔離膜、輕隔離膜)之各脫模 處理面夾有厚度5μm之丙烯酸系黏著劑層之市售之黏著劑片。自黏著片A去除剝離膜後之黏著層A於溫度25℃下之儲存模數G'1為1400kPa。 As the adhesive sheet A having the adhesive layer A, two peeling films (heavy release film, light A commercially available adhesive sheet in which an acrylic adhesive layer with a thickness of 5 μm is sandwiched between each release-treated surface of the release film. The storage modulus G'1 of the adhesive layer A at a temperature of 25° C. after removing the release film from the adhesive sheet A was 1400 kPa.
[黏著層B] [Adhesive layer B]
作為具有黏著層B之黏著片B，使用市售之黏著劑片(美國3M公司製造之「CEF3501」)，該黏著劑片係於對基材膜之單面實施有脫模處理之2片脫模膜(重隔離膜、輕隔離膜)之各者之脫模處理面，夾著厚度25μm之黏著劑層而成。自黏著片B去除剝離膜後之黏著層B於溫度25℃下之儲存模數G'2為41kPa。 As the adhesive sheet B having the adhesive layer B, a commercially available adhesive sheet ("CEF3501" manufactured by 3M Company in the United States) was used. The release surface of each mold film (heavy release film, light release film) is formed by sandwiching an adhesive layer with a thickness of 25 μm . The storage modulus G'2 of the adhesive layer B at a temperature of 25° C. after removing the release film from the adhesive sheet B was 41 kPa.
[液晶塗佈層] [LCD Coating Layer]
(第1液晶硬化相位差層) (1st liquid crystal cured retardation layer)
作為第1液晶硬化相位差層，準備向列型液晶化合物硬化而成之層、配向層及包含透明基材之賦予λ/4之相位差之層。再者，向列型液晶化合物硬化而成之層與配向層之合計厚度為2μm。向列型液晶化合物硬化而成之層係藉由於形成於透明基材上之配向層上塗佈含有向列型液晶化合物之相位差層形成用組成物並使其硬化而形成。 As the first liquid crystal cured retardation layer, a layer obtained by curing a nematic liquid crystal compound, an alignment layer, and a layer for imparting a retardation of λ/4 including a transparent substrate were prepared. Furthermore, the total thickness of the layer formed by hardening the nematic liquid crystal compound and the alignment layer was 2 μm . The layer in which the nematic liquid crystal compound is cured is formed by applying a composition for forming a retardation layer containing a nematic liquid crystal compound on an alignment layer formed on a transparent substrate, and curing it.
(第2液晶硬化相位差層) (2nd liquid crystal hardened retardation layer)
使用厚度38μm之聚對苯二甲酸乙二酯基材作為透明基材，於其單面以膜厚成為3μm之方式塗佈垂直配向層用組成物，照射20mJ/cm2之偏光紫外線而製作配向層。再者，作為該垂直配向層用組成物，係使用將丙烯酸2-苯氧基乙酯、丙烯酸四氫糠酯、二新戊四醇三丙烯酸酯、及雙(2-乙烯氧基乙基)醚以1：1：4：5之比例混合，並以4%之比率添加LUCIRIN(註冊商標)TPO作為聚合起始劑之混合物。 A polyethylene terephthalate substrate with a thickness of 38 μm was used as a transparent substrate, and a vertical alignment layer composition was coated on one side so that the film thickness became 3 μm , and polarized light of 20 mJ/cm 2 was irradiated Alignment layer made by ultraviolet light. Furthermore, as the composition for the vertical alignment layer, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, diperythritol triacrylate, and bis(2-ethyleneoxyethyl) Ether was mixed at a ratio of 1:1:4:5, and LUCIRIN (registered trademark) TPO was added at a ratio of 4% to the mixture as a polymerization initiator.
繼而，於所形成之配向層上，藉由模塗佈將含有光聚合性向列液晶(默克公司製造，RMM28B)之相位差層形成用組成物塗佈於配向層上。此處，液晶組成物中，作為溶劑，係使用將甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、及沸點為155℃之環己酮(CHN)以質量比(MEK：MIBK：CHN)計為35：30：35之比例混合而成之混合溶劑。繼而，將以固形分成為1至1.5g之方式調製之相位差層形成用組成物以塗佈量成為4至5g(wet)之方式塗佈於配向層上。 Next, on the formed alignment layer, a composition for forming a phase difference layer containing a photopolymerizable nematic liquid crystal (manufactured by Merck, RMM28B) was applied on the alignment layer by die coating. Here, in the liquid crystal composition, as a solvent, a mixture of methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CHN) with a boiling point of 155° C. in a mass ratio (MEK :MIBK:CHN) is a mixed solvent mixed in a ratio of 35:30:35. Next, the composition for retardation layer formation prepared so that the solid content may be 1-1.5g is apply|coated on the alignment layer so that the coating amount may become 4-5g (wet).
於配向層上塗佈相位差層形成用組成物後，將乾燥溫度設為75℃，將乾燥時間設為120秒鐘而實施乾燥處理。其後，藉由紫外線(UV)照射使液晶化合物聚合，獲得包含光聚合性向列型液晶化合物硬化而成之層、配向層、透明基材之正C層。光聚合性向列型液晶化合物硬化而成之層與配向層之合計厚度為4μm。 After coating the phase difference layer forming composition on the alignment layer, the drying temperature was set to 75° C., and the drying time was set to 120 seconds to perform drying treatment. Thereafter, the liquid crystal compound is polymerized by ultraviolet (UV) irradiation to obtain a positive C layer comprising a layer hardened by the photopolymerizable nematic liquid crystal compound, an alignment layer, and a transparent substrate. The total thickness of the layer formed by hardening the photopolymerizable nematic liquid crystal compound and the alignment layer was 4 μm .
(液晶塗佈層之製作) (Production of liquid crystal coating layer)
藉由紫外線硬化型接著劑，以各液晶硬化相位差層面(與透明基材為相反側之面)成為貼合面之方式將第1液晶硬化相位差層與第2液晶硬化相位差層貼合。繼而，照射紫外線而使紫外線硬化型接著劑硬化。紫外線硬化型接著劑硬化後之厚度為2μm。如此，製作具有「第1液晶硬化相位差層(2μm)/接著劑層(厚度2μm)/第2液晶硬化相位差層(厚度4μm)」之層構成之液晶塗佈層。 The first liquid crystal curable retardation layer and the second liquid crystal curable retardation layer are bonded so that each liquid crystal curable retardation layer (the surface opposite to the transparent substrate) becomes a bonded surface with an ultraviolet curable adhesive . Next, ultraviolet rays are irradiated to harden the ultraviolet curable adhesive. The thickness of the ultraviolet curable adhesive is 2 μm after hardening. In this way, a liquid crystal coating layer with a layer composition of "1st liquid crystal hardened retardation layer (2 μm )/adhesive layer (thickness 2 μm )/second liquid crystal hardened retardation layer (thickness 4 μm )" was produced .
[有機EL面板] [Organic EL panel]
作為相當於有機EL面板之代用品，係準備聚醯亞胺膜(PI膜、整體之厚度：75μm、拉伸模數6.96GPa)。 As a substitute equivalent to an organic EL panel, a polyimide film (PI film, overall thickness: 75 μm , tensile modulus: 6.96 GPa) was prepared.
<實施例1> <Example 1>
將自黏著劑片A剝離輕隔離膜而露出之黏著層A貼合於直線偏光板A之保護層2側，獲得積層體A1。對貼合面預先進行兩面電暈處理(輸出0.3kW、速度3m/分鐘)。 The adhesive layer A exposed by peeling off the light release film from the adhesive sheet A was bonded to the protective layer 2 side of the linear polarizing plate A to obtain a laminate A1. Double-sided corona treatment (output 0.3kW, speed 3m/min) was performed on the bonding surface in advance.
將自積層體A1剝離重隔離膜而露出之黏著層A貼合於液晶塗佈層之形成有第1液晶硬化相位差層之基材膜之剝離面，獲得積層體A2。對貼合面預先進行兩面電暈處理(輸出0.3kW、速度3m/分鐘)。 The adhesive layer A exposed from the layered body A1 by peeling off the heavy release film was bonded to the peeled surface of the base film on which the first liquid crystal cured retardation layer was formed on the liquid crystal coating layer to obtain the layered body A2. Double-sided corona treatment (output 0.3kW, speed 3m/min) was performed on the bonding surface in advance.
將自黏著片B剝離輕隔離膜而露出之黏著層B貼合於自積層體A2剝離用於形成第2液晶硬化相位差層之基材膜之面，獲得積層體A3。對貼合面預先進行兩面電暈處理(輸出0.3kW、速度3m/分鐘)。 The adhesive layer B exposed by peeling off the light release film from the adhesive sheet B was attached to the surface of the substrate film for forming the second liquid crystal cured retardation layer peeled from the laminate A2 to obtain a laminate A3. Double-sided corona treatment (output 0.3kW, speed 3m/min) was performed on the bonding surface in advance.
將自第3黏著劑片剝離輕隔離膜而露出之第3黏著層貼合於前面板，獲得積層體A4。對貼合面預先進行兩面電暈處理(輸出0.3kW、速度3m/分鐘)。 The third adhesive layer exposed by peeling off the light release film from the third adhesive sheet was bonded to the front panel to obtain a laminate A4. Double-sided corona treatment (output 0.3kW, speed 3m/min) was performed on the bonding surface in advance.
自積層體A4剝離重隔離膜，貼合於積層體A3之保護層1側，獲得積層體A5。對貼合面預先進行兩面電暈處理(輸出0.3kW、速度3m/分鐘)。 The heavy-duty separator was peeled off from laminate A4, and attached to the protective layer 1 side of laminate A3 to obtain laminate A5. Double-sided corona treatment (output 0.3kW, speed 3m/min) was performed on the bonding surface in advance.
剝離積層體A5之重隔離膜，貼合相當於有機EL面板之代用品(聚醯亞胺膜)，獲得具有圖2所示之構成之實施例1之積層體。將結果呈示於表1。 The heavy separator of laminate A5 was peeled off, and a substitute (polyimide film) equivalent to an organic EL panel was bonded to obtain the laminate of Example 1 having the structure shown in FIG. 2 . The results are shown in Table 1.
<實施例2至4、比較例1至4> <Examples 2 to 4, Comparative Examples 1 to 4>
除了使用表1所示之直線偏光板及黏著層以外，以與實施例1相同之方式製作實施例2至4、比較例1至4之積層體。將結果呈示於表1。 Laminates of Examples 2 to 4 and Comparative Examples 1 to 4 were produced in the same manner as in Example 1 except for using the linear polarizing plate and the adhesive layer shown in Table 1. The results are shown in Table 1.
[表1]
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010044211A (en) * | 2008-08-12 | 2010-02-25 | Sumitomo Chemical Co Ltd | Polarizing plate and image display device using the same |
| JP7042020B2 (en) * | 2016-08-15 | 2022-03-25 | 日東電工株式会社 | Laminated body for flexible image display device and flexible image display device |
| KR102126051B1 (en) * | 2017-10-23 | 2020-06-23 | 삼성에스디아이 주식회사 | Liquid crystal retardation film, polarizing plate for light emitting display apparatus comprising the same and light emitting display apparatus compsiring the same |
| JP6797163B2 (en) * | 2018-10-11 | 2020-12-09 | 住友化学株式会社 | Optical laminate and display device |
| JP2020157577A (en) * | 2019-03-26 | 2020-10-01 | 住友化学株式会社 | Laminate and display device |
| JP6934996B2 (en) * | 2019-10-09 | 2021-09-15 | 日東電工株式会社 | Flexible image display device and optical laminate used for it |
| JP6858912B2 (en) * | 2019-10-09 | 2021-04-14 | 日東電工株式会社 | Flexible image display device and optical laminate used for it |
-
2021
- 2021-06-02 JP JP2021093097A patent/JP7348928B2/en active Active
-
2022
- 2022-05-23 CN CN202280031112.6A patent/CN117280255A/en active Pending
- 2022-05-23 WO PCT/JP2022/021158 patent/WO2022255154A1/en active Application Filing
- 2022-05-23 KR KR1020237045266A patent/KR20240017371A/en unknown
- 2022-05-30 TW TW111120080A patent/TW202306212A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN117280255A (en) | 2023-12-22 |
| KR20240017371A (en) | 2024-02-07 |
| WO2022255154A1 (en) | 2022-12-08 |
| JP7348928B2 (en) | 2023-09-21 |
| JP2022185418A (en) | 2022-12-14 |
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