TW201939076A - Circular polarizing plate - Google Patents
Circular polarizing plate Download PDFInfo
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- TW201939076A TW201939076A TW108105453A TW108105453A TW201939076A TW 201939076 A TW201939076 A TW 201939076A TW 108105453 A TW108105453 A TW 108105453A TW 108105453 A TW108105453 A TW 108105453A TW 201939076 A TW201939076 A TW 201939076A
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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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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Abstract
Description
本發明係關於圓偏光板。 The present invention relates to a circularly polarizing plate.
近年來,由有機電致發光(以下亦稱為有機EL)顯示裝置所代表之影像顯示裝置正迅速普及。有機EL顯示裝置中,承載有具備偏光件及位相差膜(λ/4板)之圓偏光板。藉由配置圓偏光板,可防止外光之反射並提高影像之可見度。 In recent years, image display devices represented by organic electroluminescence (hereinafter also referred to as organic EL) display devices are rapidly spreading. An organic EL display device carries a circularly polarizing plate including a polarizer and a phase difference film (λ / 4 plate). By configuring a circular polarizer, the reflection of external light can be prevented and the visibility of the image can be improved.
因有機EL顯示裝置的興起,隨著對影像顯示裝置之薄型化之需求變得更強,亦要求圓偏光板之薄型化。目前已有探討將「由習知之樹脂膜所形成之位相差膜」變更成「由可薄型化之液晶化合物作為材料而形成之位相差膜」(參照例如專利文獻1)。使用聚合性液晶化合物而成之位相差膜,係藉由將聚合性液晶化合物塗佈於基材上並使其配向,並視需要照射光以固定配向狀態而製造者。 Due to the rise of organic EL display devices, as the demand for thinner image display devices becomes stronger, thinner circular polarizers are also required. At present, it has been studied to change the "phase retardation film formed from a conventional resin film" to "a phase retardation film formed from a thin-shaped liquid crystal compound as a material" (see, for example, Patent Document 1). A phase difference film using a polymerizable liquid crystal compound is manufactured by coating a polymerizable liquid crystal compound on a substrate and aligning it, and irradiating light as necessary to fix the alignment state.
專利文獻1:日本特開2017-54093號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2017-54093
然而,若將具有由聚合性液晶化合物所形成之位相差膜的圓偏光板以附有前面板之狀態放置於高溫環境下時,則在圓偏光板中央部分,反射光之顏色相較於初期狀態會產生變化,具體而言,有反射光變紅之問題。 However, if a circularly polarizing plate having a phase difference film formed of a polymerizable liquid crystal compound is placed in a high-temperature environment with a front plate attached, the color of the reflected light in the central portion of the circularly polarizing plate is compared to the initial stage. The state changes, specifically, there is a problem that the reflected light becomes red.
本發明之目的為提供一種圓偏光板,其具備包含由液晶化合物所硬化成之層的位相差膜,該圓偏光板可抑制以貼合蓋玻璃等前面板之狀態放置在高溫環境下後之反射光的顏色相較於初期狀態之變化。 An object of the present invention is to provide a circularly polarizing plate including a phase difference film including a layer hardened by a liquid crystal compound. The circularly polarizing plate can prevent the circularly polarizing plate from being placed in a high temperature environment after being attached to a cover glass or the like. The color of the reflected light changes from the initial state.
[1]一種圓偏光板,係具備:偏光板,係於偏光件之一面積層有第1保護膜,並於該偏光件之另一面積層有第2保護膜;以及位相差膜,係包含由聚合性液晶化合物所硬化成之層;並且,該圓偏光板符合以下條件1及條件2中的至少一者。 [1] A circular polarizing plate, comprising: a polarizing plate, a first protective film on an area layer of a polarizer, and a second protective film on another area layer of the polarizer; and a phase difference film including A layer formed by curing a polymerizable liquid crystal compound; and the circular polarizing plate satisfies at least one of the following conditions 1 and 2.
條件1:在將前述第1保護膜之透濕度作為x(g/m2‧24小時),前述第2保護膜之透濕度作為y(g/m2‧24小時)時,符合式(1)。 Condition 1: When the moisture permeability of the first protective film is x (g / m 2 ‧ 24 hours), and the moisture permeability of the second protective film is y (g / m 2 ‧ 24 hours), the formula (1 ).
1/x+1/y≧0.0030 式(1) 1 / x + 1 / y ≧ 0.0030 Equation (1)
條件2:前述偏光板之水分率為3%以下。 Condition 2: The moisture content of the polarizing plate is 3% or less.
[2]如[1]所述之圓偏光板,係符合條件1及條件2兩者。 [2] The circular polarizing plate according to [1], which satisfies both Condition 1 and Condition 2.
[3]如[1]或[2]所述之圓偏光板,其中,在前述偏光板之與積層有前述位相差膜之側為相反之側具備前面板。 [3] The circular polarizing plate according to [1] or [2], wherein a front plate is provided on a side of the polarizing plate opposite to a side where the phase difference film is laminated.
[4]如[1]至[3]中任一項所述之圓偏光板,其中,前述偏光件之厚度為13μm以下。 [4] The circular polarizing plate according to any one of [1] to [3], wherein a thickness of the polarizer is 13 μm or less.
依據本發明,在具備包含由液晶化合物所硬化成之層的位相差膜的圓偏光板中,可抑制其以貼合蓋玻璃等前面板之狀態放置在高溫環境下後之反射光的顏色相較於初期狀態之變化。 According to the present invention, in a circular polarizing plate having a phase difference film including a layer hardened by a liquid crystal compound, the color phase of reflected light after being placed in a high-temperature environment in a state in which it is bonded to a front panel such as a cover glass can be suppressed. Changes compared to the initial state.
1‧‧‧偏光板 1‧‧‧ polarizing plate
2‧‧‧位相差膜 2‧‧‧ phase contrast film
3‧‧‧有機EL顯示元件 3‧‧‧Organic EL Display Element
4‧‧‧前面板 4‧‧‧ front panel
10‧‧‧偏光件 10‧‧‧Polarizer
11‧‧‧第1保護膜 11‧‧‧The first protective film
12‧‧‧第2保護膜 12‧‧‧ 2nd protective film
13、14、16‧‧‧黏著劑層 13, 14, 16‧‧‧ Adhesive layer
15‧‧‧接著層 15‧‧‧ Adjacent layer
20、21‧‧‧由聚合性液晶化合物所硬化成之層 20, 21‧‧‧ a layer hardened by a polymerizable liquid crystal compound
100、101、103‧‧‧圓偏光板 100, 101, 103‧‧‧ circular polarizers
104、105‧‧‧有機EL顯示裝置 104, 105‧‧‧ organic EL display devices
第1圖係顯示圓偏光板之層構成之概略截面圖的一例。 FIG. 1 is an example of a schematic cross-sectional view showing a layer configuration of a circularly polarizing plate.
第2圖係顯示圓偏光板之層構成之概略截面圖的一例。 Fig. 2 is an example of a schematic cross-sectional view showing a layer configuration of a circularly polarizing plate.
第3圖係顯示有機EL顯示裝置之層構成之概略截面圖的一例。 FIG. 3 is an example of a schematic cross-sectional view showing a layer structure of an organic EL display device.
<圓偏光板> <Circular polarizer>
本發明之圓偏光板具備偏光板與位相差膜。偏光板與位相差膜可藉由例如接著層而積層。就接著層而言,可列舉例如後述之黏著劑層或接著劑層。在本發明中,偏光板係意指由偏光件及各別貼合於偏光件之兩面之保護膜所構成的積層體。 The circular polarizing plate of the present invention includes a polarizing plate and a phase difference film. The polarizing plate and the phase difference film can be laminated by, for example, bonding. Examples of the adhesive layer include an adhesive layer or an adhesive layer described later. In the present invention, the polarizing plate means a laminated body composed of a polarizer and protective films attached to both sides of the polarizer, respectively.
以下參照第1圖來說明本發明之圓偏光板之層構成的一例。此外,第1圖中,並未圖示用以各別貼合偏光件10與保護膜11、12之接著劑層。第1圖(a)所示之圓偏光板100具有使偏光板1與位相差膜2隔著 黏著劑層13而積層之層構成,其中,該偏光板1係於偏光件10之一面積層有第1保護膜11並於偏光件10之另一面積層有第2保護膜12,該位相差膜2包含由聚合性液晶化合物所硬化成之層20。更且,圓偏光板100係在位相差膜2之與偏光板1為相反側之面具有黏著劑層14。黏著劑層14可為用於貼合至有機EL顯示元件等之黏著劑層。 An example of the layer configuration of the circular polarizing plate of the present invention will be described below with reference to FIG. 1. In addition, in FIG. 1, the adhesive layers for individually bonding the polarizer 10 and the protective films 11 and 12 are not shown. The circular polarizing plate 100 shown in FIG. 1 (a) has a layer structure in which a polarizing plate 1 and a phase difference film 2 are laminated with an adhesive layer 13 interposed therebetween. The polarizing plate 1 is formed on an area of a polarizer 10. The first protective film 11 includes a second protective film 12 on the other area of the polarizer 10. The phase difference film 2 includes a layer 20 hardened by a polymerizable liquid crystal compound. Furthermore, the circularly polarizing plate 100 has an adhesive layer 14 on a surface of the phase difference film 2 opposite to the polarizing plate 1. The adhesive layer 14 may be an adhesive layer for bonding to an organic EL display element or the like.
第1圖(b)所示之圓偏光板101具有使偏光板1與位相差膜2隔著黏著劑層13而積層之層構成,其中,該偏光板1係於偏光件10之一面積層有第1保護膜11並於偏光件10之另一面積層有第2保護膜12。在圓偏光板101中,位相差膜2具有使由聚合性液晶化合物所硬化成之層20與由聚合性液晶化合物所硬化成之層21隔著接著層15而積層之層構成。更且,圓偏光板101係在位相差膜2之與偏光板1為相反側之面具有黏著劑層14。黏著劑層14可為用於貼合至有機EL顯示元件等之黏著劑層。 The circular polarizing plate 101 shown in FIG. 1 (b) has a layer structure in which a polarizing plate 1 and a phase difference film 2 are laminated with an adhesive layer 13 interposed therebetween. The polarizing plate 1 is formed on an area of a polarizer 10. The first protective film 11 has a second protective film 12 on another area of the polarizer 10. In the circularly polarizing plate 101, the phase difference film 2 has a layer in which a layer 20 hardened from a polymerizable liquid crystal compound and a layer 21 hardened from a polymerizable liquid crystal compound are laminated with an adhesive layer 15 therebetween. Furthermore, the circularly polarizing plate 101 has an adhesive layer 14 on a surface of the phase difference film 2 on the side opposite to the polarizing plate 1. The adhesive layer 14 may be an adhesive layer for bonding to an organic EL display element or the like.
如第1圖所示,位相差膜可具有1層或2層的由聚合性液晶化合物所硬化成之層。此外,位相差膜可具有用於使聚合性液晶化合物配向之配向膜或基材膜。 As shown in FIG. 1, the phase difference film may have one or two layers hardened by a polymerizable liquid crystal compound. The phase difference film may have an alignment film or a base film for aligning the polymerizable liquid crystal compound.
圓偏光板可具有第1圖所示之層以外的層。關於圓偏光板可更具有之層,可列舉前面板、遮光圖案等。前面板可配置於偏光板之與積層有位相差膜之側為相反之側。第2圖(a)所示之圓偏光板102為在圓偏光板100積層有前面板4者,並且,前面板4係隔著黏著劑層16而積層於偏光板1。第2圖(b)所示之圓偏光板103為在圓偏光板101積層有前面板4者,並且,前面板4係隔著黏著劑層16而積層於偏光板1。 The circular polarizing plate may have a layer other than the layer shown in FIG. 1. Examples of the layers that the circular polarizing plate may further include a front panel and a light-shielding pattern. The front panel may be disposed on the side of the polarizing plate opposite to the layer having the phase difference film. The circular polarizing plate 102 shown in FIG. 2 (a) is one in which the front plate 4 is laminated on the circular polarizing plate 100, and the front plate 4 is laminated on the polarizing plate 1 via an adhesive layer 16. The circular polarizing plate 103 shown in FIG. 2 (b) is one in which the front plate 4 is laminated on the circular polarizing plate 101, and the front plate 4 is laminated on the polarizing plate 1 via an adhesive layer 16.
遮光圖案可形成於前面板之偏光板側之面上。遮光圖案係形成於影像顯示裝置之框(非顯示領域),可防止使用者看見影像顯示裝置之配線。 The light-shielding pattern may be formed on a surface of the front panel on the side of the polarizing plate. The light-shielding pattern is formed on the frame (non-display area) of the image display device, and can prevent users from seeing the wiring of the image display device.
本發明之圓偏光板符合以下條件1及條件2中的至少一者。 The circularly polarizing plate of the present invention satisfies at least one of the following conditions 1 and 2.
條件1:在將前述第1保護膜之透濕度作為x(g/m2‧24小時),前述第2保護膜之透濕度作為y(g/m2‧24小時)時,符合式(1)。 Condition 1: When the moisture permeability of the first protective film is x (g / m 2 ‧ 24 hours), and the moisture permeability of the second protective film is y (g / m 2 ‧ 24 hours), the formula (1 ).
1/x+1/y≧0.0030 式(1) 1 / x + 1 / y ≧ 0.0030 Equation (1)
條件2:前述偏光板之水分率為3.00%以下。 Condition 2: The moisture content of the polarizing plate is 3.00% or less.
圓偏光板係藉由符合上述條件1及條件2中的至少一者,而使圓偏光板於放置在高溫環境下時,可防止圓偏光板之中央部分的顏色變化。圓偏光板係以符合上述條件1及條件2兩者為佳。 The circularly polarizing plate is capable of preventing the color change of the central portion of the circularly polarizing plate when the circularly polarizing plate is placed in a high-temperature environment by meeting at least one of the above conditions 1 and 2. The circularly polarizing plate preferably satisfies both the conditions 1 and 2 described above.
更詳細而言,在式(1)中,1/x+1/y為0.0030以上,以0.010以上為佳,以0.020以上為較佳,以0.050以上為更佳。上限並無特別限定,惟1/x+1/y通常係0.2以下。 More specifically, in the formula (1), 1 / x + 1 / y is 0.0030 or more, preferably 0.010 or more, more preferably 0.020 or more, and even more preferably 0.050 or more. The upper limit is not particularly limited, but 1 / x + 1 / y is usually 0.2 or less.
更詳細而言,偏光板之水分率為3.00%以下,以2.50%以下為佳,以2.00%以下為較佳。下限並無特別限制,惟偏光板之水分率通常係0.50%以上,亦可係1.00%以上。水分率之測定方法係依據後述之實施例所記載的方法。 More specifically, the moisture content of the polarizing plate is 3.00% or less, preferably 2.50% or less, and more preferably 2.00% or less. The lower limit is not particularly limited, but the moisture content of the polarizing plate is usually above 0.50%, and may also be above 1.00%. The method for measuring the water content is based on the method described in the examples described later.
本發明並未受任何限制者,惟藉由符合條件1、2而可防止反射光變紅之理由係推測如下。依據本發明者等之探討得知,來自圓偏光板之中央部分的反射光會變紅的現象,係因位相差膜之位相差值的降低所致。位相差膜之位相差值的降低,推測係因偏光板中含有的水分移動至位 相差膜而產生者。因此,「將偏光板中含有的水分率設定為預定值以下,以減少可移動至位相差膜之水分量」或是「將偏光板所具備的保護膜之透濕度設定為預定值以下,以使水分難以移動至位相差膜」皆為有效。 The present invention is not limited in any way, but the reason why the reflected light can be prevented from turning red by meeting conditions 1 and 2 is presumed as follows. According to discussions by the inventors, the phenomenon that the reflected light from the central portion of the circularly polarizing plate turns red is caused by a decrease in the phase difference value of the phase difference film. The decrease in the phase difference value of the phase difference film is presumably caused by the water contained in the polarizing plate moving to the phase difference film. Therefore, "the moisture content contained in the polarizing plate is set to a predetermined value or less to reduce the amount of water that can be moved to the phase difference film" or "the moisture permeability of the protective film provided in the polarizing plate is set to a predetermined value or less It is effective to make it difficult for water to move to the phase difference film.
條件2係基於上述推測者,是藉由將偏光板之水分率設定於上述範圍,而可防止來自圓偏光板之反射光變紅。另一方面,令人意外地,條件1係基於「關於防止圓偏光板之反射光的變色,不僅是偏光板之與位相差膜相近側之保護膜的透濕度,另外如偏光板之離位相差膜較遠側之保護膜的透濕度,亦皆屬重要」者。依據本發明者等之探討,藉由使貼合偏光板之兩面之保護膜的透濕度經選擇而符合上述條件1,即可防止來自圓偏光板之反射光變紅。 Condition 2 is based on the above-mentioned guess, and by setting the moisture content of the polarizing plate to the above range, it is possible to prevent the reflected light from the circular polarizing plate from turning red. On the other hand, surprisingly, Condition 1 is based on "the prevention of discoloration of the reflected light of the circular polarizer, not only the moisture permeability of the protective film on the side of the polarizer close to the phase difference film, but also the deviation of the polarizer The moisture permeability of the protective film on the far side of the phase difference film is also important. " According to discussions by the present inventors, by making the moisture permeability of the protective film attached to both sides of the polarizing plate selected to meet the above condition 1, the reflected light from the circular polarizing plate can be prevented from turning red.
本發明之圓偏光板在以85℃加熱400小時之情形下,面內中央(可為圓偏光板之重心之位置)之位相差值之降低量的幅度△Re(nm)係以10nm以下為佳,以8nm以下為較佳。位相差值係採用在波長547nm中的值。藉由設定於此範圍,則可使圓偏光板之顏色變化變小,且獲得外觀良好的圓偏光板。 In the case where the circular polarizing plate of the present invention is heated at 85 ° C for 400 hours, the magnitude of the reduction amount of the phase difference value in the center of the plane (which can be the position of the center of gravity of the circular polarizing plate) ΔRe (nm) is 10 nm or less as Preferably, it is preferably 8 nm or less. The phase difference value is a value at a wavelength of 547 nm. By setting in this range, the color change of the circularly polarizing plate can be made small, and a circularly polarizing plate with good appearance can be obtained.
本發明之圓偏光板的形狀並無特別限定。當圓偏光板實質上為矩形時,長邊之長度以5cm以上35cm以下為佳,以10cm以上25cm以下為較佳,短邊之長度以5cm以上25cm以下為佳,以6cm以上20cm以下為較佳。只要係如此之大小,則水分難以積聚。 The shape of the circular polarizing plate of the present invention is not particularly limited. When the circular polarizing plate is substantially rectangular, the length of the long side is preferably 5 cm to 35 cm, more preferably 10 cm to 25 cm, the length of the short side is preferably 5 cm to 25 cm, and 6 cm to 20 cm is preferred. good. As long as it is such a size, it is difficult for water to accumulate.
所謂「實質上為矩形」係意指:圓偏光板係以使各別主面之4個角落(角部分)之至少1個角部分成為鈍角之方式而經切除之形狀或設成圓形感之形狀,或是具有使與主面垂直的端面之一部份往面內方向凹陷 之部分(缺口),或是主面內之一部份亦可具有經鏤空成圓形、橢圓形、多角形及此等組合等的形狀之穿孔部分。 The so-called "substantially rectangular" means that the circularly polarizing plate has a cut-out shape or a circular shape so that at least one corner portion of the four corners (corner portions) of each main surface becomes an obtuse angle. The shape may have a portion (notch) in which a part of the end surface perpendicular to the main surface is recessed inwardly, or a part of the main surface may have a hollow, oval, or multi-layered shape. Perforated portions of the shape of the corners and these combinations.
<偏光板> <Polarizer>
本發明之偏光板係意指:由偏光件及各別貼合於偏光件之兩面之保護膜所構成的積層體。偏光板所具備的保護膜可具有後述之硬塗層、抗反射層、抗靜電層等表面處理層。偏光件與保護膜可藉由例如接著劑層或黏著劑層而積層。關於偏光板所具備的構件,係說明如下。 The polarizing plate of the present invention means a laminated body composed of a polarizer and protective films attached to both sides of the polarizer. The protective film included in the polarizing plate may have a surface treatment layer such as a hard coat layer, an anti-reflection layer, and an antistatic layer described later. The polarizer and the protective film may be laminated by, for example, an adhesive layer or an adhesive layer. The components included in the polarizing plate are described below.
(1)偏光件 (1) Polarizer
偏光板所具備的偏光件可為具有下述性質之吸收型偏光件:會吸收具有與其吸收軸呈平行的振動面之直線偏光,並且會透射具有與吸收軸呈直交(與穿透軸呈平行)的振動面之直線偏光的性質。關於第1層所具有的偏光件,可適當地使用在經單軸拉伸之聚乙烯醇系樹脂膜中使二色性色素吸附配向而成的偏光件。偏光件可藉由包含下述步驟之方法製造:例如將聚乙烯醇系樹脂膜進行單軸拉伸之步驟;藉由將聚乙烯醇系樹脂膜以二色性色素進行染色而吸附二色性色素之步驟;將吸附有二色性色素之聚乙烯醇系樹脂膜以硼酸水溶液等交聯液進行處理之步驟;以及在經交聯液處理後予以水洗之步驟。 The polarizer provided in the polarizing plate may be an absorptive polarizer having the following properties: it can absorb linearly polarized light having a vibration plane parallel to its absorption axis, and can transmit and have a line orthogonal to the absorption axis (parallel to the transmission axis ) The nature of linearly polarized light on the vibrating surface. As the polarizer included in the first layer, a polarizer in which a dichroic dye is adsorbed and aligned in a uniaxially stretched polyvinyl alcohol-based resin film can be suitably used. The polarizer can be manufactured by a method including the steps of uniaxially stretching a polyvinyl alcohol-based resin film, and adsorbing dichroism by dyeing the polyvinyl alcohol-based resin film with a dichroic dye. A step of dyeing; a step of treating a polyvinyl alcohol-based resin film to which a dichroic dye is adsorbed with a crosslinking solution such as an aqueous boric acid solution; and a step of washing with water after the crosslinking solution is treated.
就聚乙烯醇系樹脂而言,可使用將聚乙酸乙烯酯系樹脂予以皂化者。就聚乙酸乙烯酯系樹脂而言,除了作為乙酸乙烯酯之均聚物的聚乙酸乙烯酯之外,亦可列舉如與可與乙酸乙烯酯共聚合之其他單體的共聚物等。所謂可與乙酸乙烯酯共聚合之其的單體之例,係可包含不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類及具有銨基的(甲基)丙烯醯胺類等。 As the polyvinyl alcohol-based resin, a polyvinyl acetate-based resin can be used. Examples of the polyvinyl acetate-based resin include, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, copolymers such as copolymers with other monomers copolymerizable with vinyl acetate. Examples of the monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth) acrylamidoamines having an ammonium group, and the like.
本說明書中,「(甲基)丙烯酸」係意指選自由丙烯酸及甲基丙烯酸之至少一者。「(甲基)丙烯醯基」、「(甲基)丙烯酸酯」等中亦相同。 In the present specification, "(meth) acrylic acid" means at least one selected from acrylic acid and methacrylic acid. The same applies to "(meth) acrylfluorenyl" and "(meth) acrylate".
聚乙烯醇系樹脂之皂化度通常係85至100mol%,以98mol%以上為佳。聚乙烯醇系樹脂可經改性,可使用例如經醛類改性的聚乙烯基縮甲醛(poly(vinyl formal))或聚乙烯基縮醛(poly(vinyl acetal))等。聚乙烯醇系樹脂之平均聚合度通常係1000至10000,以1500至5000為佳。聚乙烯醇系樹脂之平均聚合度可根據JIS K 6726求出。 The saponification degree of polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, aldehyde-modified polyvinyl formal (poly (vinyl formal)) or polyvinyl acetal (poly (vinyl acetal)) may be used. The average degree of polymerization of the polyvinyl alcohol resin is usually 1000 to 10,000, and preferably 1500 to 5000. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.
將如此之聚乙烯醇系樹脂予以製膜而成者,係作為偏光件之原膜來使用。將聚乙烯醇系樹脂予以製膜之方法,並無特別限定,係採用習知方法。聚乙烯醇系原膜之厚度並無特別限制,惟為了使偏光件之厚度成為15μm以下,以使用5至35μm者為佳。較佳為20μm以下。 A film formed of such a polyvinyl alcohol-based resin is used as an original film of a polarizer. The method for forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a conventional method is used. The thickness of the polyvinyl alcohol-based original film is not particularly limited, but in order to reduce the thickness of the polarizer to 15 μm or less, it is preferable to use 5 to 35 μm. It is preferably 20 μm or less.
聚乙烯醇系樹脂膜之單軸拉伸,可於二色性色素之染色前、與染色同時、或染色後進行。於染色後進行單軸拉伸時,此單軸拉伸可於交聯處理前或交聯處理中進行。此外,亦可於該等複數個階段中進行單軸拉伸。 The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing the dichroic pigment. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before or during the crosslinking treatment. In addition, uniaxial stretching may be performed in these plural stages.
在單軸拉伸中,可在周速相異之輥間進行單軸拉伸,亦可使用熱輥進行單軸拉伸。此外,單軸拉伸可為在大氣中進行拉伸的乾式拉伸,亦可為使用溶劑或水將聚乙烯醇系樹脂膜在膨潤的狀態下進行拉伸的濕式拉伸。拉伸倍率通常係3至8倍。 In uniaxial stretching, uniaxial stretching may be performed between rollers having different peripheral speeds, or uniaxial stretching may be performed using a hot roller. The uniaxial stretching may be dry stretching in the air, or wet stretching in which a polyvinyl alcohol-based resin film is stretched in a swollen state using a solvent or water. The stretching ratio is usually 3 to 8 times.
關於將聚乙烯醇系樹脂膜以二色性色素進行染色之方法,係採用例如將該膜浸漬於含有二色性色素之水溶液的方法。二色性色素係使 用碘或二色性有機染料。此外,對於聚乙烯醇系樹脂膜,較佳係在染色處理前先實施於水中之浸漬處理。 As a method of dyeing a polyvinyl alcohol-based resin film with a dichroic dye, for example, a method of dipping the film in an aqueous solution containing a dichroic dye is used. The dichroic pigments use iodine or a dichroic organic dye. The polyvinyl alcohol-based resin film is preferably immersed in water before being dyed.
關於在經二色性色素染色後的交聯處理,通常採用將經染色的聚乙烯醇系樹脂膜浸漬於含有硼酸之水溶液的方法。當使用碘作為二色性色素時,該含有硼酸之水溶液係以含有碘化鉀為佳。 For the cross-linking treatment after dichroic dyeing, a method of dipping a dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid is generally adopted. When iodine is used as the dichroic dye, the aqueous solution containing boric acid preferably contains potassium iodide.
偏光件之厚度通常係30μm以下,以15μm以下為佳,以13μm以下為較佳,以10μm以下為更佳,以8μm以下為特佳。尤其是若將偏光件之厚度設定於15μm以下,則會降低每單位面積之偏光板的水分量,而為有利。偏光件之厚度通常係2μm以上,以3μm以上為佳。 The thickness of the polarizer is usually 30 μm or less, preferably 15 μm or less, more preferably 13 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. In particular, if the thickness of the polarizer is set to 15 μm or less, the moisture content of the polarizer per unit area is reduced, which is advantageous. The thickness of the polarizer is usually 2 μm or more, and preferably 3 μm or more.
就偏光件而言,例如日本特開2016-170368號公報所記載,可使用在由液晶化合物所聚合成之硬化膜中配向有二色性色素者。就二色性色素而言,可使用在波長380至800nm之範圍內具有吸收者,以使用有機染料為佳。二色性色素可列舉例如偶氮化合物。液晶化合物為可在配向之狀態下進行聚合的液晶化合物,其可在分子內具有聚合性基。此外,如WO2011/024891所記載,可由具有液晶性之二色性色素來形成偏光件。 As for a polarizer, for example, as described in Japanese Patent Application Laid-Open No. 2016-170368, a dichroic pigment can be aligned in a cured film polymerized from a liquid crystal compound. As the dichroic pigment, those having an absorption in a wavelength range of 380 to 800 nm can be used, and an organic dye is preferably used. Examples of the dichroic pigment include azo compounds. The liquid crystal compound is a liquid crystal compound which can be polymerized in an aligned state, and may have a polymerizable group in a molecule. Moreover, as described in WO2011 / 024891, a polarizer can be formed from a dichroic pigment having liquid crystallinity.
(2)保護膜 (2) Protective film
以偏光件為基準,離位相差膜較遠側之保護膜(第1保護膜)的透濕度係以500g/m2‧24小時以下為佳,以200g/m2‧24小時以下為較佳,以100g/m2‧24小時以下為更佳,亦可為50g/m2‧24小時以下。下限值並無特別限定,惟通常係超過0g/m2‧24小時。 Based on polarizers, the moisture permeability of the protective film (first protective film) on the far side of the phase difference film is preferably 500 g / m 2 ‧ 24 hours or less, and more preferably 200 g / m 2 ‧ 24 hours or less It is more preferably 100 g / m 2 ‧ 24 hours or less, and 50 g / m 2 ‧ 24 hours or less. The lower limit is not particularly limited, but usually exceeds 0 g / m 2 ‧ 24 hours.
以偏光件為基準,離位相差膜較近側之保護膜(第2保護膜)的透濕度係以500g/m2‧24小時以下為佳,以200g/m2‧24小時以下為較 佳,以100g/m2‧24小時以下為更佳,亦可為50g/m2‧24小時以下。下限值並無特別限定,惟通常係超過0g/m2‧24小時。 Based on the polarizer, the moisture permeability of the protective film (second protective film) closer to the phase difference film is preferably 500 g / m 2 ‧ 24 hours or less, and more preferably 200 g / m 2 ‧ 24 hours or less It is more preferably 100 g / m 2 ‧ 24 hours or less, and 50 g / m 2 ‧ 24 hours or less. The lower limit is not particularly limited, but usually exceeds 0 g / m 2 ‧ 24 hours.
第1保護膜與第2保護膜可為相同的透濕度,亦可為相異的透濕度。透濕度可依據JIS Z0208之透濕度試驗(Dish方法)在溫度40℃、相對濕度90%之條件下測定。 The first protective film and the second protective film may have the same moisture permeability or different moisture permeability. The moisture permeability can be measured under the conditions of a temperature of 40 ° C and a relative humidity of 90% in accordance with the moisture permeability test (Dish method) of JIS Z0208.
積層於偏光件之兩面的保護膜,可為由具有透光性(較佳為光學透明)的熱可塑性樹脂所構成之膜,該熱可塑性樹脂可舉例如:如鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)般之聚烯烴系樹脂;如三乙醯纖維素、二乙醯纖維素般之纖維素系樹脂;如聚對酞酸乙二酯、聚對酞酸丁二酯般之聚酯系樹脂;聚碳酸酯系樹脂;如甲基丙烯酸甲酯系樹脂般之(甲基)丙烯酸系樹脂;聚苯乙烯系樹脂;聚氯乙烯系樹脂;丙烯腈-丁二烯-苯乙烯系樹脂;丙烯腈-苯乙烯系樹脂;聚乙酸乙烯酯系樹脂;聚二氯亞乙烯(polyvinylidene chloride)系樹脂;聚醯胺系樹脂;聚縮醛(polyacetal)系樹脂;改性聚伸苯醚系樹脂;聚碸系樹脂;聚醚碸系樹脂;聚芳酯系樹脂;聚醯胺醯亞胺系樹脂;聚醯亞胺系樹脂等。 The protective film laminated on both sides of the polarizer may be a film made of a thermoplastic resin having translucency (preferably optically transparent). The thermoplastic resin may be, for example, a chain-like polyolefin resin (poly Polypropylene resins such as acrylic resins, cyclic polyolefin resins (norbornene resins, etc.); cellulose resins such as triethyl cellulose and diethyl cellulose; such as polyparaphthalein Polyester resins such as ethylene glycol and polybutylene terephthalate; polycarbonate resins; (meth) acrylic resins such as methyl methacrylate resins; polystyrene resins; poly Vinyl chloride resin; Acrylonitrile-butadiene-styrene resin; Acrylonitrile-styrene resin; Polyvinyl acetate resin; Polyvinylidene chloride resin; Polyamide resin; Polyacetal resins; modified polyphenylene ether resins; polyfluorene resins; polyether resins; polyarylate resins; polyamide resins; polyimide resins; polyimide resins Wait.
就鏈狀聚烯烴系樹脂而言,除了如聚乙烯樹脂(作為乙烯之均聚物的聚乙烯樹脂、或以乙烯作為主體的共聚物)、聚丙烯樹脂(作為丙烯之均聚物的聚丙烯樹脂、或以丙烯作為主體的共聚物)等鏈狀烯烴之均聚物以外,亦可列舉由2種以上之鏈狀烯烴所構成的共聚物。 The chain polyolefin resins include, for example, polyethylene resins (polyethylene resins that are homopolymers of ethylene, or copolymers mainly composed of ethylene), and polypropylene resins (polypropylenes that are homopolymers of propylene). In addition to a homopolymer of a chain olefin such as a resin or a copolymer mainly composed of propylene), a copolymer composed of two or more kinds of chain olefins may also be mentioned.
環狀聚烯烴系樹脂係以環狀烯烴作為聚合單位而聚合成之樹脂的總稱,可列舉例如日本特開平1-240517號公報、日本特開平3-14882號公報、日本特開平3-122137號公報等所記載的樹脂。環狀聚烯烴系樹脂 之具體例,可列舉如環狀烯烴之開環(共)聚合物、環狀烯烴之加成聚合物、環狀烯烴與乙烯或丙烯等鏈狀烯烴之共聚物(其代表例為無規共聚物)、及將該等經不飽和羧酸或其衍生物改性的接枝聚合物,以及該等之氫化物。其中,適用者係使用降莰烯或多環降莰烯系單體等降莰烯系單體作為環狀烯烴的降莰烯系樹脂。 Cyclic polyolefin resin is a generic term for a resin polymerized by using a cyclic olefin as a polymerization unit, and examples thereof include Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 3-14882, and Japanese Patent Laid-Open No. 3-122137. Resin described in bulletins and the like. Specific examples of the cyclic polyolefin-based resin include a ring-opened (co) polymer of a cyclic olefin, an addition polymer of a cyclic olefin, and a copolymer of a cyclic olefin and a chain olefin such as ethylene or propylene (which Representative examples are random copolymers), graft polymers modified with unsaturated carboxylic acids or derivatives thereof, and hydrides thereof. Among them, a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer as the cyclic olefin is applicable.
就聚酯系樹脂而言,除了下述纖維素酯系樹脂以外,係具有酯鍵的樹脂,一般而言為由多元羧酸或其衍生物與多元醇之聚縮物所構成者。就多元羧酸或其衍生物而言,可使用2元之二羧酸或其衍生物,可列舉例如對酞酸、間酞酸、對酞酸二甲酯、萘二甲酸二甲酯。就多元醇而言,可使用2元之二醇,可列舉例如乙二醇、丙二醇、丁二醇、新戊二醇、環己烷二甲醇。聚酯系樹脂之代表例,可列舉作為對酞酸與乙二醇之聚縮物的聚對酞酸乙二酯。 The polyester resin is a resin having an ester bond in addition to the cellulose ester resin described below, and is generally a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. As the polycarboxylic acid or a derivative thereof, a divalent dicarboxylic acid or a derivative thereof can be used, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalate. As the polyhydric alcohol, a divalent diol can be used, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. Typical examples of the polyester-based resin include polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol.
(甲基)丙烯酸系樹脂係指以具有(甲基)丙烯醯基之化合物作為主要構成單體的樹脂。(甲基)丙烯酸系樹脂之具體例包含例如:如聚甲基丙烯酸甲酯般之聚(甲基)丙烯酸酯;甲基丙烯酸甲酯-(甲基)丙烯酸共聚物;甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物;甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物;(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等);甲基丙烯酸甲酯與具有脂環族烴基之化合物的共聚物(例如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降莰酯共聚物等)。較佳係使用以聚(甲基)丙烯酸甲酯等聚(甲基)丙烯酸C1-6烷酯作為主成分的聚合物,更佳係使用以甲基丙烯酸甲酯作為主成分(50至100重量%,以70至100重量%為佳)的甲基丙烯酸甲酯系樹脂。 The (meth) acrylic resin refers to a resin containing a compound having a (meth) acrylfluorenyl group as a main constituent monomer. Specific examples of the (meth) acrylic resin include, for example, poly (meth) acrylate such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic copolymer; methyl methacrylate- (Meth) acrylate copolymer; methyl methacrylate-acrylate- (meth) acrylate copolymer; methyl (meth) acrylate-styrene copolymer (MS resin, etc.); methyl methacrylate and Copolymers of compounds having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth) acrylate copolymer, etc.). It is preferable to use a polymer containing poly (meth) acrylic acid C 1-6 alkyl ester such as poly (meth) acrylate as a main component, and more preferably to use a polymer containing methyl methacrylate as a main component (50 to 100). % By weight, preferably 70 to 100% by weight) of a methyl methacrylate resin.
纖維素酯系樹脂為纖維素與脂肪酸之酯。纖維素酯系樹脂之具體例包含三乙酸纖維素、二乙酸纖維素、三丙酸纖維素、二丙酸纖維素。此外,亦可列舉該等之共聚物、或是羥基之一部份經其他取代基修飾者。該等之中,以三乙酸纖維素(亦即三乙醯纖維素)為特佳。 The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. In addition, these copolymers or those in which a part of the hydroxyl group is modified by other substituents can also be listed. Among these, cellulose triacetate (that is, triethyl cellulose) is particularly preferred.
聚碳酸酯系樹脂係由「使單體單元隔著碳酸酯基而結合成之聚合物」所構成的工程塑膠。 Polycarbonate-based resins are engineering plastics composed of "polymers in which monomer units are bonded through carbonate groups".
關於保護膜之位相差值,將其控制成對於液晶顯示裝置等影像顯示裝置為適合的值係亦為有用。例如,在橫向電場效應顯示技術(IPS)模式之液晶顯示裝置中,以使用位相差值實質上為零的膜作為保護膜為佳。所謂位相差值實質上為零係意指:在波長550nm中之面內位相差值Re(550)為10nm以下,在波長550nm中之厚度方向位相差值Rth之絕對值為10nm以下。以在波長480至750nm中之厚度方向位相差值Rth之絕對值為15nm以下為佳。此外,為了提高當使用者有戴偏光太陽鏡等時之影像可見度,亦可將在波長550nm中之面內位相差值Re(550)設為70至140nm。 Regarding the phase difference value of the protective film, it is also useful to control it to a value suitable for an image display device such as a liquid crystal display device. For example, in a liquid crystal display device in a lateral electric field effect display technology (IPS) mode, it is preferable to use a film having a phase difference value of substantially zero as a protective film. The fact that the phase difference value is substantially zero means that the in-plane phase difference value Re (550) at a wavelength of 550 nm is 10 nm or less, and the absolute value of the phase difference value Rth in the thickness direction at a wavelength of 550 nm is 10 nm or less. The absolute value of the phase difference value Rth in the thickness direction at a wavelength of 480 to 750 nm is preferably 15 nm or less. In addition, in order to improve the visibility of the image when the user is wearing polarized sunglasses, etc., the in-plane phase difference value Re (550) at a wavelength of 550 nm can also be set to 70 to 140 nm.
例如可依據液晶顯示裝置之模式,對於保護膜進行拉伸及/或收縮加工等,以賦予適合的位相差。例如若以視角補償之目的而言,可使用單層或多層構造的位相差層(或膜)作為保護膜。 For example, according to the mode of the liquid crystal display device, the protective film may be subjected to stretching and / or shrinking processing, etc., so as to give a suitable phase difference. For example, for the purpose of viewing angle compensation, a phase difference layer (or film) having a single-layer or multi-layer structure can be used as a protective film.
保護膜之厚度通常係1至100μm,惟就強度及處理性等之觀點而言,以5至60μm為佳,以10至55μm為較佳,以15至40μm為更佳。 The thickness of the protective film is usually 1 to 100 μm, but from the viewpoints of strength and handleability, it is preferably 5 to 60 μm, more preferably 10 to 55 μm, and even more preferably 15 to 40 μm.
貼合於偏光件之兩面的保護膜,可由同種的熱可塑性樹脂所構成,亦可由異種的熱可塑性樹脂所構成。此外,厚度可相同或相異。再者,可具有相同的位相差特性,亦可具有相異的位相差特性。 The protective films attached to both sides of the polarizer may be made of the same kind of thermoplastic resin, or they may be made of different kinds of thermoplastic resin. In addition, the thicknesses may be the same or different. Furthermore, they may have the same phase difference characteristics, or they may have different phase difference characteristics.
如上述般,保護膜之至少任一者,可在其外表面(與偏光件為相反側之面)具備如硬塗層、防眩層、光擴散層、抗反射層、低折射率層、抗靜電層、防汙層等表面處理層(塗層)。此外,保護膜之厚度係包含表面處理層之厚度。 As described above, at least one of the protective films may be provided with a hard coat layer, an anti-glare layer, a light diffusion layer, an anti-reflection layer, a low refractive index layer, Surface treatment layer (coating) such as antistatic layer and antifouling layer. The thickness of the protective film includes the thickness of the surface treatment layer.
保護膜可隔著例如接著劑層或黏著劑層而與偏光件貼合。關於形成接著劑層之接著劑,係可使用水系接著劑、活性能量線硬化性接著劑或熱硬化性接著劑,以水系接著劑、活性能量線硬化性接著劑為佳。黏著劑層係可使用後述者。 The protective film may be bonded to the polarizer via, for example, an adhesive layer or an adhesive layer. As the adhesive for forming the adhesive layer, a water-based adhesive, an active energy ray-curable adhesive, or a thermosetting adhesive can be used, and a water-based adhesive and an active energy ray-curable adhesive are preferred. As the adhesive layer, the latter can be used.
就水系接著劑而言,可列舉由聚乙烯醇系樹脂水溶液所構成之接著劑、水系二液型胺甲酸乙酯系乳液接著劑等。其中,適合使用由聚乙烯醇系樹脂水溶液所構成的水系接著劑。就聚乙烯醇系樹脂而言,除了可使用將作為乙酸乙烯酯之均聚物的聚乙酸乙烯酯進行皂化處理而得的乙烯醇均聚物以外,亦可使用將乙酸乙烯酯及可與其共聚合的其他單體之共聚物進行皂化處理而得的聚乙烯醇系共聚物、或者是將該等之羥基進行部分性改性的改性聚乙烯醇系聚合物等。水系接著劑可包含醛化合物(乙二醛等)、環氧化合物、三聚氰胺系化合物、羥甲基化合物、異氰酸酯化合物、胺化合物、多價金屬鹽等交聯劑。 Examples of the water-based adhesive include an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, and a water-based two-liquid urethane-based emulsion adhesive. Among them, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is suitably used. As the polyvinyl alcohol-based resin, in addition to a vinyl alcohol homopolymer obtained by saponifying a polyvinyl acetate, which is a homopolymer of vinyl acetate, vinyl acetate and a copolymer of vinyl acetate A polyvinyl alcohol-based copolymer obtained by saponifying a copolymer of another polymerized monomer, or a modified polyvinyl alcohol-based polymer in which these hydroxyl groups are partially modified. The water-based adhesive may include a crosslinking agent such as an aldehyde compound (glyoxal, etc.), an epoxy compound, a melamine-based compound, a methylol compound, an isocyanate compound, an amine compound, or a polyvalent metal salt.
使用水系接著劑時,較佳係在將偏光件與保護膜貼合後實施用以除去水系接著劑中含有的水的乾燥步驟。乾燥步驟後,可設定例如在20至45℃之溫度下熟化的熟化步驟。 When using a water-based adhesive, it is preferable to perform a drying step to remove water contained in the water-based adhesive after bonding the polarizer and the protective film. After the drying step, an aging step can be set, for example, at a temperature of 20 to 45 ° C.
上述活性能量線硬化性接著劑係指含有會因如紫外線、可視光、電子束、X射線等活性能量線之照射而硬化的硬化性化合物之接著劑,以紫外線硬化性接著劑為佳。 The above-mentioned active energy ray-curable adhesive refers to an adhesive containing a curable compound that is cured by irradiation of active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays, and an ultraviolet-curable adhesive is preferred.
上述硬化性化合物可為陽離子聚合性之硬化性化合物或自由基聚合性之硬化性化合物。陽離子聚合性之硬化性化合物可列舉例如環氧系化合物(分子內具有1個或2個以上之環氧基的化合物)、氧雜環丁烷(oxetane)系化合物(分子內具有1個或2個以上之氧雜環丁烷環的化合物)、或此等之組合。自由基聚合性之硬化性化合物可列舉例如(甲基)丙烯酸系化合物(分子內具有1個或2個以上之(甲基)丙烯醯基氧基的化合物)、具有自由基聚合性雙鍵的其他乙烯系化合物、或此等之組合。亦可將陽離子聚合性之硬化性化合物與自由基聚合性之硬化性化合物併用。活性能量線硬化性接著劑通常更包含使上述硬化性化合物之硬化反應開始的陽離子聚合起始劑及/或自由基聚合起始劑。 The curable compound may be a cation polymerizable curable compound or a radical polymerizable curable compound. Examples of the cationically polymerizable curable compound include epoxy compounds (compounds having one or two or more epoxy groups in the molecule), and oxetane compounds (having one or two in the molecule). More than one oxetane ring compound), or combinations thereof. Examples of the radically polymerizable sclerosing compound include (meth) acrylic compounds (compounds having one or two (meth) acrylfluorenyloxy groups in the molecule), and radically polymerizable double bonds. Other vinyl compounds, or combinations thereof. A cationically polymerizable curable compound and a radical polymerizable curable compound may be used in combination. The active energy ray-curable adhesive usually further contains a cationic polymerization initiator and / or a radical polymerization initiator that starts the curing reaction of the curable compound.
在將偏光件與保護膜貼合時,為了提高接著性,可於此等之至少任一方之貼合面實施表面活性化處理。表面活性化處理可列舉如:電暈處理、電漿處理、放電處理(輝光放電處理等)、火焰處理、臭氧處理、UV臭氧處理、電離活性線處理(紫外線處理、電子束處理等)等乾式處理;如使用水或丙酮等溶媒的超音波處理、皂化處理、錨塗(Anchor Coat)處理等濕式處理。此等表面活性化處理可單獨進行,亦可組合2種以上。 When the polarizer and the protective film are bonded, in order to improve the adhesion, a surface activation treatment may be performed on at least one of the bonding surfaces. Examples of surface activation treatments include dry methods such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment, etc.), flame treatment, ozone treatment, UV ozone treatment, ionization active line treatment (ultraviolet treatment, electron beam treatment, etc.) Treatment: such as ultrasonic treatment using a solvent such as water or acetone, saponification treatment, anchor coating (Anchor Coat) treatment and other wet treatment. These surface activation treatments may be performed alone or in combination of two or more.
於偏光件之兩面貼合保護膜時,用以貼合此等保護膜之接著劑係可為同種的接著劑,亦可為異種的接著劑。 When the protective film is laminated on both sides of the polarizer, the adhesive used to attach the protective film may be the same kind of adhesive, or it may be a different kind of adhesive.
<位相差膜> <Phase difference film>
位相差膜具有由包含聚合性液晶化合物之組成物所構成的層。由包含聚合性液晶化合物之組成物所構成的層,具體而言,係意指由聚合性液晶化合物所硬化成之層。本說明書中,有時係將賦予λ/2之位相差的層、賦予λ/4之位相差的層(正A層)及正C層等總稱為位相差層。更且,位相差膜可包含後述基材、配向膜。 The phase difference film has a layer composed of a composition containing a polymerizable liquid crystal compound. The layer composed of a composition containing a polymerizable liquid crystal compound, specifically, means a layer hardened by a polymerizable liquid crystal compound. In this specification, a layer giving a phase difference of λ / 2, a layer giving a phase difference of λ / 4 (positive A layer), and a positive C layer may be collectively referred to as a phase difference layer. Furthermore, the phase difference film may include a substrate and an alignment film described later.
由聚合性液晶化合物所硬化成之層,係形成在例如設置於基材之配向膜上。前述基材具有支撐配向膜之功能,可為形成為長條基材。該基材具有作為脫模性支撐體之功能,可支撐用以轉印之位相差層。更且,係以其表面具有可剝離之程度的接著力者為佳。前述基材可列舉如作為上述保護膜之材料所例示的樹脂膜。 The layer hardened by the polymerizable liquid crystal compound is formed on, for example, an alignment film provided on a substrate. The aforementioned substrate has a function of supporting the alignment film, and may be formed into a long substrate. The substrate has a function as a release support, and can support a phase difference layer for transfer. Furthermore, it is preferable that the surface has a degree of peeling adhesion. Examples of the substrate include a resin film exemplified as a material of the protective film.
基材之厚度係無特別限定,惟以設定為例如20μm以上200μm以下之範圍為佳。若基材之厚度係20μm以上,則賦予強度。另一方面,若厚度係200μm以下,則在將基材進行剪裁加工而製成片狀基材時,可抑制加工屑的増加、剪裁刀的磨耗。 The thickness of the substrate is not particularly limited, but is preferably set to a range of, for example, 20 μm to 200 μm. When the thickness of the substrate is 20 μm or more, strength is imparted. On the other hand, when the thickness is 200 μm or less, when the substrate is subjected to a cutting process to form a sheet-like substrate, it is possible to suppress an increase in processing dust and abrasion of the cutting blade.
此外,基材可實施各種抗結塊(anti-blocking)處理。抗結塊處理可列舉例如易接著處理、捏合填料等之處理、壓紋加工(滾紋處理)等。藉由對基材實施如此之抗結塊處理,當捲取基材時,可有效地防止基材彼此之間的黏附,亦即所謂的結塊,並可以生產性高之方式生產光學膜。 In addition, the substrate may be subjected to various anti-blocking treatments. Examples of the anti-caking treatment include easy adhesion treatment, treatment of kneading fillers, and embossing (rolling treatment). By implementing such an anti-blocking treatment on the substrate, when the substrate is wound, the substrates can be effectively prevented from adhering to each other, so-called blocking, and an optical film can be produced in a highly productive manner.
由聚合性液晶化合物所硬化成之層,係隔著配向膜而形成於基材上。亦即,以基材、配向膜之順序積層,由液晶化合物所硬化成之層係積層於前述配向膜上。 A layer hardened by a polymerizable liquid crystal compound is formed on a substrate through an alignment film. That is, the substrate and the alignment film are laminated in this order, and a layer system hardened by a liquid crystal compound is laminated on the alignment film.
此外,就配向膜而言,並非限定於垂直配向膜,而可為將聚合性液晶化合物之分子軸予以水平配向的配向膜,亦可為將聚合性液晶化合物之分子軸予以傾斜配向的配向膜。就配向膜而言,較佳係具有不會因包含後述聚合性液晶化合物之組成物的塗佈等而溶解的溶媒耐性,並且具有在用以除去溶媒或配向液晶化合物之加熱處理中的耐熱性。配向膜可列舉:包含配向性聚合物之配向膜、在光配向膜及表面形成凹凸圖案或複數個溝並經配向之槽配向膜。配向膜之厚度通常為10nm至10000nm之範圍,以10nm至1000nm之範圍為佳,以500nm以下為較佳,以10nm至200nm之範圍為更佳。 In addition, the alignment film is not limited to a vertical alignment film, but may be an alignment film in which the molecular axis of the polymerizable liquid crystal compound is horizontally aligned, or an alignment film in which the molecular axis of the polymerizable liquid crystal compound is inclined. . The alignment film preferably has solvent resistance that does not dissolve due to application of a composition including a polymerizable liquid crystal compound described later, and heat resistance during heat treatment for removing the solvent or the alignment liquid crystal compound. . Examples of the alignment film include an alignment film containing an alignment polymer, a groove alignment film that forms a concave-convex pattern or a plurality of grooves on the photo-alignment film and the surface and is aligned. The thickness of the alignment film is usually in a range of 10 nm to 10000 nm, preferably in a range of 10 nm to 1000 nm, more preferably 500 nm or less, and even more preferably in a range of 10 nm to 200 nm.
用於配向膜之樹脂,只要係作為習知配向膜之材料所用的樹脂即可,並無特別限定,可使用將以往習知之單官能或多官能之(甲基)丙烯酸酯系單體在聚合起始劑下硬化而成的硬化物等。具體而言,就(甲基)丙烯酸酯系單體而言,可例示例如丙烯酸2-乙基己酯、丙烯酸環己酯、丙烯酸二乙二醇單2-乙基己基醚酯、丙烯酸二乙二醇單苯基醚酯、丙烯酸四乙二醇單苯基醚酯、三丙烯酸三羥甲基丙烷酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸異莰酯、甲基丙烯酸異莰酯、丙烯酸2-苯氧基乙酯、丙烯酸四氫呋喃甲酯、丙烯酸2-羥基丙酯、丙烯酸苄酯、甲基丙烯酸四氫呋喃甲酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸苄酯、甲基丙烯酸環己酯、甲基 丙烯酸酯、胺甲酸乙酯丙烯酸酯等。此外,就樹脂而言,可為此等之1種類,亦可為2種類以上的混合物。 The resin used for the alignment film is not particularly limited as long as it is a resin used as a material of a conventional alignment film, and conventionally known monofunctional or polyfunctional (meth) acrylate monomers can be polymerized. A hardened product obtained by curing under an initiator. Specifically, as the (meth) acrylate-based monomer, 2-ethylhexyl acrylate, cyclohexyl acrylate, diethylene glycol mono 2-ethylhexyl ether acrylate, and diethyl acrylate can be exemplified. Glycol monophenyl ether, tetraethylene glycol monophenyl ether, trimethylolpropane triacrylate, lauryl acrylate, lauryl methacrylate, isoamyl acrylate, isoamyl methacrylate, 2-phenoxyethyl acrylate, tetrahydrofuran methyl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, tetrahydrofuran methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, methacrylic acid Cyclohexyl, methacrylate, urethane acrylate, and the like. The resin may be one of these types or a mixture of two or more types.
關於本實施形態中所使用的聚合性液晶化合物之種類,並無特別限定,可從其形狀分類成棒狀型(棒狀液晶化合物)與圓盤狀型(圓盤狀液晶化合物、盤狀液晶化合物)。更且,各別有低分子型與高分子型。此外,一般而言,高分子係意指聚合度為100以上者(高分子物理‧相轉移動力學、土井正男著、2頁、岩波書店、1992)。 The type of the polymerizable liquid crystal compound used in this embodiment is not particularly limited, and can be classified into a rod-like type (rod-like liquid crystal compound) and a disk-like type (disk-like liquid crystal compound, disk-like liquid crystal) from its shape. Compound). Moreover, there are a low molecular type and a high molecular type, respectively. In addition, in general, a polymer means a polymer having a degree of polymerization of 100 or more (Polymer Physics, Phase Transition Kinetics, Masai Doi, 2 pages, Iwanami Bookstore, 1992).
本實施形態中可使用任何聚合性液晶化合物。更且,可使用2種以上之棒狀液晶化合物、2種以上之圓盤狀液晶化合物、或棒狀液晶化合物與圓盤狀液晶化合物之混合物。 Any polymerizable liquid crystal compound can be used in this embodiment. Furthermore, two or more rod-shaped liquid crystal compounds, two or more disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound can be used.
此外,就棒狀液晶化合物而言,可適宜使用例如日本特表平11-513019號公報之請求項1、或日本特開2005-289980號公報之段落[0026]至[0098]所記載者。就圓盤狀液晶化合物而言,可適宜使用例如日本特開2007-108732號公報之段落[0020]至[0067]、或日本特開2010-244038號公報之段落[0013]至[0108]所記載者。 In addition, as for the rod-shaped liquid crystal compound, for example, those described in claim 1 of Japanese Patent Application Publication No. 11-513019 or paragraphs [0026] to [0098] of Japanese Patent Application Publication No. 2005-289980 can be suitably used. As for the discotic liquid crystal compound, for example, paragraphs [0020] to [0067] of Japanese Patent Laid-Open No. 2007-108732, or paragraphs [0013] to [0108] of Japanese Patent Laid-Open No. 2010-244038 can be suitably used. Recorder.
聚合性液晶化合物可併用2種類以上。在此情形下,至少1種類係在分子內具有2個以上之聚合性基。亦即,前述由聚合性液晶化合物所硬化成之層,較佳係使具有聚合性基之液晶化合物藉由聚合而固定並形成的層。在此情形下,在成層之後就已不需顯示液晶性。 The polymerizable liquid crystal compound may be used in combination of two or more kinds. In this case, at least one species has two or more polymerizable groups in the molecule. That is, the layer hardened by the polymerizable liquid crystal compound is preferably a layer in which a liquid crystal compound having a polymerizable group is fixed by polymerization. In this case, it is no longer necessary to display liquid crystal properties after layer formation.
聚合性液晶化合物具有可進行聚合反應之聚合性基。就聚合性基而言,係以例如聚合性乙烯性不飽和基或環聚合性基等可進行加成聚合反應的官能基為佳。更具體而言,聚合性基可列舉例如(甲基)丙烯醯基、 乙烯基、苯乙烯基、烯丙基等。其中,以(甲基)丙烯醯基為佳。此外,(甲基)丙烯醯基意指包含甲基丙烯醯基及丙烯醯基之兩者的概念。 The polymerizable liquid crystal compound has a polymerizable group capable of undergoing a polymerization reaction. The polymerizable group is preferably a functional group capable of performing an addition polymerization reaction such as a polymerizable ethylenically unsaturated group or a cyclic polymerizable group. More specifically, examples of the polymerizable group include (meth) acrylfluorenyl, vinyl, styryl, and allyl. Among them, a (meth) acrylfluorenyl group is preferred. Further, (meth) acrylfluorenyl means a concept including both a methacrylfluorenyl group and an acrylfluorenyl group.
由聚合性液晶化合物所硬化成之層,如後所述,可藉由將包含聚合性液晶化合物之組成物塗佈於例如配向膜上而形成。前述組成物可包含上述聚合性液晶化合物以外的成分。例如,前述組成物以包含聚合起始劑為佳。所使用之聚合起始劑,可因應聚合反應之形式而選擇例如熱聚合起始劑、光聚合起始劑。光聚合起始劑可列舉例如α-羰基化合物、醯偶姻醚(Acyloin ether)、α-烴取代的芳香族醯偶姻化合物、多核醌化合物、三芳基咪唑二聚物與對胺基苯基酮之組合等。聚合起始劑之使用量,相對於前述塗佈液中之全固形份,以0.01至20質量%為佳,以0.5至5質量%為較佳。 The layer hardened from the polymerizable liquid crystal compound can be formed by applying a composition containing the polymerizable liquid crystal compound on, for example, an alignment film as described later. The said composition may contain components other than the said polymerizable liquid crystal compound. For example, the aforementioned composition preferably contains a polymerization initiator. The polymerization initiator used can be selected according to the form of the polymerization reaction, such as a thermal polymerization initiator and a photopolymerization initiator. Examples of the photopolymerization initiator include α-carbonyl compounds, Acyloin ether, α-hydrocarbon-substituted aromatic compounds, polynuclear quinone compounds, triarylimidazole dimers, and p-aminophenyl groups. A combination of ketones and the like. The amount of the polymerization initiator used is preferably 0.01 to 20% by mass, and more preferably 0.5 to 5% by mass relative to the total solids content in the coating liquid.
此外,就塗佈膜之均勻性及膜之強度的觀點而言,前述組成物中可包含聚合性單體。聚合性單體可列舉如自由基聚合性或陽離子聚合性之化合物。其中,以多官能性自由基聚合性單體為佳。 From the viewpoint of the uniformity of the coating film and the strength of the film, the polymerizable monomer may be contained in the composition. Examples of the polymerizable monomer include radically polymerizable and cationically polymerizable compounds. Among them, a polyfunctional radical polymerizable monomer is preferred.
另外,就聚合性單體而言,係以可與上述聚合性液晶化合物進行共聚合者為佳。具體而言,聚合性單體可列舉例如日本特開2002-296423號公報中之段落[0018]至[0020]所記載者。聚合性單體之使用量,相對於聚合性液晶化合物之全質量,以1至50質量%為佳,以2至30質量%為較佳。 The polymerizable monomer is preferably one which can be copolymerized with the polymerizable liquid crystal compound. Specific examples of the polymerizable monomer include those described in paragraphs [0018] to [0020] in Japanese Patent Application Laid-Open No. 2002-296423. The use amount of the polymerizable monomer is preferably 1 to 50% by mass, and more preferably 2 to 30% by mass relative to the total mass of the polymerizable liquid crystal compound.
此外,就塗佈膜之均勻性及膜之強度的觀點而言,前述組成物中可包含界面活性劑。作為界面活性劑,可列舉以往習知的化合物。其中,以氟系化合物為特佳。具體而言,作為界面活性劑,可列舉例如日本 特開2001-330725號公報中之段落[0028]至[0056]所記載的化合物、特願2003-295212號說明書中之段落[0069]至[0126]所記載的化合物。 From the viewpoint of the uniformity of the coating film and the strength of the film, a surfactant may be contained in the composition. Examples of the surfactant include conventionally known compounds. Among them, a fluorine-based compound is particularly preferred. Specifically, examples of the surfactant include compounds described in paragraphs [0028] to [0056] in Japanese Patent Application Laid-Open No. 2001-330725, and paragraphs [0069] to [0069] in Japanese Patent Application No. 2003-295212. 0126] The compound as described.
此外,前述組成物中可包含溶媒,以使用有機溶媒為佳。有機溶媒可列舉例如醯胺(例如N,N-二甲基甲醯胺)、亞碸(例如二甲基亞碸)、雜環化合物(例如吡啶)、烴(例如苯、己烷)、鹵烷(例如氯仿、二氯甲烷)、酯(例如乙酸甲酯、乙酸乙酯、乙酸丁酯)、酮(例如丙酮、甲基乙基酮)、醚(例如四氫呋喃、1,2-二甲氧基乙烷)。其中,以鹵烷、酮為佳。此外,可併用2種類以上之有機溶媒。 A solvent may be contained in the composition, and an organic solvent is preferably used. Examples of the organic solvent include amidine (e.g., N, N-dimethylformamide), fluorene (e.g., dimethylformamide), heterocyclic compounds (e.g., pyridine), hydrocarbons (e.g., benzene, hexane), halogen Alkanes (e.g. chloroform, dichloromethane), esters (e.g. methyl acetate, ethyl acetate, butyl acetate), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. tetrahydrofuran, 1,2-dimethoxy) Ethane). Of these, haloalkanes and ketones are preferred. In addition, two or more kinds of organic solvents may be used in combination.
另外,前述組成物中可包含各種配向劑,例如:偏光件界面側垂直配向劑、空氣界面側垂直配向劑等垂直配向促進劑,以及偏光件界面側水平配向劑、空氣界面側水平配向劑等水平配向促進劑。更且,前述組成物中,除了上述成分以外,亦可包含密著改良劑、塑化劑、聚合物等。 In addition, the aforementioned composition may include various kinds of alignment agents, for example, vertical alignment accelerators such as polarizer interface-side vertical alignment agents, air interface-side vertical alignment agents, and horizontal alignment agents on polarizer interface-side and air-interface-side horizontal alignment agents. Horizontal alignment promoter. Furthermore, the composition may contain, in addition to the above-mentioned components, an adhesion improver, a plasticizer, a polymer, and the like.
本實施形態中,位相差層之厚度以0.5μm以上為佳。此外,前述位相差層之厚度以10μm以下為佳,以5μrm以下為較佳。另外,上述之上限值及下限值可任意組合。若位相差層之厚度在前述下限值以上,則可獲得充分的耐久性。若位相差層之厚度在前述上限值以下,則有助於圓偏光板之薄層化。關於位相差層之厚度,可予以調整,以獲得賦予λ/4之位相差的層、賦予λ/2之位相差的層或正C層之期望的面內位相差值、以及厚度方向之位相差值。 In this embodiment, the thickness of the phase difference layer is preferably 0.5 μm or more. The thickness of the phase difference layer is preferably 10 μm or less, and more preferably 5 μrm or less. In addition, the above upper limit and lower limit may be arbitrarily combined. When the thickness of the phase difference layer is at least the aforementioned lower limit, sufficient durability can be obtained. If the thickness of the phase difference layer is below the aforementioned upper limit value, it will contribute to the thinning of the circular polarizing plate. Regarding the thickness of the phase difference layer, it can be adjusted to obtain the desired phase difference value of the layer giving a phase difference of λ / 4, the layer giving a phase difference of λ / 2 or the positive C layer, and the phase in the thickness direction. Difference.
位相差膜可為包含1層由聚合性液晶化合物所硬化成之層者,亦可為包含2層以上之由聚合性液晶化合物所硬化成之層者。當位相差膜包含2層由聚合性液晶化合物所硬化成之層時,以2層為「賦予λ/4 之位相差的層及正C層」或「賦予λ/4之位相差的層及賦予λ/2之位相差的層」為佳。當位相差膜包含2層由聚合性液晶化合物所硬化成之層時,可將由聚合性液晶化合物所硬化成之層各別製作在配向膜上,並隔著接著劑層或黏著劑層來積層兩者,藉此而製造位相差膜。積層兩者後,可剝離基材及配向膜。位相差膜之厚度以3至30μm為佳,以5至25μm為較佳。 The phase difference film may be one including one layer hardened by a polymerizable liquid crystal compound, or one including two or more layers hardened by a polymerizable liquid crystal compound. When the phase difference film includes two layers hardened by a polymerizable liquid crystal compound, the two layers are referred to as "a layer giving a phase difference of λ / 4 and a positive C layer" or "a layer giving a phase difference of λ / 4 and A layer with a phase difference of λ / 2 is preferred. When the phase difference film includes two layers hardened by a polymerizable liquid crystal compound, the layers hardened by the polymerizable liquid crystal compound can be individually made on an alignment film, and laminated through an adhesive layer or an adhesive layer. Both, thereby manufacturing a phase difference film. After both layers are laminated, the substrate and the alignment film can be peeled off. The thickness of the phase difference film is preferably 3 to 30 μm, and more preferably 5 to 25 μm.
<黏著劑層> <Adhesive layer>
黏著劑層可由以(甲基)丙烯酸系、橡膠系、胺甲酸乙酯(urethane)系、酯系、聚矽氧(silicone)系、聚乙烯醚系般之樹脂作為主成分的黏著劑組成物所構成。其中,較佳係以透明性、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。黏著劑層之厚度通常係3至30μm,以3至25μm為佳。 The adhesive layer may include an adhesive composition containing a (meth) acrylic-based, rubber-based, urethane-based, ester-based, silicone-based, or polyvinyl ether-based resin as a main component. Made up. Among these, an adhesive composition using a (meth) acrylic resin excellent in transparency, weather resistance, and heat resistance as a base polymer is preferred. The adhesive composition may be an active energy ray hardening type or a thermosetting type. The thickness of the adhesive layer is usually 3 to 30 μm, preferably 3 to 25 μm.
關於黏著劑組成物中所用的(甲基)丙烯酸系樹脂(基礎聚合物),可適宜使用例如以(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-乙基己酯等(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。在基礎聚合物中,較佳係將極性單體予以共聚合。極性單體可列舉例如(甲基)丙烯酸酯、(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)丙烯酸環氧丙酯等具有羧基、羥基、醯胺基、胺基、環氧基等的單體。 As the (meth) acrylic resin (base polymer) used in the adhesive composition, for example, butyl (meth) acrylate, ethyl (meth) acrylate, and isooctyl (meth) acrylate can be suitably used. A polymer or copolymer of one or two or more (meth) acrylates such as 2-ethylhexyl (meth) acrylate and the like. In the base polymer, a polar monomer is preferably copolymerized. Examples of the polar monomer include (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, and N, N- (meth) acrylate Monomers having a carboxyl group, a hydroxyl group, an amino group, an amine group, an epoxy group, and the like, such as dimethylaminoethyl ester and glycidyl (meth) acrylate.
黏著劑組成物可為僅包含上述基礎聚合物者,惟通常更含有交聯劑。交聯劑可例示如:2價以上之金屬離子,且與羧基之間會形成羧酸 金屬鹽者;聚胺化合物,且與羧基之間會形成醯胺鍵者;聚環氧化合物或多元醇,且與羧基之間會形成酯鍵者;聚異氰酸酯化合物,且與羧基之間會形成醯胺鍵者。其中,以聚異氰酸酯化合物為佳。 The adhesive composition may include only the above-mentioned base polymer, but usually further contains a crosslinking agent. Examples of the cross-linking agent include: a metal ion having a valence of two or more, and a carboxylic acid metal salt formed with a carboxyl group; a polyamine compound, and a amide bond formed with a carboxyl group; a polyepoxide compound or a polyhydric alcohol Those who form an ester bond with a carboxyl group; those who are polyisocyanate compounds and form a amide bond with a carboxyl group. Among them, a polyisocyanate compound is preferred.
<前面板> <Front panel>
前面板係配置於偏光板之視認側。前面板可隔著接著層而積層於偏光板。接著層可列舉例如前述之黏著劑層及接著劑層。如第2圖(a)、(b)所示,前面板4可隔著黏著劑層16而積層於偏光板1之第1保護膜11上。 The front panel is arranged on the viewing side of the polarizing plate. The front panel may be laminated on the polarizing plate via an adhesive layer. Examples of the adhesive layer include the aforementioned adhesive layer and adhesive layer. As shown in FIGS. 2 (a) and 2 (b), the front panel 4 may be laminated on the first protective film 11 of the polarizing plate 1 via an adhesive layer 16.
在圓偏光板積層有前面板時,來自圓偏光板之反射光容易變色為紅色。推測係因前面板多為低透濕度,偏光板中含有的水分易於積聚所致。因此,本發明之圓偏光板在具備前面板時會呈現顯著的效果。 When a circular polarizing plate is laminated with a front panel, the reflected light from the circular polarizing plate is easily discolored to red. It is presumed that most of the front panel has low moisture permeability, and the moisture contained in the polarizing plate is likely to accumulate. Therefore, the circular polarizing plate of the present invention exhibits a significant effect when it has a front panel.
前面板可列舉在玻璃、樹脂膜之至少一面包含硬塗層者等。玻璃可使用例如高穿透玻璃、強化玻璃。尤其是使用薄的透明面材時,以經實施化學強化的玻璃為佳。玻璃之厚度可設定為例如100μm至5mm。 Examples of the front panel include a hard coat layer on at least one side of glass and a resin film. As the glass, for example, high-penetration glass and tempered glass can be used. In particular, when a thin transparent surface material is used, chemically strengthened glass is preferred. The thickness of the glass can be set to, for example, 100 μm to 5 mm.
在樹脂膜之至少一面包含硬塗層而成的前面板,不像現有的玻璃般堅硬,其可具有可撓的特性。硬塗層之厚度並無特別限定,可為例如5至100μm。 The front panel including a hard coating layer on at least one side of the resin film is not as hard as existing glass, and may have flexible characteristics. The thickness of the hard coat layer is not particularly limited, and may be, for example, 5 to 100 μm.
就樹脂膜而言,可為由下述高分子所形成的膜:具有如降莰烯或多環降莰烯系單體等包含環烯烴之單體之單位的環烯烴系衍生物、纖維素(二乙醯纖維素、三乙醯纖維素、乙酸丁酸纖維素、異丁酯纖維素、丙醯纖維素、丁醯纖維素、乙醯丙醯纖維素、乙烯-乙酸乙烯酯共聚物、聚環烯烴、聚酯、聚苯乙烯、聚醯胺、聚醚醯亞胺、聚丙烯酸、聚醯亞胺、聚醯胺醯亞胺、聚醚碸、聚碸、聚乙烯、聚丙烯、聚甲基戊烯、聚氯乙烯、聚二 氯亞乙烯、聚乙烯醇、聚乙烯基縮醛、聚醚酮、聚醚醚酮、聚醚碸、聚甲基丙烯酸甲酯、聚對酞酸乙二酯、聚對酞酸丁二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚胺甲酸乙酯、環氧樹脂等。樹脂膜可使用未拉伸、單軸或雙軸拉伸膜。此等高分子可各別單獨使用或混合2種以上使用。就樹脂膜而言,較佳係:透明性及耐熱性優異的聚醯胺醯亞胺膜或聚醯亞胺膜、單軸或雙軸拉伸聚酯膜;透明性及耐熱性優異且同時可對應膜之大型化的環烯烴系衍生物膜、聚甲基丙烯酸甲酯膜;以及透明性與光學上無異向性的三乙醯纖維素及異丁酯纖維素膜。樹脂膜之厚度可為5至200μm,以20至100μm為佳。 The resin film may be a film made of a polymer such as a cycloolefin derivative and a cellulose having a unit containing a cycloolefin monomer such as norbornene or a polycyclic norbornene monomer. (Diethyl cellulose, triethyl cellulose, cellulose acetate butyrate, isobutyl cellulose, propyl cellulose, butyl cellulose, acetyl cellulose, ethylene-vinyl acetate copolymer, Polycycloolefin, polyester, polystyrene, polyimide, polyetherimide, polyacrylic acid, polyimide, polyimide, imine, polyether, polyimide, polyethylene, polypropylene, polyimide Methylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyetherketone, polyetheretherketone, polyetherfluorene, polymethylmethacrylate, polyethylene terephthalate Diester, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, epoxy resin, etc. The resin film can be unstretched, uniaxially or biaxially stretched. These polymers can be used singly or in combination of two or more kinds. For the resin film, it is preferred to be a polymer having excellent transparency and heat resistance. Fluorene amine imine film or polyimide film, uniaxially or biaxially stretched polyester film; cycloolefin derivative film, polymethacrylic acid film with excellent transparency and heat resistance, which can also support large-scale film Methyl ester films; and triethyl cellulose and isobutyl cellulose films with transparency and optical anisotropy. The thickness of the resin film may be 5 to 200 μm, and preferably 20 to 100 μm.
前述硬塗層,可藉由包含因照射光或者熱能量而形成交聯構造之反應性材料的硬塗層組成物的硬化來形成。前述硬塗層可藉由同時包含光硬化型(甲基)丙烯酸酯單體或寡聚物、以及光硬化型環氧單體或寡聚物的硬塗層組成物的硬化而形成。前述光硬化型(甲基)丙烯酸酯單體可包含選自由環氧基(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯及聚酯(甲基)丙烯酸酯所構成之群組中的1種以上。前述環氧基(甲基)丙烯酸酯,係可藉由使環氧化合物與具有(甲基)丙烯醯基之羧酸進行反應而得。 The hard coat layer can be formed by hardening a hard coat composition containing a reactive material that forms a crosslinked structure by irradiation with light or thermal energy. The hard coat layer can be formed by hardening a hard coat composition containing both a photocurable (meth) acrylate monomer or oligomer and a photocurable epoxy monomer or oligomer. The photo-curable (meth) acrylate monomer may include a group selected from the group consisting of an epoxy (meth) acrylate, a urethane (meth) acrylate, and a polyester (meth) acrylate. More than one of them. The epoxy (meth) acrylate is obtained by reacting an epoxy compound with a carboxylic acid having a (meth) acrylfluorenyl group.
硬塗層組成物可更包含選自由溶劑、光起始劑及添加劑所構成之群組中的一種以上。添加劑可包含選自由無機奈米粒子、調平劑及安定劑所構成之群組中的一種以上,此外,關於該技術領域中一般使用的各成分,可更包含例如抗氧化劑、UV吸收劑、界面活性劑、潤滑劑、防汙劑等。 The hard coat composition may further include one or more members selected from the group consisting of a solvent, a photoinitiator, and an additive. The additive may include one or more members selected from the group consisting of inorganic nano particles, a leveling agent, and a stabilizer. In addition, each component generally used in the technical field may further include, for example, an antioxidant, a UV absorber, Surfactants, lubricants, antifoulants, etc.
<遮光圖案> <Shading pattern>
遮光圖案可提供為前面板或適用前面板的顯示裝置之遮光屏(bezel)或外殼(housing)的至少一部分。遮光圖案可形成於前面板之顯示元件側。遮光圖案可隱藏顯示裝置之各配線以防止使用者看見該等配線。遮光圖案之顏色及/或材質並無特別限制,可由具有黑色、白色、金色等多種顏色的樹脂物質所形成。在一實施形態中,遮光圖案之厚度可為2μm至50μm,以4μm至30μm為佳,以6μm至15μm之範圍為較佳。此外,可對於遮光圖案賦予形狀,以抑制因遮光圖案與顯示部之間的段差而引起的氣泡混入及境界部之視認。例如,關於前述遮光圖案,在其之與顯示部之隣接面中,與形成有遮光圖案的前面板所成的傾斜角度可為0.1°至25°。 The shading pattern may be provided as at least a part of a bezel or housing of a front panel or a display device suitable for the front panel. The light-shielding pattern may be formed on the display element side of the front panel. The light-shielding pattern can hide each wiring of the display device to prevent users from seeing the wiring. The color and / or material of the light-shielding pattern is not particularly limited, and may be formed of resin materials having various colors such as black, white, and gold. In one embodiment, the thickness of the light-shielding pattern may be 2 μm to 50 μm, preferably 4 μm to 30 μm, and more preferably 6 μm to 15 μm. In addition, a shape may be given to the light-shielding pattern to prevent air bubbles from entering due to a step between the light-shielding pattern and the display portion and visual recognition of the boundary portion. For example, in the aforementioned light-shielding pattern, an inclination angle formed between the light-shielding pattern and the front panel on which the light-shielding pattern is formed may be 0.1 ° to 25 °.
<圓偏光板之製造方法> <Manufacturing method of circular polarizing plate>
將第1圖(a)所示之圓偏光板100作為例子,以說明圓偏光板的製造方法。圓偏光板100可藉由將偏光板1與位相差膜2隔著黏著劑層13來積層而製造。 The manufacturing method of the circularly polarizing plate will be described by taking the circularly polarizing plate 100 shown in FIG. 1 (a) as an example. The circular polarizing plate 100 can be manufactured by laminating a polarizing plate 1 and a phase difference film 2 with an adhesive layer 13 therebetween.
偏光板1可藉由將偏光件10與保護膜11、12隔著接著劑層分別積層而製造。就偏光板而言,可藉由準備長條構件並在以捲筒至捲筒(Roll to Roll)貼合各別構件後剪裁成預定形狀而製造,亦可在將各別構件剪裁成預定的形狀後貼合。在偏光件10貼合保護膜11、12後,可設定加熱步驟、調濕步驟,以調整偏光板之水分率。其次,在保護膜12上,將形成於剝離膜上的黏著劑層13予以積層。 The polarizing plate 1 can be manufactured by laminating the polarizer 10 and the protective films 11 and 12 separately via an adhesive layer. The polarizing plate can be manufactured by preparing a long member and cutting it into a predetermined shape after laminating each member with a roll to roll, or cutting each member into a predetermined one. Fit after shape. After the polarizer 10 is bonded to the protective films 11 and 12, a heating step and a humidity adjustment step can be set to adjust the moisture content of the polarizing plate. Next, an adhesive layer 13 formed on the release film is laminated on the protective film 12.
位相差膜2可藉由例如下述般而製造。在基材上形成配向膜,於配向膜上塗佈包含聚合性液晶化合物的塗佈液。在使聚合性液晶化合物配向之狀態下,照射活性能量線,使聚合性液晶化合物硬化。在由聚 合性液晶化合物所硬化成之層上,將形成於剝離膜上的黏著劑層14予以積層。其次,剝離基材及/或配向膜。就位相差膜2而言,可藉由準備長條構件並在以捲筒至捲筒貼合各別構件後剪裁成預定形狀而製造,亦可在將各別構件剪裁成預定的形狀後貼合。 The phase difference film 2 can be manufactured, for example, as described below. An alignment film is formed on the substrate, and a coating liquid containing a polymerizable liquid crystal compound is applied on the alignment film. When the polymerizable liquid crystal compound is aligned, the active energy ray is irradiated to harden the polymerizable liquid crystal compound. An adhesive layer 14 formed on the release film is laminated on a layer hardened by the polymerizable liquid crystal compound. Next, the substrate and / or the alignment film are peeled off. As for the phase difference film 2, it can be manufactured by preparing a long member and cutting it into a predetermined shape after laminating the respective members from a roll to a roll, or by cutting each member into a predetermined shape and pasting it. Together.
然後,將積層在黏著劑層13上的剝離膜予以剝離,藉由隔著黏著劑層13將位相差膜2與偏光板1貼合,而可製作圓偏光板100。 Then, the release film laminated on the adhesive layer 13 is peeled off, and the phase difference film 2 and the polarizing plate 1 are bonded together via the adhesive layer 13 to produce a circular polarizing plate 100.
<用途> <Use>
圓偏光板可使用於各種顯示裝置。顯示裝置係意指具有顯示元件的裝置,並包含發光元件或發光裝置作為發光源。顯示裝置可列舉例如液晶顯示裝置、有機EL顯示裝置、無機電致發光(以下亦稱為無機EL)顯示裝置、電子發射顯示裝置(例如電場發射顯示裝置(亦稱為FED)、表面電界發射顯示裝置(亦稱為SED))、電子紙(使用電子墨水或電泳元件的顯示裝置、電漿顯示裝置、投射型顯示裝置(例如柵狀光閥(Grating Light Valve,亦稱為GLV)顯示裝置、具有數位微鏡裝置(Digital Micromirror Device,亦稱為DMD)的顯示裝置)及壓電陶瓷顯示器等。液晶顯示裝置亦包含穿透型液晶顯示裝置、半穿透型液晶顯示裝置等之任一者。此等顯示裝置可為顯示2次元影像的顯示裝置,亦可為顯示3次元影像的立體顯示裝置。圓偏光板可特別有效地使用於有機EL顯示裝置或無機EL顯示裝置。 The circular polarizing plate can be used in various display devices. The display device means a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Examples of the display device include a liquid crystal display device, an organic EL display device, an inorganic electroluminescence (hereinafter also referred to as an inorganic EL) display device, an electron emission display device (such as an electric field emission display device (also referred to as a FED), and a surface electric field emission display Device (also known as SED)), electronic paper (display device using electronic ink or electrophoretic elements, plasma display device, projection display device (e.g., Grating Light Valve (also known as GLV) display device, A display device with a digital micromirror device (also known as a DMD), a piezoelectric ceramic display, and the like. The liquid crystal display device also includes any of a transmissive liquid crystal display device and a semi-transmissive liquid crystal display device. These display devices can be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images. Circular polarizers can be particularly effectively used in organic EL display devices or inorganic EL display devices.
在第3圖(a)、(b)中,有機EL顯示裝置104、105係具有如下述之層構成:隔著積層於位相差膜20上之黏著劑層14,使圓偏光板積層在有機EL顯示元件3。 In FIGS. 3 (a) and (b), the organic EL display devices 104 and 105 have the following layer structure: The circular polarizing plate is laminated on the organic layer through the adhesive layer 14 laminated on the phase difference film 20. EL display element 3.
(1)膜厚度之測定方法 (1) Method for measuring film thickness
使用Nikon股份有限公司製之數位測微計MH-15M測定。 Measurement was performed using a digital micrometer MH-15M manufactured by Nikon Corporation.
(2)透濕度之測定方法 (2) Method for measuring moisture permeability
保護膜之透濕度的測定係依據JIS Z0208之透濕度試驗(Dish方法)而進行。測定條件係在溫度40℃、相對濕度90%下進行。 The measurement of the moisture permeability of the protective film was performed in accordance with the moisture permeability test (Dish method) of JIS Z0208. The measurement conditions were performed at a temperature of 40 ° C and a relative humidity of 90%.
(3)位相差值之測定方法 (3) Method for measuring phase difference
使用位相差測定裝置KOBRA-PR(王子計測機器股份有限公司製)測定。 The measurement was performed using a phase difference measuring device KOBRA-PR (manufactured by Oji Measurement Co., Ltd.).
(4)偏光板之水分率的測定方法 (4) Method for measuring moisture content of polarizing plate
偏光板之水分率係依據乾重法算出。各別測定在105℃下乾燥2小時後之偏光板的重量W1及乾燥前之偏光板的重量W0。將此等值代入下述式,以算出偏光板之水分率。 The moisture content of the polarizing plate is calculated according to the dry weight method. The weight W1 of the polarizing plate after drying at 105 ° C for 2 hours and the weight W0 of the polarizing plate before drying were measured. This equivalent value was substituted into the following formula to calculate the moisture content of the polarizing plate.
偏光板之水分率[%]={(W0-W1)÷W0}×100 Moisture content of polarizing plate [%] = {(W0-W1) ÷ W0} × 100
<偏光件A之製作> <Production of Polarizer A>
將厚度20μm之聚乙烯醇膜(平均聚合度約2400、皂化度99.9莫耳%以上)藉由乾式拉伸而予以單軸拉伸成約4倍,然後在保持拉緊狀態下浸漬在40℃之純水40秒後,在碘/碘化鉀/水之重量比為0.052/5.7/100的水溶液中以28℃浸漬30秒,進行染色處理。其後,在碘化鉀/硼酸/水之重量比為11.0/6.2/100的水溶液中以70℃浸漬120秒。隨後,以8℃之純水洗浄15秒後,在保持300N張力的狀態下處於60℃、50秒,其次以75℃、20秒乾燥,獲得在聚乙烯醇膜中使碘吸附配向而成之厚度8μm的偏光膜。 A polyvinyl alcohol film (average degree of polymerization of about 2400, saponification degree of 99.9 mol% or more) with a thickness of 20 μm is uniaxially stretched to about 4 times by dry stretching, and then immersed in a tensioned state at 40 ° C. After 40 seconds of pure water, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.052 / 5.7 / 100 at 28 ° C. for 30 seconds to perform a dyeing treatment. Thereafter, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 11.0 / 6.2 / 100 at 70 ° C. for 120 seconds. Subsequently, it was washed with pure water at 8 ° C for 15 seconds, and maintained at a tension of 300N at 60 ° C and 50 seconds, followed by drying at 75 ° C and 20 seconds to obtain iodine adsorption and alignment in a polyvinyl alcohol film. A polarizing film with a thickness of 8 μm.
<偏光件B之製作> <Production of Polarizer B>
除了使用厚度30μm之聚乙烯醇膜(平均聚合度約2400、皂化度99.9莫耳%以上)取代厚度20μm之聚乙烯醇膜以外,以與偏光件(A)之製作相同的方法,獲得在聚乙烯醇膜中使碘吸附配向而成之厚度13μm的偏光件(B)。 A polyvinyl alcohol film with a thickness of 30 μm (average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% or more) was used instead of a polyvinyl alcohol film with a thickness of 20 μm. A polarizer (B) with a thickness of 13 μm formed by iodine adsorption and alignment in the vinyl alcohol film.
<偏光件C之製作> <Production of Polarizer C>
除了使用厚度60μm之聚乙烯醇膜(平均聚合度約2400、皂化度99.9莫耳%以上)取代厚度20μm之聚乙烯醇膜以外,以與偏光件(A)之製作相同的方法,獲得在聚乙烯醇膜中使碘吸附配向而成之厚度23μm的偏光件(C)。 A polyvinyl alcohol film with a thickness of 60 μm (average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% or more) was used instead of a polyvinyl alcohol film with a thickness of 20 μm. A polarizer (C) having a thickness of 23 μm formed by iodine adsorption and alignment in the vinyl alcohol film.
<偏光件D之製作> <Production of Polarizer D>
除了使用厚度75μm之聚乙烯醇膜(平均聚合度約2400、皂化度99.9莫耳%以上)取代厚度20μm之聚乙烯醇膜以外,以與偏光件(A)之製作相同的方法,獲得在聚乙烯醇膜中使碘吸附配向而成之厚度28μm的偏光件(D)。 A polyvinyl alcohol film with a thickness of 75 μm (average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% or more) was used instead of a polyvinyl alcohol film with a thickness of 20 μm. A polarizer (D) with a thickness of 28 μm formed by iodine adsorption and alignment in the vinyl alcohol film.
<水系接著劑之調製> <Preparation of water-based adhesive>
相對於水100重量部,將經羧基改性之聚乙烯醇〔從Kuraray股份有限公司購入,商品名「KL-318」〕3重量部溶解,在其水溶液中添加1.5重量部之作為水溶性環氧樹脂的聚醯胺環氧系添加劑〔從田岡化學工業股份有限公司購入,商品名「Sumirez(註冊商標)650(30)」、固形分濃度30重量%之水溶液〕,以調製水系接著劑。 With respect to 100 parts by weight of water, 3 parts by weight of carboxyl-modified polyvinyl alcohol [purchased from Kuraray Co., Ltd., trade name "KL-318"] was dissolved, and 1.5 parts by weight of water solution was added as a water-soluble ring. Polyamine epoxy-based additive of oxyresin [purchased from Taoka Chemical Industry Co., Ltd., trade name "Sumirez (registered trademark) 650 (30)", 30% by weight solid solution in water] to prepare an aqueous adhesive.
<黏著劑層之準備> <Preparation of Adhesive Layer>
黏著劑層A:準備在剝離膜上形成的厚度為25μm之丙烯酸系黏著劑層。 Adhesive layer A: An acrylic adhesive layer having a thickness of 25 μm is prepared on a release film.
黏著劑層B:準備在剝離膜上形成的厚度為5μm之丙烯酸系黏著劑層。 Adhesive layer B: An acrylic adhesive layer having a thickness of 5 μm is prepared on a release film.
黏著劑層C:準備在剝離膜上形成的厚度為20μm之丙烯酸系黏著劑層。 Adhesive layer C: An acrylic adhesive layer having a thickness of 20 μm was prepared on a release film.
<保護膜之準備> <Preparation of protective film>
準備以下之保護膜。 Prepare the following protective films.
保護膜A:厚度20μm之降莰烯系樹脂膜。 Protective film A: a norbornene-based resin film having a thickness of 20 μm.
保護膜B:在一面形成有硬塗層的降莰烯系樹脂膜,保護膜B之厚度為52μm。 Protective film B: a norbornene-based resin film having a hard coat layer formed on one side, and the thickness of the protective film B is 52 μm.
保護膜C:在一面形成有硬塗層之TAC膜,保護膜C之厚度為31μm。 Protective film C: A TAC film with a hard coat layer formed on one side, and the thickness of the protective film C is 31 μm.
保護膜D:在一表面形成有硬塗層之降莰烯系樹脂膜,保護膜D之厚度為29μm。 Protective film D: a norbornene-based resin film having a hard coat layer formed on one surface thereof, and the thickness of the protective film D is 29 μm.
保護膜E:厚度40μm之TAC膜。 Protective film E: TAC film with a thickness of 40 μm.
保護膜F:厚度13μm之降莰烯系樹脂膜。 Protective film F: a norbornene-based resin film having a thickness of 13 μm.
保護膜G:厚度25μm之TAC膜。 Protective film G: TAC film with a thickness of 25 μm.
保護膜H:厚度20μm之TAC膜。 Protective film H: TAC film with a thickness of 20 μm.
<位相差膜之製作> <Production of Phase Difference Film>
將下述構造之光配向性材料5份(重量平均分子量:30000)與環戊酮(溶媒)95份作為成分而混合,所獲得的混合物在80℃攪拌1小時,獲得配向膜形成用組成物。 5 parts (weight average molecular weight: 30,000) of the photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as ingredients, and the obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming an alignment film. .
相對於將以下所示之聚合性液晶化合物A及聚合性液晶化合物B以90:10之質量比混合的混合物,添加調平劑(F-556;DIC公司 製)1.0份及作為聚合起始劑之2-二甲基胺基-2-芐基-1-(4-嗎啉基芐基)丁-1-酮(「Irgacure 369(Irg369)」、BASF日本股份有限公司製)6份。 1.0 part of a leveling agent (F-556; manufactured by DIC Corporation) and a polymerization initiator were added to a mixture in which the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below were mixed at a mass ratio of 90:10. 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinylbenzyl) butan-1-one ("Irgacure 369 (Irg369)", manufactured by BASF Japan Co., Ltd.).
更且,添加N-甲基-2-吡咯啶酮(NMP)以使固形分濃度成為13%,藉由在80℃攪拌1小時,獲得位相差層形成用組成物。 Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%, and the composition for forming a phase difference layer was obtained by stirring at 80 ° C for 1 hour.
聚合性液晶化合物A係以日本特開2010-31223號公報所記載之方法製造。此外,聚合性液晶化合物B係依據日本特開2009-173893號公報所記載之方法製造。以下表示各別之分子構造。 The polymerizable liquid crystal compound A is produced by a method described in Japanese Patent Application Laid-Open No. 2010-31223. The polymerizable liquid crystal compound B is produced by a method described in Japanese Patent Application Laid-Open No. 2009-173893. The respective molecular structures are shown below.
[聚合性液晶化合物A] [Polymerizable liquid crystal compound A]
[聚合性液晶化合物B] [Polymerizable liquid crystal compound B]
[包含基材、配向膜、由聚合性液晶化合物所硬化成之層的積層體之製造] [Production of a laminate including a substrate, an alignment film, and a layer hardened by a polymerizable liquid crystal compound]
就基材而言,係在50μm厚之環狀聚烯烴系膜[日本Zeon股份有限公司製之商品名「ZF-14-50」]上實施電暈處理。使用棒式塗佈器將配向膜形成用組成物塗佈在經實施電暈處理之面。將配向膜形成用組成物之塗膜在80℃乾燥1分鐘。使用偏光UV照射裝置[Ushio電機股份有限公司之商品 名「SPOT CURE SP-9」],在波長313nm中之積算光量:100mJ/cm2下,以軸角度45°之方式,將偏光UV照射至塗膜,獲得配向膜。 The base material was subjected to a corona treatment on a 50 μm-thick cyclic polyolefin-based film [trade name “ZF-14-50” manufactured by Zeon Corporation of Japan]. The composition for forming an alignment film was applied to the surface subjected to the corona treatment using a rod coater. The coating film of the composition for forming an alignment film was dried at 80 ° C. for 1 minute. Using a polarized UV irradiation device [trade name "SPOT CURE SP-9" of Ushio Denki Co., Ltd.], at a wavelength of 313nm of the cumulative light amount: 100mJ / cm 2 , the polarized UV was irradiated at an axis angle of 45 ° to Coating film to obtain alignment film.
隨後,使用棒式塗佈器將位相差層形成用組成物塗佈在配向膜上,以120℃乾燥1分鐘。藉由使用高壓汞燈[Ushio電機股份有限公司之商品名:「Unicure VB-15201BY-A」],對於乾燥後之塗膜照射紫外線(氮氣氛圍下、在波長365nm中之積算光量:500mJ/cm2),使聚合性液晶化合物進行聚合。藉此而獲得包含基材、配向膜及由聚合性液晶化合物所硬化成之層的積層體。 Subsequently, the composition for forming a phase difference layer was coated on an alignment film using a bar coater, and dried at 120 ° C. for 1 minute. By using a high-pressure mercury lamp [Ushio Electric Co., Ltd.'s trade name: "Unicure VB-15201BY-A"], the dried coating film is irradiated with ultraviolet light (under a nitrogen atmosphere, the accumulated light amount at a wavelength of 365 nm: 500 mJ / cm 2 ) Polymerizing a polymerizable liquid crystal compound. Thereby, a laminated body including a substrate, an alignment film, and a layer hardened by a polymerizable liquid crystal compound is obtained.
依據上述方法製造的由聚合性液晶化合物所硬化成之層的面內位相差值Re(λ),係隔著黏著劑將積層體貼合於玻璃,並在將作為基材之環狀聚烯烴系膜予以剝離後,使用測定機[王子計測機器股份有限公司,商品名「KOBRA-WPR」]而進行測定。各波長中之位相差值Re(λ)的測定結果為Re(450)=121nm、Re(550)=142nm、Re(650)=146nm,由聚合性液晶化合物所硬化成之層係發揮作為位相差膜之功能。基於該等值而算出Re(450)/Re(550)=0.85、Re(650)/Re(550)=1.03。 The in-plane phase difference value Re (λ) of the layer hardened by the polymerizable liquid crystal compound manufactured according to the above method is used for bonding the laminated body to glass via an adhesive, and the cyclic polyolefin system to be used as a base material. After the film was peeled off, the measurement was performed using a measuring machine [Oji Measurement Co., Ltd., trade name "KOBRA-WPR"]. The measurement results of the phase difference values Re (λ) at each wavelength were Re (450) = 121 nm, Re (550) = 142 nm, and Re (650) = 146 nm. The layer system hardened by the polymerizable liquid crystal compound functions as a bit. Function of phase contrast film. Based on these values, Re (450) / Re (550) = 0.85 and Re (650) / Re (550) = 1.03.
<前面板之準備> <Preparation of the front panel>
準備Corning公司製之厚度為0.4mm的玻璃板。 A glass plate having a thickness of 0.4 mm manufactured by Corning was prepared.
[實施例1] [Example 1]
隔著上述水系接著劑將保護膜B貼合在偏光件A之一面,並隔著上述水系接著劑將保護膜A貼合在另一面。實施乾燥處理,製作偏光板。偏光板之水分率為1.11%。 The protective film B is bonded to one surface of the polarizer A through the water-based adhesive, and the protective film A is bonded to the other surface through the water-based adhesive. A drying process is performed to produce a polarizing plate. The moisture content of the polarizer is 1.11%.
在偏光板之保護膜A上積層黏著劑層B,將剝離膜予以剝離。在露出之黏著劑層B上積層上述積層體,以使由聚合性液晶化合物所硬化成之層成為貼合面,然後剝離基材。藉此而製作由保護膜B/偏光件A/保護膜A/黏著劑層B/位相差膜所構成的圓偏光板。 An adhesive layer B is laminated on the protective film A of the polarizing plate, and the release film is peeled off. The laminated body is laminated on the exposed adhesive layer B so that the layer hardened by the polymerizable liquid crystal compound becomes a bonding surface, and then the substrate is peeled off. Thereby, a circular polarizing plate composed of the protective film B / the polarizer A / the protective film A / the adhesive layer B / the phase difference film was produced.
[實施例2至4、比較例1至2] [Examples 2 to 4, Comparative Examples 1 to 2]
除了將偏光件、保護膜、偏光板之水分率變更成以下表1所示般以外,以相同的方法製作圓偏光板。此外,藉由調節乾燥溫度及乾燥時間來調整偏光板之水分率。 A circularly polarizing plate was produced in the same manner except that the moisture content of the polarizer, the protective film, and the polarizing plate was changed to those shown in Table 1 below. In addition, the moisture content of the polarizing plate is adjusted by adjusting the drying temperature and the drying time.
<耐熱試驗> <Heat resistance test>
在製作的圓偏光板之位相差膜上積層黏著劑層A。將剝離膜予以剝離,隔著露出之黏著劑層A將圓偏光板積層在玻璃板。更且,在偏光板之與位相差膜側為相反側之保護膜(第1保護膜)上積層黏著劑層C。將剝離膜予以剝離,在露出之黏著劑層C上積層前面板。藉此而製作由玻璃板(前面板)/黏著劑層C/圓偏光板/黏著劑層A/玻璃板所構成的評價用樣品。 An adhesive layer A is laminated on the phase difference film of the produced circular polarizing plate. The release film was peeled, and the circularly polarizing plate was laminated | stacked on the glass plate via the exposed adhesive layer A. Furthermore, an adhesive layer C is laminated on a protective film (first protective film) on the polarizing plate opposite to the phase difference film side. The release film was peeled, and a front panel was laminated on the exposed adhesive layer C. Thereby, an evaluation sample composed of a glass plate (front panel) / adhesive layer C / circular polarizing plate / adhesive layer A / glass plate was prepared.
將評價用樣品投入85℃之烘箱400小時。測定投入前後之圓偏光板的面內位相差值,並算出其差分△Re。此外,測定圓偏光板之面內之中央部分的位相差值。測定面內位相差值之波長為547nm。將以上之結果表示於表1。在實施例之圓偏光板中,位相差值之降低程度較少,且耐熱試驗後之反射光無著色。另一方面,在比較例之圓偏光板中,位相差值之降低程度較大,且反射光著色為紅色。 The sample for evaluation was put into an oven at 85 ° C for 400 hours. The in-plane phase difference value of the circular polarizing plate before and after the measurement was measured, and the difference ΔRe was calculated. Moreover, the phase difference value of the center part in the surface of a circularly polarizing plate was measured. The wavelength at which the phase difference in the plane was measured was 547 nm. The above results are shown in Table 1. In the circular polarizing plate of the embodiment, the degree of phase difference reduction was small, and the reflected light after the heat resistance test was not colored. On the other hand, in the circular polarizing plate of the comparative example, the degree of phase difference reduction was large, and the reflected light was colored red.
依據本發明,在具備包含由液晶化合物所硬化成之層的位相差膜的圓偏光板中,可抑制其以貼合蓋玻璃之狀態放置在高溫環境下後之相較於初期之反射光的顏色變化,故乃屬有用者。 According to the present invention, in a circular polarizing plate having a phase difference film including a layer hardened by a liquid crystal compound, it is possible to suppress the reflected light compared to the initial reflected light when the circular polarizing plate is placed in a high temperature environment with the cover glass attached. Color changes are useful.
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JP7271721B2 (en) * | 2019-12-17 | 2023-05-11 | 富士フイルム株式会社 | organic electroluminescence display |
JP2021117334A (en) * | 2020-01-24 | 2021-08-10 | 住友化学株式会社 | Optical stack and display device |
JP2021144076A (en) * | 2020-03-10 | 2021-09-24 | 株式会社トッパンTomoegawaオプティカルフィルム | Polarizing plate and display device using the same |
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