TWI793310B - Polarizing plate and display device - Google Patents
Polarizing plate and display device Download PDFInfo
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- TWI793310B TWI793310B TW108113610A TW108113610A TWI793310B TW I793310 B TWI793310 B TW I793310B TW 108113610 A TW108113610 A TW 108113610A TW 108113610 A TW108113610 A TW 108113610A TW I793310 B TWI793310 B TW I793310B
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- Prior art keywords
- film
- polarizing plate
- retardation
- layer
- resin
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Images
Classifications
-
- 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
-
- 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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Polarising Elements (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
本發明係關於偏光板及顯示裝置。 The invention relates to a polarizing plate and a display device.
近年來，有機電致發光(以下也稱為有機EL)顯示裝置為代表的影像顯示裝置正急速普及中。在有機EL顯示裝置中係安裝有具備偏光片及相位差膜(λ/4板)的圓偏光板。藉由配置圓偏光板，防止外部光線的反射，可提高畫面的辨識性。 In recent years, image display devices typified by organic electroluminescence (hereinafter also referred to as organic EL) display devices are rapidly spreading. In an organic EL display device, a circular polarizing plate including a polarizing plate and a retardation film (λ/4 plate) is mounted. By configuring circular polarizers, the reflection of external light can be prevented, and the visibility of the screen can be improved.
由於有機EL顯示裝置的興起，隨著對影像顯示裝置的薄型化的需求變強，還要求圓偏光板的薄型化。檢討從傳統的樹脂膜成形的相位差膜，變更為可薄型化的液晶化合物為材料所形成的相位差膜(例如參考專利文獻1)。具有相位差膜的圓偏光板若放置於高溫環境下，則會存在圓偏光板的色調，從初期狀態變為藍色或紅色的問題。具體而言，圓偏光板為矩形時，圓偏光板的四邊附近的反射色調，有時會分別變為藍色或紅色。 Due to the rise of organic EL display devices, as the demand for thinner image display devices has become stronger, thinner circular polarizing plates have also been demanded. Review the retardation film formed from the conventional resin film, and change it to a retardation film formed of a liquid crystal compound that can be thinned (for example, refer to Patent Document 1). If the circular polarizing plate with the retardation film is placed in a high-temperature environment, there will be a problem that the color tone of the circular polarizing plate will change from the initial state to blue or red. Specifically, when the circular polarizing plate is rectangular, the reflection color near the four sides of the circular polarizing plate may be blue or red, respectively.
[專利文獻1]日本公開專利特開2017-54093號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2017-54093
本發明的目的，係為了解決上述課題，提供一種具有相位差膜的圓偏光板，其即使放置於高溫環境下後，反射色調的面內變化亦小。 The object of the present invention is to solve the above-mentioned problems, and to provide a circular polarizing plate having a retardation film, which has a small in-plane change in reflection color tone even after being placed in a high-temperature environment.
[1]一種圓偏光板，其係具有偏光板與相位差膜；其中前述相位差膜包含具有正的複折射性的相位差層；前述偏光板包含厚度15μm以下的偏光片，且在前述偏光片的兩面具有保護膜；前述偏光片與前述相位差膜之間的保護膜為具有負的複折射性的無配向膜。 [1] A circular polarizing plate, which has a polarizing plate and a retardation film; wherein the aforementioned retardation film includes a retardation layer with positive birefringence; the aforementioned polarizing plate includes a polarizer with a thickness of 15 μm or less, and the aforementioned polarizer There are protective films on both sides of the sheet; the protective film between the polarizer and the retardation film is a non-alignment film with negative birefringence.
[2]如[1]記載的圓偏光板，其中前述具有負的複折射性的無配向膜包含選自(甲基)丙烯酸系樹脂、聚苯乙烯系樹脂、馬來醯亞胺系樹脂所組成群組中的至少1種。 [2] The circular polarizing plate as described in [1], wherein the above-mentioned non-oriented film having negative birefringence comprises a material selected from the group consisting of (meth)acrylic resins, polystyrene resins, and maleimide resins. At least one of the groups is formed.
[3]如[1]或[2]記載的圓偏光板，其中前述具有負的複折射性的無配向膜的面內相位差值為10nm以下。 [3] The circular polarizing plate according to [1] or [2], wherein the in-plane retardation value of the negative birefringent non-alignment film is 10 nm or less.
[4]如[1]至[3]中任一項記載的圓偏光板，其中前述相位差層為由聚合性液晶化合物硬化而成的層。 [4] The circular polarizing plate according to any one of [1] to [3], wherein the retardation layer is a layer cured from a polymerizable liquid crystal compound.
[5]一種顯示裝置，其中，[1]至[4]中任一項記載的圓偏光板係積層於顯示元件。 [5] A display device in which the circular polarizing plate according to any one of [1] to [4] is laminated on a display element.
根據本發明，可提供一種具有相位差膜的圓偏光板，其即使放置於高溫環境下後，反射色調的面內變化亦小。 According to the present invention, it is possible to provide a circularly polarizing plate having a retardation film having a small in-plane change in reflection color even after being placed in a high-temperature environment.
1‧‧‧偏光板 1‧‧‧Polarizer
2‧‧‧相位差膜 2‧‧‧retardation film
3‧‧‧有機EL顯示元件 3‧‧‧Organic EL display element
4‧‧‧前面板 4‧‧‧Front panel
5‧‧‧點 5 o'clock
10‧‧‧偏光片 10‧‧‧Polarizer
11、12‧‧‧保護膜 11, 12‧‧‧Protective film
13、14、16‧‧‧黏著劑層 13, 14, 16‧‧‧adhesive layer
15‧‧‧接著層 15‧‧‧adhesion layer
20、21‧‧‧由聚合性液晶化合物硬化而成的層 20, 21‧‧‧Layer hardened by polymerizable liquid crystal compound
100、101、102‧‧‧圓偏光板 100, 101, 102‧‧‧Circular polarizer
104、105‧‧‧有機EL顯示裝置 104, 105‧‧‧Organic EL display device
第1圖係表示圓偏光板的層構成的概略剖面圖的一例。 Fig. 1 is an example of a schematic cross-sectional view showing a layer configuration of a circular polarizing plate.
第2圖係表示有機EL顯示裝置的層構成的概略剖面圖的一例。 FIG. 2 is an example of a schematic cross-sectional view showing a layer structure of an organic EL display device.
第3圖係評估用的樣品的上視圖。 Fig. 3 is a top view of a sample used for evaluation.
(術語及符號的定義) (Definition of terms and symbols)
本說明書的術語及符號的定義，如下述。 Definitions of terms and symbols used in this specification are as follows.
(1)折射率(nx、ny、nz) (1) Refractive index (nx, ny, nz)
「nx」為面內的折射率成為最大的方向(亦即慢軸方向)的折射率，「ny」為面內與慢軸垂直的方向的折射率，「nz」為厚度方向的折射率。 "nx" is the refractive index in the direction in which the in-plane refractive index becomes the largest (that is, the slow axis direction), "ny" is the in-plane refractive index in the direction perpendicular to the slow axis, and "nz" is the refractive index in the thickness direction.
(2)面內的相位差值 (2) In-plane phase difference
面內的相位差值(Re[λ])為23℃、波長λ(nm)的膜的面內相位差值。Re[λ1在膜的厚度為d時，可由Re[λ]=(nx-ny)×d求得。 The in-plane retardation value (Re[λ]) is the in-plane retardation value of the film at 23° C. and wavelength λ (nm). Re[λ1 can be obtained by Re[λ]=(nx-ny)×d when the thickness of the film is d.
(3)厚度方向的相位差值 (3) The phase difference value in the thickness direction
厚度方向的相位差值(Rth[λ])為23℃、波長λ(nm)的膜的厚度方向的相位差值。Rth[λ]在膜的厚度為d時，可由Rth[λ]=((nx+ny)/2-nz)×d求得。 The retardation value in the thickness direction (Rth[λ]) is the retardation value in the thickness direction of the film at 23° C. and wavelength λ (nm). Rth[λ] can be obtained by Rth[λ]=((nx+ny)/2-nz)×d when the thickness of the film is d.
(4)無配向膜 (4) No alignment film
本發明所使用的無配向膜，係指波長590nm的膜的面內相位差值Re[590]滿足10nm以下的膜。再者，厚度方向的相位差值Rth[λ]滿足15nm以下時，因可顯著地抑制耐熱測試時的顏色變化，所以較理想。 The non-oriented film used in the present invention refers to a film whose in-plane retardation value Re[590] satisfies 10 nm or less at a wavelength of 590 nm. Furthermore, when the retardation value Rth[λ] in the thickness direction satisfies 15 nm or less, it is preferable because the color change during the heat resistance test can be significantly suppressed.
〈圓偏光板〉 〈Circular Polarizer〉
本發明的圓偏光板具備偏光板及相位差膜。偏光板與相位差膜例如可隔著接著層積層。接著層例如為後述的黏著劑層、接著劑層。於本發明所謂之偏光板係指由偏光片與貼合於偏光片的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 retardation film. The polarizing plate and the retardation film may be laminated via, for example, an adhesive layer. The adhesive layer is, for example, an adhesive layer and an adhesive layer described later. The so-called polarizing plate in the present invention refers to a laminate composed of a polarizing plate and protective films attached to both sides of the polarizing plate.
以下，參考第1圖說明本發明的圓偏光板的層構成之一例。再者，於第1圖中沒有顯示用以分別貼合偏光片10與保護膜11、12的接著劑層。第1圖(a)所示的圓偏光板100具有將偏光板1以及包含由聚合性液晶化合物硬化而成的層20之相位差膜2隔著黏著劑層13積層的層構成，其中，偏光板1係在偏光片10的一面積層有第1保護膜11以及在偏光片10的另一面積層有第2保護膜12。再者，圓偏光板100在相位差膜2之與偏光板1相反側的面具有黏著劑層14。黏著劑層14，可為對有機EL顯示元件等貼合用的黏著劑層。 Hereinafter, an example of the layer configuration of the circular polarizing plate of the present invention will be described with reference to FIG. 1 . Furthermore, the adhesive layer for laminating the
第1圖(b)所示的圓偏光板101，具有將偏光板1以及相位差膜2隔著黏著劑層13積層的層構成，其中，偏光板1係在偏光片10的一面積層有第1保護膜11以及在偏光片10的另一面積層有第2保護膜12。於圓偏光板101中，相位差膜2具有由聚合性液晶化合物硬化而成的層20及由聚合性液晶化合物硬化而成的層21隔著接著層15積層的層構 成。再者，圓偏光板101在相位差膜2之與偏光板1相反側的面，具有黏著劑層14。黏著劑層14，可為對有機EL顯示元件等貼合用的黏著劑層。 The circular polarizing
第1圖所示的相位差膜可具有1層的相位差層，亦可具有2層以上的相位差層。而且，相位差膜可具有用以在製造階段使聚合性液晶化合物配向的配向膜。 The retardation film shown in FIG. 1 may have one retardation layer, or may have two or more retardation layers. Also, the retardation film may have an alignment film for aligning the polymerizable liquid crystal compound at the manufacturing stage.
圓偏光板可具有第1圖所示的層以外的層。圓偏光板可更具有的層例如為前面板、遮光圖案等。前面板可配置於偏光板的積層有相位差膜之側的相反側。 The circular polarizing plate may have layers other than those shown in FIG. 1 . The layers that the circular polarizing plate may have are, for example, a front plate, a light-shielding pattern, and the like. The front plate may be disposed on the opposite side of the polarizing plate on which the retardation film is laminated.
遮光圖案可形成於前面板的偏光板側的面上。遮光圖案可形成於影像顯示裝置的相框(非顯示區域)，使使用者看不到影像顯示裝置的配線。 The light-shielding pattern may be formed on the face of the front panel on the polarizer side. The light-shielding pattern can be formed on the photo frame (non-display area) of the image display device, so that the user cannot see the wiring of the image display device.
圓偏光板的主面的形狀，實質上可為矩形。所謂主面係指對應顯示面具有最大面積的面。所謂實質上為矩形，係指4個角(角落部)中至少1個角落部可為切為鈍角的形狀、倒圓的形狀，垂直主面的端面的一部分亦可為具有凹向面內方向的凹部(缺口)，主面內的一部分具有挖空成圓形、橢圓形、多角形及該等的組合等的形狀之穿孔部。 The shape of the main surface of the circular polarizing plate may be substantially rectangular. The so-called main surface refers to the surface with the largest area corresponding to the display surface. The term "substantially rectangular" means that at least one of the four corners (corners) may be obtusely cut or rounded, and a part of the end surface perpendicular to the main surface may have a concave in-plane direction A part of the main surface has a hollowed-out hole in a shape such as a circle, an ellipse, a polygon, or a combination thereof.
圓偏光板的大小無特別限制。圓偏光板實質上為矩形的情況，長邊的長度為6cm以上35cm以下較理想，10cm以上30cm以下更理想，短邊的長度為5cm以上30cm以下較理想，6cm以上25cm以下更理想。 The size of the circular polarizing plate is not particularly limited. When the circular polarizing plate is substantially rectangular, the length of the long side is preferably 6 cm to 35 cm, more preferably 10 cm to 30 cm, the short side is preferably 5 cm to 30 cm, and more preferably 6 cm to 25 cm.
〈偏光板〉 <Polarizing plate>
於本發明中，所謂偏光板，係指由偏光片及貼合於偏光片的單面或兩面的保護膜所構成的積層體。偏光板所具備的保護膜，可具有後述的硬塗層、抗反射層、抗靜電層等的表面處理層。偏光板與保護膜，可例如隔著接著劑層、黏著劑層而積層。以下說明偏光板所具備的構件。 In the present invention, a polarizing plate refers to a laminate composed of a polarizing plate and protective films bonded to one or both sides of the polarizing plate. The protective film included in the polarizing plate may have surface treatment layers such as a hard coat layer, an antireflection layer, and an antistatic layer described later. The polarizing plate and the protective film can be laminated via an adhesive layer or an adhesive layer, for example. The members included in the polarizing plate will be described below.
(1)偏光片 (1) Polarizer
偏光板所具備的偏光片，可為具有吸收具有平行其吸收軸的振動面的直線偏光，透射具有垂直吸收軸(平行透過軸)的振動面的直線偏光的性質之吸收型偏光片。具有第1層的偏光片，可適合使用二色性色素吸附配向於單軸延伸的聚乙烯醇系樹脂膜之偏光片。偏光片可藉由例如包含單軸延伸聚乙烯醇系樹脂膜的步驟；用二色性色素染色聚乙烯醇系樹脂膜而使二色性色素吸附的步驟；將吸附有二色性色素的聚乙烯醇系樹脂膜使用硼酸水溶液等的交聯液來處理的步驟；以及在藉由交聯液處理後之水洗步驟；的方法而製造。 The polarizer included in the polarizing plate may be an absorption type polarizer having a property of absorbing linearly polarized light having a vibration plane parallel to its absorption axis and transmitting linearly polarized light having a vibration plane perpendicular to the absorption axis (parallel to the transmission axis). As the polarizer having the first layer, a polarizer in which a dichroic dye is adsorbed and aligned on a uniaxially stretched polyvinyl alcohol-based resin film can be suitably used. The polarizer can be obtained by, for example, including a step of uniaxially stretching a polyvinyl alcohol-based resin film; a step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb a dichroic dye; The vinyl alcohol-based resin film is produced by a step of treating a cross-linking solution such as an aqueous solution of boric acid; and a step of washing with water after the treatment with the cross-linking solution;
聚乙烯醇系樹脂膜可使用聚乙酸乙烯酯樹脂皂化者。作為聚乙酸乙烯酯者，除乙酸乙烯酯的均聚物之聚乙酸乙烯酯外，可舉例如乙酸乙烯酯及可與其共聚合的其他單體的共聚物等。作為可與乙酸乙烯酯共聚合的其他單體，例如不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類以及具有銨基的(甲基)丙烯醯胺類等。 As the polyvinyl alcohol-based resin film, polyvinyl acetate resin saponified can be used. Examples of polyvinyl acetate include, for example, copolymers of vinyl acetate and other monomers that can be copolymerized with it, in addition to polyvinyl acetate that is a homopolymer of vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylamides having an ammonium group.
於本說明書，所謂「(甲基)丙烯酸」，係指選自丙烯酸及甲基丙烯酸中的至少一者。於「(甲基)丙烯醯基」、「(甲基)丙烯酸酯」等亦同。 In this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. The same applies to "(meth)acryl", "(meth)acrylate", etc.
聚乙烯醇系樹脂的皂化度，通常為85至100莫耳%以上，較理想為98莫耳%以上。聚乙烯醇系樹脂可經改質，可使用例如醛類改質的聚乙烯醇縮甲醛或聚乙烯醇縮乙醛等。聚乙烯醇系樹脂的平均聚合度，通常為1000至10000，較理想為1500至5000。聚乙烯醇系樹脂的平均聚合度可根據JIS K6726求得。 The degree of saponification of the polyvinyl alcohol-based resin is usually 85 to 100 mole % or more, preferably 98 mole % or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000. The average degree of polymerization of a polyvinyl alcohol-type resin can be calculated|required based on JISK6726.
如此將聚乙烯醇系樹脂製膜者，可使用作為偏光片的原料膜。聚乙烯醇系樹脂製膜的方法，無特別限制，可採用習知的方法。聚乙烯醇系原料膜的厚度，無特別限制，為了使偏光片的厚度為15μm以下，使用5至35μm者較理想。更理想為20μm以下。 The polyvinyl alcohol-type resin film-formed in this way can be used as a raw material film of a polarizer. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be used. The thickness of the polyvinyl alcohol-based raw material film is not particularly limited, but it is preferably 5 to 35 μm in order to make the thickness of the polarizer 15 μm or less. More preferably, it is 20 μm or less.
聚乙烯醇系樹脂膜的單軸延伸，可在藉由二色性色素的染色前、與染色同時或染色後進行。於單軸延伸在染色後進行的情況，該單軸延伸可在硼酸處理前或硼酸處理中進行。而且，可在該等的複數階段進行單軸延伸。 The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. In the case where uniaxial extension is performed after staining, the uniaxial extension can be performed before or during boric acid treatment. Also, uniaxial stretching can be performed in these plural stages.
單軸延伸時可在轉速不同的滾輪間進行單軸延伸，亦可使用熱滾輪進行單軸延伸。而且，單軸延伸可為在大氣中進行延伸的乾式延伸，亦可為使用溶劑或水，使聚乙烯醇系樹脂膜在膨脹的狀態下進行延伸的濕式延伸。延伸倍率通常為3至8倍。 During uniaxial stretching, uniaxial stretching can be performed between rollers with different rotation speeds, or uniaxial stretching can be performed with hot rollers. Furthermore, the uniaxial stretching may be dry stretching in which the stretching is carried out in the atmosphere, or wet stretching in which the polyvinyl alcohol-based resin film is stretched in a swollen state using a solvent or water. The elongation ratio is usually 3 to 8 times.
作為聚乙烯醇系樹脂膜用二色性色素染色的方法，例如可採用將該膜浸漬於含有二色性色素的水溶液的方法。二色性色素係使用碘或二色性有機染料。再者，聚乙烯醇系樹脂膜在染色處理前，較理想為先實施對水的浸漬處理。 As a method of dyeing a polyvinyl alcohol-type resin film with a dichroic dye, for example, a method of immersing the film in an aqueous solution containing a dichroic dye can be employed. As a dichroic dye, iodine or a dichroic organic dye is used. In addition, it is preferable that the polyvinyl alcohol-type resin film implements the immersion process with water before a dyeing process.
作為藉由二色性色素的染色後的交聯處理，採用將染色的聚乙烯醇系樹脂膜浸漬於含有硼酸的水溶液的方法。於使用碘作為二色性色素的情況，該含有硼酸的水溶液較理想為含有碘化鉀。 As a crosslinking treatment after dyeing by a dichroic dye, a method of immersing a dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid is employed. When using iodine as a dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide.
偏光片的厚度，通常為15μm以下，較理想為13μm以下，更理想為10μm以下，再更理想為8μm以下。偏光片的厚度，通常為2μm以上，較理想為3μm以上。由本發明人等的檢討，得知顯示圓偏光板的色調變化是因相位差膜的相位差值的變化引起。再者，得知相位差膜的相位差值的變化，係因於放置在高溫環境下的圓偏光板的偏光板尺寸收縮時的應力所引起。所以，從減低因偏光片的收縮的影響的觀點，偏光片的厚度為15μm以下，在防止反射色調的變化上為有效。 The thickness of the polarizer is usually not more than 15 μm, more preferably not more than 13 μm, more preferably not more than 10 μm, still more preferably not more than 8 μm. The thickness of the polarizer is usually at least 2 μm, preferably at least 3 μm. From the examination of the inventors of the present invention, it was found that the change in the color tone of the display circular polarizing plate is caused by the change in the retardation value of the retardation film. Furthermore, it is known that the change of the retardation value of the retardation film is caused by the stress caused by the shrinkage of the polarizer of the circular polarizer placed in a high-temperature environment. Therefore, from the viewpoint of reducing the influence of shrinkage of the polarizer, the thickness of the polarizer is 15 μm or less, which is effective in preventing changes in reflection color.
偏光片可使用例如日本公開專利特開2016-170368號公報記載，在液晶化合物聚合的硬化膜中使二色性色素配向者。二色性色素可使用波長380至800nm範圍內具有吸收者，使用有機染料則較理想。二色性色素可舉例如偶氮化合物。 As the polarizer, for example, a dichroic dye aligned in a cured film obtained by polymerizing a liquid crystal compound as described in JP-A-2016-170368 can be used. Dichroic pigments can be used with absorbers in the wavelength range of 380 to 800nm, and organic dyes are ideal. As a dichroic dye, an azo compound is mentioned, for example.
液晶化合物可為在配向下會聚合的液晶化合物，分子內可具有聚合性基。而且，如國際公開專利WO2011/024891記載，可從具有液晶性的二色性色素形成偏光片。 The liquid crystal compound may be a liquid crystal compound that polymerizes under alignment, and may have a polymerizable group in the molecule. Furthermore, as described in International Laid-Open Patent WO2011/024891, a polarizer can be formed from a dichroic dye having liquid crystallinity.
偏光片的收縮力較理想為2.0N/2mm以下，更理想為1.8N/2mm以下，更加理想為1.5N/2mm以下。再者，偏光片的收縮力的測定方法，係根據後述的實施例記載的方法。 The shrinkage force of the polarizer is preferably 2.0 N/2mm or less, more preferably 1.8 N/2mm or less, still more preferably 1.5 N/2mm or less. In addition, the measuring method of the shrinkage force of a polarizing plate is based on the method described in the Example mentioned later.
(2)保護膜 (2) Protective film
本發明的圓偏光板在偏光片的兩面具有保護膜。位於偏光片與相位差膜之間的保護膜，具有負的複折射性。此處，所謂負的複折射性係指在與樹脂的延伸方向垂直之方向顯現為慢軸者。相位差膜由於使用具有正的複折射性之相位差層，隨著偏光片的熱收縮會顯現與相位差膜顯現的相位差相反的相位差，咸信可縮小顏色變化。此處，所謂正的複折射性，係指在平行樹脂的延伸方向之方向顯現為慢軸者。 The circular polarizing plate of the present invention has protective films on both surfaces of the polarizer. The protective film located between the polarizer and the retardation film has negative birefringence. Here, negative birefringence means that a slow axis appears in the direction perpendicular to the extending direction of the resin. Since the phase difference film uses a phase difference layer with positive birefringence, a phase difference opposite to that of the phase difference film will appear as the polarizer shrinks thermally, and it is believed that the color change can be reduced. Here, the positive birefringence means that a slow axis appears in a direction parallel to the extending direction of the resin.
積層於偏光片的兩面之保護膜，可為具有透光性(較理想為光學上透明)的熱塑性樹脂，例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)的聚烯烴系樹脂；如三乙醯基纖維素、二乙醯基纖維素的纖維素系樹脂；如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯的聚酯系樹脂；聚碳酸酯系樹脂；如甲基丙烯酸甲酯系樹脂之(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；聚偏氯乙烯系樹脂；聚醯胺系樹脂；聚縮醛系樹脂；改質聚苯醚系樹脂；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；聚醯亞胺系樹脂等所成的膜。 The protective film laminated on both sides of the polarizer can be a thermoplastic resin with light transmission (ideally optically transparent), such as chain polyolefin resin (polypropylene resin, etc.), cyclic polyolefin resin ( polyolefin-based resins such as norcamphene-based resins); cellulose-based resins such as triacetylcellulose and diacetylcellulose; such as polyethylene terephthalate, polybutylene terephthalate Polyester-based resins; polycarbonate-based resins; (meth)acrylic resins such as methyl methacrylate-based resins; polystyrene-based resins; polyvinyl chloride-based resins; acrylonitrile‧butadiene‧benzene Vinyl resin; Acrylonitrile‧Styrene resin; Polyvinyl acetate resin; Polyvinylidene chloride resin; Polyamide resin; Polyacetal resin; Modified polyphenylene ether resin; Polyethylene resin Polyether-based resins; polyarylate-based resins; polyamide-imide-based resins;
特別是偏光片與相位差膜之間所使用的保護膜，使用具有負的複折射性者較理想。亦即，使用包含選自(甲基)丙烯酸系樹脂、聚苯乙烯系樹脂、馬來醯亞胺系樹脂所組成群組中的至少1種的膜較理想。藉由使用如此的樹脂膜作為保護膜，即使加工為不規則形狀的情況，可為耐久性佳的偏光板。 In particular, the protective film used between the polarizer and the retardation film is preferably one having negative birefringence. That is, it is preferable to use a film containing at least one selected from the group consisting of (meth)acrylic resins, polystyrene resins, and maleimide resins. By using such a resin film as a protective film, even when processed into an irregular shape, a durable polarizing plate can be obtained.
(甲基)丙烯酸系樹脂係以具有(甲基)丙烯醯基的化合物作為主要構成單體的樹脂。(甲基)丙烯酸系樹脂的具體例，例如包括聚甲基丙烯酸甲酯的聚(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的化合物的共聚物(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)。較理想地使用如聚(甲基)丙烯酸甲酯的聚(甲基)丙烯酸C1-6烷酯為主成分的聚合物，更理想為甲基丙烯酸甲酯為主成分(50至100重量%，較理想為70至100重量%)的甲基丙烯酸甲酯系樹脂。 The (meth)acrylic resin is a resin having a compound having a (meth)acryl group as a main constituent monomer. Specific examples of (meth)acrylic resins include, for example, poly(meth)acrylates including polymethyl methacrylate; methyl methacrylate-(meth)acrylic acid copolymer; methyl methacrylate-(meth)acrylic acid copolymer; base) acrylate copolymer; methyl methacrylate-acrylate-(meth)acrylic acid copolymer; methyl methacrylate-styrene copolymer (MS resin, etc.); methyl methacrylate and alicyclic Copolymers of hydrocarbon-based compounds (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth)acrylate copolymer, etc.). It is more desirable to use a poly(meth)acrylate C 1-6 alkyl ester-based polymer such as poly(meth)acrylate as the main component, more desirably methyl methacrylate as the main component (50 to 100% by weight , more desirably 70 to 100% by weight) of methyl methacrylate resin.
前述(甲基)丙烯酸系樹脂膜的波長590nm的面內相位差值Re，較理想為10nm以下，更理想為7nm以下，更加理想為5nm以下，特別理想為3nm以下，最理想為1nm以下。波長590nm的(甲基)丙烯酸系樹脂膜的厚度方向的相位差值Rth，較理想為15nm以下，更理想為10nm以下，更加理想為5nm以下，特別理想為3nm以下，最理想為1nm以下。只要是面內相位差值及厚度方向的相位差值為如此的範圍，無損後述的相位差膜的特性，可顯著地抑制耐熱測試時的顏色變化。為了使面內相位差值及厚度方向的相位差值為如此的範圍，可使用例如具有後述戊二醯亞胺(Glutarimide)構造的(甲基)丙烯酸系樹脂。 The in-plane retardation value Re of the (meth)acrylic resin film at a wavelength of 590 nm is preferably 10 nm or less, more preferably 7 nm or less, still more preferably 5 nm or less, particularly preferably 3 nm or less, most preferably 1 nm or less. The retardation value Rth in the thickness direction of the (meth)acrylic resin film at a wavelength of 590 nm is preferably 15 nm or less, more preferably 10 nm or less, still more preferably 5 nm or less, particularly preferably 3 nm or less, most preferably 1 nm or less. As long as the in-plane retardation value and the retardation value in the thickness direction are within such a range, the color change during the heat resistance test can be significantly suppressed without impairing the characteristics of the retardation film described later. In order to set the in-plane retardation value and the retardation value in the thickness direction within such ranges, for example, a (meth)acrylic resin having a glutarimide structure described later can be used.
前述(甲基)丙烯酸系樹脂在具有負的複折射性範圍，較理想為可具有顯現正的複折射的構造單元。若具有顯現正的複折射的構造單元及顯現負的複折射的構造單元，則可藉由調整其存在比例，而控制(甲 基)丙烯酸系樹脂膜的相位差，可得到低相位差的(甲基)丙烯酸系樹脂膜。顯現正的複折射的構造單元，可舉例如構成內酯環、聚碳酸酯、聚乙烯醇、乙酸纖維素、聚酯、聚芳酯、聚醯亞胺、聚烯烴等的構造單元、後述通式(1)表示的構造單元。顯現負的複折射的構造單元，例如來自苯乙烯系單體、馬來醯亞系單體等的構造單元、聚甲基丙烯酸甲酯的構造單元、後述通式(3)表示的構造單元等。 The aforementioned (meth)acrylic resin preferably has a structural unit exhibiting positive birefringence in the range of negative birefringence. If there is a structural unit exhibiting positive birefringence and a structural unit exhibiting negative birefringence, the phase difference of the (meth)acrylic resin film can be controlled by adjusting the ratio of their presence, and a low phase difference ( Meth)acrylic resin film. Structural units exhibiting positive birefringence include, for example, structural units constituting lactone rings, polycarbonates, polyvinyl alcohol, cellulose acetate, polyesters, polyarylates, polyimides, polyolefins, etc., which will be described later. A structural unit represented by formula (1). Structural units exhibiting negative birefringence, for example, structural units derived from styrene-based monomers, maleimide monomers, etc., structural units of polymethyl methacrylate, structural units represented by general formula (3) described later, etc. .
作為前述(甲基)丙烯酸系樹脂，使用具有內酯環構造或戊二醯亞胺構造的(甲基)丙烯酸系樹脂較理想。具有內酯環構造或戊二醯亞胺構造的(甲基)丙烯酸系樹脂，耐熱性佳。更理想地為具有戊二醯亞胺構造的(甲基)丙烯酸系樹脂。若使用具有戊二醯亞胺構造的(甲基)丙烯酸系樹脂的話，如上述，可得到低透濕且相位差及紫外線穿透率小的(甲基)丙烯酸系樹脂膜。具有戊二醯亞胺構造的(甲基)丙烯酸系樹脂(以下亦稱為戊二醯亞胺樹脂)，例如記載於日本公開專利特開2006-309033號公報、特開2006-317560號公報、特開2006-328329號公報、特開2006-328334號公報、特開2006-337491號公報、特開2006-337492號公報、特開2006-337493號公報、特開2006-337569號公報、特開2007-009182號公報、特開2009-161744號公報。該等的記載，在本說明書援用作為參考。 As the (meth)acrylic resin, it is preferable to use a (meth)acrylic resin having a lactone ring structure or a glutarimide structure. A (meth)acrylic resin having a lactone ring structure or a glutarimide structure has excellent heat resistance. More preferably, it is a (meth)acrylic resin having a glutarimide structure. When a (meth)acrylic resin having a glutarimide structure is used, as described above, a (meth)acrylic resin film having low moisture permeability and a small retardation and ultraviolet transmittance can be obtained. (Meth)acrylic resins having a glutarimide structure (hereinafter also referred to as glutarimide resins) are described, for example, in JP-A-2006-309033, JP-A-2006-317560, JP 2006-328329, JP 2006-328334, JP 2006-337491, JP 2006-337492, JP 2006-337493, JP 2006-337569, JP Publication No. 2007-009182 and Japanese Patent Application Publication No. 2009-161744. These descriptions are incorporated by reference in this specification.
較理想地上述戊二醯亞胺樹脂，包含下述通式(1)表示的構造單元(以下亦稱為戊二醯亞胺單元)及下述通式(2)表示的構造單元(以下亦稱為(甲基)丙烯酸酯單元)。 Preferably, the above-mentioned glutarimide resin comprises a structural unit represented by the following general formula (1) (hereinafter also referred to as a glutarimide unit) and a structural unit represented by the following general formula (2) (hereinafter also referred to as called (meth)acrylate units).
於式(1)中，R1及R2分別獨立為氫或碳數1至8的烷基，R3為包含氫、碳數1至18的烷基、碳數3至12的環烷基或碳數5至15的芳香環的取代基。於式(2)中，R4及R5分別獨立為氫或碳數1至8的烷基，R6為包含氫、碳數1至18的烷基、碳數3至12的環烷基或碳數5至15的芳香環的取代基。 In formula (1), R 1 and R 2 are independently hydrogen or an alkyl group with 1 to 8 carbons, and R 3 is a cycloalkyl group containing hydrogen, an alkyl group with 1 to 18 carbons, or a cycloalkyl group with 3 to 12 carbons Or a substituent of an aromatic ring having 5 to 15 carbon atoms. In formula (2), R 4 and R 5 are independently hydrogen or an alkyl group with 1 to 8 carbons, and R 6 is a cycloalkyl group containing hydrogen, an alkyl group with 1 to 18 carbons, or a cycloalkyl group with 3 to 12 carbons Or a substituent of an aromatic ring having 5 to 15 carbon atoms.
戊二醯亞胺樹脂視需要可再包含下述通式(3)表示的構造單元(以下亦稱為芳香族乙烯基單元)。 The glutarimide resin may further contain a structural unit (hereinafter also referred to as an aromatic vinyl unit) represented by the following general formula (3) if necessary.
於式(3)中，R7為氫或碳數1至8的烷基，R8為碳數6至10的芳香基。 In formula (3), R 7 is hydrogen or an alkyl group having 1 to 8 carbons, and R 8 is an aryl group having 6 to 10 carbons.
於上述通式(1)中，較理想地，R1及R2分別獨立為氫或甲基，R3為氫、甲基、丁基或環己基，更理想地R1為甲基，R2為氫，R3為甲基。 In the above general formula (1), ideally, R1 and R2 are independently hydrogen or methyl, R3 is hydrogen, methyl, butyl or cyclohexyl, more ideally R1 is methyl, R 2 is hydrogen and R 3 is methyl.
上述戊二醯亞胺樹脂，作為戊二醯亞胺單元，可包含單一種，亦可包含不同上述通式(1)之R1、R2及R3的複數種類。 The above-mentioned glutarimide resin may contain a single type of glutarimide unit, or may contain plural types different from R 1 , R 2 and R 3 of the above general formula (1).
戊二醯亞胺單元可藉由上述通式(2)表示的(甲基)丙烯酸酯單元醯亞胺化而形成。而且，戊二醯亞胺單元，亦可藉由馬來酸酐等的酸酐或如此的酸酐與碳數1至20的直鏈或分支狀的醇的半酯；丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、衣康酸、衣康酸酐、巴豆酸(crotonic acid)、富馬酸(fumaric acid)、檸康酸(citraconic acid)等的α,β-乙烯性不飽和羧酸等醯亞胺化而形成。 The glutarimide unit can be formed by imidization of the (meth)acrylate unit represented by the said general formula (2). Moreover, the glutarimide unit can also be obtained by acid anhydrides such as maleic anhydride or half esters of such anhydrides and linear or branched alcohols with 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid, etc. formed by amination.
於上述通式(2)中，較理想地R4及R5分別獨立為氫或甲基，R6為氫或甲基，更理想地R4為氫，R5為甲基，R6為甲基。 In the above general formula (2), preferably R4 and R5 are independently hydrogen or methyl, R6 is hydrogen or methyl, more ideally R4 is hydrogen, R5 is methyl, R6 is methyl.
上述戊二醯亞胺樹脂，作為(甲基)丙烯酸酯單元，可包含單一種，亦可包含不同上述通式(2)之R4、R5及R6的複數種類。 The above-mentioned glutarimide resin may contain a single type as a (meth)acrylate unit, or may contain plural types different from R 4 , R 5 , and R 6 in the above-mentioned general formula (2).
上述戊二醯亞胺樹脂中，作為上述通式(3)表示的芳香族乙烯基單元，較理想地包含苯乙烯、α-甲基苯乙烯等，更理想地包含苯乙烯。藉由具有如此的芳香族乙烯基單元，減少戊二醯亞胺單元的正的複折射性，可得到更低相位差的(甲基)丙烯酸系樹脂膜。 In the glutarimide resin, the aromatic vinyl unit represented by the general formula (3) preferably includes styrene, α-methylstyrene, and the like, and more preferably includes styrene. By having such an aromatic vinyl unit, the positive birefringence of the glutarimide unit can be reduced, and a (meth)acrylic resin film with a lower retardation can be obtained.
上述戊二醯亞胺樹脂中，作為芳香族乙烯基單元，可包含單一種，亦可包含不同R7及R8的複數種類。 In the above-mentioned glutarimide resin, the aromatic vinyl unit may contain a single type, or may contain plural types different from R 7 and R 8 .
上述戊二醯亞胺樹脂之上述戊二醯亞胺單元的含量，例如隨R3的構造等而改變較理想。戊二醯亞胺單元的含量，以戊二醯亞胺樹脂的總構造單元為基準，較理想為1重量%至80重量%，更理想為1重量%至70重量%，更加理想為1重量%至60重量%，特別理想為1重量%至50重量%。只要是戊二醯亞胺單元的含量為如此的範圍，可得到耐熱性佳、低相位差的(甲基)丙烯酸系樹脂膜。 The content of the above-mentioned glutarimide unit in the above-mentioned glutarimide resin is preferably changed depending on, for example, the structure of R 3 . The content of the glutarimide unit is based on the total structural units of the glutarimide resin, preferably 1% by weight to 80% by weight, more preferably 1% by weight to 70% by weight, more preferably 1% by weight % to 60% by weight, particularly preferably 1% to 50% by weight. If the content of the glutarimide unit is within such a range, a (meth)acrylic resin film having good heat resistance and a low retardation can be obtained.
上述戊二醯亞胺樹脂之上述芳香族乙烯基單元的含量，可依據目的、期望的特性來適當地設定。依據用途，芳香族乙烯基單元的含量也可為零。於包含芳香族乙烯基單元的情況，其含量，以戊二醯亞胺樹脂的戊二醯亞胺單元為基準，較理想為10重量%至80重量%，更理想為20重量%至80重量%，更加理想為20重量%至60重量%，特別理想為20重量%至50重量%。只要是芳香族乙烯基單元的含量為如此的範圍，可得到低相位差且耐熱性及機械強度佳的(甲基)丙烯酸系樹脂膜。 The content of the above-mentioned aromatic vinyl unit in the above-mentioned glutarimide resin can be appropriately set according to the purpose and desired characteristics. Depending on the application, the content of the aromatic vinyl unit may also be zero. In the case of containing an aromatic vinyl unit, the content is preferably 10% by weight to 80% by weight, more preferably 20% by weight to 80% by weight, based on the glutarimide unit of the glutarimide resin. %, more preferably 20% by weight to 60% by weight, particularly preferably 20% by weight to 50% by weight. As long as the content of the aromatic vinyl unit is within such a range, a (meth)acrylic resin film having a low retardation and good heat resistance and mechanical strength can be obtained.
於上述戊二醯亞胺樹脂中，視需要，可再與戊二醯亞胺單元、(甲基)丙烯酸酯單元及芳香族乙烯基單元以外的其他構造單元共聚合。作為其他構造單元，可舉例如由丙烯腈、甲基丙烯腈等腈系單體、馬 來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等的醯亞胺系單體所構成的構造單元。該等的其他構造單元，在上述戊二醯亞胺樹脂中，可直接共聚合，亦可接枝共聚合。 In the above-mentioned glutarimide resin, if necessary, other structural units other than the glutarimide unit, (meth)acrylate unit, and aromatic vinyl unit may be further copolymerized. As other structural units, for example, nitrile monomers such as acrylonitrile and methacrylonitrile, maleimide, N-methylmaleimide, N-phenylmaleimide, N- A structural unit composed of imide-based monomers such as cyclohexylmaleimide. These other structural units may be directly copolymerized or graft-copolymerized in the above-mentioned glutarimide resin.
上述(甲基)丙烯酸系樹脂膜，依據目的，可含有任意適合的添加劑。作為添加劑，可舉例如受阻酚系、磷系、硫系等的抗氧化劑；耐光安定劑、紫外線吸收劑、耐候安定劑、熱安定劑等的安定劑；玻璃纖維、碳纖維等的補強材料；近紅外線吸收劑；磷酸三(二溴丙基)酯、磷酸三烯丙酯、氧化銻等的難燃劑；陰離子系、陽離子系、非離子系的界面活性劑等的抗靜電劑；無機顏料、有機顏料、染料等的著色劑；有機填充劑、無機填充劑；樹脂改質劑；塑化劑；潤滑劑；相位差減少劑等。所含有的添加劑的種類、組合、含量等，可依據目的、期望的特性來適當地設定。 The said (meth)acrylic-type resin film may contain arbitrary appropriate additives according to the objective. As additives, for example, antioxidants such as hindered phenol series, phosphorus series, and sulfur series; stabilizers such as light-resistant stabilizers, ultraviolet absorbers, weather-resistant stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; Infrared absorbers; flame retardants such as tris(dibromopropyl) phosphate, triallyl phosphate, antimony oxide, etc.; antistatic agents such as anionic, cationic, and nonionic surfactants; inorganic pigments, Coloring agents for organic pigments and dyes; organic fillers, inorganic fillers; resin modifiers; plasticizers; lubricants; phase difference reducers, etc. The type, combination, content, etc. of the additives to be contained can be appropriately set according to the purpose and desired characteristics.
作為上述(甲基)丙烯酸系樹脂膜的製造方法，無特別限制，例如可為將(甲基)丙烯酸系樹脂、紫外線吸收劑及視需要的其他聚合物、添加劑等，用任意適合的混合方法充分地混合，先成為熱塑性樹脂組成物後，可將其成形為膜。或者，將(甲基)丙烯酸系樹脂、紫外線吸收劑及視需要的其他聚合物、添加劑等成為各溶液後，混合成文均勻的混合液後，將其成形為膜。 The method for producing the (meth)acrylic resin film is not particularly limited, and for example, a (meth)acrylic resin, an ultraviolet absorber, and optionally other polymers, additives, etc. may be mixed by any suitable mixing method. After sufficiently mixing to form a thermoplastic resin composition, it can be formed into a film. Alternatively, the (meth)acrylic resin, ultraviolet absorber, other polymers, additives, and the like are prepared as respective solutions, and a uniform liquid mixture is mixed to form a film.
在製造上述熱塑性樹脂組成物，可用例如萬能混合機等的任意適合的混合機，混合上述膜的原料後，將所得之混合物擠出混練。於該情況中，用於擠出混練的混合機，無特別限制，例如單軸擠出機、二軸擠出機等的擠出機、加壓捏合機等的任意適合的混合機。 In producing the above-mentioned thermoplastic resin composition, any suitable mixer such as a universal mixer can be used to mix the raw materials of the above-mentioned film, and then the obtained mixture is extruded and kneaded. In this case, the mixer used for extrusion kneading is not particularly limited, and any suitable mixer such as extruders such as single-screw extruders and twin-screw extruders, pressurized kneaders, and the like is not particularly limited.
作為上述膜成形的方法，例如溶液鑄膜法(溶液流注法)、熔融擠出法、壓延法(calendaring)、壓縮成形法等的任意適合的膜成形法。熔融擠出法較理想。因熔融擠出法不使用溶劑，可減少製造成本及因溶劑產生的對地球環境、作業環境的負擔。 As the above-mentioned film forming method, for example, any appropriate film forming method such as solution casting method (solution casting method), melt extrusion method, calendaring method (calendaring), compression molding method and the like. Melt extrusion is ideal. Since the melt-extrusion method does not use solvents, it can reduce manufacturing costs and the burden on the global environment and work environment caused by solvents.
作為上述熔融擠出法，例如T型模頭法、膨脹法等。成形溫度，較理想為150至350℃，更理想為200至300℃。 Examples of the melt extrusion method include a T-die method, an expansion method, and the like. The molding temperature is preferably 150 to 350°C, more preferably 200 to 300°C.
用上述T型模頭法進行膜成形的情況，在習知的單軸擠出機、二軸擠出機的前端部安裝T型模頭，捲取擠出成膜狀的膜，可得到卷狀的膜。此時，適當地調整捲取的卷的溫度，在擠出方向上進行延伸，可進行單軸延伸。而且，藉由在垂直擠出方向上進行膜的延伸，可進行同時2軸延伸、逐次2軸延伸等。 In the case of film forming by the above-mentioned T-die method, a T-die is installed at the front end of a known single-screw extruder or a two-screw extruder, and the film is rolled and extruded into a film shape to obtain a rolled film. shaped membrane. At this time, the temperature of the rolled roll is appropriately adjusted, and the stretching is performed in the extrusion direction, whereby uniaxial stretching can be performed. Furthermore, by stretching the film in a direction perpendicular to the extrusion, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed.
上述(甲基)丙烯酸系樹脂，只要是可得到上述所期望的相位差，可為未延伸膜或延伸膜的任一種。於延伸膜的情況，可為1軸延伸膜或2軸延伸膜。於2軸延伸膜的情況，可為同時2軸延伸膜或逐次2軸延伸膜。 The above-mentioned (meth)acrylic resin may be either an unstretched film or a stretched film as long as the above-mentioned desired phase difference can be obtained. In the case of a stretched film, it may be a 1-axis stretched film or a 2-axis stretched film. In the case of a biaxially stretched film, it may be a simultaneously biaxially stretched film or a sequentially biaxially stretched film.
上述延伸溫度，在膜原料的熱塑性樹脂組成物的玻璃轉化溫度附近較理想，具體而言較理想為(玻璃轉化溫度-30℃)至(玻璃轉化溫度+30℃)，更理想為(玻璃轉化溫度-20℃)至(玻璃轉化溫度+20℃)的範圍內。延伸溫度未達(玻璃轉化溫度-30℃)時，所得的膜的霧度變大，或者膜撕裂、破裂，有無法得到指定的延伸倍率的傾向。相反地，延伸溫度超過(玻璃轉化溫度+30℃)時，所得的膜的厚度不均勻性變大、延伸率、撕 裂傳播強度及抗疲勞等的力學性質有無法充分改善的傾向。再者，容易產生膜有黏附於滾輪的問題的傾向。 The above stretching temperature is preferably around the glass transition temperature of the thermoplastic resin composition of the film material, specifically, (glass transition temperature - 30°C) to (glass transition temperature + 30°C), more preferably (glass transition temperature temperature -20°C) to (glass transition temperature +20°C). When the stretching temperature is lower than (glass transition temperature - 30° C.), the haze of the obtained film increases, or the film is torn or cracked, and a predetermined stretching ratio tends not to be obtained. Conversely, when the stretching temperature exceeds (glass transition temperature + 30°C), the thickness unevenness of the resulting film becomes large, and mechanical properties such as elongation, tear propagation strength, and fatigue resistance tend not to be sufficiently improved. Furthermore, there is a tendency for the film to have problems sticking to the rollers.
上述延伸倍率，較理想為1.1至3倍，更理想為1.3至2.5倍。只要是延伸倍率為如此的範圍，可大幅地改善膜的延伸率、撕裂傳播速度及耐揉疲勞等的力學性質。作為結果，厚度不均勻性變小，複折射實質上為零(所以相位差小)，再者可製造霧度小的膜。 The aforementioned elongation ratio is preferably 1.1 to 3 times, more preferably 1.3 to 2.5 times. As long as the elongation ratio is in such a range, mechanical properties such as elongation ratio, tear propagation speed, and kneading fatigue resistance of the film can be greatly improved. As a result, thickness unevenness becomes small, birefringence becomes substantially zero (so that retardation is small), and a film with low haze can be produced.
上述(甲基)丙烯酸系樹脂膜，為了安定化其光學等向性、機械特性，延伸處理後，可進行熱處理(退火處理)等。熱處理的條件，可採用任意適合的條件。 The above-mentioned (meth)acrylic resin film may be subjected to heat treatment (annealing treatment) or the like after stretching in order to stabilize the optical isotropy and mechanical properties. As for the conditions of the heat treatment, any appropriate conditions can be adopted.
上述(甲基)丙烯酸系樹脂膜的光彈性係數，較理想為-3至-100×10-13Pa-1，更理想為-5至-70×10-13Pa-1，更加理想為-15至-50×10-13Pa-1。再者，光彈性係數，係後述的實施例記載的方法所測定的值。 The photoelastic coefficient of the above-mentioned (meth)acrylic resin film is preferably -3 to -100×10 -13 Pa -1 , more preferably -5 to -70×10 -13 Pa -1 , still more preferably - 15 to -50×10 -13 Pa -1 . In addition, the photoelastic coefficient is a value measured by the method described in the Example mentioned later.
上述(甲基)丙烯酸系樹脂膜的厚度，較理想為10μm至200μm，更理想為20μm至100μm。厚度未達10μm時，強度有降低之虞。厚度超過200μm時，透明性有降低之虞。 The thickness of the (meth)acrylic resin film is preferably from 10 μm to 200 μm, more preferably from 20 μm to 100 μm. When the thickness is less than 10 μm, the strength may decrease. When the thickness exceeds 200 μm, there is a possibility that the transparency may decrease.
作為第1保護膜11，可使用與前述相同的膜，可使用其他的樹脂膜。使用例如烯烴系樹脂膜、聚酯系樹脂膜、纖維素系樹脂膜較理想。 As the first
作為鏈狀聚烯烴系樹脂，除聚乙烯樹脂(乙烯的均聚物之聚乙烯樹脂、乙烯為主體的共聚物)、聚丙烯樹脂(丙烯的均聚物之聚丙烯樹脂、丙烯為主體的共聚物)的鏈狀烯烴的均聚物外，可舉例如2種以上的鏈狀烯烴所構成的共聚物。 As the chain polyolefin resin, except polyethylene resin (polyethylene resin of homopolymer of ethylene, copolymer mainly of ethylene), polypropylene resin (polypropylene resin of homopolymer of propylene, copolymer mainly of propylene) In addition to homopolymers of chain olefins, for example, copolymers composed of two or more kinds of chain olefins can be mentioned.
環狀聚烯烴系樹脂係以環狀烯烴為聚合單元而聚合的樹脂的總稱，例如日本公開專利特開平1-240517號公報、特開平3-14882號公報、特開平3-122137號公報等記載的樹脂。列舉環狀聚烯烴系樹脂的具體例，有環狀烯烴的開環(共)聚合物、環狀烯烴的加成聚合物、環狀烯烴與如乙烯、丙烯的鏈狀烯烴的共聚物(代表為無規共聚物)及該等用不飽和羧酸、其衍生物改質的接枝聚合物以及該等的氫化物。其中，作為環狀烯烴，使用降莰烯、多環降莰烯系單體等的降莰烯系單體之降莰烯系樹脂較理想。 Cyclic polyolefin-based resin is a general term for resins polymerized with cyclic olefins as polymerization units, such as those described in Japanese Laid-Open Patent Publication No. 1-240517, Japanese Patent Laid-Open No. 3-14882, and Japanese Patent Laid-Open No. 3-122137 resin. Specific examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (representative It is a random copolymer) and these graft polymers modified with unsaturated carboxylic acids and their derivatives and their hydrogenated products. Among them, as the cyclic olefin, a noramphene-based resin using a noramphene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferable.
聚酯系樹脂，係除下述纖維素酯系樹脂外，具有酯鍵結的樹脂，一般為多元羧酸或其衍生物與多元醇的縮聚物所構成者。作為多元羧酸或其衍生物，可使用2元二羧酸或其衍生物，例如對苯二甲酸、間苯二甲酸、對苯二甲酸二甲酯、萘二甲酸二甲酯。作為多元醇，可使用2元二醇，例如乙二醇、丙二醇、丁二醇、新戊二醇、環己烷二甲醇。作為聚酯系樹脂的代表例，例如對苯二甲酸與乙二醇的縮聚物的聚對苯二甲酸乙二酯。 Polyester-based resins are resins having ester bonds other than the following cellulose ester-based resins, and are generally composed of polycondensates of polycarboxylic acids or their derivatives and polyhydric alcohols. As the polyvalent carboxylic acid or derivatives thereof, dicarboxylic acids or derivatives thereof such as terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalate can be used. As the polyhydric alcohol, dihydric diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexanedimethanol can be used. As a representative example of the polyester-based resin, polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol, is exemplified.
纖維素酯系樹脂係纖維素與脂肪酸的酯。纖維素酯系樹脂的具體例，包括纖維素三乙酸酯、纖維素二乙酸酯、纖維素三丙酸酯、纖維素二丙酸酯。而且，可舉使用該等的共聚物、羥基的一部分用其他取代基修飾者。該等之中，特別理想為纖維素三乙酸酯(三乙醯基纖維素)。 Cellulose ester-based resins are esters of cellulose and fatty acids. Specific examples of cellulose ester-based resins include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Furthermore, those using these copolymers and modifying a part of the hydroxyl group with other substituents are mentioned. Among these, cellulose triacetate (triacetyl cellulose) is particularly desirable.
保護膜11的相位差值設為在波長550nm的面內相位差值Re(550)為70至210nm時，可提高使用者戴太陽眼鏡等的情況之畫面的辨識性。 When the retardation value of the
保護膜11的厚度通常為1至100μm，從強度、操作性的觀點，較理想為5至60μm，更理想為10至55μm，更加理想為15至40μm。 The thickness of the
如上述，保護膜11在其外表面(與偏光片側相反側的面)，可具備如硬塗層、抗眩層、光擴散層、抗反射層、低折射率層、抗靜電層或防汙層的表面處理層(塗佈層)。再者，保護膜11的厚度，包含表面處理層的厚度。 As described above, the
保護膜可例如隔著接著劑層或黏著劑層貼合於偏光片。形成接著劑層的接著劑可使用水系接著劑、活性能量線硬化性接著劑或熱硬化性接著劑，較理想為水系接著劑、活性能量線硬化性接著劑。黏著劑層可使用後述者。 The protective film can be bonded to the polarizer via an adhesive layer or an adhesive layer, for example. As the adhesive for forming the adhesive layer, water-based adhesives, active energy ray-curable adhesives, or thermosetting adhesives can be used, preferably water-based adhesives and active energy ray-curable adhesives. As the adhesive layer, those described later can be used.
水系接著劑例如有由聚乙烯醇系樹脂水溶液所成的接著劑、水系二液型胺酯系乳膠接著劑等。其中，適合使用由聚乙烯醇系樹脂水溶液所成的水系接著劑。作為聚乙烯醇系樹脂者，除乙酸乙烯酯的均聚物之聚乙酸乙烯酯皂化處理所得之聚乙烯醇同元聚合物外，可使用乙酸乙烯酯及可與其共聚合的其他單體的共聚物皂化處理所得之聚乙烯醇系共聚物或該等的羥基部分地改質之改質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、三聚氰胺化合物、羥甲基化合物、異氰酸酯系化合物、胺化合物、多價金屬鹽等的交聯劑。 The water-based adhesive includes, for example, an adhesive made of a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based latex adhesive, and the like. Among these, water-based adhesives made of polyvinyl alcohol-based resin aqueous solutions are suitably used. As polyvinyl alcohol-based resins, in addition to polyvinyl alcohol homopolymers obtained by saponification of polyvinyl acetate homopolymers, copolymers of vinyl acetate and other monomers that can be copolymerized with it can be used. Polyvinyl alcohol-based copolymers obtained by saponification treatment or modified polyvinyl alcohol-based polymers whose hydroxyl groups are partially modified. The water-based adhesive may contain cross-linking agents such as aldehyde compounds (glyoxal, etc.), epoxy compounds, melamine compounds, methylol compounds, isocyanate compounds, amine compounds, and polyvalent metal salts.
於使用水系接著劑的情況，偏光片與保護膜貼合後，實施為了除去包含於水系接著劑中的水之乾燥步驟較理想。乾燥步驟後，可設置例如在20至45℃的溫度下熟化的熟化步驟。 In the case of using a water-based adhesive, after bonding the polarizer and the protective film, it is desirable to perform a drying step for removing water contained in the water-based adhesive. After the drying step, an aging step of aging at a temperature of, for example, 20 to 45° C. may be provided.
上述所謂活性能量線硬化性接著劑，係含有藉由紫外線、可見光、電子線或X射線的活性能量線的照射而硬化的硬化性化合物之接著劑，較理想為紫外線硬化性接著劑。 The active energy ray-curable adhesive mentioned above is an adhesive containing a curable compound that is cured by irradiation of active energy rays such as ultraviolet rays, visible light, electron rays, or X-rays, and is preferably an ultraviolet-curable adhesive.
上述硬化性化合物可為陽離子聚合性的硬化性化合物、自由基聚合性的硬化性化合物。陽離子聚合性的硬化性化合物例如為環氧系化合物(分子內具有1個或2個以上的環氧基的化合物)、氧雜環丁烷(oxetane)系化合物(分子內具有1個或2個以上的氧雜環丁烷基的化合物)或該等的組合。自由基聚合性的硬化性化合物例如為(甲基)丙烯酸系化合物(分子內具有1個或2個以上的(甲基)丙烯醯氧基的化合物)、具有自由基聚合性的雙鍵的其他乙烯系化合物或該等的組合。亦可併用陽離子聚合性的硬化性化合物及自由基聚合性的硬化性化合物。活性能量線硬化性接著劑通常再包含為了起始上述硬化性化合物的硬化反應之陽離子聚合起始劑及/或自由基聚合起始劑。 The aforementioned curable compound may be a cation polymerizable curable compound or a radical polymerizable curable compound. Cationic polymerizable curable compounds are, for example, epoxy-based compounds (compounds having one or more epoxy groups in the molecule), oxetane (oxetane)-based compounds (having one or two epoxy groups in the molecule). the above oxetanyl compound) or a combination thereof. Radical polymerizable curable compounds are, for example, (meth)acrylic compounds (compounds having one or more (meth)acryloxy groups in the molecule), and other compounds having radical polymerizable double bonds. Vinyl compounds or combinations thereof. A cation polymerizable curable compound and a radical polymerizable curable compound may also be used together. The active energy ray-curable adhesive usually further contains a cationic polymerization initiator and/or a radical polymerization initiator for initiating the curing reaction of the above-mentioned curable compound.
偏光片與保護膜貼合時，為了提高接著性，在該等的至少一貼合面可實施表面活性化處理。表面活性化處理例如為電暈處理、電漿處理、放電處理(電弧放電處理等)、火焰處理、臭氧處理、UV臭氧處理及電離輻射處理(紫外線處理、電子線處理等)的乾式處理；如使用水、丙酮等的溶劑的超音波處理、皂化處理及錨定處理的濕式處理。該等的表面活性化處理可單獨進行，亦可組合2個以上。 When the polarizer is bonded to the protective film, in order to improve the adhesion, at least one of the bonding surfaces can be subjected to surface activation treatment. Surface activation treatment is, for example, dry treatment of corona treatment, plasma treatment, discharge treatment (arc discharge treatment, etc.), flame treatment, ozone treatment, UV ozone treatment and ionizing radiation treatment (ultraviolet treatment, electron beam treatment, etc.); Wet treatment of ultrasonic treatment, saponification treatment, and anchor treatment using solvents such as water and acetone. These surface-activating treatments may be performed alone or in combination of two or more.
於偏光片的兩面貼合保護膜的情況，貼合該等的保護膜用的接著劑可為相同種的接著劑，亦可為不同種的接著劑。 When bonding a protective film to both surfaces of a polarizer, the adhesive agent for bonding these protective films may be the same kind of adhesive agent, and may be different kinds of adhesive agents.
〈相位差膜〉 <Retardation film>
本發明的圓偏光板具有相位差膜，前述相位差膜具有相位差層。相位差層具有由包含聚合性液晶化合物的組成物所構成的層較理想。所謂由包含聚合性液晶化合物的組成物所構成的層，具體而言係指由聚合性液晶化合物硬化而成的層。於本說明書，賦予λ/2的相位差的層、賦予λ/4的相位差的層(正A層)及正C層等，總稱為相位差層。再者，相位差膜亦可包含後述的配向膜。 The circular polarizing plate of the present invention has a retardation film, and the retardation film has a retardation layer. The retardation layer preferably 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 refers to a layer cured from a polymerizable liquid crystal compound. In this specification, the layer imparted with a retardation of λ/2, the layer imparted with a retardation of λ/4 (positive A layer), the positive C layer, and the like are collectively referred to as retardation layers. Furthermore, the retardation film may also include an alignment film described later.
由聚合性液晶化合物硬化而成的層，例如形成於設置於基材之配向膜上。前述基材具有支持配向膜的功能，可為形成為長條狀的基材。該基材係作為離型性支持體發揮功能，可支持轉印用的相位差層。再者，其表面具有可剝離的程度之接著力者較理想。前述基材例如為作為上述保護膜的材料而例示的樹脂膜。 The layer cured from the polymerizable liquid crystal compound is, for example, formed on an alignment film provided on a substrate. The aforementioned substrate has the function of supporting the alignment film, and may be a strip-shaped substrate. This substrate functions as a release support and can support a retardation layer for transfer. Furthermore, it is more desirable that the surface has peelable adhesive force. The aforementioned base material is, for example, the resin film exemplified as the material of the aforementioned protective film.
基材的厚度無特別限制，例如20μm以上200μm以下的範圍較理想。基材的厚度為20μm以上時，可賦予強度。另一方面，厚度為200μm以下時，在裁切加工基材成為片狀基材時，可抑制加工屑的增加、裁切刀的磨損。 The thickness of the base material is not particularly limited, for example, it is preferably in the range of 20 μm or more and 200 μm or less. Strength can be imparted when the thickness of a base material is 20 micrometers or more. On the other hand, when the thickness is 200 μm or less, when the cut base material is a sheet base material, the increase of machining waste and the wear of the cutting blade can be suppressed.
再者，基材可實施各種防止結塊的處理。防止結塊的處理例如有易接著處理、捏合填充劑等的處理、壓花加工(滾花處理等)等。藉由對基材實施如此的防止結塊的處理，在捲取基材時，可有效地防止基材之間的黏附、即所謂的結塊，可生產性高地製造光學膜。 Furthermore, the substrate can be subjected to various anti-caking treatments. The blocking prevention treatment includes, for example, an easy-adhesive treatment, a treatment such as kneading a filler, embossing (knurling treatment, etc.), and the like. By performing such blocking prevention treatment on the base material, it is possible to effectively prevent the adhesion between the base materials, that is, the so-called blocking when the base material is taken up, and to manufacture an optical film with high productivity.
由聚合性液晶化合物硬化而成的層係隔著配向膜形成於基材上。亦即，於前述配向膜上依序積層基材、配向膜、由聚合性液晶化合物硬化而成的層積層。 The layers formed by hardening the polymerizable liquid crystal compound are formed on the base material through the alignment film. That is, the base material, the alignment film, and the lamination layer hardened by the polymerizable liquid crystal compound are sequentially laminated on the aforementioned alignment film.
再者，配向膜不限於垂直配向膜，可為使聚合性液晶化合物的分子軸水平配向的配向膜，亦可為使聚合性液晶化合物的分子軸傾斜配向的配向膜。配向膜較理想為具有不因塗佈後述包含聚合性液晶化合物的組成物等而溶解的耐溶劑性，而且具有為了除去溶劑、液晶化合物配向的加熱處理的耐熱性。配向膜可舉例如包含配向性聚合物的配向膜、光配向膜、及表面形成凹凸形狀、複數溝槽而配向的溝槽配向膜。配向膜的厚度通常為10nm至10000nm的範圍，較理想為10nm至1000nm的範圍，更理想為500nm以下，更加理想為10nm至200nm的範圍。於相位差膜具有配向膜的情況，配向膜的厚度增加時，易於增加穿刺彈性模數。配向膜的厚度為上述範圍時，可賦予聚合性液晶化合物適度的剛性及韌性，可賦予高膜強度。 Furthermore, the alignment film is not limited to a vertical alignment film, and may be an alignment film that aligns the molecular axes of the polymerizable liquid crystal compound horizontally, or may be an alignment film that aligns the molecular axes of the polymerizable liquid crystal compound obliquely. The alignment film preferably has solvent resistance not to be dissolved by application of a composition containing a polymerizable liquid crystal compound described later, and heat resistance for solvent removal and heat treatment for alignment of the liquid crystal compound. The alignment film can be, for example, an alignment film containing an alignment polymer, a photo-alignment film, and a groove alignment film in which a concave-convex shape and a plurality of grooves are formed on the surface for alignment. The thickness of the alignment film is usually in the range of 10 nm to 10000 nm, more preferably in the range of 10 nm to 1000 nm, more preferably less than 500 nm, and more preferably in the range of 10 nm to 200 nm. In the case where the retardation film has an alignment film, when the thickness of the alignment film increases, the puncture elastic modulus tends to increase. When the thickness of the alignment film is within the above range, moderate rigidity and toughness can be imparted to the polymerizable liquid crystal compound, and high film strength can be imparted.
作為配向膜所使用的樹脂，只要是使用作為習知的配向膜的材料之樹脂，則無特別限制，可使用傳統習知的單官能基或多官能基的(甲基)丙烯酸酯系單體在聚合起始劑下硬化的硬化物等。具體而言作為(甲基)丙烯酸酯系單體，例如丙烯酸2-乙基己酯、丙烯酸環己酯、二乙二醇單2-乙基己基醚丙烯酸酯、二乙二醇單苯基醚丙烯酸酯、四乙二醇單苯基醚丙烯酸酯、三羥甲基丙烷三丙烯酸酯、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、丙烯酸四氫呋喃酯、丙烯酸2-羥基丙酯、丙烯酸苯甲酯、甲基丙烯酸四氫呋喃酯、丙烯酸2-羥基乙酯、甲基丙烯酸苯甲酯、甲基丙烯酸環己酯、甲基丙烯酸、胺酯丙烯酸酯等。再者，樹脂可為此等的1種，也可為2種以上的混合物。 As the resin used for the alignment film, as long as it is the resin used as the material of the known alignment film, there is no special limitation, and conventionally known monofunctional or polyfunctional (meth)acrylate monomers can be used. A cured product that hardens with a polymerization initiator, etc. Specifically, as (meth)acrylate-based monomers, for example, 2-ethylhexyl acrylate, cyclohexyl acrylate, diethylene glycol mono-2-ethylhexyl ether acrylate, diethylene glycol monophenyl ether Acrylates, tetraethylene glycol monophenyl ether acrylate, trimethylolpropane triacrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-phenoxy acrylate Ethyl acrylate, tetrahydrofuryl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, tetrahydrofuryl methacrylate, 2-hydroxyethyl acrylate, benzyl methacrylate, cyclohexyl methacrylate, methacrylic acid , urethane acrylate, etc. In addition, resin may be these 1 type, and may be a mixture of 2 or more types.
本實施態樣所使用的聚合性液晶化合物的種類無特別限制，由其形狀，可分類為棒狀(棒狀液晶化合物)及圓盤狀(圓盤狀液晶化合物、盤狀液晶化合物)。再者，分別有低分子型及高分子型。再者，所謂高分子，一般係指聚合度為100以上者(高分子物理‧相變動力學、土井正難著、2頁、岩波書店、1992)。 The type of polymerizable liquid crystal compound used in this embodiment is not particularly limited, and can be classified into rod-shaped (rod-shaped liquid crystal compound) and disk-shaped (disco-shaped liquid crystal compound, discotic liquid crystal compound) according to its shape. Furthermore, there are low molecular type and high molecular type respectively. Furthermore, the so-called polymers generally refer to those with a degree of polymerization of 100 or more (Polymer Physics‧Phase Transition Dynamics, Masazu Doi, 2 pages, Iwanami Shoten, 1992).
於本實施態樣，可使用任何的聚合性液晶化合物。再者，可使用2種以上的棒狀液晶化合物、2種以上的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的混合物。 In this embodiment, any polymerizable liquid crystal compound can be used. Furthermore, two or more rod-shaped liquid crystal compounds, two or more kinds of discotic liquid crystal compounds, or a mixture of rod-shaped liquid crystal compounds and discotic liquid crystal compounds can be used.
再者，作為棒狀液晶化合物，可適合使用例如特表平11-513019號公報的請求項1或特開2005-289980號公報的段落[0026]至[0098]記載者。作為圓盤狀液晶化合物，可適合使用例如特開2007-108732號公報的段落[0020]至[0067]或特開2010-244038號公報的段落[0013]至[0108]記載者。 Furthermore, as the rod-shaped liquid crystal compound, for example, those described in
聚合性液晶化合物可併用2種以上。該情況中，至少1種為分子內具有2個以上的聚合性基。亦即，由前述聚合性液晶化合物硬化而成的層，較理想為具有聚合性基的液晶化合物藉由聚合而固定所形成的層。該情況中，在成為層後已不再需要顯示液晶性。 Two or more kinds of polymerizable liquid crystal compounds may be used in combination. In this case, at least one type has two or more polymerizable groups in the molecule. That is, the layer formed by hardening the polymerizable liquid crystal compound is preferably a layer formed by fixing the liquid crystal compound having a polymerizable group by polymerization. In this case, it is no longer necessary to exhibit liquid crystallinity after becoming a layer.
聚合性液晶化合物具有可聚合反應的聚合性基。聚合性基例如為聚合性乙烯性不飽和基、環聚合性基等的可加成聚合反應的官能基較理想。更具體而言，聚合性基例如為(甲基)丙烯醯基、乙烯基、苯乙烯基、烯丙基等。其中，(甲基)丙烯醯基較理想。再者，所謂(甲基)丙烯醯基，包含甲基丙烯醯基及丙烯醯基的概念。 The polymerizable liquid crystal compound has a polymerizable group that can be polymerized. The polymerizable group is preferably, for example, a functional group capable of addition polymerization such as a polymerizable ethylenically unsaturated group and a ring polymerizable group. More specifically, the polymerizable group is, for example, a (meth)acryl group, a vinyl group, a styryl group, an allyl group, or the like. Among them, a (meth)acryl group is preferable. Furthermore, the so-called (meth)acryl group includes the concept of methacryl group and acryl group.
如後述，由聚合性液晶化合物硬化而成的層可藉由塗佈包含聚合性液晶化合物的組成物於例如配向膜上，並照射活性能量線而形成。於前述組成物亦可包含上述聚合性液晶化合物以外的成分。例如，於前述組成物包含聚合起始劑則較理想。關於所使用的聚合起始劑，係依據聚合反應的型式，選擇例如熱聚合起始劑、光聚合起始劑。例如，光聚合起始劑例如有α-羰基化合物、醇酮基醚、α-烴基取代芳香族醇酮基化合物、多核醌化合物、三芳香基咪唑二聚物與對-胺基苯基酮的組合。相對於前述塗佈液中的全部固體成分而言，聚合起始劑的使用量較理想為0.01至20質量%，更理想為0.5至5質量%。 As will be described later, the layer cured from the polymerizable liquid crystal compound can be formed by coating a composition containing the polymerizable liquid crystal compound on, for example, an alignment film and irradiating active energy rays. Components other than the above-mentioned polymerizable liquid crystal compound may also be included in the aforementioned composition. For example, it is preferable to include a polymerization initiator in the aforementioned composition. The polymerization initiator used is selected according to the type of polymerization reaction, such as thermal polymerization initiator and photopolymerization initiator. For example, photopolymerization initiators such as α-carbonyl compounds, alcohol ketone ethers, α-hydrocarbyl substituted aromatic alcohol ketone compounds, polynuclear quinone compounds, triaryl imidazole dimers, and p-aminophenyl ketones combination. The amount of the polymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, relative to the total solid content in the coating liquid.
而且，從塗佈膜的均勻性及膜的強度的點而言，於前述組成物可包含聚合性單體。聚合性單體例如為自由基聚合性或陽離子聚合性的化合物。其中，較理想為多官能性自由基聚合性單體。 Furthermore, from the viewpoint of the uniformity of the coating film and the strength of the film, a polymerizable monomer may be contained in the aforementioned composition. The polymerizable monomer is, for example, a radically polymerizable or cationically polymerizable compound. Among them, polyfunctional radically polymerizable monomers are more preferable.
再者，聚合性單體為可與上述聚合性液晶化合物共聚合者則較理想。相對聚合性液晶化合物的全部質量而言，聚合性單體的使用量較理想為1至50質量%，更理想為2至30質量%。 Furthermore, it is preferable that the polymerizable monomer is copolymerizable with the above-mentioned polymerizable liquid crystal compound. The amount of the polymerizable monomer used is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, relative to the total mass of the polymerizable liquid crystal compound.
而且，從塗佈膜的均勻性及膜的強度的點而言，於前述組成物中可包含界面活性劑。界面活性劑例如為傳統習知的化合物。其中，特別理想為氟系化合物。 Furthermore, from the viewpoint of the uniformity of the coating film and the strength of the film, a surfactant may be contained in the aforementioned composition. Surfactants are, for example, conventionally known compounds. Among them, fluorine-based compounds are particularly preferable.
而且，於前述組成物可包含溶劑，使用有機溶劑則較理想。有機溶劑例如為醯胺(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)、鹵化烷(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，較理想為鹵化烷、酮。而且，可併用2種以上的有機溶劑。 Furthermore, the aforementioned composition may contain a solvent, and it is preferable to use an organic solvent. Organic solvents are, for example, amides (such as N,N-dimethylformamide), argonoxides (such as dimethylsulfoxide), heterocyclic compounds (such as pyridine), hydrocarbons (such as benzene, hexane), halogenated 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). Among them, alkyl halides and ketones are more preferable. Furthermore, two or more organic solvents may be used in combination.
而且，於前述組成物中，可包含偏光片界面側垂直配向劑、空氣界面側垂直配向劑等垂直配向促進劑以及偏光片界面側水平配向劑、空氣界面側水平配向劑等水平配向促進劑之各種配向劑。再者，於前述組成物，除上述成分以外，可包括黏合改進劑、塑化劑、聚合物等。 Moreover, in the aforementioned composition, vertical alignment promoters such as vertical alignment agents on the interface side of the polarizer and vertical alignment agents on the air interface side, and horizontal alignment promoters such as horizontal alignment agents on the interface side of the polarizer and horizontal alignment agents on the air interface side may be included. Various aligning agents. Furthermore, the aforementioned composition may include, in addition to the aforementioned components, an adhesion improver, a plasticizer, a polymer, and the like.
上述活性能量線包含紫外線、可見光、電子線、X射線，較理想為紫外線。前述活性能量線的光源例如為低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈、鹵素燈、碳弧燈、鎢燈、鎵燈、準分子雷射、在波長範圍為380至440nm發光的LED光源、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈等。 The above-mentioned active energy rays include ultraviolet rays, visible light, electron rays, and X-rays, preferably ultraviolet rays. The light sources of the aforementioned active energy lines are, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, and emit light in the wavelength range of 380 to 440 nm. LED light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.
紫外線的照射強度，通常在紫外線B波的情況(波長區域280至320nm)為10mW/cm2至3,000mW/cm2。紫外線照射強度較理想為在光陽離子聚合起始劑及光自由基聚合起始劑的活性化有效的波長區域的強度。照射紫外線的時間通常為0.1秒至10分鐘，較理想為0.1秒至5分鐘，更理想為0.1秒至3分鐘，更加理想為0.1秒至1分鐘。 The irradiation intensity of ultraviolet rays is usually 10 mW/cm 2 to 3,000 mW/cm 2 in the case of ultraviolet B waves (wavelength region 280 to 320 nm). The intensity of ultraviolet irradiation is preferably an intensity in a wavelength range in which the activation of the photocationic polymerization initiator and the photoradical polymerization initiator is effective. The time for irradiating ultraviolet rays is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and still more preferably 0.1 second to 1 minute.
紫外線可照射1次或分成複數次照射。紫外線照射複數次較理想。根據所使用的聚合起始劑，波長365nm的累積光量為700mJ/cm2以上較理想，更理想為1,100mJ/cm2以上，更加理想為1,300mJ/cm2以上。為上述累積光量時，因提高構成相位差膜的聚合性液晶化合物的聚合率，在提高耐熱性上有利。波長365nm的累積光量為2,000 mJ/cm2以下較理想，1,800mJ/cm2以下更理想。上述累積光量時，可能導致相位差膜著色。 Ultraviolet rays can be irradiated once or divided into multiple times. It is ideal to irradiate ultraviolet rays multiple times. Depending on the polymerization initiator used, the cumulative light intensity at a wavelength of 365 nm is preferably 700 mJ/cm 2 or more, more preferably 1,100 mJ/cm 2 or more, and still more preferably 1,300 mJ/cm 2 or more. When the accumulated light amount is the above, it is advantageous in improving heat resistance because the polymerization rate of the polymerizable liquid crystal compound constituting the retardation film is increased. The cumulative light intensity at a wavelength of 365nm is preferably 2,000 mJ/cm 2 or less, more preferably 1,800 mJ/cm 2 or less. When the amount of accumulated light is above, the retardation film may be colored.
於本實施態樣中，相位差層的厚度為0.5μm以上較理想。而且，前述相位差層的厚度為10μm以下較理想，5μm以下更理想。再者，上述的上限值及下限值，可任意地組合。相位差層的厚度為前述的下限值以上時，可得到充分的耐久性。相位差層的厚度為前述的上限值以下時，可貢獻圓偏光板的薄層化。相位差層的厚度，可以得到賦予λ/4的層、賦予λ/2的層或正C層所期望的面內相位差值及厚度方向的相位差值的方式調整。 In this embodiment, the thickness of the retardation layer is preferably 0.5 μm or more. Furthermore, the thickness of the retardation layer is preferably 10 μm or less, more preferably 5 μm or less. In addition, the above-mentioned upper limit and lower limit can be combined arbitrarily. Sufficient durability is acquired as the thickness of a retardation layer is more than the said lower limit. When the thickness of a retardation layer is below the said upper limit, it can contribute to thinning of a circularly polarizing plate. The thickness of the retardation layer can be adjusted so as to obtain a desired in-plane retardation value and retardation value in the thickness direction for the layer imparted with λ/4, the layer imparted with λ/2, or the positive C layer.
相位差膜可為包含1層的由聚合性液晶化合物硬化而成的層，亦可為包含2層以上的由聚合性液晶化合物硬化而成的層。於相位差膜為包含2層的由聚合性液晶化合物硬化而成的層的情況，2層為賦予λ/4的層與正C層的組合，或者賦予λ/4的層與賦予λ/2的層的組合則較理想。於相位差膜為包含2層之由聚合性液晶化合物硬化而成的層的情況，較宜為分別在配向膜上製作由聚合性液晶化合物硬化而成的層，並將兩者隔著接著劑層、黏著劑層積層，藉此製造相位差膜。可在將兩者積層後，剝離基材及配向膜。相位差膜的厚度較理想為3至30μm，更理想為5至25μm。 The retardation film may include one layer cured from a polymerizable liquid crystal compound, or may include two or more layers cured from a polymerizable liquid crystal compound. In the case where the retardation film is a layer composed of two layers cured by a polymerizable liquid crystal compound, the two layers are a combination of a λ/4-imparted layer and a positive C layer, or a λ/4-imparted layer and a λ/2-imparted layer. The combination of layers is ideal. In the case where the retardation film consists of two layers hardened by a polymerizable liquid crystal compound, it is preferable to form a layer hardened by a polymerizable liquid crystal compound on the alignment film, and separate the two layers with an adhesive. Layers and adhesives are laminated to produce retardation films. After laminating the two, the substrate and the alignment film can be peeled off. The thickness of the retardation film is preferably 3 to 30 μm, more preferably 5 to 25 μm.
上述相位差膜的光彈性係數較理想為3至100×10-13Pa-1，更理想為5至70×10-13Pa-1，更加理想為15至60×10-13Pa-1，又更加理想為20至60×10-13Pa-1。再者，光彈性係數係後述的實施例記載的方法所測定的值。 The photoelastic coefficient of the retardation film is preferably 3 to 100×10 -13 Pa -1 , more preferably 5 to 70×10 -13 Pa -1 , still more preferably 15 to 60×10 -13 Pa -1 , More preferably, it is 20 to 60×10 -13 Pa -1 . In addition, the photoelastic coefficient is the value measured by the method described in the Example mentioned later.
〈黏著劑層〉 <Adhesive layer>
黏著劑層可用以(甲基)丙烯酸系、橡膠系、胺酯系、酯系、聚矽氧系、聚乙烯醚系的樹脂為主成分的黏著劑組成物來構成。其中，適合使用以透明性、耐候性、耐熱性等佳的(甲基)丙烯酸系樹脂為基質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。黏著劑層的厚度通常為3至30μm，較理想為3至25μm。 The adhesive layer can be composed of an adhesive composition mainly composed of (meth)acrylic, rubber, urethane, ester, silicone, or polyvinyl ether resins. Among them, an adhesive composition using a (meth)acrylic resin having excellent transparency, weather resistance, heat resistance, etc. as a matrix polymer is suitably used. The adhesive composition may be an active energy ray curing type or a thermosetting type. The thickness of the adhesive layer is usually 3 to 30 μm, preferably 3 to 25 μm.
作為黏著劑組成物所使用的(甲基)丙烯酸系樹脂(基質聚合物)，適合使用例如將(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯般之(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。較理想為於基質聚合物共聚合極性單體。極性單體例如為(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、N,N-二甲基胺基乙基(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯的具有羧基、羥基、醯胺基、胺基、環氧基等的單體。 As the (meth)acrylic resin (matrix polymer) used in the adhesive composition, for example, butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, A polymer or copolymer of one or more (meth)acrylates such as 2-ethylhexyl (meth)acrylate as a monomer. Ideally, the polar monomers are copolymerized with the matrix polymer. Polar monomers such as (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl A monomer having a carboxyl group, a hydroxyl group, an amido group, an amino group, an epoxy group, etc., such as (meth)acrylate and glycidyl (meth)acrylate.
黏著劑組成物可為只包含上述基質聚合物者，但通常再含有交聯劑。交聯劑可例示有屬於2價以上的金屬離子並與羧基間形成羧酸金屬鹽者；屬於聚胺化合物並與羧基間形成醯胺鍵者；屬於聚環氧化合物、聚醇並與羧基間形成酯鍵者；屬於聚異氰酸酯化合物並與羧基間形成醯胺鍵者。其中，較理想為聚異氰酸酯化合物。 The adhesive composition may only contain the above-mentioned matrix polymer, but usually further contains a crosslinking agent. Examples of the cross-linking agent include metal ions having a valence of two or more and forming a metal carboxylate salt with carboxyl groups; polyamine compounds and forming amide bonds with carboxyl groups; polyepoxides, polyalcohols and carboxyl groups. Those who form ester bonds; belong to polyisocyanate compounds and form amide bonds with carboxyl groups. Among these, polyisocyanate compounds are more preferable.
〈前面板〉 <Front panel>
前面板配置於偏光板的觀看側。前面板可隔著接著層積層於偏光板。接著層例如為前述的黏著劑層、接著劑層。如第2圖(a)、(b)所示，前面板4可隔著黏著劑層16積層在偏光板1之保護膜11上。 The front panel is arranged on the viewing side of the polarizer. The front panel can be laminated on the polarizing plate through the next layer. The adhesive layer is, for example, the aforementioned adhesive layer and adhesive layer. As shown in (a) and (b) of FIG. 2 , the
前面板例如為在玻璃、樹脂膜的至少一面包含硬塗層者。玻璃可使用例如高穿透玻璃、強化玻璃。特別是使用薄透明材料的情況，較理想為實施化學強化的玻璃。玻璃的厚度可為例如100μm至5mm。 The front panel includes, for example, a hard coat layer on at least one side of glass or a resin film. As the glass, for example, high transmission glass and tempered glass can be used. Especially when using a thin transparent material, chemically strengthened glass is preferable. The thickness of the glass may be, for example, 100 μm to 5 mm.
樹脂膜的至少一面包含硬塗層所成的前面板，不像現有的玻璃般地堅硬，可具有可撓性。硬塗層的厚度無特別限制，可為例如5至100μm。 At least one side of the resin film includes a hard coat layer, which is not as hard as conventional glass and can be flexible. The thickness of the hard coat layer is not particularly limited, and may be, for example, 5 to 100 μm.
樹脂膜可為具有如降莰烯或多環降莰烯系單體的包含環烯烴的單體的單元之環烯烴系衍生物、纖維素(二乙醯基纖維素、三乙醯基纖維素、乙醯基纖維素丁酸酯、異丁酯纖維素、丙醯基纖維素、丁醯基纖維素、乙醯基丙醯基纖維素)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、聚偏二氯乙烯、聚乙烯醇、聚乙烯醇縮醛、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、聚胺酯、環氧樹脂等的高分子所形成的膜。樹脂膜可使用未延伸、1軸或2軸延伸膜。該等高分子可分別單獨使用，亦可混合2種以上使用。樹脂膜較理想為透明性及耐熱性佳的聚醯胺醯亞胺膜或聚醯亞胺膜、1軸或2軸延伸的聚酯膜、透明性及耐熱性佳且可對應膜的大型化的環烯烴系衍生膜、聚甲基丙烯酸甲酯及透明性及無光學各向異性的三乙 醯基纖維素及異丁酯纖維素膜。樹脂膜的厚度為5至200μm，較理想為20至100μm。 The resin film may be a cycloolefin-based derivative having a unit of a cycloolefin-containing monomer such as norcamphene or a polycyclic norbornene-based monomer, cellulose (diacetyl cellulose, triacetyl cellulose , Acetyl cellulose butyrate, isobutyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose) ethylene-vinyl acetate copolymer, polycycloolefin, polyester, Polystyrene, polyamide, polyetherimide, polyacrylic acid, polyimide, polyamideimide, polyether, polyethylene, polypropylene, polymethylpentene, polychloride Ethylene, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether ketone, polymethyl methacrylate, polyethylene terephthalate, polyethylene terephthalate Films made of polymers such as butylene dicarboxylate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy resin. As the resin film, unstretched, 1-axis or 2-axis stretched film can be used. These polymers may be used alone or in combination of two or more. The resin film is preferably a polyamide-imide film or a polyimide film with excellent transparency and heat resistance, or a 1-axis or 2-axis stretched polyester film, which has excellent transparency and heat resistance and can be used to increase the size of the film. Cycloolefin derived film, polymethyl methacrylate and transparent and non-optical anisotropic triacetyl cellulose and isobutyl cellulose film. The thickness of the resin film is 5 to 200 μm, preferably 20 to 100 μm.
前述硬塗層可藉由包含照射光或熱能而形成交聯構造的反應性材料之硬塗組成物的硬化而形成。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，及光硬化型環氧基單體或寡聚物之硬塗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環氧基(甲基)丙烯酸酯、胺酯(甲基)丙烯酸酯及聚酯(甲基)丙烯酸酯構成所組成群組中的1種以上。前述環氧基(甲基)丙烯酸酯可藉由對環氧化合物使(甲基)丙烯醯基的羧酸反應而得。 The aforementioned hard coat layer can be formed by curing a hard coat composition including a reactive material that forms a crosslinked structure by irradiation with light or heat energy. The above-mentioned hard coat layer can be formed by hardening a hard coat composition including a photocurable (meth)acrylate monomer or oligomer and a photocurable epoxy monomer or oligomer at the same time. The aforementioned photocurable (meth)acrylate monomers may include epoxy (meth)acrylates, urethane (meth)acrylates, and polyester (meth)acrylates. 1 or more. The said epoxy (meth)acrylate can be obtained by reacting the carboxylic acid of a (meth)acryl group with respect to an epoxy compound.
硬塗組成物可再包含選自光起始劑及添加劑所組成群組中的一個以上。添加劑可包含選自無機奈米粒子、調平劑及安定劑所組成群組中的一個以上，於此之外，就本技術領域通常使用的各成分而言，可再包含例如抗氧化劑、UV吸收劑、界面活性劑、潤滑劑、防汙劑等。 The hard coating composition may further include one or more selected from the group consisting of photoinitiators and additives. Additives can include more than one selected from the group consisting of inorganic nanoparticles, leveling agents, and stabilizers. In addition, for each component commonly used in this technical field, it can further include, for example, antioxidants, UV Absorbents, surfactants, lubricants, antifouling agents, etc.
〈遮光圖案〉 <shading pattern>
遮光圖案可提供作為前面板或適用前面板的顯示裝置的外框或殼體的至少一部分。遮光圖案可隱藏顯示裝置的各配線，不讓使用者見到。遮光圖案的顏色及/或材質無特別限制，可用具有黑色、白色、金色等的多種顏色的樹脂物質形成。於一實施態樣，遮光圖案的厚度可為2μm至50μm，較理想為4μm至30μm，更理想為6μm至15μm的範圍。而且，為了抑制因遮光圖案與顯示部之間的階差而混入的氣泡及邊界的辨識度，可對遮光圖案賦予形狀。 The light-shielding pattern may be provided as a front panel or at least a part of a frame or a case of a display device to which the front panel is applied. The light-shielding pattern can hide each wiring of the display device and prevent users from seeing it. The color and/or material of the light-shielding pattern is not particularly limited, and it can be formed by resin materials with various colors such as black, white, and gold. In an embodiment, the thickness of the light-shielding pattern may be in the range of 2 μm to 50 μm, more preferably 4 μm to 30 μm, more preferably 6 μm to 15 μm. Furthermore, in order to suppress visibility of air bubbles and boundaries mixed in due to the step difference between the light-shielding pattern and the display portion, a shape may be given to the light-shielding pattern.
〈圓偏光板的製造方法〉 <Manufacturing method of circular polarizing plate>
第1圖(a)所示的圓偏光板100為例，說明圓偏光板的製造方法。圓偏光板100可藉由將偏光板1及相位差膜2隔著黏著劑層13積層而製造。 The circular
偏光板1可藉由將偏光片10及保護膜11、12分別隔著接著劑層積層而製造。關於偏光板，可準備長條狀的構件，用捲至捲(roll to roll)貼合各構件後，裁切為指定的形狀而製造，亦可將各構件裁切為指定的形狀後貼合。於偏光片10貼合保護膜11、12後，可設置加熱步驟、調濕步驟。 The
相位差膜2例如可用下述方式製造。於基材上形成配向膜，在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的狀態下，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硬化而成的層上，使形成於剝離膜上的黏著劑層14積層。然後，剝離基材及/或配向膜。然後，在保護膜12上，使形成於剝離膜上的黏著劑層13積層。關於相位差膜2，可準備長條狀的構件，用捲至捲方式貼合各構件後，裁切為指定的形狀而製造，亦可將各構件裁切為指定的形狀後貼合。 The
然後，剝離積層於黏著劑層13的剝離膜，隔著黏著劑層13貼合相位差膜2與偏光板1，藉此可製作圓偏光板100。 Then, the release film laminated on the
〈用途〉 〈Purpose〉
圓偏光板可使用於各種顯示裝置。所謂顯示裝置，係指具有顯示元件的裝置，包括發光元件或發光裝置作為發光源。顯示裝置例如為液晶顯示裝置、有機EL顯示裝置、無機電致發光(以下也稱為無機EL裝置)顯示裝置、電子發射顯示裝置(例如電場發射顯示裝置(也稱為FED)、表面場發 射顯示裝置(也稱為SED))、電子紙(使用電子墨水、電泳元件的顯示裝置)、電漿顯示裝置、投射型顯示裝置(例如光柵光閥(也稱為GLV)顯示裝置、具有數位微鏡裝置(也稱為DMD)顯示裝置)及壓電陶瓷顯示器等。液晶顯示裝置包含穿透型液晶顯示裝置、半穿透型液晶顯示裝置等的任一種。該等顯示裝置可為顯示二維影像的顯示裝置，亦可為顯示三維影像的立體顯示裝置。圓偏光板使用在有機EL顯示裝置或無機EL顯示裝置上係特別有效。 Circular polarizers can be used in various display devices. The so-called display device refers to a device having a display element, including a light-emitting element or a light-emitting device as a light-emitting source. The display device is, for example, a liquid crystal display device, an organic EL display device, an inorganic electroluminescence (hereinafter also referred to as an inorganic EL device) display device, an electron emission display device (such as an electric field emission display device (also referred to as an FED), a surface field emission display device, etc. device (also called SED)), electronic paper (display device using electronic ink, electrophoretic element), plasma display device, projection display device (such as grating light valve (also called GLV) display device, with digital micromirror device (also known as DMD) display device) and piezoelectric ceramic display, etc. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, and the like. These display devices may be display devices for displaying two-dimensional images, or may be stereoscopic display devices for displaying three-dimensional images. The circular polarizing plate is particularly effective when used in an organic EL display device or an inorganic EL display device.
於第2圖(a)、(b)中，有機EL顯示裝置104、105具有圓偏光板隔著積層在相位差膜20上的黏著劑層14積層於有機EL顯示元件3的層構成。 In (a) and (b) of FIG. 2 , the organic
以下，顯示實施例以更具體地說明本發明，但本發明不限於該等例。例中，表示含量或使用量的份及%，除非另有說明，其係重量基準。再者，以下的例之各物性的測定係使用以下的方法進行。 Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to these examples. In the examples, parts and % indicating the content or usage amount are based on weight unless otherwise stated. In addition, the measurement of each physical property of the following example was performed using the following method.
(1)膜厚的測定方法 (1) Measuring method of film thickness
使用尼康(Nikon)股份有限公司製的數位測微計MH-15測定。 Measurement was performed using a digital micrometer MH-15 manufactured by Nikon Corporation.
(2)相位差值測定方法 (2) Phase difference measurement method
使用相位差測定裝置KOBRA-WPR(王子計測機器股份有限公司製)進行測定。 The measurement was performed using a phase difference measuring device KOBRA-WPR (manufactured by Oji Scientific Instruments Co., Ltd.).
(3)反射色調的測定方法 (3) Measuring method of reflection hue
使用分光測色計(Konica MinoltaJAPAN股份有限公司商品名：CM-2600d)，實施反射色調(a＊、b＊)的測定。反射色調係光源為D65時的值，以SCI方式(包含正反射光)進行測定。 The reflection color tone (a*, b*) was measured using a spectrophotometer (Konica Minolta Japan Co., Ltd. product name: CM-2600d). Reflected color is the value when the light source is D65, measured by the SCI method (including regular reflection light).
(4)光彈性係數的測定方法 (4) Determination method of photoelastic coefficient
使用相位差測定裝置KOBRA-WPR(王子計測機器公司製)，夾住樣品(大小1.5cm×6cm)的兩端，賦予應力(0.5N至8N)，測定樣品中央的相位差值(23℃/波長550nm)，從應力與相位差值的函數的斜率算出。於本說明書中，具有正的複折射性的樣品記為正值，具有負的複折射的樣品記為負值。再者，關於相位差膜的光彈性係數的測定樣品，係使用製作相位差膜/後述的黏著劑A/後述的保護膜C所構成的積層體，以使該積層體的慢軸與前述測定用樣品的長邊成為平行的方式切出的測定用樣品。使用夾住該測定用樣品的兩短邊，賦予應力測定所得之值。要對樣品做積層時，於積層前對積層面實施電暈處理。 Using the phase difference measurement device KOBRA-WPR (manufactured by Oji Scientific Instruments Co., Ltd.), both ends of the sample (size 1.5 cm × 6 cm) are clamped, and a stress (0.5 N to 8 N) is applied to measure the phase difference value (23 ° C / wavelength 550nm), calculated from the slope of the function of stress and phase difference. In this specification, a sample having positive birefringence is represented as a positive value, and a sample having negative birefringence is represented as a negative value. Furthermore, regarding the measurement sample of the photoelastic coefficient of the retardation film, a laminate composed of the retardation film/adhesive A described later/protective film C described later is used, so that the slow axis of the laminate is consistent with the aforementioned measurement A sample for measurement cut out so that the long sides of the sample become parallel. The value obtained by the stress measurement was imparted using both short sides of the measurement sample sandwiched therebetween. When the sample is to be laminated, corona treatment should be performed on the laminated surface before lamination.
(5)偏光片的收縮力的測定方法 (5) Determination of shrinkage force of polarizer
以偏光片的吸收軸方向為長軸的方式，用荻野精機股份有限公司製作的超級切割機切為寬度2mm×長度50mm的分片。將所得的條狀偏光膜作為收縮力測定用樣品。將收縮力測定用樣品裝設於熱機械分析裝置〔日立高科技科學公司製的”TMA/6100”〕，夾頭間距離設置為10mm，並於測試片於溫度20℃/相對濕度55%的室內放置充分的時間後，設定成使樣品的室內溫度從20℃以1分鐘升溫至80℃，升溫後，將樣品的室內溫度維持在80℃。升溫後，放置4小時後，在80℃的環境下，量測測定樣品的 長邊方向的收縮力。於該量測中，靜負重為0mN，使用SUS製探針作為輔助具。 With the absorption axis direction of the polarizer as the major axis, it was cut into pieces with a width of 2 mm x a length of 50 mm with a super cutter manufactured by Ogino Seiki Co., Ltd. The obtained strip-shaped polarizing film was used as a sample for contraction force measurement. Set the sample for shrinkage force measurement in a thermomechanical analysis device ["TMA/6100" manufactured by Hitachi High-Tech Science Co., Ltd.], set the distance between chucks to 10mm, and place the sample on the test piece at a temperature of 20°C/relative humidity of 55%. After leaving in the room for a sufficient time, the room temperature of the sample was set to be raised from 20° C. to 80° C. in 1 minute, and the room temperature of the sample was maintained at 80° C. after the temperature rise. After heating up, after standing for 4 hours, under the environment of 80°C, the shrinkage force in the longitudinal direction of the sample was measured. In this measurement, the static load was 0 mN, and a probe made of SUS was used as an aid.
[製造例1]偏光膜的製作 [Manufacturing example 1] Production of polarizing film
將厚度20μm的聚乙烯醇膜(平均聚合度約2400、皂化度99.9莫耳%以上)藉由乾式延伸，進行約4倍的單軸延伸，再者，保持緊張狀態浸漬於40℃的純水40秒後，在28℃下浸漬於碘/碘化鉀/水的重量比為0.052/5.7/100的水溶液30秒，進行染色處理。然後，在70℃下浸漬於碘化鉀/硼酸/水的重量比為11.0/6.2/100的水溶液120秒。然後，在8℃的純水洗淨15秒後，保持在300N的張力狀態下，以60℃下50秒、然後75℃下20秒進行乾燥，得到碘吸附配向於聚乙烯醇膜的厚度8μm的吸收型偏光片。所得的偏光片的收縮力為1.5N/2mm。 A polyvinyl alcohol film with a thickness of 20 μm (the average degree of polymerization is about 2400, and the degree of saponification is more than 99.9 mole%) is uniaxially stretched by about 4 times by dry stretching, and then immersed in pure water at 40°C while maintaining tension After 40 seconds, 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 process. Then, it was immersed in the aqueous solution whose weight ratio of potassium iodide/boric acid/water was 11.0/6.2/100 at 70 degreeC for 120 second. Then, after washing with pure water at 8°C for 15 seconds, drying was carried out at 60°C for 50 seconds at 60°C and then at 75°C for 20 seconds under a tension state of 300 N to obtain a polyvinyl alcohol film with iodine adsorption and alignment with a thickness of 8 μm. absorbing polarizer. The contraction force of the obtained polarizer was 1.5 N/2 mm.
[製造例2]相位差膜的製作 [Manufacturing example 2] Production of retardation film
混合下述構造的光配向性材料5份(重量平均分子量：30000)與環戊酮(溶劑)95份作為成分，所得的混合物在80℃下攪拌1小時，得到配向膜形成用組成物。 5 parts of photo-alignment material (weight average molecular weight: 30000) having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a composition for forming an alignment film.
對以下所示的聚合性液晶化合物A及聚合性液晶化合物B以90：10質量比混合之混合物，添加調平劑(F-556；DIC公司製)及屬於聚合起始劑 的2-二甲基胺基-2-苯甲基-1-(4-嗎啉基苯基)丁-1-酮(「Irgacure 369(Irg369)」、BASF JAPAN股份有限公司製)6份。 To the mixture of the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below at a mass ratio of 90:10, add a leveling agent (F-556; manufactured by DIC Corporation) and 2-dimethyl as a polymerization initiator 6 parts of amino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (“Irgacure 369 (Irg369)”, manufactured by BASF JAPAN Co., Ltd.).
再者，以使固體成分濃度成為13%的方式，添加N-甲基-2-吡咯啶酮(NMP)，在80℃下攪拌1小時，得到液晶硬化膜形成用組成物。 Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that solid content concentration might become 13 %, and it stirred at 80 degreeC for 1 hour, and obtained the composition for liquid crystal cured film formation.
聚合性液晶化合物A係用特開2010-31223號公報記載的方法製造。而且，聚合性液晶化合物B係根據特開2009-173893號公報記載的方法製造。 The polymerizable liquid crystal compound A was produced by the method described in JP-A-2010-31223. In addition, the polymerizable liquid crystal compound B was produced according to the method described in JP-A-2009-173893.
[由基材、配向膜、由液晶化合物硬化而成的層所構成的積層體的製造] [Manufacture of a laminate consisting of a substrate, an alignment film, and a layer cured from a liquid crystal compound]
於作為基材之50μm厚度的環烯烴系膜〔日本ZEON(股)公司製的商品名「ZF-14-50」〕上實施電暈處理後，用棒塗器塗佈配向膜形成用組成物，在80℃乾燥1分鐘，使用偏光UV照射裝置〔Ushio電機(股)的商品名「SPOT CURE SP-9」〕，以波長313nm的累積光量：100mJ/cm2，軸角度為45°，實施偏光UV曝光。然後，對配向膜使用棒塗器，塗佈配向液晶硬化膜形成用組成物，在120℃乾燥1分鐘後，使用高壓水銀燈〔Ushio電機(股)的商品名「UNICURE VB-15201BY-A」〕，藉由照射紫外線(氮氣環境下、波長365nm的累積光量：500mJ/cm2)，形成由液晶化合物硬化而成的層，得到由基材、配向膜、由液晶化合物硬化而成的層所構成的積層體。 After performing corona treatment on a cycloolefin-based film with a thickness of 50 μm [Nippon Zeon Co., Ltd. product name "ZF-14-50"] as a base material, the composition for forming an alignment film was coated with a bar coater , dried at 80°C for 1 minute, using a polarized UV irradiation device [Ushio Electric Co., Ltd. trade name "SPOT CURE SP-9"], with a wavelength of 313nm cumulative light intensity: 100mJ/cm 2 , and an axis angle of 45°. Polarized UV exposure. Next, apply a composition for forming an aligned liquid crystal cured film on the alignment film using a bar coater, dry it at 120°C for 1 minute, and then use a high-pressure mercury lamp [Ushio Electric Co., Ltd. trade name "UNICURE VB-15201BY-A"] , by irradiating ultraviolet light (accumulative light intensity of wavelength 365nm in nitrogen atmosphere: 500mJ/cm 2 ), a layer made of liquid crystal compound is formed, and a layer composed of a substrate, an alignment film, and a layer made of liquid crystal compound is formed layered body.
用上述方法製造的由液晶化合物硬化而成的層的面內的相位差值Re(λ)，係在隔著黏著劑貼合於玻璃後，剝離基材的環烯烴系膜後進行測定。測定各波長的相位差值Re(λ)的結果，Re(450)=121nm、Re(550)=142nm、Re(650)=146nm、Re(450)/Re(550)=0.85、Re(650)/Re(550)=1.03。而且，所得的相位差膜的光彈性係數為53.9×10-13Pa-1。 The in-plane retardation value Re(λ) of the layer cured from the liquid crystal compound produced by the above method was measured after the cycloolefin-based film of the substrate was peeled off after bonding to glass through an adhesive. The results of measuring the retardation value Re(λ) of each wavelength, Re(450)=121nm, Re(550)=142nm, Re(650)=146nm, Re(450)/Re(550)=0.85, Re(650 )/Re(550)=1.03. Furthermore, the photoelastic coefficient of the obtained retardation film was 53.9×10 -13 Pa -1 .
[保護膜的準備] [preparation of protective film]
保護膜A：在厚度25μm的降莰烯系樹脂所構成的延伸膜，形成厚度3μm的硬塗層的膜〔日本製紙公司製的商品名「COP25ST-HC」〕 Protective film A: A stretched film made of a norbornene-based resin with a thickness of 25 μm and a hard coat layer with a thickness of 3 μm [manufactured by Nippon Paper Co., Ltd. under the trade name “COP25ST-HC”]]
保護膜B：厚度20μm的具有正的複折射性的三乙醯基纖維素膜〔FUJIFILM公司製的商品名「ZRG20SL」〕。保護膜B的波長590nm之面內相位差值Re為1.1nm，厚度方向的相位差值Rth為1.3nm。光彈性係數為94×10-13Pa-1。 Protective film B: a triacetylcellulose film [trade name "ZRG20SL" manufactured by FUJIFILM Co., Ltd.] having a thickness of 20 μm and having positive birefringence. The in-plane retardation value Re of the wavelength 590nm of the protective film B was 1.1nm, and the retardation value Rth in the thickness direction was 1.3nm. The photoelastic coefficient is 94×10 -13 Pa -1 .
保護膜C：厚度23μm的具有正的複折射性的降莰烯系樹脂膜〔日本ZEON公司製的商品名「ZF-14-023」〕。保護膜C的波長590nm之面內相位差值Re為0.7nm，厚度方向的相位差值Rth為4.2nm。光彈性係數為16×10-13Pa-1。 Protective film C: a norbornene-based resin film [trade name "ZF-14-023" manufactured by Nippon Zeon Co., Ltd.] having positive birefringence with a thickness of 23 μm. The in-plane retardation value Re of the wavelength 590nm of the protective film C was 0.7nm, and the retardation value Rth in the thickness direction was 4.2nm. The photoelastic coefficient is 16×10 -13 Pa -1 .
保護膜D： Protective film D:
依以下的順序製作甲基丙烯酸系樹脂膜b。作為甲基丙烯酸系樹脂者，準備甲基丙烯酸甲酯/丙烯酸甲酯=96%/4%(重量比)的共聚物。而且，作為橡膠粒子者，準備三層構造的彈性體粒子，該三層構造之最內層為由對甲基丙烯酸甲酯使用少量的甲基丙烯酸烯丙酯所聚合而成的硬質聚合物所構成，中間層為由以丙烯酸丁酯為主成分且使用苯乙烯及少量的甲基丙烯酸烯丙酯所聚合而成的軟質彈性體所構成，最外層為由對甲基丙烯酸甲酯使用少量的丙烯酸乙酯所聚合而成的硬質聚合物所構成者，到中間層的彈性體為止的平均粒徑為240nm。再者，於該橡膠粒子，最內層與中間層的合計重量為粒子全部的70%。 The methacrylic resin film b was prepared in the following procedure. As the methacrylic resin, a copolymer of methyl methacrylate/methyl acrylate=96%/4% (weight ratio) was prepared. Furthermore, as rubber particles, elastomer particles having a three-layer structure are prepared. Composition, the middle layer is composed of butyl acrylate as the main component and the soft elastomer polymerized with styrene and a small amount of allyl methacrylate, and the outermost layer is made of methyl methacrylate with a small amount of The hard polymer formed by polymerizing ethyl acrylate has an average particle diameter of 240nm up to the elastomer of the middle layer. In addition, in this rubber particle, the total weight of the innermost layer and the middle layer is 70% of the whole particle.
用超級混合機混合上述甲基丙烯酸系樹脂70重量%及上述橡膠粒子30重量%，用二軸擠出機，進行熔融混練成為顆粒。將該顆粒 投入65mm
保護膜E： Protective film E:
特開2010-284840號公報的製造例1記載的醯亞胺化MS樹脂顆粒(重量平均分子量：105,000)100重量份，在100.5kPa、100℃，乾燥12小時，用單軸擠出機，以模具溫度270℃，從T型模頭擠出，成形為膜狀(厚度160μm)。再者，將該膜在其傳送方向150℃的環境下進行延伸(厚度80μm)，然後在垂直膜的傳送方向的方向150℃的環境下進行延伸，得到厚度40μm的具有負的複折射性的保護膜((甲基)丙烯酸系樹脂膜)。保護膜E的波長590nm之面內相位差值Re為0.5nm，厚度方向的相位差值Rth為0.82nm。光彈性係數為-9×10-13Pa-1。 100 parts by weight of imidized MS resin pellets (weight average molecular weight: 105,000) described in Production Example 1 of JP-A-2010-284840 were dried at 100.5 kPa and 100° C. for 12 hours, and dried with a single-screw extruder to The mold temperature was 270° C., and it was extruded from a T-die to form a film (thickness: 160 μm). Furthermore, the film was stretched in an environment of 150° C. in the conveying direction (thickness 80 μm), and then stretched in an environment of 150° C. in a direction perpendicular to the conveying direction of the film to obtain a film having negative birefringence with a thickness of 40 μm. Protective film ((meth)acrylic resin film). The in-plane retardation value Re of the wavelength 590nm of the protective film E was 0.5nm, and the retardation value Rth in the thickness direction was 0.82nm. The photoelastic coefficient is -9×10 -13 Pa -1 .
保護膜F：三乙醯基纖維素膜〔Konica Minolta Opto公司製的商品名「KC4CZW」〕。保護膜F的波長590nm之面內相位差值Re為1.2nm，厚度方向的相位差值Rth為-1.1nm。光彈性係數為75×10-13Pa-1。 Protective film F: Triacetyl cellulose film [trade name "KC4CZW" manufactured by Konica Minolta Opto]. The in-plane retardation value Re of the wavelength 590nm of the protective film F was 1.2nm, and the retardation value Rth in the thickness direction was -1.1nm. The photoelastic coefficient is 75×10 -13 Pa -1 .
[接著劑A的調製] [Preparation of Adhesive A]
對水100重量份溶解羧基改質聚乙烯醇〔Kuraray公司製「KL-318」〕3重量份，於該水溶液添加水溶性環氧樹脂的聚醯胺環氧系添加劑〔田岡 化學工業公司製商品名「SUMIREZ RESIN(登記商標)650(30)」、固體成分濃度30重量%的水溶液〕1.5重量份，以調製接著劑A。 3 parts by weight of carboxyl-modified polyvinyl alcohol ["KL-318" manufactured by Kuraray Co.] was dissolved in 100 parts by weight of water, and a polyamide epoxy-based additive of a water-soluble epoxy resin was added to the aqueous solution [manufactured by Tagoka Chemical Industry Co., Ltd. Adhesive A was prepared using 1.5 parts by weight of "SUMIREZ RESIN (registered trademark) 650 (30)" and an aqueous solution with a solid content concentration of 30% by weight].
[接著劑B的調製] [Preparation of Adhesive B]
混合下述所示的陽離子硬化性成分a1至a3及陽離子聚合起始劑後，再混合陽離子聚合起始劑及敏化劑後，進行脫泡，調製光硬化型接著劑B。再者，下述的調配量係依據固體成分量者。 After mixing the cation-curable components a1 to a3 and the cationic polymerization initiator shown below, the cationic polymerization initiator and the sensitizer were mixed, and defoaming was performed to prepare the light-curable adhesive B. In addition, the compounding quantity mentioned below is based on the solid content quantity.
‧陽離子硬化性成分a1(70份)： ‧Cation-hardening component a1 (70 parts):
3’,4’-環氧基環己烷甲酸3’,4’-環氧基環己基甲酯(商品名：CEL2021P、DAICEL公司製) 3',4'-Epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexyl methyl ester (trade name: CEL2021P, manufactured by DAICEL)
‧陽離子硬化性成分a2(20份)： ‧Cation-hardening component a2 (20 parts):
新戊二醇二縮水甘油醚(商品名：EX-211、NAGASE CHEMTEX公司製) Neopentyl glycol diglycidyl ether (trade name: EX-211, manufactured by NAGASE CHEMTEX Co., Ltd.)
‧陽離子硬化性成分a3(10份)： ‧Cation hardening component a3 (10 parts):
2-乙基己基縮水甘油醚(商品名：EX-121、NAGASE CHEMTEX公司製) 2-Ethylhexyl glycidyl ether (trade name: EX-121, manufactured by NAGASE CHEMTEX Co., Ltd.)
‧陽離子聚合起始劑(2.25份(固體成分量))： ‧Cationic polymerization initiator (2.25 parts (solid content)):
商品名：CPI-100(San Apro公司製)的50%碳酸丙烯酯溶液 Trade name: 50% propylene carbonate solution of CPI-100 (manufactured by San Apro)
‧敏化劑(2份)： ‧Sensitizer (2 parts):
1,4-二環氧基萘 1,4-Diepoxynaphthalene
[黏著劑層的準備] [Preparation of Adhesive Layer]
黏著劑A：厚度5μm的片狀黏著劑(Lintech公司製「NCF #L2」) Adhesive A: Sheet-shaped adhesive with a thickness of 5 μm (“NCF #L2” manufactured by Lintech Co., Ltd.)
黏著劑B：厚度25μm的片狀黏著劑(Lintech公司製「P-3132」) Adhesive B: Sheet-shaped adhesive with a thickness of 25 μm (“P-3132” manufactured by Lintech Co., Ltd.)
[反射板的準備] [Preparation of reflector]
準備OLED裝置(三星電子公司商品名：Galaxy-Tab S8.4)的不點燈面板，作為反射板。 A non-lighting panel of an OLED device (trade name of Samsung Electronics: Galaxy-Tab S8.4) was prepared as a reflector.
[製造例2]單面附保護膜偏光板的製作 [Manufacturing example 2] Production of a polarizing plate with a protective film on one side
於製造例1所得的偏光膜的一面，塗佈接著劑A，貼合保護膜A。此時，以保護膜A的延伸方向對偏光片的吸收軸為45度的方式貼合。然後，進行乾燥，得到單面附保護膜偏光板。 Adhesive A was applied to one side of the polarizing film obtained in Production Example 1, and protective film A was bonded together. At this time, it bonded so that the extension direction of the protective film A might become 45 degrees with respect to the absorption axis of the polarizer. Then, drying was performed to obtain a polarizing plate with a protective film on one side.
[實施例1] [Example 1]
於製造例2所得的單面附保護膜偏光板的偏光膜面，以1μm的厚度，塗佈接著劑B，貼合保護膜D。然後，照射紫外線〔Fusion UV system公司製的”H bulb”、累積光量400mJ/cm2〕，使接著劑硬化，得到兩面附保護膜偏光板。在所得的兩面附保護膜偏光板的保護膜D側，隔著黏著劑A，貼合相位差膜。此處，以相位差膜的慢軸對偏光膜的吸收軸成為逆時針45度的方式貼合。再者，在與相位差膜的黏著劑層A側相反側的面，貼合黏著劑N，得到附黏著劑圓偏光板。再者，該等的材料的貼合時，在各材料的貼合面實施電暈處理。 On the polarizing film surface of the polarizing plate with a protective film on one side obtained in Production Example 2, the adhesive agent B was applied to a thickness of 1 μm, and the protective film D was attached. Then, ultraviolet rays ["H bulb" manufactured by Fusion UV system, cumulative light intensity: 400 mJ/cm 2 ] were irradiated to harden the adhesive to obtain a polarizing plate with protective films on both sides. A retardation film was bonded to the protective film D side of the obtained polarizing plate with a protective film on both surfaces through the adhesive A. Here, it bonded so that the slow axis of a retardation film might become counterclockwise 45 degrees with respect to the absorption axis of a polarizing film. Furthermore, the adhesive N was bonded to the surface opposite to the adhesive layer A side of the retardation film, and an adhesive-attached circular polarizing plate was obtained. In addition, when bonding these materials, corona treatment is given to the bonding surface of each material.
將所得的圓偏光板，在以偏光膜的吸收軸為長邊為基準，成為逆時針45。的方式裁切為140mm×70mm。剝離剝離膜，隔著露出的丙烯酸系黏著劑，將圓偏光板貼合於無鹼玻璃(Corning公司製、EAGLE XG)。 The resulting circular polarizing plate was set at 45 degrees counterclockwise on the basis of the long side of the absorption axis of the polarizing film. The way to cut to 140mm × 70mm. The release film was peeled off, and the circular polarizing plate was bonded to an alkali-free glass (manufactured by Corning, Eagle XG) through the exposed acrylic adhesive.
[實施例2] [Example 2]
於實施例1，除使用保護膜E，取代保護膜D外，同樣地製作圓偏光板，製作評估用樣品。 In Example 1, except that the protective film E was used instead of the protective film D, a circular polarizing plate was produced in the same manner, and a sample for evaluation was produced.
[比較例1] [Comparative example 1]
於實施例1，除使用保護膜B，取代保護膜D外，同樣地製作圓偏光板，製作評估用樣品。 In Example 1, except that the protective film B was used instead of the protective film D, a circular polarizing plate was produced in the same manner, and a sample for evaluation was produced.
[比較例2] [Comparative example 2]
於實施例1，除使用保護膜C，取代保護膜D外，同樣地製作圓偏光板，製作評估用樣品。 In Example 1, except that the protective film C was used instead of the protective film D, a circular polarizing plate was produced in the same manner, and a sample for evaluation was produced.
[比較例3] [Comparative example 3]
於實施例1，除使用保護膜F，取代保護膜D外，同樣地製作圓偏光板，製作評估用樣品。 In Example 1, except that the protective film F was used instead of the protective film D, a circular polarizing plate was produced in the same manner, and a sample for evaluation was produced.
[耐熱測試前後的色調評估] [Evaluation of color tone before and after heat resistance test]
如此所得的各評估樣品，投入80℃的烤箱168小時，於反射板上配置評估用樣品，進行反射色調的測定。測定點係第3圖表示的點。第3圖所示的9個點，從圓偏光板的端部朝內側5mm的區域的點，短邊方向約30mm間隔，長邊方向約65mm間隔。 Each evaluation sample thus obtained was placed in an oven at 80° C. for 168 hours, and the evaluation sample was placed on a reflective plate to measure the reflection color tone. The measurement points are the points shown in Fig. 3 . The nine dots shown in Fig. 3 are located at intervals of about 30 mm in the short side direction and about 65 mm in the long side direction for the dots in the area 5 mm inward from the end of the circular polarizing plate.
作為面內均勻性的評估，在各測定點a＊及b＊畫在顏色座標的情況，以距離最遠的2點間的距離，進行評估。亦即，在2點間，下述式的值為最大值，作為評估結果。 As an evaluation of the in-plane uniformity, when the measurement points a* and b* are plotted on the color coordinates, the distance between the two points that are farthest away is used for evaluation. That is, between two points, the value of the following expression is the maximum value as an evaluation result.
△a＊b＊=〔(△a＊)2+(Ab＊)2〕1/2 △a*b*=[(△a*) 2 +(Ab*) 2 ] 1/2
△a＊、△b＊表示任意2點間的a＊、b＊的差。 Δa* and Δb* represent the difference between a* and b* between arbitrary two points.
辨識性評估 Discriminant assessment
A：△a＊b＊≦0.8 完全沒有看到熱不均勻性 A: △a＊b＊≦0.8 No thermal unevenness was seen at all
B：0.8<△a＊b＊≦1.0 看到非常輕微地的熱不均勻性 B: 0.8<△a＊b＊≦1.0 Very slight thermal non-uniformity can be seen
C：1.0<△a＊b＊≦1.8 約略看到熱不均勻性 C: 1.0<△a*b*≦1.8 thermal inhomogeneity can be seen roughly
D：1.8<△a＊b＊ 明顯地看到熱不均勻性 D: 1.8<△a*b* Heat inhomogeneity is clearly seen
評估結果表示於表1。 The evaluation results are shown in Table 1.
根據本發明，因可提供一種具有相位差膜的圓偏光板，其即使放置於高溫環境下後，反射色調的面內變化亦小，故為有用。特別是具有包含由聚合性液晶化合物硬化而成的層的相位差膜的圓偏光板被放置在高溫環境下時，容易產生圓偏光板的反射色調的面內變化，但是根據本發明，具有包含由聚合性液晶化合物硬化而成的層的相位差膜的圓偏光板即使放置在高溫環境下，亦可充分抑制色調變化。 According to the present invention, it is useful to provide a circularly polarizing plate having a retardation film having a small in-plane change in reflection color even after being placed in a high-temperature environment. In particular, when a circular polarizing plate having a retardation film comprising a layer hardened by a polymerizable liquid crystal compound is placed in a high-temperature environment, in-plane changes in the reflection color of the circular polarizing plate are likely to occur, but according to the present invention, a The circular polarizing plate of the retardation film whose layer is cured from the polymerizable liquid crystal compound can sufficiently suppress the change in color tone even if it is placed in a high-temperature environment.
所以，本發明的圓偏光板可有效地使用於顯示裝置，特別是有機EL顯示裝置、無機EL顯示裝置。 Therefore, the circular polarizing plate of the present invention can be effectively used for display devices, particularly organic EL display devices and inorganic EL display devices.
1‧‧‧偏光板 1‧‧‧Polarizer
2‧‧‧相位差膜 2‧‧‧retardation film
10‧‧‧偏光片 10‧‧‧Polarizer
11、12‧‧‧保護膜 11, 12‧‧‧Protective film
13、14‧‧‧黏著劑層 13, 14‧‧‧adhesive layer
15‧‧‧接著層 15‧‧‧adhesion layer
20、21‧‧‧由聚合性液晶化合物硬化而成的層 20, 21‧‧‧Layer hardened by polymerizable liquid crystal compound
100、101‧‧‧圓偏光板 100, 101‧‧‧Circular Polarizer
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| JP2018-091961 | 2018-05-11 | ||
| JP2018091961A JP2019197181A (en) | 2018-05-11 | 2018-05-11 | Polarizing plate and display device |
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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 |
| CN114930209A (en) * | 2020-01-29 | 2022-08-19 | 富士胶片株式会社 | Polarizing plate and display device |
| CN115485611A (en) * | 2020-04-24 | 2022-12-16 | 株式会社可乐丽 | Liquid crystal display protection plate, liquid crystal display protection plate with curved surface and manufacturing method thereof |
| CN113568198A (en) * | 2021-07-08 | 2021-10-29 | 业成科技（成都）有限公司 | Laminating method of polaroid and display thereof |
| JP7516457B2 (en) | 2022-05-10 | 2024-07-16 | 日東電工株式会社 | Lens portion, laminate, display, manufacturing method of display, and display method |
| JP7516458B2 (en) | 2022-05-10 | 2024-07-16 | 日東電工株式会社 | Lens portion, laminate, display, manufacturing method of display, and display method |
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| TW201411205A (en) * | 2012-08-31 | 2014-03-16 | Sumitomo Chemical Co | Circularly polarizing plate and display apparatus |
| JP2015212816A (en) * | 2014-04-16 | 2015-11-26 | 三菱化学株式会社 | Retardation film, circularly polarizing plate, and image display device |
| TW201727289A (en) * | 2015-12-10 | 2017-08-01 | Nitto Denko Corp | Circular polarizing plate and flexible image display device using same |
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| JP2002372622A (en) * | 2001-06-14 | 2002-12-26 | Nitto Denko Corp | Composite optical retardation plate, circularly polarizing plate and liquid crystal display, organic el display device |
| JPWO2009016888A1 (en) * | 2007-07-30 | 2010-10-14 | コニカミノルタオプト株式会社 | Circular polarization element, electroluminescence element |
| JP2009103900A (en) * | 2007-10-23 | 2009-05-14 | Nitto Denko Corp | Laminated optical film, liquid crystal panel, and liquid crystal display |
| JP5189834B2 (en) * | 2007-12-20 | 2013-04-24 | 富士フイルム株式会社 | Liquid crystal display device and polarizing plate |
| JP5446109B2 (en) * | 2008-03-28 | 2014-03-19 | Ｄｉｃ株式会社 | Hydroxybenzoic acid derivative and method for producing polymerizable compound |
| RU2444034C1 (en) * | 2008-04-07 | 2012-02-27 | Шарп Кабусики Кайся | Liquid crystal display |
| JP2009288334A (en) * | 2008-05-27 | 2009-12-10 | Teijin Ltd | Phase difference film, laminated polarizing film, and liquid crystal display device |
| JP2016053724A (en) * | 2010-02-23 | 2016-04-14 | 山本光学株式会社 | Circularly polarizing plate, circularly polarizing lens, and circularly polarizing spectacles |
| JP5912277B2 (en) * | 2010-04-22 | 2016-04-27 | 株式会社日本触媒 | Optical film, polarizer protective film, polarizing plate, and image display device |
| US8520175B2 (en) * | 2010-05-27 | 2013-08-27 | Benq Materials Corp. | Patterned retarder film and method for manufacturing the same |
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| TW201411205A (en) * | 2012-08-31 | 2014-03-16 | Sumitomo Chemical Co | Circularly polarizing plate and display apparatus |
| JP2015212816A (en) * | 2014-04-16 | 2015-11-26 | 三菱化学株式会社 | Retardation film, circularly polarizing plate, and image display device |
| TW201727289A (en) * | 2015-12-10 | 2017-08-01 | Nitto Denko Corp | Circular polarizing plate and flexible image display device using same |
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