TWI822718B - Polarizing plate - Google Patents
Polarizing plate Download PDFInfo
- Publication number
- TWI822718B TWI822718B TW107146963A TW107146963A TWI822718B TW I822718 B TWI822718 B TW I822718B TW 107146963 A TW107146963 A TW 107146963A TW 107146963 A TW107146963 A TW 107146963A TW I822718 B TWI822718 B TW I822718B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- adhesive layer
- retardation
- adhesive
- polarizing plate
- Prior art date
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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Abstract
Description
本發明係有關於一種偏光板。 The invention relates to a polarizing plate.
近年來，以液晶顯示裝置及有機電致發光顯示裝置(以下亦稱為有機EL)作為代表之畫像顯示裝置係急速地普及。畫像顯示裝置係廣泛地使用有具備偏光片及相位差層之偏光板。 In recent years, image display devices represented by liquid crystal display devices and organic electroluminescence display devices (hereinafter also referred to as organic EL) have been rapidly popularized. Image display devices widely use polarizing plates equipped with polarizers and retardation layers.
最近，由於有機EL的興起，伴隨著對畫像顯示裝置的薄型化之要求增強，亦要求偏光板薄型化。而且，注目於可撓性用途而從先前的相位差膜，進行著使用韌性較高的聚合性液晶化合物作為相位差層的原料之研究(例如參照專利文獻1)。 Recently, due to the rise of organic EL, the demand for thinner image display devices has increased, and there is also a demand for thinner polarizing plates. Furthermore, focusing on flexible applications, research has been conducted on using a polymerizable liquid crystal compound with high toughness as a raw material of the retardation layer from conventional retardation films (see, for example, Patent Document 1).
[專利文獻1]日本特開2017-54093號公報 [Patent Document 1] Japanese Patent Application Publication No. 2017-54093
另一方面，嘗試偏光板的薄型化時，亦有偏光板的耐久性不充分之問題。特別是偏光板被暴露在高溫、高濕的環境時，造成在偏光板 產生皺紋之不良。 On the other hand, when trying to reduce the thickness of the polarizing plate, there is also a problem that the durability of the polarizing plate is insufficient. Especially when the polarizing plate is exposed to a high temperature and high humidity environment, the polarizing plate will The problem of wrinkles.
偏光板的皺紋，係使以有機EL為代表之畫像顯示裝置的畫像變形。因此前述偏光板的皺紋有顯著地損害畫像顯示裝置的可見性之問題。伴隨著行動電話等的防水技術進步，在高溫、高濕環境的浴室、蒸氣浴室等使用行動電話等之人們增加。因此，對於在高溫、高濕的環境具有耐久性的偏光板之需求提高。 The wrinkles in the polarizing plate deform the image of the image display device represented by organic EL. Therefore, the aforementioned wrinkles on the polarizing plate significantly impair the visibility of the image display device. As waterproofing technology for mobile phones and the like advances, more and more people use mobile phones and the like in bathrooms, steam baths, etc. in high-temperature and high-humidity environments. Therefore, there is an increasing demand for polarizing plates that are durable in high-temperature and high-humidity environments.
本發明係鑒於此種情形而進行，其課題係提供一種即便在高溫、高濕的環境下，亦能夠抑制偏光板產生皺紋之耐久性較高的偏光板。 The present invention was made in view of this situation, and an object thereof is to provide a highly durable polarizing plate that can suppress wrinkles in the polarizing plate even in a high-temperature, high-humidity environment.
本發明者等經專心研討之結果，發現以下的偏光板係能夠解決上述課題。 As a result of intensive research, the present inventors found that the following polarizing plate can solve the above-mentioned problems.
亦即，本發明係具有以下的構成。 That is, the present invention has the following configuration.
[1]一種偏光板，係依序包含偏光片、第1黏著劑層、相位差層、及第2黏著劑層；將前述第1黏著劑層的儲存彈性模數設為E1(Pa)，將前述第1黏著劑層的厚度設為T1(μm)，將前述第2黏著劑層的儲存彈性模數設為E2(Pa)，將前述第2黏著劑層的厚度設為T2(μm)時，係滿足Log(E1/T1)+Log(E2/T2)≧6.4。 [1] A polarizing plate, which sequentially includes a polarizer, a first adhesive layer, a retardation layer, and a second adhesive layer; the storage elastic modulus of the first adhesive layer is set to E 1 (Pa) , let the thickness of the first adhesive layer be T 1 (μm), let the storage elastic modulus of the second adhesive layer be E 2 (Pa), and let the thickness of the second adhesive layer be T 2 (μm), the system satisfies Log(E 1 /T 1 )+Log(E 2 /T 2 )≧6.4.
[2]如[1]所述之偏光板，其中前述相位差層之穿刺強度為100gf以下。 [2] The polarizing plate according to [1], wherein the puncture strength of the retardation layer is 100 gf or less.
[3]如[1]或[2]所述之偏光板，其滿足下列(1)及(2)的任一者，(1)前述Log(E1/T1)為3.1以上，(2)前述Log(E2/T2)為3.0以上。 [3] The polarizing plate as described in [1] or [2], which satisfies any one of the following (1) and (2), (1) the aforementioned Log(E 1 /T 1 ) is 3.1 or more, (2) ) The aforementioned Log(E 2 /T 2 ) is 3.0 or more.
[4]如[1]至[3]項中任一項所述之偏光板，其中前述第1黏著劑層及前述第2黏著劑層的至少一者的儲存彈性模數為20,000Pa以上。 [4] The polarizing plate according to any one of [1] to [3], wherein at least one of the first adhesive layer and the second adhesive layer has a storage elastic modulus of 20,000 Pa or more.
[5]如[1]至[4]項中任一項所述之偏光板，其中前述第1黏著劑層及前述第2黏著劑層的至少一者的厚度為40μm以下。 [5] The polarizing plate according to any one of [1] to [4], wherein at least one of the first adhesive layer and the second adhesive layer has a thickness of 40 μm or less.
[6]如[1]至[5]項中任一項所述之偏光板，其至少包含第1相位差層及第2相位差層作為前述相位差層。 [6] The polarizing plate according to any one of [1] to [5], which includes at least a first retardation layer and a second retardation layer as the retardation layer.
[7]如[6]所述之偏光板，其中前述相位差層為隔著接著劑層至少將第1相位差層及第2相位差層積層而成之積層體。 [7] The polarizing plate according to [6], wherein the retardation layer is a laminate in which at least a first retardation layer and a second retardation layer are laminated via an adhesive layer.
[8]如[7]所述之偏光板，其中前述積層體之穿刺強度為100gf以下。 [8] The polarizing plate according to [7], wherein the laminated body has a puncture strength of 100 gf or less.
依照本發明，能夠提供一種即便在高溫、高濕的環境下，亦能夠抑制偏光板產生皺紋之耐久性較高的偏光板。 According to the present invention, it is possible to provide a highly durable polarizing plate that can suppress wrinkles on the polarizing plate even in a high-temperature, high-humidity environment.
11‧‧‧偏光片 11‧‧‧Polarizer
12‧‧‧第1黏著劑層 12‧‧‧1st adhesive layer
13‧‧‧第2黏著劑層 13‧‧‧Second adhesive layer
14‧‧‧相位差層 14‧‧‧Phase difference layer
15‧‧‧第1相位差層 15‧‧‧The first phase difference layer
16‧‧‧第2相位差層 16‧‧‧Second phase difference layer
17‧‧‧第1接著層 17‧‧‧1st bonding layer
18‧‧‧第2接著層 18‧‧‧Second bonding layer
19‧‧‧第3相位差層 19‧‧‧The third phase difference layer
100、101、102‧‧‧偏光板 100, 101, 102‧‧‧Polarizing plate
第1圖係顯示第1實施形態之偏光板的構成之概略剖面圖的一個例子。 Fig. 1 is an example of a schematic cross-sectional view showing the structure of the polarizing plate according to the first embodiment.
第2圖係顯示第2實施形態之包含2層相位差層之偏光板的構成之概略剖面圖的一個例子。 Fig. 2 is an example of a schematic cross-sectional view showing the structure of a polarizing plate including two retardation layers according to the second embodiment.
第3圖係顯示第2實施形態之包含3層相位差層之偏光板的構成之概略剖面圖的一個例子。 Fig. 3 is an example of a schematic cross-sectional view showing the structure of a polarizing plate including three retardation layers according to the second embodiment.
以下，詳細地說明本發明之偏光板的具體實施形態。又，本發明係不限定於以下的實施形態，在不變更本發明的要旨之範圍能夠進行 各種變更。 Hereinafter, specific embodiments of the polarizing plate of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be carried out within the scope that does not change the gist of the present invention. Various changes.
[第1實施形態] [First Embodiment]
<偏光板> <Polarizing plate>
在本說明書中，所謂「偏光板」，係具備偏光片及相位差層之光學膜。第1實施形態的偏光板係依序具備偏光片、第1黏著劑層、相位差層、及第2黏著劑層。 In this specification, the so-called "polarizing plate" refers to an optical film including a polarizing plate and a retardation layer. The polarizing plate of the first embodiment includes a polarizer, a first adhesive layer, a retardation layer, and a second adhesive layer in this order.
第1圖係顯示第1實施形態之偏光板的構成之概略剖面圖的一個例子。如第1圖顯示，偏光板100係依序將偏光片11、第1黏著劑層12、相位差層14、及第2黏著劑層13積層而成。 Fig. 1 is an example of a schematic cross-sectional view showing the structure of the polarizing plate according to the first embodiment. As shown in Figure 1, the polarizing plate 100 is formed by laminating the polarizer 11, the first adhesive layer 12, the retardation layer 14, and the second adhesive layer 13 in sequence.
在此，相位差層14係例如將供給λ/2的相位差之層、供給λ/4的相位差之層、及正C層、以及該等層的組合積層而得到之層。作為組合而得到之積層體，可舉出供給λ/2的相位差之層與供給λ/4的相位差之層之積層體、供給λ/4的相位差之層與正C層之積層體等作為例子。 Here, the phase difference layer 14 is, for example, a layer obtained by laminating a layer providing a phase difference of λ/2, a layer providing a phase difference of λ/4, a positive C layer, or a combination of these layers. Examples of the laminated body obtained by combining include a laminated body in which a layer is provided with a phase difference of λ/2 and a layer in which a phase difference is provided in λ/4, and a laminated body in which a layer is provided with a phase difference of λ/4 and a positive C layer. etc. as an example.
在本說明書中，所謂「供給λ/2的相位差之層」，係指使某特定波長的直線偏光之偏光方位變換90°之相位差層。在本說明書中，所謂「供給λ/4的相位差之層」，係指使某特定波長之直線偏光變換成為圓偏光(或將圓偏光變換成為直線偏光)之相位差層。相位差層14係供給λ/4的相位差之層時，具備偏光片11、及相位差層14之偏光板100，係能夠作為圓偏光板的功能。在本說明書中，所謂「正C層」，係指將在面內之慢軸方向的折射率設為Nx，將在其面內之快軸方向的折射率設為Ny，將在其厚度方向之折射率設為Nz時，滿足Nz>Nx≧Ny的關係之層。Nx之值與Ny之值的差，係以Ny之值的0.5%以內為佳，以0.3%以內為較佳。在0.5%以內的 話，能夠實質上看作Nx=Ny。 In this specification, the term "layer that provides a phase difference of λ/2" refers to a phase difference layer that changes the polarization direction of linearly polarized light of a specific wavelength by 90°. In this specification, the term "layer that provides a phase difference of λ/4" refers to a phase difference layer that converts linearly polarized light of a specific wavelength into circularly polarized light (or converts circularly polarized light into linearly polarized light). When the retardation layer 14 is a layer that provides a phase difference of λ/4, the polarizing plate 100 including the polarizer 11 and the retardation layer 14 can function as a circular polarizing plate. In this specification, the so-called "positive C layer" means that the refractive index in the slow axis direction in the plane is Nx, the refractive index in the fast axis direction in the plane is Ny, and the refractive index in the thickness direction is Nx. When the refractive index is set to Nz, it is a layer that satisfies the relationship Nz>Nx≧Ny. The difference between the value of Nx and the value of Ny is preferably within 0.5% of the value of Ny, and preferably within 0.3%. Within 0.5% If so, it can be essentially regarded as Nx=Ny.
將如上述的構成之偏光板在高溫、高濕環境下保存時有產生皺紋之情形。本發明者等進行研討時，另外亦確認在高溫、高濕環境下保存後產生皺紋之偏光板，其相位差層會產生變形。此種現象，係暗示在高溫、高濕環境下會使相位差層產生變形之應力起作用。使相位差層變形之應力，認為與相位差層接觸之黏著劑所造成的影響為較大。 When the polarizing plate having the above structure is stored in a high-temperature and high-humidity environment, wrinkles may occur. During their studies, the present inventors also confirmed that the retardation layer of a polarizing plate that develops wrinkles after being stored in a high-temperature, high-humidity environment will be deformed. This phenomenon implies that the stress that causes deformation of the retardation layer occurs in a high temperature and high humidity environment. The stress that deforms the retardation layer is believed to be greater due to the adhesive in contact with the retardation layer.
本發明者等進一步研討之結果，發現在如上述構成的偏光板中，藉由控制與相位差層接觸之黏著劑層的構成，將偏光板保持在高溫、高濕環境之後，能夠抑制產生皺紋。亦即，得到在如上述構成的偏光板中，藉由控制與相位差層接觸之黏著劑的構成，能夠抑制施加在相位差層的應力之構想，而完成了本發明。 As a result of further studies, the present inventors found that in the polarizing plate having the above structure, by controlling the composition of the adhesive layer in contact with the retardation layer, the generation of wrinkles can be suppressed after the polarizing plate is kept in a high-temperature, high-humidity environment. . That is, in the polarizing plate having the above structure, the stress applied to the retardation layer can be suppressed by controlling the composition of the adhesive in contact with the retardation layer, and the present invention was completed.
以下，詳細地說明構成本實施形態的偏光板100之各層。 Hereinafter, each layer constituting the polarizing plate 100 of this embodiment will be described in detail.
<偏光片> <Polarizer>
本實施形態的偏光板100係具有偏光片11。在本說明書中，所謂「偏光片」係指入射無偏光的光線時，具備使具有對吸收軸為正交的振動面之直線偏光透射的性質之光學膜。 The polarizing plate 100 of this embodiment has the polarizing plate 11 . In this specification, the term "polarizer" refers to an optical film that has the property of transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis when unpolarized light is incident thereon.
作為偏光片，能夠採用任意適當的偏光片。例如，形成偏光片之樹脂膜可為單層的樹脂膜，亦可為二層以上的積層膜。偏光片亦可為使二色性色素配向在聚合性液晶化合物且使聚合性液晶化合物聚合而成之硬化膜。 As the polarizing plate, any appropriate polarizing plate can be used. For example, the resin film forming the polarizing plate may be a single-layer resin film or a laminated film of two or more layers. The polarizer may be a cured film obtained by aligning a dichroic dye to a polymerizable liquid crystal compound and polymerizing the polymerizable liquid crystal compound.
作為由單層樹脂膜所構成之偏光片的具體例，可舉出對聚乙烯醇(以下亦略記為PVA)系薄膜、部分甲縮醛化PVA系薄膜、乙烯．乙酸 乙烯酯共聚物系部分皂化膜等親水性高分子膜，施行使用碘、二色性染料等二色性物質之染色處理、及延伸處理而成之物，可舉出PVA的脫水處理物、聚氯乙烯的脫鹽酸處理物等的多烯系配向膜等。因為具有優異的光學特性，所以使用以碘將PVA系薄膜染色且單軸延伸而得到的偏光片為佳。 Specific examples of polarizers composed of a single-layer resin film include polyvinyl alcohol (hereinafter also abbreviated as PVA)-based films, partially methylalized PVA-based films, and ethylene. Acetic acid Vinyl ester copolymer is a hydrophilic polymer film such as a partially saponified film, which is dyed with dichroic substances such as iodine and dichroic dyes, and stretched. Examples include dehydrated PVA, polyethylene Polyene-based alignment films such as dehydrochloric acid-treated vinyl chloride products. Since it has excellent optical properties, it is preferable to use a polarizer obtained by dyeing a PVA-based film with iodine and uniaxially stretching it.
為PVA系薄膜的原料之聚乙烯醇系樹脂，係能夠藉由將聚乙酸乙烯系樹脂皂化而製造。聚乙酸乙烯系樹脂亦能夠為乙酸乙烯酯的同元聚合物之聚乙酸乙烯酯、以及乙酸乙烯酯和能夠與乙酸乙烯酯共聚合的其它單體之共聚物。作為能夠與乙酸乙烯酯共聚合的其它單體，例如可舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基之丙烯醯胺類等。 Polyvinyl alcohol-based resin, which is a raw material of PVA-based films, can be produced by saponifying polyvinyl acetate-based resin. The polyvinyl acetate resin can also be polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and other monomers that can be copolymerized with vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamide having an ammonium group.
聚乙烯醇系樹脂的皂化度通常係為85至100莫耳%左右，較佳為98莫耳%以上。聚乙烯醇系樹脂亦可經改質，例如亦能夠使用經醛類改質之聚乙烯基甲縮醛、聚乙烯基縮醛等。聚乙烯醇系樹脂的聚合度通常係1,000至10,000左右，較佳為1,500至5,000左右。 The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin can also be modified. For example, polyvinyl methylal, polyvinyl acetal, etc. modified by aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.
此種將聚乙烯醇系樹脂製膜而成之物亦能夠使用作為PVA系薄膜。將聚乙烯醇系樹脂製膜之方法並無特別限定，能夠使用習知的方法製膜。PVA系薄膜的膜厚係例如10至100μm左右，較佳為10至50μm左右。 Such a polyvinyl alcohol-based resin film can also be used as a PVA-based film. The method of forming a polyvinyl alcohol-based resin film is not particularly limited, and a conventional method can be used to form the film. The film thickness of the PVA-based film is, for example, about 10 to 100 μm, preferably about 10 to 50 μm.
偏光片的厚度係以2μm以上為佳，以3μm以上為較佳，以5μm以上為更佳。又，前述偏光片的厚度係以30μm以下為佳，以20μm以下為較佳，以15μm以下為更佳。而且，上述上限值及下限值係能夠任意地組合。 The thickness of the polarizing plate is preferably 2 μm or more, more preferably 3 μm or more, and more preferably 5 μm or more. In addition, the thickness of the polarizing plate is preferably 30 μm or less, more preferably 20 μm or less, and more preferably 15 μm or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
偏光片的厚度變薄時，則偏光片端部的碘在高溫、高濕的環境下容易脫離。因此偏光片的厚度係以5μm以上為佳。又，偏光片的厚度較厚時，偏光片在冷熱交換試驗容易產生裂紋。因此偏光片的厚度係以15μm以下為佳。 When the thickness of the polarizer becomes thinner, the iodine at the edge of the polarizer is easily detached in a high-temperature and high-humidity environment. Therefore, the thickness of the polarizer is preferably 5 μm or more. In addition, when the thickness of the polarizer is thick, the polarizer is prone to cracks during the heat and cold exchange test. Therefore, the thickness of the polarizer is preferably 15 μm or less.
在本說明書中，「層的厚度」係意味著在偏光板之層的積層方向的尺寸。作為在本實施形態之「層」，例如可舉出偏光片、黏著劑層、接著劑層、相位差層、保護膜等。層的厚度係例如能夠藉由使用白色干渉式之非接觸膜厚計、或使用接觸式膜厚計而測定層的任意點且算出其平均值而得到。使用非接觸式膜厚計時，能夠不必接觸測定對象而精密地測定，且即便測定對象為積層體之一部分的層，亦能夠不必將各層剝離而進行測定對象之膜厚。 In this specification, the "thickness of a layer" means the size in the stacking direction of the layers of the polarizing plate. Examples of the "layer" in this embodiment include a polarizing plate, an adhesive layer, an adhesive layer, a retardation layer, and a protective film. The thickness of the layer can be obtained, for example, by measuring any point of the layer using a white interference-type non-contact film thickness meter or using a contact-type film thickness meter and calculating the average value. The use of a non-contact film thickness meter enables precise measurement without contacting the measurement object, and even if the measurement object is a layer of a part of the laminated body, the film thickness of the object can be measured without peeling off each layer.
又，在偏光片的一面、或兩面積層有後述保護膜時，前述偏光片的厚度係不包含前述保護膜的厚度。 Furthermore, when a protective film described later is laminated on one side or both surfaces of the polarizing plate, the thickness of the polarizing plate does not include the thickness of the protective film.
前述偏光片亦可在一面或兩面隔著後述黏著劑層、或接著劑層而積層保護膜。作為能夠積層在偏光片的一面或兩面之保護膜，例如能夠使用由具有優異的透明性、機械強度、熱安定性、水分隔離性、等方性、延伸性等之熱塑性樹脂所形成的薄膜。作為此種熱塑性樹脂的具體例，能夠舉出三乙酸纖維素等纖維素樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、耐綸、芳香族聚醯胺等聚醯胺樹脂、聚醯亞胺樹脂、聚乙烯、聚丙烯、乙烯．丙烯共聚物等聚烯烴樹脂、具有環系及降莰烯構造之環狀聚烯烴樹脂(亦稱為降莰烯系樹脂)、(甲基)丙烯酸樹脂、聚芳香酯(polyarylate)樹脂、聚苯乙烯樹脂、聚 乙烯醇樹脂、以及該等樹脂的混合物。 The polarizer may have a protective film laminated on one or both surfaces via an adhesive layer or adhesive layer to be described later. As a protective film that can be laminated on one or both sides of the polarizer, for example, a film made of a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, stretchability, etc. can be used. Specific examples of such thermoplastic resins include cellulose resins such as cellulose triacetate, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyether resins, and polyurethane resins. , polycarbonate resin, nylon, aromatic polyamide and other polyamide resins, polyimide resin, polyethylene, polypropylene, ethylene. Polyolefin resins such as propylene copolymers, cyclic polyolefin resins with cyclic and norbornene structures (also called norbornene resins), (meth)acrylic resins, polyarylate resins, polyphenylene vinyl, poly Vinyl alcohol resins, and mixtures of such resins.
將保護膜積層在偏光片的兩面時，二片保護膜的樹脂組成可相同亦可不同。 When the protective films are laminated on both sides of the polarizer, the resin compositions of the two protective films may be the same or different.
由熱塑性樹脂所形成之薄膜，為了提升與由PVA系樹脂及二色性物質所構成的偏光片之密著性，亦可施行表面處理(例如電暈處理等)，亦可形成底漆層(亦稱為底塗層)等的薄層。 In order to improve the adhesion between the film formed of thermoplastic resin and the polarizer composed of PVA resin and dichroic substance, surface treatment (such as corona treatment, etc.) may be performed, or a primer layer may be formed ( Also called a thin layer of undercoat), etc.
保護膜在溫度40℃、濕度90%RH的透濕度，係以1至1500g/m2．24hr為佳。保護膜的透濕度大於1500g/m2．24hr時，在高溫高濕環境下，包含前述保護膜之偏光板容易產生皺紋。保護膜的透濕度越低，包含前述保護膜之偏光板防止產生皺紋的效果越顯著，在溫度40℃、濕度90%RH的透濕度係以1000g/m2．24hr以下為較佳，以100g/m2．24hr以下為更佳。透濕度係能夠依據JIS Z 0208：1976而測定。 The moisture permeability of the protective film at a temperature of 40°C and a humidity of 90%RH ranges from 1 to 1500g/m 2 . 24hr is preferred. The moisture permeability of the protective film is greater than 1500g/m 2 . At 24 hours, in a high temperature and high humidity environment, the polarizing plate containing the aforementioned protective film is prone to wrinkles. The lower the moisture permeability of the protective film, the more significant the wrinkle prevention effect of the polarizing plate containing the aforementioned protective film is. The moisture permeability at a temperature of 40°C and a humidity of 90% RH is based on 1000g/m 2 . 24hr or less is better, 100g/m 2 . Less than 24 hours is better. The moisture permeability system can be measured in accordance with JIS Z 0208:1976.
前述保護膜的厚度係以3μm以上為佳，以5μm以上為較佳。又，前述保護的厚度係以50μm以下為佳，以30μm以下為較佳。而且，上述上限值及下限值係能夠任意地組合。 The thickness of the protective film is preferably 3 μm or more, and more preferably 5 μm or more. In addition, the thickness of the aforementioned protection is preferably 50 μm or less, and more preferably 30 μm or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
在偏光片的一面或兩面具有保護膜時，因為能夠充分地增強偏光片，所以偏光板的各種耐久性提升。 When a protective film is provided on one or both sides of a polarizer, the polarizer can be fully reinforced, thereby improving various durability properties of the polarizer.
<第1黏著劑層> <1st adhesive layer>
偏光片與相位差層，係隔著第1黏著劑層而被積層。 The polarizer and the retardation layer are laminated via the first adhesive layer.
在本說明書中，所謂「黏著劑」係指為柔軟的橡膠狀，藉由將其本身貼附在前述偏光片、前述保護膜等的被黏著物而顯現接著性。又，後述活性能量線硬化型黏著劑係能夠藉由照射能量線而調整接著力。 In this specification, the so-called "adhesive" refers to a soft rubber-like substance that exhibits adhesion by attaching itself to an adherend such as the polarizer and the protective film. In addition, the active energy ray curable adhesive system described below can adjust the adhesive force by irradiating energy rays.
作為構成第1黏著劑層之黏著劑，並無特別限制而能夠使用先前習知之具有優異的光學透明性之黏著劑，例如能夠使用具有丙烯酸系、胺甲酸酯系、聚矽氧系、聚乙烯基醚系等基質聚合物之黏著劑。又，亦可使用活性能量線硬化型黏著劑、熱硬化型黏著劑等。該等黏著劑之中，以將具有優異的透明性、黏著力、再剝離性(以下亦稱為再加工性)、耐候性、耐熱性等之丙烯酸系樹脂作為基質聚合物之黏著劑為佳。在本實施形態，第1黏著劑層係以由含有(甲基)丙烯酸系樹脂(1)、交聯劑(2)、矽烷化合物(3)之黏著劑組成物的反應生成物所構成為佳。 The adhesive constituting the first adhesive layer is not particularly limited and conventionally known adhesives with excellent optical transparency can be used. For example, acrylic, urethane, polysiloxane, polysiloxane, etc. can be used. Adhesive for vinyl ether and other matrix polymers. In addition, active energy ray-curable adhesives, thermosetting adhesives, etc. can also be used. Among these adhesives, an acrylic resin having excellent transparency, adhesion, re-peelability (hereinafter also referred to as reworkability), weather resistance, heat resistance, etc. as a matrix polymer is preferred. . In this embodiment, the first adhesive layer is preferably composed of a reaction product of an adhesive composition containing (meth)acrylic resin (1), cross-linking agent (2), and silane compound (3). .
[(甲基)丙烯酸系樹脂(1)] [(Meth)acrylic resin (1)]
在本實施形態，在構成第1黏著劑層之黏著劑組成物所含有的(甲基)丙烯酸系樹脂(1)，係以源自下述式(I)表示之(甲基)丙烯酸烷酯的結構單元(以下亦稱為「結構單元(I)」)作為主成分(例如，含有50質量%以上的結構單元(I))之聚合物(以下亦稱為「(甲基)丙烯酸酯聚合物」)為佳。 In this embodiment, the (meth)acrylic resin (1) contained in the adhesive composition constituting the first adhesive layer is derived from an alkyl (meth)acrylate represented by the following formula (I) A polymer (hereinafter also referred to as "(meth)acrylate polymerization") having a structural unit (hereinafter also referred to as "structural unit (I)") as a main component (for example, a polymer containing 50 mass % or more of structural unit (I)) "thing") is better.
在本說明書中，所謂「源自」，係意味著由於(甲基)丙烯酸烷酯等化合物進行聚合，所以化學結構產生變化。 In this specification, "derived from" means that the chemical structure changes due to polymerization of compounds such as alkyl (meth)acrylate.
式(I)中，R10係表示氫原子或甲基，R20係表示碳數1至20的烷基，前述烷基係可具有直鏈狀、分枝狀或環狀的任一結構，前述烷基的氫原子係可經碳數1至10的烷氧基取代。 In the formula (I), R 10 represents a hydrogen atom or a methyl group, and R 20 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group may have any linear, branched or cyclic structure, The hydrogen atom of the aforementioned alkyl group may be substituted by an alkoxy group having 1 to 10 carbon atoms.
又，在本說明書中，所謂「(甲基)丙烯酸」，係意味著可為丙烯酸或甲基丙烯酸的任一者。(甲基)丙烯酸酯等的「(甲基)」亦是相同的意思。 In addition, in this specification, "(meth)acrylic acid" means either acrylic acid or methacrylic acid. "(Meth)" such as (meth)acrylate also has the same meaning.
作為式(I)表示之(甲基)丙烯酸酯，例如可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸異己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正及異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸第三丁酯等。作為含烷氧基的丙烯酸烷酯之具體例，可舉出(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等。尤其是以含有(甲基)丙烯酸正丁酯或(甲基)丙烯酸2-乙基己酯為佳，以含有(甲基)丙烯酸正丁酯為特佳。 Examples of the (meth)acrylate represented by the formula (I) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, (meth)acrylic acid n-Heptyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n- and isononyl (meth)acrylate, (meth)acrylic acid n-decyl ester, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, Tert-butyl (meth)acrylate, etc. Specific examples of the alkoxy group-containing alkyl acrylate include 2-methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and the like. In particular, it is preferred to contain n-butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate, and particularly preferred to contain n-butyl (meth)acrylate.
(甲基)丙烯酸酯聚合物亦可含有源自結構單元(I)以外的其它單體之結構單元。源自其它單體之結構單元可為1種亦可為2種以上。作為(甲基)丙烯酸酯聚合物能夠含有的其它單體，可舉出具有極性官能基之單體、具有芳香族基之單體、及丙烯醯胺系單體。 The (meth)acrylate polymer may also contain structural units derived from monomers other than structural unit (I). The number of structural units derived from other monomers may be one type or two or more types. Examples of other monomers that the (meth)acrylate polymer can contain include monomers having polar functional groups, monomers having aromatic groups, and acrylamide-based monomers.
作為具有極性官能基之單體，可舉出具有極性官能基之(甲基)丙烯酸酯。作為極性官能基，可舉出羥基、羧基、取代胺基、未取代胺基等。作為極性官能基，亦可舉出環氧基等雜環基等。 Examples of the monomer having a polar functional group include (meth)acrylate having a polar functional group. Examples of the polar functional group include a hydroxyl group, a carboxyl group, a substituted amino group, an unsubstituted amino group, and the like. Examples of polar functional groups include heterocyclic groups such as epoxy groups and the like.
(甲基)丙烯酸酯聚合物中源自極性官能基的單體之結構單元的含量，係相對於(甲基)丙烯酸酯聚合物的總結構單元100質量份，以 20質量份以下為佳，較佳為0.1質量份以上且20質量份以下，更佳為0.1質量份以上且10質量份以下，特佳為0.5質量份以上且10質量份以下。 The content of structural units of monomers derived from polar functional groups in the (meth)acrylate polymer is based on 100 parts by mass of the total structural units of the (meth)acrylate polymer. 20 parts by mass or less is preferred, 0.1 parts by mass or more and 20 parts by mass or less is more preferred, 0.1 parts by mass or more and 10 parts by mass or less is more preferred, and 0.5 parts by mass or more and 10 parts by mass or less is particularly preferred.
作為具有芳香族基之單體，可舉出在分子內具有1個(甲基)丙烯醯基及1個以上的芳香環(例如、苯環、萘環等)且具有苯基、苯氧基乙基、或苄基之(甲基)丙烯酸酯。藉由含有該等結構單元，能夠抑制偏光板在高溫、高濕環境下產生的白點現象。 Examples of the monomer having an aromatic group include one (meth)acrylyl group and one or more aromatic rings (for example, benzene ring, naphthalene ring, etc.) in the molecule and a phenyl group and a phenoxy group. Ethyl or benzyl (meth)acrylate. By containing these structural units, the white spot phenomenon produced by the polarizing plate in a high-temperature and high-humidity environment can be suppressed.
(甲基)丙烯酸酯聚合物中源自芳香族基的單體之結構單元的含量，相對於(甲基)丙烯酸酯聚合物的總結構單元100質量份，以50質量份以下為佳，較佳為4質量份以上且50質量份以下，更佳為4質量份以上且25質量份以下。 The content of the structural unit of the monomer derived from the aromatic group in the (meth)acrylate polymer is preferably 50 parts by mass or less relative to 100 parts by mass of the total structural units of the (meth)acrylate polymer. Preferably, it is 4 parts by mass or more and 50 parts by mass or less, and more preferably, it is 4 parts by mass or more and 25 parts by mass or less.
作為丙烯醯胺系單體，可舉出N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(丁氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺等。藉由含有該等結構單元，能夠抑制後述抗靜電劑等添加物的滲出。 Examples of the acrylamide-based monomer include N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-(2-methylpropoxymethyl)acrylamide, etc. By containing these structural units, it is possible to suppress the bleeding of additives such as antistatic agents described later.
而且，作為源自結構單元(I)以外的其它單體之結構單元，亦可含有源自苯乙烯系單體之結構單元、源自乙烯系單體之結構單元、及源自在分子內具有複數個(甲基)丙烯醯基之結構單元等。 Furthermore, as structural units derived from monomers other than structural unit (I), structural units derived from styrene-based monomers, structural units derived from vinyl-based monomers, and structural units derived from having in the molecule Structural units of multiple (meth)acrylyl groups, etc.
(甲基)丙烯酸系樹脂(1)的重量平均分子量(以下亦簡稱「Mw」)係以50萬至250萬為佳。重量平均分子量為50萬以上時，能夠使在高溫、高濕的環境下之第1黏著劑層的耐久性提升。重量平均分子量為250萬以下時，將含有黏著劑組成物之塗佈液進行塗佈時的操作性變為良好。重量平均分子量(Mw)與數量平均分子量(以下亦簡稱「Mn」)之比表 示之分子量分布(Mw/Mn)通常係2至10。在本說明書中，所謂「重量平均分子量」及「數量平均分子量」，係使用凝膠滲透層析法(GPC)法而測定之聚苯乙烯換算值。 The weight average molecular weight (hereinafter also referred to as "Mw") of the (meth)acrylic resin (1) is preferably 500,000 to 2.5 million. When the weight average molecular weight is 500,000 or more, the durability of the first adhesive layer can be improved in high temperature and high humidity environments. When the weight average molecular weight is 2.5 million or less, the workability when applying a coating liquid containing the adhesive composition becomes good. Ratio table of weight average molecular weight (Mw) and number average molecular weight (hereinafter also referred to as "Mn") The molecular weight distribution (Mw/Mn) shown is usually from 2 to 10. In this specification, the "weight average molecular weight" and "number average molecular weight" are polystyrene-converted values measured using the gel permeation chromatography (GPC) method.
(甲基)丙烯酸系樹脂(1)於使其溶解在乙酸乙酯而成為濃度20質量%的溶液時，在25℃之黏度係以20Pa．s以下為佳，以0.1至15Pa．s為較佳。(甲基)丙烯酸樹脂(1)在25℃之黏度為前述範圍內時，係有助於包含使用前述樹脂所形成的第1黏著劑層之偏光板的耐久性提升和再加工(rework)性。前述黏度係能夠使用布魯克菲爾德(Brookfield)黏度計而測定。 When the (meth)acrylic resin (1) is dissolved in ethyl acetate to form a solution with a concentration of 20% by mass, the viscosity at 25°C is 20 Pa. s or less is better, ranging from 0.1 to 15Pa. s is better. When the viscosity of the (meth)acrylic resin (1) at 25°C is within the aforementioned range, it contributes to improved durability and reworkability of the polarizing plate including the first adhesive layer formed using the aforementioned resin. . The aforementioned viscosity system can be measured using a Brookfield viscometer.
從黏著性及耐久性並存之觀點而言，(甲基)丙烯酸系樹脂(1)的玻璃轉移溫度係以-60℃至-10℃為佳。又，玻璃轉移溫度係能夠使用示差掃描熱量計(DSC)而測定。 From the viewpoint of both adhesion and durability, the glass transition temperature of the (meth)acrylic resin (1) is preferably -60°C to -10°C. In addition, the glass transition temperature can be measured using a differential scanning calorimeter (DSC).
(甲基)丙烯酸系樹脂(1)亦可含有2種以上的(甲基)丙烯酸酯聚合物。作為此種(甲基)丙烯酸酯聚合物，例如可舉出以源自前述(甲基)丙烯酸酯的結構單元(I)作為主成分之物且重量平均分子量在如5萬至30萬的範圍之較低分子量的(甲基)丙烯酸酯聚合物。 The (meth)acrylic resin (1) may contain two or more types of (meth)acrylic acid ester polymers. Examples of such (meth)acrylate polymers include those containing the structural unit (I) derived from the (meth)acrylate as a main component and having a weight average molecular weight in the range of, for example, 50,000 to 300,000. A lower molecular weight (meth)acrylate polymer.
[交聯劑(2)] [Cross-linking agent (2)]
形成第1黏著劑層之黏著劑組成物，係以含有交聯劑(2)為佳。作為交聯劑(2)，可舉出常用的交聯劑(例如異氰酸酯化合物、環氧化合物、吖環丙烷化合物、金屬鉗合物化合物、過氧化物等)，特別是從黏著劑組成物的適用期、交聯速度、及偏光板的耐久性等的觀點而言，係以異氰酸酯系化合物為佳。 The adhesive composition forming the first adhesive layer preferably contains the cross-linking agent (2). Examples of the cross-linking agent (2) include commonly used cross-linking agents (such as isocyanate compounds, epoxy compounds, azinecyclopropane compounds, metal chelate compounds, peroxides, etc.), especially those from adhesive compositions. From the viewpoints of pot life, cross-linking speed, and durability of the polarizing plate, isocyanate-based compounds are preferred.
作為異氰酸酯系化合物，係以在分子內具有至少2個異氰酸 基(-NCO)之化合物為佳，例如可舉出脂肪族異氰酸酯系化合物(例如六亞甲基二異氰酸酯等)、脂環族異氰酸酯系化合物(例如異佛爾酮二異氰酸酯)、氫化苯二甲基二異氰酸酯、氫化二苯基甲烷二異氰酸酯、芳香族異氰酸酯系化合物(例如甲苯二異氰酸酯、苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯等)等。又，交聯劑(2)亦可為前述異氰酸酯化合物藉由多元醇化合物而得到的加成物(加成體)[例如藉由甘油、三羥甲基丙烷等而得到的加成物]、使前述異氰酸酯化合物與異三聚氰酸酯化合物、縮二脲(biuret)型化合物、聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等加成反應而成之胺甲酸酯預聚合物型的異氰酸酯化合物等的衍生物。交聯劑(2)係能夠單獨或組合2種以上而使用。該等化合物之中，從耐久性的觀點而言，係以甲苯二異氰酸酯、苯二甲基二異氰酸酯、六亞甲基二異氰酸酯及該等二異氰酸酯的多元醇化合物或該等二異氰酸酯的異三聚氰酸酯化合物為佳。 The isocyanate compound is one that has at least two isocyanates in the molecule. Preferred are compounds with a group (-NCO). Examples include aliphatic isocyanate compounds (such as hexamethylene diisocyanate, etc.), alicyclic isocyanate compounds (such as isophorone diisocyanate), hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, aromatic isocyanate compounds (such as toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.), etc. . Furthermore, the cross-linking agent (2) may be an adduct (adduct) of the isocyanate compound obtained from a polyol compound [for example, an adduct obtained from glycerin, trimethylolpropane, etc.], The aforementioned isocyanate compound and isocyanate compound, biuret type compound, polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol Derivatives of urethane prepolymer type isocyanate compounds formed by addition reactions. The cross-linking agent (2) can be used alone or in combination of two or more types. Among these compounds, from the viewpoint of durability, toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and polyol compounds of these diisocyanates or isotriesters of these diisocyanates Polycyanate compounds are preferred.
交聯劑(2)的比例相對於(甲基)丙烯酸系樹脂(1)100質量份，例如可為0.01至10質量份，較佳為0.1至3質量份，更佳為0.1至1質量份。在上述上限值以下時，對提升耐久性為有利的，在上述下限值以上時，對抑制產生氣體且提升再加工性為有利的。 The proportion of the cross-linking agent (2) relative to 100 parts by mass of the (meth)acrylic resin (1) can be, for example, 0.01 to 10 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 1 part by mass. . When it is below the above-mentioned upper limit, it is advantageous to improve durability, and when it is above the above-mentioned lower limit, it is advantageous to suppress gas generation and improve reworkability.
[矽烷化合物(3)] [Silane compound (3)]
黏著劑組成物係能夠含有矽烷化合物(3)。藉由含有矽烷化合物(3)，能夠提高第1黏著劑層與積層在前述第1黏著劑層之層的密著性。亦可使用2種以上的矽烷化合物(3)。 The adhesive composition can contain a silane compound (3). By containing the silane compound (3), the adhesion between the first adhesive layer and the layer laminated on the first adhesive layer can be improved. Two or more silane compounds (3) may be used.
作為矽烷化合物(3)，例如可舉出乙烯基三甲氧基矽烷、乙烯 基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、3-環氧丙氧基丙基三甲氧基砂烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基乙氧基二甲基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙醯氧基丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷等。 Examples of the silane compound (3) include vinyltrimethoxysilane, ethylene Triethoxysilane, Vinyl(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropyloxypropyltrimethoxysilane, 3-hydrothiopropyl Trimethoxysilane, etc.
又，矽烷化合物(3)能夠含有源自上述矽烷化合物(3)之寡聚物。 Moreover, the silane compound (3) can contain the oligomer derived from the said silane compound (3).
在黏著劑組成物之矽烷化合物(3)的含量，相對於(甲基)丙烯酸系樹脂(1)100質量份，通常係0.01至10質量份，以0.03至5質量份為佳，較佳為0.05至2質量份，更佳為0.1至1質量份。矽烷化合物(3)的含量為0.01質量份以上時，第1黏著劑層與被黏著物的密著性容易提升。含量為10質量份以下時，能夠抑制矽烷化合物(3)從第1黏著劑層滲出。 The content of the silane compound (3) in the adhesive composition is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, based on 100 parts by mass of the (meth)acrylic resin (1). 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass. When the content of the silane compound (3) is 0.01 parts by mass or more, the adhesion between the first adhesive layer and the adherend is easily improved. When the content is 10 parts by mass or less, exudation of the silane compound (3) from the first adhesive layer can be suppressed.
[其它成分(4)] [Other ingredients (4)]
形成第1黏著劑層之黏著劑組成物能夠單獨或含有2種以上之紫外線吸收劑、抗靜電劑、溶劑、交聯觸媒、黏著賦予樹脂(膠黏劑(tackifier))、塑化劑等添加劑。又，在黏著劑組成物調配紫外線硬化性化合物而形成第1黏著劑層後，照射紫外線使其硬化而成為較硬的黏著劑層亦為有用者。 The adhesive composition forming the first adhesive layer can be alone or contain two or more types of ultraviolet absorbers, antistatic agents, solvents, cross-linking catalysts, adhesion-imparting resins (tackifiers), plasticizers, etc. Additives. In addition, it is also useful to mix an ultraviolet curable compound with the adhesive composition to form the first adhesive layer, and then irradiate the ultraviolet ray to harden it to form a relatively hard adhesive layer.
第1黏著劑層的厚度係以3μm以上為佳，以5μm以上為較佳。又，第1黏著劑層的厚度係以40μm以下為佳，以30μm以下為較佳。而且，上述上限值及下限值係能夠任意地組合。 The thickness of the first adhesive layer is preferably 3 μm or more, and more preferably 5 μm or more. In addition, the thickness of the first adhesive layer is preferably 40 μm or less, and more preferably 30 μm or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
第1黏著劑層的厚度為前述下限值以上時，能夠將偏光片與相位差層充分地貼合。第1黏著劑層的厚度為前述上限值以下時，相位差層不容易 產生偏移，且抑制伴隨著相位差層變形而引起偏光板產生皺紋之效果提高。 When the thickness of the first adhesive layer is not less than the aforementioned lower limit, the polarizer and the retardation layer can be sufficiently bonded. When the thickness of the first adhesive layer is below the aforementioned upper limit, the retardation layer will not easily The effect of generating offset and suppressing wrinkles in the polarizing plate caused by deformation of the retardation layer is improved.
在製造本實施形態的積層體時，使用較強的壓力且隔著第1黏著劑將偏光片與相位差層貼合時，相較於使用較弱的壓力貼合時，第1黏著劑層的厚度有變薄之情形。這是因為第1黏著劑層係具有伸縮性所致，但是將偏光片與相位差層貼合後，若暫時放置，則第1黏著劑層的厚度係恢復如原來。因此使用較強的壓力隔著第1黏著劑將偏光片與相位差層貼合時，例如能夠藉由放置5分鐘後而測定第1黏著劑層的厚度，得到一定值。 When manufacturing the laminated body of this embodiment, when strong pressure is used to bond the polarizer and the retardation layer via the first adhesive, compared with when weak pressure is used to bond the polarizer and the retardation layer, the first adhesive layer The thickness has become thinner. This is because the first adhesive layer is stretchable. However, after the polarizer and the retardation layer are bonded and left temporarily, the thickness of the first adhesive layer will return to its original state. Therefore, when strong pressure is used to bond the polarizer and the retardation layer through the first adhesive, a certain value can be obtained by measuring the thickness of the first adhesive layer after leaving it for 5 minutes, for example.
第1黏著劑層的儲存彈性模數係以20,000Pa以上為佳，以25,000Pa以上為較佳，以50,000Pa以上為更佳。又，第1黏著劑層的儲存彈性模數係以150,000Pa以下為佳。而且，上述上限值及下限值係能夠任意地組合。 The storage elastic modulus of the first adhesive layer is preferably 20,000 Pa or more, more preferably 25,000 Pa or more, and more preferably 50,000 Pa or more. In addition, the storage elastic modulus of the first adhesive layer is preferably 150,000 Pa or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
「儲存彈性模數」係表示黏著劑層的硬度之指標。第1黏著劑層的儲存彈性模數為前述下限值以上時，因為第1黏著劑層具有充分的硬度，所以在偏光片與相位差層之間不容易產生偏移，而且抑制伴隨著相位差層變形所致之偏光板產生皺紋之效果提高。第1黏著劑層的儲存彈性模數為前述上限值以下時，在將黏著劑層與相位差層貼合後，不容易在前述黏著劑層與相位差層之間產生氣泡，而且抑制伴隨著氣泡產生所致之偏光板產生皺紋之效果提高。 "Storage elastic modulus" is an index indicating the hardness of the adhesive layer. When the storage elastic modulus of the first adhesive layer is equal to or higher than the lower limit, the first adhesive layer has sufficient hardness, so that the shift between the polarizer and the retardation layer is less likely to occur, and the phase change associated with the phase is suppressed. The effect of wrinkles on the polarizing plate caused by differential layer deformation is improved. When the storage elastic modulus of the first adhesive layer is less than the upper limit value, after the adhesive layer and the retardation layer are bonded together, bubbles are less likely to be generated between the adhesive layer and the retardation layer, and bubbles are less likely to follow the retardation layer. The effect of wrinkles on the polarizing plate caused by bubbles is improved.
在本說明書中，「第1黏著劑層的儲存彈性模數」係能夠使用市售的黏彈性測定裝置而測定。作為黏彈性測定裝置，係例如後述實施例所顯示，能夠使用Physica公司製MCR300。「第1黏著劑層的儲存彈 性模數」係採用依據JIS K7244-6於25℃所測得的值。 In this specification, "storage elastic modulus of the first adhesive layer" can be measured using a commercially available viscoelasticity measuring device. As a viscoelasticity measuring device, MCR300 manufactured by Physica Corporation can be used, as shown in the examples described below. "Storage bomb of the first adhesive layer "Elastic modulus" is the value measured at 25°C in accordance with JIS K7244-6.
將第1黏著劑層的儲存彈性模數設為E1(Pa)，將第1黏著劑層的厚度設為T1(μm)時，Log(E1/T1)通常係3.1以上，以3.3以上為佳，以3.5以上為較佳，以3.8以上為更佳。又，前述Log(E1/T1)係以5.0以下為佳。而且，上述上限值及下限值係能夠任意地組合。 When the storage elastic modulus of the first adhesive layer is E 1 (Pa) and the thickness of the first adhesive layer is T 1 (μm), Log(E 1 /T 1 ) is usually 3.1 or more, so 3.3 or above is better, 3.5 or above is better, and 3.8 or above is even better. In addition, the aforementioned Log(E 1 /T 1 ) is preferably 5.0 or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
前述Log(E1/T1)為前述下限值以上時，第1黏著劑層的厚度係與儲存彈性模數取得平衡且能夠將偏光片與相位差層堅固地貼合。因此，結果上抑制伴隨著相位差層變形所致之偏光板產生皺紋之效果提高。 When the aforementioned Log (E 1 /T 1 ) is equal to or greater than the aforementioned lower limit, the thickness of the first adhesive layer is balanced with the storage elastic modulus and the polarizer and the retardation layer can be firmly bonded. Therefore, the effect of suppressing wrinkles in the polarizing plate caused by deformation of the retardation layer is improved as a result.
前述Log(E1/T1)為前述上限值以下時，在將黏著劑層與相位差層貼合時，不容易在前述黏著劑層與相位差層之間產生氣泡，而且能夠抑制伴隨著氣泡產生所致之相位差層變形，且抑制偏光板產生皺紋之效果提高。 When the aforementioned Log (E 1 /T 1 ) is equal to or less than the aforementioned upper limit, when the adhesive layer and the retardation layer are bonded together, bubbles are less likely to be generated between the adhesive layer and the retardation layer, and the accompanying air bubbles can be suppressed. It prevents the deformation of the retardation layer caused by the generation of bubbles and improves the effect of suppressing wrinkles in the polarizing plate.
<第2黏著劑層> <Second adhesive layer>
第2黏著劑層係積層在相位差層之與第1黏著劑層接觸的面為相反側的面。偏光板係隔著第2黏著劑層積層在例如顯示面板等。 The second adhesive layer is laminated on the surface of the retardation layer opposite to the surface in contact with the first adhesive layer. The polarizing plate is laminated on, for example, a display panel via a second adhesive layer.
作為構成在相位差層與例如顯示面板等的積層所使用的第2黏著劑層之黏著劑，可無特別限制地使用先前習知之具有優異的光學透明性之黏著劑。作為構成第2黏著劑層之黏著劑，能夠使用與作為構成第1黏著劑層之黏著劑所例示者相同者相同者。第1黏著劑層與第2黏著劑層之儲存彈性模數及厚度可各自相同亦可不同。 As the adhesive constituting the second adhesive layer used in a lamination of a retardation layer and, for example, a display panel, a conventionally known adhesive having excellent optical transparency can be used without particular limitation. As the adhesive constituting the second adhesive layer, the same ones as those exemplified as the adhesive constituting the first adhesive layer can be used. The storage elastic modulus and thickness of the first adhesive layer and the second adhesive layer may be the same or different.
又，作為第2黏著劑層的黏著劑，亦能夠使用活性能量線硬化型黏著劑。「活性能量線硬化型黏著劑」係具有受到紫外線、電子射線等能量線的照射而硬化之性質。因為活性能量線硬化型黏著劑係即便在能 量線照射前亦具有黏著性，所以是能夠與薄膜等的被黏著物密著且具有藉由能量線的照射而硬化來調整密著力的性質之黏著劑。在本實施形態，作為在第2黏著劑層所使用的黏著劑係以活性能量線硬化型黏著劑為佳，其中以紫外線硬化型黏著劑為較佳。 In addition, as the adhesive of the second adhesive layer, an active energy ray curable adhesive can also be used. "Active energy ray curable adhesive" has the property of being hardened by exposure to energy rays such as ultraviolet rays and electron rays. Because the active energy ray-hardening adhesive system can It has adhesive properties even before irradiation with energy rays, so it can adhere closely to adherends such as films and has the property of being hardened by irradiation with energy rays to adjust the adhesion force. In this embodiment, the adhesive used in the second adhesive layer is preferably an active energy ray-curing adhesive, and particularly an ultraviolet curing adhesive is preferred.
活性能量線硬化型黏著劑通常係含有丙烯酸系黏著劑及能量線聚合性化合物作為主成分。通常進一步調配有交聯劑，而且按照必要亦能夠調配光聚合起始劑、光敏化劑等。 Active energy ray curable adhesives usually contain an acrylic adhesive and an energy ray polymerizable compound as main components. Usually, a crosslinking agent is further prepared, and a photopolymerization initiator, a photosensitizer, etc. can also be prepared as necessary.
使用活性能量線硬化型黏著劑將相位差層與例如顯示面板貼合時，首先係隔著活性能量線硬化型黏著劑將相位差層積層在顯示面板上。其次，照射如紫外線、可見光、電子射線、X射線之活性能量線而使由活性能量線硬化型黏著劑所構成之黏著劑層硬化。作為活性能量線，係以紫外線為佳，作為此時的光源，係能夠使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、鹵化金屬燈等。 When the retardation layer is bonded to, for example, a display panel using an active energy ray-curing adhesive, the retardation layer is first laminated on the display panel via the active energy ray-curing adhesive. Secondly, active energy rays such as ultraviolet rays, visible light, electron rays, and X-rays are irradiated to harden the adhesive layer composed of the active energy ray curable adhesive. As the active energy ray, ultraviolet rays are preferred. As the light source at this time, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc. can be used.
第2黏著劑層的厚度係以3μm以上為佳，以5μm以上為較佳。又，第2黏著劑層的厚度係以40μm以下為佳，以30μm以下為較佳。而且，上述上限值及下限值係能夠任意地組合。 The thickness of the second adhesive layer is preferably 3 μm or more, and more preferably 5 μm or more. In addition, the thickness of the second adhesive layer is preferably 40 μm or less, and more preferably 30 μm or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
第2黏著劑層的厚度為前述下限值以上時，能夠將相位差層與例如顯示面板等充分地貼合。第2黏著劑層的厚度為前述上限值以下時，隔著第2黏著劑層而被積層的相位差層與例如顯示面板不容易產生偏移。因此，能夠將相位差層牢固地固定且偏光片與相位差層不容易偏移。結果抑制伴隨著相位差層變形所致之偏光板產生皺紋之效果提高。 When the thickness of the second adhesive layer is equal to or greater than the aforementioned lower limit, the retardation layer can be sufficiently bonded to, for example, a display panel. When the thickness of the second adhesive layer is equal to or less than the upper limit, the retardation layer laminated via the second adhesive layer and, for example, the display panel are less likely to shift. Therefore, the retardation layer can be firmly fixed, and the polarizer and the retardation layer are less likely to shift. As a result, the effect of suppressing wrinkles in the polarizing plate caused by deformation of the retardation layer is improved.
在製造本實施形態的積層體時，隔著第2黏著劑且使用較強的壓力將相位差層與例如顯示面板等貼合時，相較於使用較弱的壓力貼合時，第2黏著劑層的厚度有變薄之情形。這是因為第2黏著劑層係具有伸縮性而產生，但是將相位差層與例如顯示面板等貼合後，若暫時放置，則第2黏著劑層的厚度係恢復如原來。因此使用較強的壓力隔著第2黏著劑將相位差層與例如顯示面板等貼合時，例如能夠藉由放置5分鐘後而測定第2黏著劑層的厚度，得到一定值。 When manufacturing the laminated body of this embodiment, when the retardation layer is bonded to, for example, a display panel via the second adhesive and strong pressure is used, the second adhesive force is stronger than when the second adhesive is bonded using weaker pressure. The thickness of the agent layer may become thinner. This is because the second adhesive layer has elasticity. However, after the retardation layer is bonded to, for example, a display panel and left temporarily, the thickness of the second adhesive layer returns to its original state. Therefore, when strong pressure is used to bond the retardation layer to, for example, a display panel through the second adhesive, a certain value can be obtained by measuring the thickness of the second adhesive layer after leaving it for 5 minutes.
第2黏著劑層的儲存彈性模數係以20,000Pa以上為佳，以25,000Pa以上為較佳，以50,000Pa以上為更佳。又，第2黏著劑層的儲存彈性模數係以150,000Pa以下為佳。而且，上述上限值及下限值係能夠任意地組合。 The storage elastic modulus of the second adhesive layer is preferably 20,000 Pa or more, more preferably 25,000 Pa or more, and more preferably 50,000 Pa or more. In addition, the storage elastic modulus of the second adhesive layer is preferably 150,000 Pa or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
如前述，儲存彈性模數係表示黏著劑層的硬度之指標。第2黏著劑層的儲存彈性模數為前述下限值以上時，因為第2黏著劑層係具有充分的硬度，所以相位差層與例如顯示面板不容易產生偏移且能夠將相位差層牢固地固定，結果偏光片與相位差層不容易產生偏移，且抑制伴隨著相位差層變形所致之偏光板產生皺紋之效果提高。第2黏著劑層的儲存彈性模數為前述上限值以下時，與被黏著物基材之密著性及耐衝擊性提高。具體而言，將黏著劑層與相位差層貼合時不容易在前述黏著劑層與相位差層之間產生氣泡，而且能夠抑制伴隨著氣泡產生所致之相位差層變形且抑制偏光板產生皺紋之效果提高。第2黏著劑為活性能量線硬化型黏著劑時，能夠在照射能量線而使第2黏著劑硬化成為目標硬度之後，進行測定儲存彈性模數。 As mentioned above, the storage elastic modulus is an index indicating the hardness of the adhesive layer. When the storage elastic modulus of the second adhesive layer is equal to or higher than the aforementioned lower limit, since the second adhesive layer has sufficient hardness, the retardation layer is less likely to deviate from, for example, a display panel and the retardation layer can be firmly held As a result, the polarizer and the retardation layer are less likely to shift, and the effect of suppressing wrinkles on the polarizing plate caused by deformation of the retardation layer is improved. When the storage elastic modulus of the second adhesive layer is below the aforementioned upper limit, the adhesion to the adherend base material and the impact resistance are improved. Specifically, when the adhesive layer and the retardation layer are bonded together, bubbles are not easily generated between the adhesive layer and the retardation layer, and the deformation of the retardation layer caused by the generation of bubbles can be suppressed and the generation of the polarizing plate can be suppressed. The effect of wrinkles is improved. When the second adhesive is an active energy ray-curable adhesive, the storage elastic modulus can be measured after the second adhesive is cured to a target hardness by irradiating energy rays.
在本說明書中，「第2黏著劑層的儲存彈性模數」之測定， 能夠與已說明的「第1黏著劑層的儲存彈性模數」之測定相同地進行。 In this specification, the measurement of "storage elastic modulus of the second adhesive layer", It can be performed in the same manner as the measurement of the "storage elastic modulus of the first adhesive layer" described above.
將第2黏著劑層的儲存彈性模數設為E2(Pa)，將第2黏著劑層的厚度設為T2(μm)時，Log(E2/T2)係以3.0以上為佳，以3.3以上為較佳，以3.5以上為更佳。又，前述Log(E2/T2)通常係7.0以下，以5.0以下為佳。又，上述限值及下限值係能夠任意地組合。 When the storage elastic modulus of the second adhesive layer is E 2 (Pa) and the thickness of the second adhesive layer is T 2 (μm), Log(E 2 /T 2 ) is preferably 3.0 or more. , 3.3 or above is preferred, 3.5 or above is even better. In addition, the aforementioned Log(E 2 /T 2 ) is usually 7.0 or less, preferably 5.0 or less. In addition, the above-mentioned limit value and the lower limit value can be combined arbitrarily.
前述Log(E2/T2)為前述下限值以上時，第2黏著劑層的厚度與儲存彈性模數取得平衡，而且相位差層與例如顯示面板不容易產生偏移且能夠將相位差層牢固地固定。因此，結果偏光片與相位差層不容易偏移，且抑制伴隨著相位差層變形所致之偏光板產生皺紋之效果提高。 When the aforementioned Log (E 2 /T 2 ) is equal to or greater than the aforementioned lower limit, the thickness of the second adhesive layer and the storage elastic modulus are balanced, and the retardation layer is less likely to deviate from, for example, the display panel, and the retardation can be reduced. The layers are firmly fixed. Therefore, as a result, the polarizer and the retardation layer are less likely to shift, and the effect of suppressing wrinkles in the polarizing plate caused by deformation of the retardation layer is improved.
前述Log(E2/T2)為前述上限值以下時，在將黏著劑層與相位差層貼合時，不容易在前述黏著劑層與相位差層之間產生氣泡，而且能夠抑制伴隨著氣泡產生所致之相位差層變形且抑制偏光板產生皺紋之效果提高。 When the aforementioned Log (E 2 /T 2 ) is equal to or less than the aforementioned upper limit, when the adhesive layer and the retardation layer are bonded together, bubbles are less likely to be generated between the adhesive layer and the retardation layer, and accompanying bubbles can be suppressed. The effect of deforming the retardation layer caused by the generation of bubbles and suppressing wrinkles in the polarizing plate is improved.
在本實施形態，Log(E1/T1)+Log(E2/T2)之值為6.4以上，以6.8以上為佳，以7.0以上為較佳。 In this embodiment, the value of Log(E 1 /T 1 )+Log(E 2 /T 2 ) is 6.4 or more, preferably 6.8 or more, and more preferably 7.0 or more.
Log(E1/T1)+Log(E2/T2)之值為前述下限值以上時，因為能夠將偏光片與相位差層、及相位差層與例如顯示面板堅固地貼合，結果抑制伴隨著相位差層變形所致之偏光板產生皺紋之效果提高。 When the value of Log(E 1 /T 1 )+Log(E 2 /T 2 ) is equal to or higher than the aforementioned lower limit value, the polarizer and the retardation layer, and the retardation layer and, for example, a display panel can be firmly bonded, As a result, the effect of suppressing wrinkles in the polarizing plate caused by deformation of the retardation layer is improved.
又，Log(E1/T1)+Log(E2/T2)係以9.0以下為佳，亦可為8.0以下。 In addition, Log(E 1 /T 1 )+Log(E 2 /T 2 ) is preferably 9.0 or less, and may be 8.0 or less.
Log(E1/T1)+Log(E2/T2)之值為前述範圍內時，將黏著劑層與相位差層貼合時，在前述黏著劑層與相位差層之間不容易產生氣泡，而且能夠抑制伴隨著氣泡產生所致之相位差層變形且抑制偏光板產生皺紋之效果提高。 When the value of Log(E 1 /T 1 )+Log(E 2 /T 2 ) is within the above range, when the adhesive layer and the retardation layer are bonded, it is not easy to connect the adhesive layer and the retardation layer. Bubbles are generated, and the deformation of the retardation layer caused by the bubble generation can be suppressed, thereby improving the effect of suppressing wrinkles in the polarizing plate.
上述上限值及下限值，係能夠任意地組合。 The upper limit value and the lower limit value mentioned above can be combined arbitrarily.
在本實施形態，係以滿足以下(1)及(2)的任一者為佳，以滿足以下(1-1)及(2-1)的任一者為較佳。而且，以滿足以下(1)及(2)之兩者為佳，以滿足以下(1-1)及(2-1)之兩者為較佳。 In this embodiment, it is preferable to satisfy any one of the following (1) and (2), and it is more preferable to satisfy any one of the following (1-1) and (2-1). Furthermore, it is preferable to satisfy both of the following (1) and (2), and it is preferable to satisfy both of the following (1-1) and (2-1).
(1)Log(E1/T1)為3.1以上。 (1)Log(E 1 /T 1 ) is 3.1 or more.
(2)Log(E2/T2)為3.0以上。 (2) Log(E 2 /T 2 ) is 3.0 or more.
(1-1)Log(E1/T1)為3.8以上。 (1-1)Log(E 1 /T 1 ) is 3.8 or more.
(2-1)Log(E2/T2)為3.5以上。 (2-1)Log(E 2 /T 2 ) is 3.5 or more.
在溫度40℃、濕度90%，第1黏著劑層及第2黏著劑層的水蒸氣穿透度係各自以1,000至10,000g/m2．24h為佳，亦可為2,000至9,000g/m2．24h。前述水蒸氣穿透度係能夠使用Systech ILLINOIS公司製的Lyssy水蒸氣穿透度計L80 Series而測定。黏著劑層的水蒸氣穿透度較高時，因為黏著劑強烈地受到高溫、高濕環境之影響，所以容易產生伴隨著相位差層的變形引起偏光板產生皺紋。為黏著劑單體而不容易測定水蒸氣穿透度時，亦可藉由將黏著劑貼合在透濕性較高的基材上且從與透濕性較高的基材之比來算出水蒸氣穿透度。 At a temperature of 40°C and a humidity of 90%, the water vapor penetration of the first adhesive layer and the second adhesive layer is 1,000 to 10,000g/m 2 respectively. 24h is preferred, and it can also be 2,000 to 9,000g/m 2 . 24h. The aforementioned water vapor penetration can be measured using the Lyssy water vapor penetration meter L80 Series manufactured by Systech ILLINOIS. When the water vapor penetration of the adhesive layer is high, because the adhesive is strongly affected by high temperature and high humidity environments, it is easy to cause deformation of the retardation layer and cause wrinkles in the polarizer. When it is difficult to measure the water vapor transmission rate due to the adhesive alone, it can also be calculated by bonding the adhesive to a base material with higher moisture permeability and calculating it from the ratio to the base material with higher moisture permeability. Water vapor penetration.
<相位差層> <Phase difference layer>
相位差層14係具有由含有液晶化合物之液晶材料(亦稱為液晶組成物)所構成之層。所謂由含有液晶化合物之液晶材料所構成之層，具體而言係意味著液晶化合物硬化而成之層。在本說明書中，係有將供給λ/2的相位差之層、供給λ/4的相位差之層及正C層等總稱為相位差層之情形。而且，相位差層亦可包含後述的透明基材、配向層。 The retardation layer 14 has a layer made of a liquid crystal material (also called a liquid crystal composition) containing a liquid crystal compound. The layer composed of a liquid crystal material containing a liquid crystal compound specifically means a layer in which the liquid crystal compound is hardened. In this specification, the layer providing a phase difference of λ/2, the layer providing a phase difference of λ/4, the positive C layer, etc. may be collectively referred to as a phase difference layer. Furthermore, the retardation layer may include a transparent base material and an alignment layer described below.
液晶化合物硬化而成之層係例如形成在透明基材所設置的 配向層上。所謂「透明基材」係指能夠透射光，特別是具有能夠透射可見光程度的透明性之基材。在本說明書中，所謂「透明性」，係指對波長380至780nm範圍的可見光區域的光線之透射率為80%以上之特性。 The layer system formed by hardening the liquid crystal compound is formed on a transparent substrate, for example. on the alignment layer. The so-called "transparent substrate" refers to a substrate that can transmit light, especially a substrate that is transparent enough to transmit visible light. In this specification, "transparency" refers to the characteristic of a transmittance of 80% or more for light in the visible light region with a wavelength ranging from 380 to 780 nm.
前述透明基材亦可為具有支撐配向層的功能且形成長條之基材。該透明基材係能夠作為脫模性支撐體的功能且支撐轉印用的相位差層。而且，其表面係以具有能夠剝離的程度之接著力者為佳。 The aforementioned transparent substrate may also be a substrate that has the function of supporting the alignment layer and forms a long strip. The transparent base material can function as a release support and support the retardation layer for transfer. Furthermore, it is preferable that the surface has an adhesive force capable of being peeled off.
作為前述透明基材，例如能夠舉出玻璃基材及塑膠基材，較佳為塑膠基材。作為構成塑膠基材之塑膠，例如可舉出聚乙烯、聚丙烯、降莰烯系聚合物等聚烯烴、環狀烯烴系樹脂、聚乙烯醇、聚對苯二甲酸乙二酯、聚甲基丙烯酸酯、聚丙烯酸酯、三乙酸纖維素、二乙酸纖維素及纖維素乙酸酯丙酸酯等纖維素酯、聚萘二甲酸乙二酯、聚碳酸酯、聚碸、聚醚碸、聚醚酮、聚苯硫(polyphenylene sulfide)及聚苯醚。尤其是就能夠容易地從市場取得或具有優異的透明性而言，特佳可舉出纖維素酯、環狀烯烴系樹脂、聚對苯二甲酸乙二酯或聚甲基丙烯酸酯。作為透明基材，可為由該等材料所構成之單層，亦可為積層2種以上而成之積層體。又，設為複數層的積層體時亦可積層相同組成的層。 Examples of the transparent base material include a glass base material and a plastic base material, and a plastic base material is preferred. Examples of the plastic constituting the plastic base material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers, cyclic olefin-based resins, polyvinyl alcohol, polyethylene terephthalate, and polymethyl Acrylate, polyacrylate, cellulose triacetate, cellulose diacetate and cellulose acetate propionate and other cellulose esters, polyethylene naphthalate, polycarbonate, polyether, polyether Ether ketone, polyphenylene sulfide (polyphenylene sulfide) and polyphenylene ether. Particularly preferred examples include cellulose esters, cyclic olefin-based resins, polyethylene terephthalate, and polymethacrylate in terms of being easily available on the market or having excellent transparency. The transparent base material may be a single layer made of these materials, or a laminate in which two or more types are laminated. Moreover, when it is a laminated body of a plurality of layers, layers of the same composition may be laminated.
透明基材的厚度並無特別限定，例如以設為20μm以上且200μm以下的範圍為佳。若透明基材的厚度為20μm以上，則能夠賦予強度。另一方面，厚度為200μm以下時，在將透明基材進行裁斷加工而成為單片透明基材時，能夠抑制加工屑的增加及裁斷刀刃的磨耗。 The thickness of the transparent base material is not particularly limited, but it is preferably in the range of 20 μm or more and 200 μm or less, for example. If the thickness of the transparent base material is 20 μm or more, strength can be provided. On the other hand, when the thickness is 200 μm or less, when the transparent base material is cut into a single transparent base material, the increase in processing chips and the wear of the cutting blade can be suppressed.
透明基材亦可經施行各種抗結塊處理。作為抗結塊處理，可舉出易接著處理、摻合填料等之處理、壓花加工(滾紋處理(knurling process))等。藉由對透明基材施行此種抗結塊處理，能夠有效地防止在將透明基材捲取時在基材之間產生貼附亦即所謂的結塊且能夠生產性較高地製造光學膜。 Transparent substrates can also be treated with various anti-caking treatments. Examples of the anti-caking treatment include easy-adhesion treatment, treatment by blending fillers, etc., and embossing (knurling). process)) etc. By subjecting the transparent base material to such an anti-blocking treatment, it is possible to effectively prevent so-called blocking that occurs between base materials when winding up the transparent base material, and to produce an optical film with high productivity.
液晶化合物硬化而成之層，係隔著配向層而形成在透明基材上。亦即，相位差層係依序將透明基材、及配向層積層且將液晶化合物硬化而成之層積層在前述配向層上。 A layer made of a hardened liquid crystal compound is formed on a transparent substrate via an alignment layer. That is, the retardation layer is a laminate obtained by sequentially laminating a transparent base material and an alignment layer and curing a liquid crystal compound on the alignment layer.
配向層不限定為垂直配向層，亦可為使液晶化合物的分子軸水平配向之配向層，亦可為使液晶化合物的分子軸傾斜配向之配向層。作為配向膜，係具有不因使用含有後述的液晶化合物塗佈液進行塗佈等而溶解之溶劑耐受性，而且，以在溶劑的除去和液晶化合物的配向用加熱處理時具有耐熱性者為佳。作為配向膜，可舉出含有配向性聚合物之配向膜、在光配向膜及表面形成凹凸圖案和複數條溝且使其配向之溝配向膜。配向膜的厚度通常係10nm至10000nm的範圍，以10nm至1000nm的範圍為佳，較佳為500nm以下，更佳為10nm至200nm的範圍。 The alignment layer is not limited to a vertical alignment layer, and may also be an alignment layer that aligns the molecular axes of the liquid crystal compound horizontally, or an alignment layer that aligns the molecular axes of the liquid crystal compound obliquely. The alignment film should have solvent resistance such that it does not dissolve due to coating using a coating liquid containing a liquid crystal compound described later, and should have heat resistance during heat treatment for removal of the solvent and alignment of the liquid crystal compound. good. Examples of the alignment film include an alignment film containing an alignment polymer and a groove alignment film in which a concave-convex pattern and a plurality of grooves are formed and aligned on a photo-alignment film and its surface. The thickness of the alignment film is usually in the range of 10 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm, preferably below 500 nm, and more preferably in the range of 10 nm to 200 nm.
作為在配向層所使用的樹脂，只要為被使用作為習知配向膜的材料之樹脂，就沒有特別限定，而且能夠使用使先前習知單官能或多官能的(甲基)丙烯酸酯系單體在聚合起始劑下硬化而成之硬化物等。具體而言，作為(甲基)丙烯酸酯系單體，係例如能夠例示丙烯酸2-乙基己酯、丙烯酸環己酯、二乙二醇單2-乙基己醚丙烯酸酯、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、丙烯酸四氫糠酯、丙烯酸2-羥基丙酯、丙烯酸苄酯、甲基丙烯 酸四氫糠酯、甲基丙烯酸2-羥基丙酯、甲基丙烯酸苄酯、甲基丙烯酸環己酯、甲基丙烯酸、胺甲酸酯丙烯酸酯等。使用在配向層之樹脂，可為使該等樹脂1種類硬化而成之硬化物，亦可為使2種類以上的混合物硬化而成之硬化物。 The resin used in the alignment layer is not particularly limited as long as it is a resin used as a material for a conventional alignment film, and conventionally known monofunctional or polyfunctional (meth)acrylate monomers can be used. Hardened products obtained by hardening in the presence of polymerization initiators. Specifically, examples of the (meth)acrylate-based monomer include 2-ethylhexyl acrylate, cyclohexyl acrylate, diethylene glycol mono-2-ethylhexyl ether acrylate, and diethylene glycol. Monophenyl ether acrylate, tetraethylene glycol monophenyl ether acrylate, trimethylolpropane triacrylate, lauryl acrylate, lauryl methacrylate, isocamphenyl acrylate, isocamphenyl methacrylate, acrylic acid 2-phenoxyethyl ester, tetrahydrofurfuryl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, methacrylate Tetrahydrofurfuryl acid, 2-hydroxypropyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, methacrylic acid, urethane acrylate, etc. The resin used in the alignment layer may be a cured product obtained by curing one type of resin, or may be a cured product obtained by curing a mixture of two or more types of resin.
在本實施形態所使用的液晶化合物之種類並無限定。從其形狀能夠分類成為棒狀型(棒狀液晶化合物)及圓盤狀型(圓盤狀液晶化合物、碟狀液晶化合物)。而且，各別有低分子型及高分子型。又，所謂高分子，通常係指聚合度為100以上之物(高分子物理．相轉移動力、土井正男著、第2頁、岩波書店、1992年)。 The type of liquid crystal compound used in this embodiment is not limited. Based on their shapes, they can be classified into rod-shaped type (rod-shaped liquid crystal compound) and disc-shaped type (disc-shaped liquid crystal compound, disc-shaped liquid crystal compound). Moreover, there are low molecular type and high molecular type respectively. In addition, the so-called polymer usually refers to a substance with a degree of polymerization of 100 or more (Polymer Physics. Phase Transfer Dynamics, by Masao Doi, page 2, Iwanami Shoten, 1992).
在本實施形態，能夠使用任何液晶化合物。亦可使用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之混合物。 In this embodiment, any liquid crystal compound can be used. It is also possible to use two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disc-shaped liquid crystal compounds, or a mixture of rod-shaped liquid crystal compounds and disc-shaped liquid crystal compounds.
作為棒狀液晶化合物，能夠適合使用在特表平11-513019號公報的請求項1、特開2005-289980號公報的段落[0026]至[0098]等記載之液晶化合物。作為圓盤狀液晶化合物，例如能夠適合使用在特開2007-108732號公報的段落[0020]至[0067]、特開2010-244038號公報的段落[0013]至[0108]等記載的液晶化合物。 As the rod-shaped liquid crystal compounds, liquid crystal compounds described in claim 1 of Japanese Patent Application Publication No. 11-513019, paragraphs [0026] to [0098] of Japanese Patent Application Publication No. 2005-289980, etc. can be suitably used. As the disk-shaped liquid crystal compound, for example, the liquid crystal compounds described in paragraphs [0020] to [0067] of Japanese Patent Application Laid-Open No. 2007-108732, paragraphs [0013] to [0108] of Japanese Patent Application Laid-Open No. 2010-244038, etc. can be suitably used. .
前述液晶化合物硬化而成之層，係以使用具有聚合性基之棒狀液晶化合物、或具有聚合性基之圓盤狀液晶化合物而形成為較佳。藉此，能夠減低光學特性之溫度變化和濕度變化。 The layer formed by curing the liquid crystal compound is preferably formed using a rod-shaped liquid crystal compound having a polymerizable group or a disc-shaped liquid crystal compound having a polymerizable group. Thereby, temperature changes and humidity changes in optical characteristics can be reduced.
作為液晶化合物，亦可併用2種類以上。此時，係以至少1種類在分子內具有2個以上的聚合性基為佳。亦即，前述液晶化合物硬化 而成之層，係以具有聚合性基之棒狀液晶化合物或具有聚合性基之圓盤狀液晶化合物藉由聚合而被固定且形成之層為佳。此時，成為層之後，係已經不必顯示液晶性。 As the liquid crystal compound, two or more types may be used in combination. In this case, it is preferable that at least one type has two or more polymerizable groups in the molecule. That is, the aforementioned liquid crystal compound hardens The layer formed is preferably a layer in which a rod-shaped liquid crystal compound having a polymerizable group or a disk-shaped liquid crystal compound having a polymerizable group is fixed by polymerization and formed. At this time, after forming a layer, it is no longer necessary to display liquid crystallinity.
棒狀液晶化合物或圓盤狀液晶化合物係具有聚合性基時，其聚合性基的種類並無特別限制。作為聚合性基，例如以聚合性乙烯性不飽和基、環聚合性基等能夠加成聚合反應之官能基為佳。更具體地，作為聚合性基，係例如能夠舉出(甲基)丙烯醯基、乙烯基、苯乙烯基、烯丙基等。其中以(甲基)丙烯醯基為佳。又，所謂(甲基)丙烯醯基係包含甲基丙烯醯基及丙烯醯基的兩者之概念。 When the rod-shaped liquid crystal compound or the disk-shaped liquid crystal compound has a polymerizable group, the type of the polymerizable group is not particularly limited. As the polymerizable group, functional groups capable of addition polymerization such as polymerizable ethylenically unsaturated groups and cyclopolymerizable groups are preferred. More specifically, examples of the polymerizable group include (meth)acrylyl group, vinyl group, styryl group, allyl group, and the like. Among them, (meth)acrylyl group is preferred. In addition, the (meth)acrylyl group is a concept including both a methacrylic group and an acrylyl group.
液晶化合物硬化而成之層如後述般，能夠藉由將含有液晶化合物塗佈液塗佈在例如配向層上而形成。前述塗佈液亦可含有上述液晶化合物以外的成分。例如前述塗佈液亦可含有聚合起始劑。所使用的聚合起始劑，係能夠按照聚合反應的形式而選擇例如熱聚合起始劑和光聚合起始劑。例如作為光聚合起始劑，可舉出α-羰基化合物、醯偶姻醚(acyloin ether)、α-烴取代芳香族醯偶姻化合物、多核苯醌化合物、三芳基咪唑二聚物與對胺基苯基酮之組合等。聚合起始劑的使用量，係相對於前述塗佈液中的總固體成分，以0.01至20質量%為佳，以0.5至5質量%為較佳。 The layer in which the liquid crystal compound is hardened can be formed by applying a coating liquid containing the liquid crystal compound on, for example, an alignment layer, as will be described later. The coating liquid may contain components other than the above-mentioned liquid crystal compound. For example, the coating liquid may contain a polymerization initiator. The polymerization initiator used can be selected according to the form of the polymerization reaction, such as a thermal polymerization initiator and a photopolymerization initiator. Examples of photopolymerization initiators include α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear benzoquinone compounds, triarylimidazole dimers, and p-amines. Combinations of phenyl ketones, etc. The usage amount of the polymerization initiator is preferably 0.01 to 20 mass%, more preferably 0.5 to 5 mass%, based on the total solid content in the coating liquid.
就塗佈膜的均勻性及膜強度而言，前述塗佈液亦可含有聚合性單體。作為聚合性單體，可舉出自由基聚合性或陽離子聚合性的化合物。其中以多官能性自由基聚合性單體為佳。 In terms of the uniformity and film strength of the coating film, the coating liquid may contain a polymerizable monomer. Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Among them, polyfunctional radically polymerizable monomers are preferred.
作為聚合性單體，係以能夠與上述具有聚合性基之液晶化合物(以下亦稱為聚合性液晶化合物)共聚合之物為佳。作為具體的聚合性單 體，例如可舉出在特開2002-296423號公報中的段落[0018]至[0020]記載之物。相對於液晶化合物的總質量，聚合性單體的使用量以1至50質量%為佳，以2至30質量%為較佳。 The polymerizable monomer is preferably one that can be copolymerized with the above-mentioned liquid crystal compound having a polymerizable group (hereinafter also referred to as a polymerizable liquid crystal compound). As a specific polymeric unit Examples of the body include those described in paragraphs [0018] to [0020] of Japanese Patent Application Laid-Open No. 2002-296423. The usage amount of the polymerizable monomer is preferably 1 to 50% by mass, and more preferably 2 to 30% by mass relative to the total mass of the liquid crystal compound.
就塗佈膜的均勻性及膜強度而言，前述塗佈液亦可含有界面活性劑。作為界面活性劑，可舉出先前習知的化合物。其中以氟系化合物為特佳。作為具體的界面活性劑，例如可舉出特開2001-330725號公報中的段落[0028]至[0056]記載的化合物、及在特願2003-295212號說明書中的段落[0069]至[0126]記載之化合物。 In terms of the uniformity and film strength of the coating film, the aforementioned coating liquid may also contain a surfactant. Examples of surfactants include conventionally known compounds. Among them, fluorine-based compounds are particularly preferred. Specific examples of surfactants include compounds described in paragraphs [0028] to [0056] of Japanese Patent Application Laid-Open No. 2001-330725, and paragraphs [0069] to [0126] of Japanese Patent Application Publication No. 2003-295212. ] recorded compounds.
前述塗佈液亦可含有溶劑且能夠適合使用有機溶劑。作為有機溶劑，例如可舉出醯胺(N,N-二甲基甲醯胺等)、亞碸(二甲基亞碸等)、雜環化合物(吡啶等)、烴(苯、己烷等)、烷基鹵化物(氯仿、二氯甲烷等)、酯(乙酸甲酯、乙酸乙酯、乙酸丁酯等)、酮(丙酮、甲基乙基酮等)、醚(四氫呋喃、1,2-二甲氧基乙烷等)。其中，以烷基鹵化物、酮為佳。亦可併用2種類以上的有機溶劑作為前述塗佈液。 The coating liquid may contain a solvent, and an organic solvent may be suitably used. Examples of organic solvents include amides (N,N-dimethylformamide, etc.), styrene (dimethylsyanide, etc.), heterocyclic compounds (pyridine, etc.), hydrocarbons (benzene, hexane, etc.) ), alkyl halides (chloroform, dichloromethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethers (tetrahydrofuran, 1,2 - dimethoxyethane, etc.). Among them, alkyl halides and ketones are preferred. Two or more types of organic solvents may be used together as the coating liquid.
前述塗佈液亦可有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所謂之水平配向促進劑之各種配向劑。前述塗佈液係除了上述成分以外，亦可含有密著改良劑、塑化劑、聚合物等。 The aforementioned coating liquid may also contain vertical alignment accelerators such as vertical alignment agents on the polarizer interface side and vertical alignment agents on the air interface side, and so-called horizontal alignment accelerators such as horizontal alignment agents on the polarizer interface side and horizontal alignment agents on the air interface side. Various aligning agents. In addition to the above-mentioned components, the coating liquid may also contain an adhesion improving agent, a plasticizer, a polymer, etc.
在本實施形態，相位差層的厚度係以0.5μm以上為佳。前述相位差層的厚度係以10μm以下為佳，以5μm以下為較佳。而且，上述上限值及下限值係能夠任意地組合。 In this embodiment, the thickness of the retardation layer is preferably 0.5 μm or more. The thickness of the retardation layer is preferably 10 μm or less, and more preferably 5 μm or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
相位差層的厚度為前述下限值以上時，能夠得到充分的耐久性。相位 差層的厚度為前述上限值以下時，能夠有助於偏光板的薄層化。 When the thickness of the retardation layer is equal to or greater than the aforementioned lower limit, sufficient durability can be obtained. Phase When the thickness of the difference layer is equal to or less than the aforementioned upper limit, it can contribute to thinning the polarizing plate.
相位差層的厚度係能夠以可得到供給λ/4的相位差之層、供給λ/2的相位差之層、或正C層所需要的面內相位差值、及厚度方向的相位差值之方式調整。 The thickness of the retardation layer can be such that a layer providing a retardation of λ/4, a layer providing a retardation of λ/2, or a positive C layer can obtain the in-plane retardation value and the retardation value in the thickness direction required way to adjust.
在本實施形態，相位差層的穿刺強度並無特別限定。若使用穿刺強度較弱的相位差層則，在高溫、高濕的環境下容易在偏光板產生皺紋。依照本實施形態，即便包含穿刺強度較弱的相位差層之偏光板，亦能夠抑制產生皺紋。 In this embodiment, the puncture strength of the retardation layer is not particularly limited. If a retardation layer with weak puncture strength is used, wrinkles will easily occur on the polarizing plate in a high-temperature, high-humidity environment. According to this embodiment, even if the polarizing plate includes a retardation layer with weak puncture strength, the occurrence of wrinkles can be suppressed.
在本申請發明，偏光板係包括包含複數相位差層之積層體時，作為相位差層的穿刺強度，係採用對該積層體之穿刺強度。上述積層體係包含用以將相位差層之間貼合之接著層及配向層時，係採用對亦包含該等層的積層體之穿刺強度。 In the present invention, when the polarizing plate includes a laminated body including a plurality of retardation layers, the puncture strength of the laminated body is used as the puncture strength of the retardation layer. When the above-mentioned laminate system includes an adhesive layer and an alignment layer for bonding the retardation layers, the puncture strength of the laminate that also includes these layers is used.
相位差層的穿刺強度可為100gf以下，亦可為95gf以下，亦可為90gf以下，亦可為80gf以下。相位差層的穿刺強度係以10gf以上為佳，亦可為30gf以上，亦可為50gf以上。 The puncture strength of the retardation layer may be 100gf or less, 95gf or less, 90gf or less, or 80gf or less. The puncture strength of the retardation layer is preferably 10gf or more, may be 30gf or more, or may be 50gf or more.
在偏光板所包含的相位差層為1層時，此種穿刺強度的相位差層係能夠藉由例如減小構成相位差層之層的厚度來得到。 When the retardation layer included in the polarizing plate is one layer, such a puncture-strength retardation layer can be obtained by, for example, reducing the thickness of the layers constituting the retardation layer.
在偏光板所包含的相位差層為複數相位差層的積層體時，此種穿刺強度的相位差層係能夠藉由例如藉由接著劑的種類和厚度、相位差層的厚度來得到。 When the retardation layer included in the polarizing plate is a laminate of a plurality of retardation layers, such a puncture-strength retardation layer can be obtained by, for example, the type and thickness of the adhesive and the thickness of the retardation layer.
穿刺強度係將穿刺輔助具對相位差層垂直地進行穿刺且相位差層破裂時之強度。穿刺強度係例如能夠藉由具備測力傳感器之壓縮試 驗機而測定。壓縮試驗機的例子，可舉出KATO TECH股份有限公司製的手握式壓縮試驗機“KES-G5型”；及股份有限公司島津製作所製的小型桌上型試驗機“EZ Test(註冊商標)”等。 The puncture strength refers to the strength when the puncture auxiliary tool vertically punctures the retardation layer and the retardation layer ruptures. The puncture strength can be determined, for example, by a compression test with a load cell. Determined by testing the machine. Examples of compression testing machines include the hand-held compression testing machine "KES-G5 type" manufactured by KATO TECH Co., Ltd.; and the small desktop testing machine "EZ Test (registered trademark) manufactured by Shimadzu Corporation. "wait.
測定係在開有穿刺輔助具能夠通過之直徑15mm以下的圓形孔穴之2片試樣平台之間，夾住相位差層而進行。穿刺輔助具為圓柱狀棒，其接觸相位差層之前端係具備球形或半球形的穿刺針。前端球形部或半球形部之直徑為1mm 
作為相位差層在溫度40℃濕度90%RH之透濕度比，係以0.5至1.0的範圍為佳。透濕度比係指使用以下的方法所算出的值。因為相位差層單體時厚度和機械特性較低，所以測定透濕度為困難的。因此，係隔著黏著劑而將相位差層與透濕性較高的基材貼合且測定透濕度。透濕度的測定，係能夠使用與保護膜的透濕度之測定相同的方法而進行。透濕度比係藉由所測定的透濕度與基材的透濕度之比而算出。 The moisture permeability ratio of the phase difference layer at a temperature of 40°C and a humidity of 90% RH is preferably in the range of 0.5 to 1.0. The water vapor permeability ratio is a value calculated using the following method. Since the thickness and mechanical properties of the retardation layer alone are low, it is difficult to measure the moisture permeability. Therefore, the retardation layer was bonded to a base material with high moisture permeability via an adhesive, and the moisture permeability was measured. The measurement of the water vapor transmission rate can be performed using the same method as the measurement of the water vapor transmission rate of the protective film. The water vapor permeability ratio is calculated from the ratio of the measured water vapor permeability to the water vapor permeability of the base material.
透濕度比越低，抑制在高溫、高濕環境下產生皺紋為越有效。 The lower the moisture permeability ratio, the more effective it is in inhibiting wrinkles in high temperature and high humidity environments.
在本說明書中，所謂「偏光板的總厚度」，係意味著偏光板積層方向的尺寸。亦即，所謂「在第1實施形態之偏光板的總厚度」，係意味著將偏光片的厚度、第1黏著劑層的厚度、相位差層的厚度、第2黏著劑層的厚度、在其它偏光板所包含的全部光學膜層、黏著劑層、接著劑層的厚度進行合計而成之厚度。偏光板的總厚度係不包含最後未殘留在顯示裝置之構件。作為最後未殘留在顯示裝置之構件，可舉出積層在偏光板 之與顯示面板為相反側的面之表面保護膜、及積層在第2黏著劑層上之隔離膜。該等層係在顯示裝置的製造過程被剝離除去且在最後未殘留在顯示裝置。 In this specification, the "total thickness of the polarizing plate" means the size in the stacking direction of the polarizing plate. That is, "the total thickness of the polarizing plate in the first embodiment" means that the thickness of the polarizing plate, the thickness of the first adhesive layer, the thickness of the retardation layer, the thickness of the second adhesive layer, The thickness is the sum of the thicknesses of all optical film layers, adhesive layers, and adhesive layers included in other polarizing plates. The total thickness of the polarizing plate does not include components that are not ultimately left in the display device. Examples of components that do not remain in the display device include polarizing plates laminated on them. A surface protective film on the side opposite to the display panel, and an isolation film laminated on the second adhesive layer. These layers are peeled off and removed during the manufacturing process of the display device and do not remain in the display device at the end.
偏光板的總厚度，係例如能夠藉由使用測微計而測定偏光板的任意5點且算出其平均值而得到。 The total thickness of the polarizing plate can be obtained, for example, by measuring five arbitrary points of the polarizing plate using a micrometer and calculating the average value.
偏光板的總厚度，亦能夠藉由各別測定偏光片的厚度、第1黏著劑層的厚度、相位差層的厚度、第2黏著劑層的厚度、在其它偏光板所包含的全部光學膜層、黏著劑層、接著劑層的厚度且將其值層合計而得到。 The total thickness of the polarizing plate can also be determined by individually measuring the thickness of the polarizing plate, the thickness of the first adhesive layer, the thickness of the retardation layer, the thickness of the second adhesive layer, and all optical films included in other polarizing plates. The thickness of the layer, adhesive layer, and adhesive layer is calculated by adding up the thickness of each layer.
偏光片的厚度，第1黏著劑層的厚度、相位差層的厚度、第2黏著劑層的厚度、其它偏光板所包含的全部光學膜層、黏著劑層、接著劑層的厚度係能夠使用本說明書記載的方法而測定。 The thickness of the polarizer, the thickness of the first adhesive layer, the thickness of the retardation layer, the thickness of the second adhesive layer, and the thickness of all optical film layers, adhesive layers, and adhesive layers included in other polarizers can be used. measured using the method described in this manual.
在第1實施形態之偏光板的總厚度係以30μm以上為佳。又，前述偏光板的總厚度係以500μm以下為佳，以300μm以下為較佳，以100μm以下為更佳。而且，上述上限值及下限值係能夠任意地組合。 The total thickness of the polarizing plate in the first embodiment is preferably 30 μm or more. In addition, the total thickness of the polarizing plate is preferably 500 μm or less, more preferably 300 μm or less, and more preferably 100 μm or less. Furthermore, the upper limit value and the lower limit value mentioned above can be combined arbitrarily.
偏光板的總厚度為前述上限值以下時，係能夠有助於偏光板的薄層化。偏光板的總厚度為前述下限值以上時，偏光板的強度提升。 When the total thickness of the polarizing plate is equal to or less than the aforementioned upper limit, it can contribute to thinning the polarizing plate. When the total thickness of the polarizing plate is above the aforementioned lower limit, the strength of the polarizing plate increases.
[第2實施形態] [Second Embodiment]
第2實施形態的偏光板係包含至少2層相位差層。作為在第2實施形態的偏光板所包含的相位差層之層數，並無特別限定，可舉出2層、3層作為例子。 The polarizing plate of the second embodiment includes at least two retardation layers. The number of retardation layers included in the polarizing plate of the second embodiment is not particularly limited, and examples thereof include two layers and three layers.
包含2層相位差層之第2實施形態的偏光板，係依序具備偏光片、第 1黏著劑層、第1相位差層、第1接著層、第2相位差層、及第2黏著劑層之偏光板。 The polarizing plate of the second embodiment including two retardation layers is provided with a polarizer, a polarizer, and a second retardation layer in this order. 1 Polarizing plate with an adhesive layer, a first retardation layer, a first bonding layer, a second retardation layer, and a second adhesive layer.
第2圖係顯示包含2層相位差層之第2實施形態的偏光板的構成之概略剖面圖的一個例子。如第2圖顯示，偏光板101係依序將偏光片11、第1黏著劑層12、第1相位差層15、第1接著層17、第2相位差層16、及第2黏著劑層13積層而成。 FIG. 2 is an example of a schematic cross-sectional view showing the structure of the polarizing plate of the second embodiment including two retardation layers. As shown in Figure 2, the polarizing plate 101 sequentially combines the polarizer 11, the first adhesive layer 12, the first retardation layer 15, the first adhesive layer 17, the second retardation layer 16, and the second adhesive layer. 13 layers.
包含3層相位差層之第2實施形態的偏光板，係依序具備偏光片、第1黏著劑層、第1相位差層、第1接著層、第2相位差層、第2接著層、第3相位差層、及第2黏著劑層之偏光板。 The polarizing plate of the second embodiment including three retardation layers has a polarizer, a first adhesive layer, a first retardation layer, a first adhesive layer, a second retardation layer, a second adhesive layer, in this order. Polarizing plate with a third retardation layer and a second adhesive layer.
第3圖係顯示包含3層相位差層之第2實施形態的偏光板的構成之概略剖面圖的一個例子。如第3圖顯示，偏光板102係依序將偏光片11、第1黏著劑層12、第1相位差層15、第1接著層17、第2相位差層16、第2接著層18、第3相位差層19、及第2黏著劑層13積層而成。 FIG. 3 is an example of a schematic cross-sectional view showing the structure of the polarizing plate of the second embodiment including three retardation layers. As shown in Figure 3, the polarizing plate 102 sequentially combines the polarizer 11, the first adhesive layer 12, the first phase difference layer 15, the first adhesive layer 17, the second phase difference layer 16, the second adhesive layer 18, The third retardation layer 19 and the second adhesive layer 13 are laminated.
又，針對與上述第1實施形態相同態樣的構成要素(偏光片11、第1黏著劑層12、第2黏著劑層13)係附加相同符號且省略其說明。 In addition, the same components (polarizer 11, first adhesive layer 12, and second adhesive layer 13) as those in the above-mentioned first embodiment are denoted by the same reference numerals and their descriptions are omitted.
<包含複數相位差層之積層體> <Laminated body including complex phase difference layers>
偏光板包含2層相位差層時，第1相位差層15、及第2相位差層16係隔著第1接著層17而積層。 When the polarizing plate includes two retardation layers, the first retardation layer 15 and the second retardation layer 16 are laminated via the first adhesive layer 17 .
偏光板係包含3層相位差層時，第1相位差層15、及第2相位差層16係隔著第1接著層17而積層，而且隔著第2接著層18將第2相位差層16、及第3相位差層19積層而成。 When the polarizing plate includes three retardation layers, the first retardation layer 15 and the second retardation layer 16 are laminated via the first adhesive layer 17 , and the second retardation layer is laminated via the second adhesive layer 18 . 16, and the third phase difference layer 19 are laminated.
第1相位差層15、第2相位差層16、及第3相位差層19為 相位差層，各別例如能夠為供給λ/2的相位差之層、供給λ/4的相位差之層、或正C層。 The first phase difference layer 15, the second phase difference layer 16, and the third phase difference layer 19 are The phase difference layer can be, for example, a layer providing a phase difference of λ/2, a layer providing a phase difference of λ/4, or a positive C layer.
作為本實施形態之一態樣，偏光板係包含2層相位差層時，較佳是第1相位差層15及第2相位差層16的任一者為作為供給λ/4的相位差之層的功能，另一者為作為供給λ/2的相位差之層的功能，或是第1相位差層15及第2相位差層16的任一者為作為供給λ/4的相位差之層的功能，另一者為作為正C層的功能。 As an aspect of this embodiment, when the polarizing plate includes two retardation layers, it is preferable that either the first retardation layer 15 or the second retardation layer 16 supplies a retardation of λ/4. The other one functions as a layer that supplies a phase difference of λ/2, or either the first phase difference layer 15 and the second phase difference layer 16 functions as a layer that supplies a phase difference of λ/4. The function of the layer, the other is the function of the positive C layer.
偏光板係包含3層相位差層時，較佳是第1相位差層15、第2相位差層16、及第3相位差層19的任一者為作為供給λ/4的相位差之層的功能，其它二者為作為正C層的功能。 When the polarizing plate includes three retardation layers, it is preferable that any one of the first retardation layer 15 , the second retardation layer 16 , and the third retardation layer 19 is a layer that provides a retardation of λ/4. function, the other two functions as the positive C layer.
第1相位差層15、第2相位差層16、及第3相位差層19的厚度及構成材料，係以能夠得到供給λ/4的相位差之層、供給λ/2的相位差之層、或正C層所需要的面內相位差值、厚度方向的相位差值之方式調整。 The thickness and constituent materials of the first phase difference layer 15 , the second phase difference layer 16 , and the third phase difference layer 19 are such that a layer providing a phase difference of λ/4 and a layer providing a phase difference of λ/2 can be obtained. , or adjust the in-plane phase difference value and the phase difference value in the thickness direction required by the positive C layer.
在包含2層相位差層之偏光板，第1相位差層15係作為供給λ/2的相位差之層的功能，且第2相位差層16係作為供給λ/4的相位差之層的功能時，第1相位差層15的厚度係例如1μm以上且10μm以下，第2相位差層16的厚度係例如1μm以上且10μm以下。在包含2層相位差層之偏光板，第1相位差層15係作為供給λ/4的相位差之層的功能，且第2相位差層16係作為正C層的功能時，第1相位差層15的厚度係例如1μm以上且10μm以下，第2相位差層16的厚度係例如1μm以上且10μm以下。 In a polarizing plate including two retardation layers, the first retardation layer 15 functions as a layer providing a retardation of λ/2, and the second retardation layer 16 functions as a layer providing a retardation of λ/4. In function, the thickness of the first retardation layer 15 is, for example, 1 μm or more and 10 μm or less, and the thickness of the second retardation layer 16 is, for example, 1 μm or more and 10 μm or less. In a polarizing plate including two retardation layers, the first retardation layer 15 functions as a layer that provides a phase difference of λ/4, and the second retardation layer 16 functions as a positive C layer. The thickness of the difference layer 15 is, for example, 1 μm or more and 10 μm or less, and the thickness of the second phase difference layer 16 is, for example, 1 μm or more and 10 μm or less.
在第1相位差層、第2相位差層、及第3相位差層的各自之透明基材、配向層、液晶化合物，係能夠使用與在第1實施形態已例示者相同者。第1相位差層、第2相位差層、及第3相位差層的組成可以相同亦可不同。第1相位差層、第2相位差層、及第3相位差層的各厚度，係各別能夠使用在第1實施形態已說明之層厚度的測定方法而得到。 The same transparent base materials, alignment layers, and liquid crystal compounds as those exemplified in the first embodiment can be used for each of the first retardation layer, the second retardation layer, and the third retardation layer. The compositions of the first phase difference layer, the second phase difference layer, and the third phase difference layer may be the same or different. Each thickness of the first retardation layer, the second retardation layer, and the third retardation layer can be obtained using the layer thickness measurement method described in the first embodiment.
第1相位差層、第2相位差層、及第3相位差層係各別為與第1實施形態的相位差層相同的構成且依序將透明基材、配向層、相位差層積層而成。透明基材、及配向層亦可被剝離。 The first retardation layer, the second retardation layer, and the third retardation layer each have the same structure as the retardation layer of the first embodiment, and are formed by laminating a transparent base material, an alignment layer, and a retardation layer in this order. become. The transparent substrate and alignment layer can also be peeled off.
偏光板係包含2層相位差層時，係隔著第1接著層將第1相位差層及第2相位差層積層而成。亦即，包含2層相位差層之積層體，亦可為依序將第1相位差層、第1接著層、及第2相位差層積層而成之積層體。 When the polarizing plate includes two retardation layers, the first retardation layer and the second retardation layer are laminated via the first adhesive layer. That is, the laminated body including two retardation layers may be a laminated body in which the first retardation layer, the first adhesive layer, and the second retardation layer are laminated in this order.
偏光板係包含3層相位差層時，例如隔著第1接著層將第1相位差層及第2相位差層積層而成，且隔著第2接著層將第2相位差層及第3相位差層積層而成。亦即，包含3層相位差層之積層體，可為依序將第1相位差層、第1接著層、第2相位差層、第2接著層、及第3相位差層積層而成之積層體。 When the polarizing plate includes three retardation layers, for example, the first retardation layer and the second retardation layer are laminated with the first adhesive layer interposed therebetween, and the second retardation layer and the third retardation layer are laminated with the second adhesive layer interposed therebetween. Phase difference layers are laminated. That is, the laminated body including three retardation layers may be formed by laminating the first retardation layer, the first adhesive layer, the second retardation layer, the second adhesive layer, and the third retardation layer in this order. Laminated body.
在本說明書中，「接著層」係意味著接著劑層或黏著劑層。作為黏著劑層，係能夠適合使用前述之物。在本實施形態，從防止產生皺紋之觀點而言，係以使用接著劑層作為接著層為佳。構成接著劑層之「接著劑」，係設為塗佈在基材時能夠以液狀塗佈在基材，藉由進行固化而顯現接著性(亦即至固化為止係不顯現接著性)之物。 In this specification, "adhesive layer" means an adhesive layer or an adhesive layer. As the adhesive layer, those described above can be suitably used. In this embodiment, from the viewpoint of preventing wrinkles, it is preferable to use an adhesive layer as the adhesive layer. The "adhesive" constituting the adhesive layer is one that can be applied to the base material in a liquid form when applied to the base material, and can develop adhesiveness by curing (that is, it does not exhibit adhesiveness until cured). things.
<接著劑層> <Adhesive layer>
作為將第1相位差層與第2相位差層、及第2相位差層與第3相位差層貼合之接著劑，例如可舉出水系接著劑、或活性能量線硬化性接著劑。作為水系接著劑，例如可舉出使聚乙烯醇系樹脂溶解或分散於水中而成之接著劑。作為活性能量線硬化性接著劑，例如可舉出藉由照射如紫外線、可見光、電子射線、X射線的活性能量線而硬化之含有硬化性化合物的接著劑。硬化後的活性能量線硬化性接著劑之儲存彈性模數，多半的情形係比水系接著劑的儲存彈性模數更高。因為相位差層間的接著劑層的儲存彈性模數較高時，相位差層之間不容易產生偏移，故以使用活性能量線硬化性接著劑為佳。 Examples of the adhesive that bond the first retardation layer and the second retardation layer and the second retardation layer and the third retardation layer include a water-based adhesive or an active energy ray-curable adhesive. Examples of water-based adhesives include adhesives obtained by dissolving or dispersing polyvinyl alcohol-based resin in water. Examples of active energy ray-curable adhesives include adhesives containing curable compounds that are cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. In most cases, the storage elastic modulus of active energy line curable adhesives after hardening is higher than the storage elastic modulus of water-based adhesives. Because when the storage elastic modulus of the adhesive layer between the retardation layers is high, the retardation layers are less likely to shift, so it is better to use an active energy ray-curable adhesive.
作為活性能量線硬化性接著劑，就顯示良好的接著性而言，以含有陽離子聚合性硬化性化合物、及自由基聚合性硬化性化合物的任一者或兩者為佳。活性能量線硬化性接著劑亦能夠進一步含有陽離子聚合起始劑、及自由基聚合起始劑的任一者或兩者，用以使上述硬化性化合物的硬化反應開始。 The active energy ray curable adhesive preferably contains any one or both of a cationic polymerizable curable compound and a radical polymerizable curable compound in order to exhibit good adhesion. The active energy ray curable adhesive agent may further contain any one or both of a cationic polymerization initiator and a radical polymerization initiator in order to start the curing reaction of the curable compound.
作為陽離子聚合性硬化性化合物，例如能夠舉出環氧系化合物(在分子內具有1個或2個以上的環氧基之化合物)、氧雜環丁烷(oxetane)系化合物(在分子內具有1個或2個以上的氧雜環丁烷環之化合物)、或該等化合物的組合。 Examples of the cationically polymerizable curable compound include epoxy compounds (compounds having one or more epoxy groups in the molecule) and oxetane compounds (compounds having Compounds with one or more oxetane rings), or combinations of these compounds.
作為自由基聚合性硬化性化合物，能夠舉出(甲基)丙烯酸系化合物(在分子內具有1個或2個以上的(甲基)丙烯醯基氧基之化合物)、具有自由基聚合性雙鍵之其它乙烯系化合物、該等化合物的組合等。 Examples of the radically polymerizable curable compound include (meth)acrylic compounds (compounds having one or more (meth)acryloxy groups in the molecule), radically polymerizable bis(meth)acrylic compounds. Bonds to other vinyl compounds, combinations of these compounds, etc.
活性能量線硬化性接著劑係能夠按照必要而含有陽離子聚合促進劑、離子捕捉劑、抗氧化劑、鏈轉移劑、黏著賦予劑、熱塑性樹脂、填充劑、流動調整劑、塑化劑、消泡劑、抗靜電劑、調平劑、溶劑等添加劑。 The active energy ray curable adhesive system can contain a cationic polymerization accelerator, an ion scavenger, an antioxidant, a chain transfer agent, an adhesion-imparting agent, a thermoplastic resin, a filler, a flow regulator, a plasticizer, and a defoaming agent as necessary. , antistatic agents, leveling agents, solvents and other additives.
使用接著劑而將第1相位差層與第2相位差層、及第2相位差層與第3相位差層貼合時，係首先，將接著劑塗佈在第1相位差層與第2相位差層之任一者的接合面或兩者的接合面、及在第2相位差層與第3相位差層之任一者的接合面或兩者的接合面。 When using an adhesive to bond the first retardation layer and the second retardation layer, and the second retardation layer and the third retardation layer, the adhesive is first applied to the first retardation layer and the second retardation layer. The joint surface of any one of the retardation layers or the joint surface of both, and the joint surface of either the second retardation layer and the third retardation layer or the joint surface of both.
作為將接著劑塗佈在上述接合面之方法，採用使用模塗佈器、刮刀式塗佈器(comma coater)、逆輥塗佈器、凹版塗佈器、棒塗佈器、繞線棒塗佈器、刮刀片塗佈器、氣動刮塗器等之通常的塗佈技術即可。 As a method for applying the adhesive to the above-mentioned joint surface, a die coater, a comma coater, a reverse roll coater, a gravure coater, a rod coater, or a wire rod coater can be used. Common coating techniques such as spreader, blade applicator, pneumatic blade applicator, etc. are sufficient.
針對使用水系接著劑時之乾燥方法，並無特別限定，例如能夠採用使用熱風乾燥機和紅外線乾燥機而乾燥之方法。 The drying method when using a water-based adhesive is not particularly limited. For example, a drying method using a hot air dryer or an infrared dryer can be used.
使用活性能量線硬化性接著劑時，係照射如紫外線、可見光、電子射線、X射線的活性能量線而使活性能量線硬化性接著劑硬化。作為活性能量線，係以紫外線為佳，作為此時的光源，係能夠使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、鹵化金屬燈等。 When an active energy ray-curable adhesive is used, active energy rays such as ultraviolet rays, visible light, electron rays, and X-rays are irradiated to harden the active energy ray-curable adhesive. As the active energy ray, ultraviolet rays are preferred. As the light source at this time, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc. can be used.
接著劑層的厚度係以10μm以下為佳，以5μm以下為較佳。 The thickness of the adhesive layer is preferably 10 μm or less, and more preferably 5 μm or less.
接著劑層的厚度為前述上限值以下時，在第1相位差層與第2相位差層、及第2相位差層與第3相位差層之間不容易產生浮起和剝落。 When the thickness of the adhesive layer is below the upper limit, floating and peeling are less likely to occur between the first retardation layer and the second retardation layer, and between the second retardation layer and the third retardation layer.
所謂「在第2實施形態之偏光板的總厚度」，係意味著將偏 光片的厚度、第1黏著劑層的厚度、第1相位差層的厚度、第1接著層的厚度、第2相位差層的厚度、第2黏著劑層的厚度、在其它偏光板所包含的全部光學膜層(第3相位差層等)、黏著劑層、接著劑層(第2接著層等)的厚度合計而成之厚度。與上述相同地，偏光板的總厚度係不包含最後在未殘留在顯示裝置的構件。 The so-called "total thickness of the polarizing plate in the second embodiment" means that the polarizing plate The thickness of the light sheet, the thickness of the first adhesive layer, the thickness of the first retardation layer, the thickness of the first adhesive layer, the thickness of the second retardation layer, the thickness of the second adhesive layer, are included in other polarizing plates The thickness is the total thickness of all optical film layers (third retardation layer, etc.), adhesive layer, and adhesive layer (second adhesive layer, etc.). Similarly to the above, the total thickness of the polarizing plate does not include components that are not left in the display device at the end.
在本實施形態之偏光板的總厚度，係例如能夠藉由使用測微計測定偏光板的任意5點且算出測定值的平均值而得到。 The total thickness of the polarizing plate in this embodiment can be obtained, for example, by measuring five arbitrary points on the polarizing plate using a micrometer and calculating the average of the measured values.
偏光板的總厚度，係例如亦能夠藉由各別測定偏光片的厚度、第1黏著劑層的厚度、第1相位差層的厚度、接著層的厚度、第2相位差層的厚度、第2黏著劑層的厚度、在其它偏光板所包含的全部光學膜層、黏著劑層、接著劑層的厚度，將其值合計而得到。 The total thickness of the polarizing plate can also be determined by separately measuring the thickness of the polarizing plate, the thickness of the first adhesive layer, the thickness of the first retardation layer, the thickness of the adhesive layer, the thickness of the second retardation layer, and the thickness of the second retardation layer. 2 The thickness of the adhesive layer, the thickness of all optical film layers, adhesive layers, and adhesive layers included in other polarizing plates are obtained by adding up their values.
偏光片的厚度、第1黏著劑層的厚度、第1相位差層的厚度、接著層的厚度、第2相位差層的厚度、第2黏著劑層的厚度、在其它偏光板所包含的全部光學膜層、黏著劑層、接著劑層的厚度係能夠使用本說明書記載的方法而測定。 The thickness of the polarizer, the thickness of the first adhesive layer, the thickness of the first retardation layer, the thickness of the adhesive layer, the thickness of the second retardation layer, the thickness of the second adhesive layer, and all the other polarizing plates The thickness of the optical film layer, adhesive layer, and adhesive layer can be measured using the method described in this specification.
在第2實施形態之偏光板的總厚度係以500μm以下為佳，以300μm以下為較佳。在第2實施形態之偏光板的總厚度係以30μm以上為佳。 The total thickness of the polarizing plate in the second embodiment is preferably 500 μm or less, and more preferably 300 μm or less. The total thickness of the polarizing plate in the second embodiment is preferably 30 μm or more.
偏光板的總厚度為前述上限值以下時，能夠有助於偏光板的薄層化。偏光板的總厚度為前述下限值以上時，偏光板的強度提升。 When the total thickness of the polarizing plate is equal to or less than the aforementioned upper limit, it can contribute to thinning the polarizing plate. When the total thickness of the polarizing plate is above the aforementioned lower limit, the strength of the polarizing plate increases.
<<偏光板的製造方法>> <<Manufacturing method of polarizing plate>>
以下說明製造本發明的偏光板之方法的例子。 Examples of methods for manufacturing the polarizing plate of the present invention will be described below.
[偏光片的製造方法] [Manufacturing method of polarizer]
偏光片通常係能夠經過下列步驟而製造：將PVA系薄膜進行單軸延伸之步驟；使用二色性色素將PVA系薄膜進行染色而使該PVA系薄膜吸附二色性色素之步驟；使用硼酸水溶液處理吸附有二色性色素之PVA系薄膜而使其交聯之步驟；及在使用硼酸水溶液進行交聯處理後進行水洗之步驟(以下亦稱為硼酸處理)。 Polarizers can usually be manufactured through the following steps: a step of uniaxially stretching a PVA film; a step of dyeing the PVA film with a dichroic dye so that the PVA film adsorbs the dichroic dye; and using a boric acid aqueous solution. The step of cross-linking the PVA film to which the dichroic pigment is adsorbed; and the step of cross-linking with a boric acid aqueous solution and then washing with water (hereinafter also referred to as boric acid treatment).
PVA系薄膜的單軸延伸，係能夠在使用二色性色素進行染色之前、與染色同時、或染色之後進行。在染色之後進行單軸延伸時，該單軸延伸可在硼酸處理前進行，亦可在硼酸處理中進行。當然亦能夠在此顯示的複數階段進行單軸延伸。單軸延伸係能夠採用下列方法：在周速不同之輥筒之間，於薄膜搬運方向進行單軸延伸之方法；使用熱輥於薄膜搬運方向進行單軸延伸方法；使用拉幅機於寬度方向進行延伸之方法等。又，單軸延伸可藉由在大氣中進行延伸之乾式延伸而進行，亦可藉由使用水等溶劑，在使PVA系薄膜膨潤之狀態下進行延伸之濕式延伸。延伸倍率通常係3至8倍左右。 The uniaxial stretching of the PVA-based film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. When uniaxial extension is performed after dyeing, the uniaxial extension may be performed before boric acid treatment or during boric acid treatment. Of course, uniaxial extension is also possible in the plural stages shown here. The uniaxial stretching system can adopt the following methods: uniaxial stretching in the film conveying direction between rollers with different peripheral speeds; uniaxial stretching in the film conveying direction using a hot roller; and uniaxial stretching in the width direction using a tenter. Methods for extension, etc. In addition, uniaxial stretching can be performed by dry stretching in which the PVA-based film is stretched in the atmosphere, or by wet stretching in which the PVA-based film is stretched using a solvent such as water. The extension ratio is usually about 3 to 8 times.
PVA系薄膜之使用二色性色素進行之染色，例如能夠使用將PVA系薄膜浸漬在含有二色性色素的水溶液之方法而進行。作為二色性色素，具體而言，係能夠使用碘和二色性有機染料。又，PVA系薄膜係以在染色處理前，預先施行浸漬在水中而膨潤之處理為佳。 Dyeing of a PVA-based film using a dichroic dye can be performed, for example, by immersing the PVA-based film in an aqueous solution containing a dichroic dye. As the dichroic dye, specifically, iodine and a dichroic organic dye can be used. In addition, the PVA film is preferably immersed in water and swollen before dyeing.
使用碘作為二色性色素時，通常係採用將PVA系薄膜浸漬在含有碘及碘化鉀之水溶液而進行染色之方法。在該水溶液之碘的含量，係水每100質量份，通常為0.01至1質量份左右，碘化鉀的含量係水每 100質量份，通常為0.5至20質量份左右。在染色所使用的水溶液之溫度，通常係20至40℃左右。又，在該水溶液的浸漬時間(染色時間)通常係20至1,800秒鐘左右。 When using iodine as a dichroic dye, a method of immersing a PVA film in an aqueous solution containing iodine and potassium iodide for dyeing is usually used. The iodine content in the aqueous solution is expressed as 100 parts by mass of water, usually about 0.01 to 1 part by mass. The content of potassium iodide is expressed as 100 parts by mass of water. 100 parts by mass, usually about 0.5 to 20 parts by mass. The temperature of the aqueous solution used for dyeing is usually around 20 to 40°C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 20 to 1,800 seconds.
另一方面，使用二色性有機染料作為二色性色素時，通常係採用將PVA系薄膜浸漬在含有水溶性二色性有機染料之水溶液而進行染色之方法。在該水溶液之二色性有機染料的含量係水每100質量份，通常為0.0001至10質量份左右，較佳為0.001至1質量份。該染料水溶液亦可含有如硫酸鈉的無機鹽作為染色助劑。在染色所使用的二色性有機染料水溶液之溫度通常係20至80℃左右。又，在該水溶液的浸漬時間(染色時間)通常係10至1,800秒鐘左右。 On the other hand, when a dichroic organic dye is used as a dichroic pigment, a method of immersing a PVA-based film in an aqueous solution containing a water-soluble dichroic organic dye and dyeing is usually used. The content of the dichroic organic dye in the aqueous solution is based on 100 parts by mass of water, usually about 0.0001 to 10 parts by mass, preferably 0.001 to 1 part by mass. The aqueous dye solution may also contain inorganic salts such as sodium sulfate as dyeing auxiliaries. The temperature of the dichroic organic dye aqueous solution used in dyeing is usually around 20 to 80°C. In addition, the immersion time (dying time) in the aqueous solution is usually about 10 to 1,800 seconds.
使用二色性色素進行染色後之硼酸處理，係能夠使用將經染色的PVA系薄膜浸漬在含硼酸的水溶液之方法來進行。在含硼酸的水溶液之硼酸的含量，水每100質量份，通常為2至15質量份左右，較佳為5至12質量份。使用碘作為二色性色素時，該含硼酸的水溶液係以含有碘化鉀為佳。在含硼酸的水溶液之碘化鉀的含量，係水每100質量份，通常為0.1至15質量份左右，較佳為5至12質量份。在含硼酸的水溶液的浸漬時間通常係60至1,200秒鐘左右，較佳為150至600秒鐘，更佳為200至400秒鐘。含硼酸的水溶液之溫度通常係50℃以上，較佳為50至85℃，更佳為60至80℃。 Boric acid treatment after dyeing with a dichroic dye can be performed by immersing the dyed PVA-based film in an aqueous solution containing boric acid. The boric acid content of the boric acid-containing aqueous solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass per 100 parts by mass of water. When iodine is used as the dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide. The content of potassium iodide in the aqueous solution containing boric acid is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass per 100 parts by mass of water. The immersion time in the boric acid-containing aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually above 50°C, preferably 50 to 85°C, more preferably 60 to 80°C.
硼酸處理後的PVA系薄膜，通常係進行水洗處理。水洗處理係例如能夠使用將經硼酸處理的PVA系薄膜浸漬在水中之方法而進行。在水洗處理之水的溫度通常係5至40℃左右。又，浸漬時間通常係1至 120秒鐘左右。 PVA-based films treated with boric acid are usually washed with water. The water washing treatment can be performed, for example, by immersing a boric acid-treated PVA-based film in water. The temperature of the water used in the water washing process is usually around 5 to 40°C. In addition, the soaking time is usually 1 to About 120 seconds.
水洗後係施行乾燥處理而得到偏光片。乾燥處理係能夠使用熱風乾燥機和遠紅外線加熱器而進行。乾燥處理的溫度通常係30至100℃左右，較佳為50至80℃。乾燥處理的時間通常係60至600秒鐘左右，較佳為120至600秒鐘。藉由乾燥處理，偏光片中的水分率係能夠減低至實用程度為止。其水分率係相對於偏光片的總質量，通常為5至20質量%左右，較佳為8至15質量%。水分率為5質量%以上時，因為偏光片係具有充分的可撓性，能夠抑制在乾燥後產生損傷或斷裂。又，水分率為20質量%以下時，偏光片係具有充分的熱安定性。 After washing with water, a drying process is performed to obtain a polarizing plate. The drying process can be performed using a hot air dryer and a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The time of drying treatment is usually about 60 to 600 seconds, preferably 120 to 600 seconds. Through the drying process, the moisture content in the polarizer can be reduced to a practical level. The moisture content is usually about 5 to 20 mass%, preferably 8 to 15 mass%, relative to the total mass of the polarizer. When the moisture content is 5% by mass or more, the polarizer system has sufficient flexibility and can prevent damage or breakage after drying. In addition, when the water content is 20% by mass or less, the polarizing plate system has sufficient thermal stability.
如以上進行而能夠製造二色性色素吸附配向在PVA系薄膜而成之偏光片。 By proceeding as above, a polarizing plate in which the dichroic dye is adsorbed and aligned on the PVA-based film can be produced.
又，上述所得到的偏光片，亦可進一步隔著上述接著劑將保護膜貼合在該偏光片的一面或兩面。 Furthermore, the polarizing plate obtained above may be further bonded to one or both sides of the polarizing plate with a protective film via the adhesive.
[第1黏著劑層及第2黏著劑層的製造方法] [Method for manufacturing the first adhesive layer and the second adhesive layer]
如前述，第1黏著劑層及第2黏著劑層係以由將丙烯酸系樹脂作為基質聚合物之黏著劑所形成為佳。 As mentioned above, the first adhesive layer and the second adhesive layer are preferably formed of an adhesive using an acrylic resin as a matrix polymer.
前述(甲基)丙烯酸系樹脂(1)通常能夠使用溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等習知的聚合方法而製造。在(甲基)丙烯酸系樹脂(1)的製造中，通常係在聚合起始劑的存在下進行聚合。聚合起始劑的使用量係相對於構成(甲基)丙烯酸系樹脂(1)之全部單體的合計100質量份，通常為0.001至5質量份。(甲基)丙烯酸系樹脂(1)亦能夠使用藉由紫外線等活性能量線而聚合之方法而製造。 The (meth)acrylic resin (1) can generally be produced using a conventional polymerization method such as a solution polymerization method, a block polymerization method, a suspension polymerization method, or an emulsion polymerization method. In the production of the (meth)acrylic resin (1), polymerization is usually performed in the presence of a polymerization initiator. The usage amount of the polymerization initiator is usually 0.001 to 5 parts by mass relative to a total of 100 parts by mass of all monomers constituting the (meth)acrylic resin (1). The (meth)acrylic resin (1) can also be produced using a method of polymerizing with active energy rays such as ultraviolet rays.
作為聚合起始劑，可舉出熱聚合起始劑及光聚合起始劑。作為光聚合起始劑，可舉出4-(2-羥乙氧基)苯基(2-羥基-2-丙基)酮。作為熱聚合起始劑，可舉出2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、2,2’-偶氮雙(2-羥甲基丙腈)等偶氮化合物、過氧化月桂醯、第三丁基過氧化氫、過氧化苯甲醯、過氧化苯甲酸第三丁酯、異丙苯過氧化氫、過氧化二碳酸二異丙酯、過氧化二碳酸二丙酯、過氧化新癸酸第三丁酯、過氧化三甲基乙酸第三丁酯、過氧化(3,5,5-三甲基己醯)等有機過氧化物、過硫酸鉀、過硫酸銨、過氧化氫等無機過氧化物。又，將過氧化物及還原劑併用而成之氧化還原系起始劑亦能夠使用作為聚合起始劑。 Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one. Examples of thermal polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane) Alkane-1-nitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentane) nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) and other azo compounds, lauryl peroxide , tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, peroxide tert-butyl neodecanoate, tert-butyl peroxytrimethylacetate, peroxide (3,5,5-trimethylhexanoic acid) and other organic peroxides, potassium persulfate, ammonium persulfate, peroxide Hydrogen and other inorganic peroxides. Furthermore, a redox-based initiator that uses a peroxide and a reducing agent together can also be used as a polymerization initiator.
(甲基)丙烯酸系樹脂(1)係較佳是能夠使用溶液聚合法而製造。具體而言，係將所需要的單體與有機溶劑混合，而且在氮氣環境下將熱聚合起始劑添加在所得到的溶液。能夠藉由將所得到的混合物於40℃至90℃左右，較佳為60℃至80℃左右攪拌3至10小時左右，而得到(甲基)丙烯酸酯聚合物。為了控制聚合反應，亦可在聚合反應中將單體、熱聚合起始劑或其兩者連續或間歇地添加至反應系統內，或是在溶解於有機溶劑的狀態下添加至反應系統內。作為有機溶劑，可舉出甲苯、二甲苯等芳香族烴溶劑、乙酸乙酯、乙酸丁酯等酯溶劑、丙醇、異丙醇等脂肪族醇溶劑、丙酮、甲基乙基酮、甲基異丁基酮等酮溶劑。 The (meth)acrylic resin (1) can preferably be produced using a solution polymerization method. Specifically, the required monomers are mixed with an organic solvent, and a thermal polymerization initiator is added to the resulting solution in a nitrogen atmosphere. The (meth)acrylate polymer can be obtained by stirring the obtained mixture at about 40°C to 90°C, preferably about 60°C to 80°C for about 3 to 10 hours. In order to control the polymerization reaction, the monomer, the thermal polymerization initiator, or both may be continuously or intermittently added to the reaction system during the polymerization reaction, or added to the reaction system in a state of being dissolved in an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, aliphatic alcohol solvents such as propanol and isopropyl alcohol, acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone.
如此進行而得到的(甲基)丙烯酸系樹脂(1)，係能夠與前述交聯劑(2)、前述矽烷化合物(3)、進而按照必要之有機溶劑混合而得到黏著劑 組成物的塗佈溶液。作為有機溶劑，係能夠使用與在上述液相聚合所使用的溶液相同之物。能夠將前述塗佈溶液例如塗佈在被黏著物且進行乾燥而形成黏著劑層。又，亦能夠將前述塗佈溶液例如塗佈在隔離膜上且進行乾燥而將黏著劑層形成在隔離膜上。 The (meth)acrylic resin (1) obtained in this way can be mixed with the cross-linking agent (2), the silane compound (3), and an organic solvent as necessary to obtain an adhesive. Coating solution of the composition. As the organic solvent, the same thing as the solution used in the above-mentioned liquid phase polymerization can be used. For example, the coating solution can be applied to an adherend and dried to form an adhesive layer. Alternatively, the coating solution may be applied on a separator and dried to form an adhesive layer on the separator.
作為將前述黏著劑組成物的塗佈溶液塗佈在被黏著物或隔離膜上之方法，係採用使用模塗佈器、刮刀式塗佈器、逆輥塗佈器、凹版塗佈器、棒塗佈器、繞線棒塗佈器、刮刀片塗佈器、氣動刮塗器等之通常的塗佈技術即可。 As a method of applying the coating solution of the aforementioned adhesive composition to an adherend or a release film, a die coater, a blade coater, a reverse roll coater, a gravure coater, or a rod is used. Common coating techniques such as coaters, wire-bar coaters, doctor blade coaters, and pneumatic blade coaters are sufficient.
隔離膜係以由塑膠膜及剝離層所構成為佳。作為塑膠膜，例如可舉出聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、及聚萘二甲酸乙二酯膜等聚酯膜、聚丙烯膜等聚烯烴膜。 The isolation film is preferably composed of a plastic film and a peeling layer. Examples of the plastic film include polyester films such as polyethylene terephthalate films, polybutylene terephthalate films, and polyethylene naphthalate films, and polyolefin films such as polypropylene films.
剝離層係例如能夠由剝離層形成用組成物所形成，作為構成剝離層形成用組成物之主要成分(樹脂)，係無限定，可舉出聚矽氧樹脂、醇酸樹脂、丙烯酸樹脂、及長鏈烷基樹脂等。 The release layer can be formed, for example, from a release layer-forming composition. The main component (resin) constituting the release layer-forming composition is not limited, and examples thereof include polysilicone resin, alkyd resin, acrylic resin, and Long chain alkyl resin, etc.
第1黏著劑層及第2黏著劑層的各儲存彈性模數係能夠按照黏著劑組成物的種類而調整。 Each storage elastic modulus of the first adhesive layer and the second adhesive layer can be adjusted according to the type of adhesive composition.
第1黏著劑層及第2黏著劑層的各厚度，係能夠按照含有黏著劑組成物之溶液的塗佈條件而調節。為了使黏著劑層的厚度薄化，減小塗佈厚度為有效。 Each thickness of the first adhesive layer and the second adhesive layer can be adjusted according to the coating conditions of the solution containing the adhesive composition. In order to reduce the thickness of the adhesive layer, it is effective to reduce the coating thickness.
[相位差層的製造方法] [Method for manufacturing phase difference layer]
相位差層係如前述，可具有液晶化合物硬化而成之層，進而具有透明基材、及配向層。 As mentioned above, the retardation layer may have a layer made of a hardened liquid crystal compound, a transparent base material, and an alignment layer.
配向層係由如上述的樹脂所構成之層，將含有形成前述樹脂的單體之配向層用組成物塗佈在透明基材而使其乾燥，隨後，藉由施行預定硬化處理而形成。使用如此進行而形成的硬化物來構成配向層。 The alignment layer is a layer composed of the above-mentioned resin, and is formed by applying a composition for the alignment layer containing a monomer forming the above-mentioned resin on a transparent base material, drying it, and then subjecting it to a predetermined hardening treatment. The alignment layer is formed using the hardened product thus formed.
作為配向層用組成物中所使用的溶劑(稀釋溶劑)，係只要能夠使配向材料溶解於所需要的濃度，就沒有特別限定、例如能夠例示苯、己烷等烴系溶劑、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、環己酮(CHN)等酮系溶劑、四氫呋喃、1,2-二甲氧基乙烷、丙二醇單***等醚系溶劑、氯仿、二氯甲烷等鹵化烷基系溶劑、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯等酯系溶劑、N,N-二甲基甲醯胺等醯胺系溶劑、二甲基亞碸等亞碸系溶劑、環己烷等環己烷(anone)系溶劑、甲醇、乙醇、異丙醇等醇類系溶劑。溶劑可為1種類，亦可為2種類以上的溶劑之混合溶劑。 The solvent (dilution solvent) used in the alignment layer composition is not particularly limited as long as it can dissolve the alignment material at a required concentration. Examples thereof include hydrocarbon solvents such as benzene and hexane, and methylethyl solvents. Ketone solvents such as ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone (CHN), ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, propylene glycol monoethyl ether, chloroform, dimethicone, etc. Halogenated alkyl solvents such as methyl chloride, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, amide solvents such as N,N-dimethylformamide, Methyl styrene and other styrene-based solvents, cyclohexane and other other cyclohexane (anone)-based solvents, methanol, ethanol, isopropyl alcohol and other alcohol-based solvents. The solvent may be one type or a mixed solvent of two or more types of solvents.
作為將前述配向層用組成物塗佈在透明基材之方法，係採用使用模塗佈器、刮刀式塗佈器、逆輥塗佈器、凹版塗佈器、棒塗佈器、繞線棒塗佈器、刮刀片塗佈器、氣動刮塗器等之通常的塗佈技術即可。 As a method of coating the aforementioned alignment layer composition on a transparent substrate, a die coater, a blade coater, a reverse roll coater, a gravure coater, a rod coater, or a wire-wound rod is used. Common coating techniques such as coaters, blade coaters, and pneumatic blade coaters are sufficient.
液晶化合物硬化而成之層，係能夠藉由將含有聚合性液晶化合物之塗佈液塗佈在前述配向層且使其乾燥，隨後施行預定硬化處理而形成。使用如此進行而形成的硬化物來構成相位差層。 The layer in which the liquid crystal compound is hardened can be formed by applying a coating liquid containing a polymerizable liquid crystal compound to the alignment layer, drying the coating liquid, and then performing a predetermined hardening treatment. The hardened material thus formed is used to form a retardation layer.
相對於含有前述聚合性液晶化合物之塗佈液的總質量，前述聚合性液晶化合物的含量並無特別限定，能夠設為5至40質量%的範圍內。欲按照塗佈在配向層上之塗佈方法而調整黏度等時，係調整前述聚合性液晶化合物的含量即可。聚合性液晶化合物能夠單獨1種或混合2種以上而使用。 The content of the polymerizable liquid crystal compound is not particularly limited with respect to the total mass of the coating liquid containing the polymerizable liquid crystal compound, and can be in the range of 5 to 40 mass %. When it is desired to adjust the viscosity etc. according to the coating method on the alignment layer, the content of the aforementioned polymerizable liquid crystal compound may be adjusted. A polymerizable liquid crystal compound can be used individually by 1 type or in mixture of 2 or more types.
含有上述聚合性液晶化合物之塗佈液，通常係被溶解在如已說明的溶劑(稀釋溶劑)，以對前述聚合性液晶化合物的聚合反應為惰性的溶劑為佳。 The coating liquid containing the above-mentioned polymerizable liquid crystal compound is usually dissolved in a solvent (dilution solvent) as described above, preferably a solvent that is inert to the polymerization reaction of the above-mentioned polymerizable liquid crystal compound.
作為塗佈含有聚合性液晶化合物的塗佈液之方法，係採用習知的方法，例如繞線棒塗佈法、擠出塗佈法、直輥凹版塗佈法、逆輥凹版塗佈法、及模塗佈法等即可。 As a method of applying a coating liquid containing a polymerizable liquid crystal compound, a conventional method is used, such as a wire bar coating method, an extrusion coating method, a straight roll gravure coating method, a reverse roll gravure coating method, And die coating method etc. can be used.
藉由使形成在配向層上之膜所含有的聚合性液晶化合物聚合，而得到相位差層。聚合方法係按照聚合性液晶化合物的聚合性基種類而選擇即可。前述聚合性基為光聚合性基時，能夠使用光聚合法而聚合。又，聚合性基為熱聚合性基時，能夠使用熱聚合法而聚合。在本實施形態的相位差層的製造方法，係以光聚合法為佳。因為光聚合法沒有將透明基材加熱至高溫的必要，所以能夠使用耐熱性較低的透明基材。光聚合法係藉由對由含有聚合性液晶化合物之液晶組成物所構成之膜，照射可見光、或紫外光而進行。就操作容易而言，係以紫外光為佳。 The retardation layer is obtained by polymerizing the polymerizable liquid crystal compound contained in the film formed on the alignment layer. The polymerization method may be selected according to the type of polymerizable group of the polymerizable liquid crystal compound. When the polymerizable group is a photopolymerizable group, it can be polymerized using a photopolymerization method. In addition, when the polymerizable group is a thermally polymerizable group, it can be polymerized using a thermal polymerization method. The method for manufacturing the retardation layer in this embodiment is preferably a photopolymerization method. Since the photopolymerization method does not require heating the transparent substrate to a high temperature, a transparent substrate with low heat resistance can be used. The photopolymerization method is performed by irradiating a film composed of a liquid crystal composition containing a polymerizable liquid crystal compound with visible light or ultraviolet light. In terms of ease of operation, ultraviolet light is better.
[包含複數相位差層之積層體的製造方法] [Method for manufacturing a laminated body including a plurality of retardation layers]
在第2實施形態之作為包含複數相位差層之積層體的製造方法的一個例子，係說明包含2層相位差層之積層體的製造方法。隔著第1接著層將第1相位差層與第2相位差層積層。 In the second embodiment, as an example of a method of manufacturing a laminated body including a plurality of retardation layers, a method of manufacturing a laminated body including two retardation layers will be described. The first phase difference layer and the second phase difference layer are laminated via the first adhesive layer.
隔著第1接著層將第1相位差層與第2相位差層積層時，係將上述的黏著劑層、水系接著劑、或活性能量線硬化性接著劑塗佈在第1相位差層及第2相位差層的任一者或兩者而將第1相位差層的第2相位差層貼合。 When the first retardation layer and the second retardation layer are laminated via the first adhesive layer, the above-mentioned adhesive layer, water-based adhesive, or active energy ray-curable adhesive is applied to the first retardation layer and the second retardation layer. Either or both of the second retardation layers are bonded to the first retardation layer and the second retardation layer.
使用水系接著劑時，隨後能夠藉由使用前述乾燥方法使接著劑固化而得到包含2層相位差層之積層體。另一方面，使用活性能量線硬化性接著劑時，能夠藉由對接著劑照射以紫外線以為例之能量線而得到包含複數相位差層之積層體。 When using a water-based adhesive, the adhesive can be cured using the aforementioned drying method to obtain a laminate including two retardation layers. On the other hand, when an active energy ray-curable adhesive is used, a laminate including a plurality of retardation layers can be obtained by irradiating the adhesive with energy rays such as ultraviolet rays.
包含複數相位差層之積層體能夠為依序將透明基材、配向層、第1相位差層、第1接著層、第2相位差層、配向層、透明基材積層而成之積層體。透明基材及配向層係能夠在將相位差層貼合在偏光板之前剝離。 The laminate including a plurality of retardation layers can be a laminate in which a transparent base material, an alignment layer, a first retardation layer, a first adhesive layer, a second retardation layer, an alignment layer, and a transparent base material are laminated in this order. The transparent base material and alignment layer can be peeled off before the retardation layer is bonded to the polarizing plate.
又，包含3層相位差層之積層體，係與隔著第1接著層將第1相位差層與第2相位差層積層相同地，能夠藉由進一步隔著第2接著層將第2相位差層與第3相位差層積層而得到。 In addition, in the laminate including three retardation layers, in the same manner as the first retardation layer and the second retardation layer are laminated with the first adhesive layer interposed therebetween, the second phase difference layer can be further laminated with the second adhesive layer interposed therebetween. The difference layer and the third phase difference layer are laminated.
[第1實施形態之偏光板的製造方法] [Method for manufacturing polarizing plate of first embodiment]
以下說明相位差層為1層之第1實施形態的偏光板100的製造方法之例子。在本實施形態所使用的偏光片、黏著劑層、及相位差層係能夠使用藉由上述方法而製造之物。 An example of a method of manufacturing the polarizing plate 100 according to the first embodiment in which the retardation layer is one layer will be described below. The polarizer, adhesive layer, and retardation layer used in this embodiment can be those produced by the above-mentioned method.
作為黏著劑，係能夠使用前述之黏著劑組成物或形成在隔離膜上之黏著劑層。以下，作為例子，係說明使用形成在隔離膜上之黏著劑作為第1黏著劑層、及第2黏著劑層之情況。 As the adhesive, the aforementioned adhesive composition or an adhesive layer formed on the isolation film can be used. Hereinafter, as an example, the case of using the adhesive formed on a separator as a 1st adhesive layer and a 2nd adhesive layer is demonstrated.
將偏光片11與第1黏著劑層12進行積層。具體而言，係藉由將位於第1黏著劑層12之與積層有隔離膜之面為相反位置之黏著劑層的面與偏光片11的一面貼合，而能夠將偏光片11與第1黏著劑層12積層。 The polarizer 11 and the first adhesive layer 12 are laminated. Specifically, the polarizer 11 and the first adhesive layer 11 can be bonded together by bonding the surface of the first adhesive layer 12 opposite to the surface on which the isolation film is laminated and the surface of the polarizer 11 . The adhesive layer 12 is laminated.
隨後，將第1黏著劑層12與相位差層14積層。 Subsequently, the first adhesive layer 12 and the retardation layer 14 are laminated.
藉由將相位差層14貼合在第1黏著劑層12之剝下隔離膜而露出的面，而能夠將第1黏著劑層12與相位差層14積層。而且，接觸第1黏著劑層12之相位差層14的面，係將透明基材剝下而露出之配向層的面、或將透明基材及配向層剝下而露出之相位差層的面。 By bonding the retardation layer 14 to the surface of the first adhesive layer 12 exposed by peeling off the separator, the first adhesive layer 12 and the retardation layer 14 can be laminated. Moreover, the surface of the retardation layer 14 that contacts the first adhesive layer 12 is the surface of the alignment layer exposed by peeling off the transparent base material, or the surface of the retardation layer exposed by peeling off the transparent base material and the alignment layer. .
隨後，將相位差層14與第2黏著劑層13積層。 Subsequently, the retardation layer 14 and the second adhesive layer 13 are laminated.
藉由將位於第2黏著劑層13之與積層有隔離膜之面為相反位置的面與相位差層14貼合，而能夠將相位差層14與第2黏著劑層13積層。又，接觸第2黏著劑層13之相位差層14的面，係位於相位差層14之與第1黏著劑層12接觸的面為相反側位置的面。 The retardation layer 14 and the second adhesive layer 13 can be laminated by bonding the surface of the second adhesive layer 13 opposite to the surface on which the isolation film is laminated to the retardation layer 14 . In addition, the surface of the retardation layer 14 that contacts the second adhesive layer 13 is located on the opposite side of the surface of the retardation layer 14 that contacts the first adhesive layer 12 .
如此進行而得到之第1實施形態的偏光板100，亦可隔者第2黏著劑層13而積層在顯示面板等。 The polarizing plate 100 of the first embodiment obtained in this manner may be laminated on a display panel or the like via the second adhesive layer 13 .
[第2實施形態之偏光板的製造方法] [Method for manufacturing polarizing plate of second embodiment]
以下說明含有至少2層相位差層之第2實施形態的偏光板101及偏光板102的製造方法之例子。在本實施形態所使用的偏光片、黏著劑層、及相位差層係能夠使用藉由上述方法而製造之物。 An example of a manufacturing method of the polarizing plate 101 and the polarizing plate 102 of the second embodiment including at least two retardation layers will be described below. The polarizer, adhesive layer, and retardation layer used in this embodiment can be those produced by the above-mentioned method.
作為黏著劑，係能夠使用前述之黏著劑組成物或形成在隔離膜上之黏著劑層。以下，作為例子，係說明使用形成在隔離膜上之黏著劑層作為第1黏著劑層、及第2黏著劑層之情況。 As the adhesive, the aforementioned adhesive composition or an adhesive layer formed on the isolation film can be used. Hereinafter, as an example, the case of using the adhesive layer formed on a separator as a 1st adhesive layer and a 2nd adhesive layer is demonstrated.
將偏光片11與第1黏著劑層12積層。具體而言，係藉由將位於第1黏著劑層12之與積層有隔離膜之面為相反位置的面與偏光片11的一面貼合，而能夠將偏光片11與第1黏著劑層12積層。 The polarizer 11 and the first adhesive layer 12 are laminated. Specifically, the polarizer 11 and the first adhesive layer 12 can be bonded together by bonding the surface of the first adhesive layer 12 that is opposite to the surface on which the isolation film is laminated to one surface of the polarizer 11 . Lamination.
隨後，將第1黏著劑層12與包含複數相位差層之積層體(以 下，有時將該積層體稱為「相位差層的積層體」)積層。 Subsequently, the first adhesive layer 12 and a laminate including a plurality of retardation layers (to Below, this laminated body is sometimes called a "laminated body of a phase difference layer") laminated body.
藉由將相位差層的積層體貼合在將第1黏著劑層12的隔離膜剝下而露出的面，能夠將第1黏著劑層12與相位差層的積層體積層。又，接觸第1黏著劑層12之相位差層的積層體的面，係將位於相位差層之積層體的兩端的位置之透明基材的任一者剝下而露出之配向層的面或將位於相位差層之積層體的兩端位置之透明基材及配向層的任一者剝下而露出之相位差層的面。 By bonding the laminated body of the retardation layer to the surface exposed by peeling off the separator of the first adhesive layer 12, the laminated volume of the first adhesive layer 12 and the retardation layer can be laminated. In addition, the surface of the laminate of the retardation layer that contacts the first adhesive layer 12 is the surface of the alignment layer exposed by peeling off either of the transparent substrates located at both ends of the laminate of the retardation layer. Either one of the transparent base material and the alignment layer located at both ends of the laminate of the retardation layer is peeled off to expose the surface of the retardation layer.
隨後，將相位差層的積層體與第2黏著劑層13積層。 Subsequently, the laminate of the retardation layer and the second adhesive layer 13 are laminated.
藉由將在第2黏著劑層13之與積層有隔離膜的面為相反位置的面與前述相位差層的積層體貼合，能夠將相位差層的積層體與第2黏著劑層13積層。又，接觸第2黏著劑層13之相位差層的積層體的面，係位於與相位差層的積層體接觸第1黏著劑層12的面為相反側位置的面，將透明基材剝下而露出之配向層的面、或將透明基材及配向層剝下露出之相位差層的面。 By bonding the surface of the second adhesive layer 13 opposite to the surface on which the separator is laminated to the laminate of the retardation layer, the laminate of the retardation layer and the second adhesive layer 13 can be laminated. In addition, the surface of the retardation layer laminate contacting the second adhesive layer 13 is located on the opposite side to the surface of the retardation layer laminate contacting the first adhesive layer 12, and the transparent base material is peeled off The surface of the alignment layer that is exposed, or the surface of the retardation layer that is exposed by peeling off the transparent substrate and the alignment layer.
如此進行而得到之第2實施形態的偏光板101，亦可隔著第2黏著劑層13而積層在顯示面板等。 The polarizing plate 101 of the second embodiment obtained in this manner may be laminated on a display panel or the like via the second adhesive layer 13 .
使用如以上構成的偏光板時，即便在高溫、高濕的環境下，亦能夠抑制伴隨著相位差層變形引起偏光板產生皺紋。 When a polarizing plate having the above structure is used, even in a high-temperature, high-humidity environment, wrinkles in the polarizing plate caused by deformation of the retardation layer can be suppressed.
<用途> <Purpose>
本偏光板係能夠使用在各式各樣的顯示裝置。所謂顯示裝置，係具有顯示元件之裝置，包含發光元件或發光裝置作為發光源。作為顯示裝置，例如可舉出液晶顯示裝置、有機EL顯示裝置、無機電致發光(以下亦稱為 無機EL)顯示裝置、電子放出顯示裝置(例如電場放射顯示裝置(亦稱為FED)、表面電場放射顯示裝置(亦稱為SED))、電子紙(使用電子印墨和電泳動元件之顯示裝置)、電漿顯示裝置、投射型顯示裝置(例如柵光閥(亦稱為GLV；Grating Light Valve)顯示裝置、具有數位微鏡元件(亦稱為DMD；digital micromirror device)之顯示裝置)及壓電陶瓷顯示器等。 This polarizing plate 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 source. Examples of display devices include liquid crystal display devices, organic EL display devices, and inorganic electroluminescence (hereinafter also referred to as Inorganic EL) display devices, electron emission display devices (such as electric field emission display devices (also known as FED), surface electric field emission display devices (also known as SED)), electronic paper (display devices using electronic ink and electrophoretic elements) ), plasma display devices, projection display devices (such as grating light valve (also known as GLV; Grating Light Valve) display devices, display devices with digital micromirror devices (also known as DMD; digital micromirror device)) and pressure Electric ceramic displays, etc.
液晶顯示裝置亦包含穿透式液晶顯示裝置、半穿透式液晶顯示裝置等的任一者。該等顯示裝置可為顯示二維畫像之顯示裝置，亦可為顯示三維畫像之立體顯示裝置。 The liquid crystal display device also 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 that display two-dimensional images, or they may be three-dimensional display devices that display three-dimensional images.
本偏光板係能夠特別有效地使用在特別是有機EL顯示裝置或無機EL顯示裝置。 This polarizing plate can be used particularly effectively in an organic EL display device or an inorganic EL display device.
以下，使用實施例更詳細地說明本發明，但是本發明不限定於該等實施例。各種測定及評估係如以下進行。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Various measurements and evaluations were performed as follows.
[重量平均分子量(Mw)的測定] [Measurement of weight average molecular weight (Mw)]
黏著劑層形成用(甲基)丙烯酸樹脂的重量平均分子量(Mw)係使用凝膠滲透層析法(GPC)在以下的條件所測定之聚苯乙烯換算的重量平均分子量。 The weight average molecular weight (Mw) of the (meth)acrylic resin for adhesive layer formation is a polystyrene-equivalent weight average molecular weight measured using gel permeation chromatography (GPC) under the following conditions.
[測定條件] [Measurement conditions]
．GPC測定裝置：TOSOH股份有限公司製，HLC-8020 ． GPC measuring device: Made by TOSOH Co., Ltd., HLC-8020
．GPC管柱(依序通過下列)：TOSOH股份有限公司製 ． GPC column (pass the following in order): Made by TOSOH Co., Ltd.
TSK guard column HXL-H TSK guard column HXL-H
TSK gel GMHXL(×2) TSK gel GMHXL(×2)
TSK gel G2000HXL TSK gel G2000HXL
．測定溶劑：四氫呋喃 ． Determination solvent: tetrahydrofuran
．測定溫度：40℃ ． Measuring temperature: 40℃
[黏著劑的儲存彈性模數的測定] [Measurement of storage elastic modulus of adhesive]
黏著劑層的儲存彈性模數係使用以下的方法而測定。 The storage elastic modulus of the adhesive layer is measured using the following method.
將黏著劑層以厚度成為0.2mm之方式積層複數片。從所得到的黏著劑層沖切直徑8mm的圓柱體且將其作為儲存彈性模數G’的測定用試樣。 A plurality of adhesive layers are laminated so that the thickness becomes 0.2mm. A cylinder with a diameter of 8 mm was punched out from the obtained adhesive layer and used as a sample for measuring the storage elastic modulus G'.
針對上述試樣，依據JIS K7244-6且使用黏彈性測定裝置(Physica公司製，MCR300)，而且使用扭曲剪切法在以下的條件下測定儲存彈性模數(Pa)。 Regarding the above-mentioned sample, the storage elastic modulus (Pa) was measured under the following conditions using a viscoelasticity measuring device (MCR300 manufactured by Physica Corporation) in accordance with JIS K7244-6 and using the torsional shear method.
[測定條件] [Measurement conditions]
正向力FN：1N Normal force F N : 1N
應變γ：1% Strain γ: 1%
頻率：1Hz Frequency: 1Hz
溫度：25℃ Temperature: 25℃
[黏著劑層的厚度的測定] [Measurement of thickness of adhesive layer]
黏著劑層的厚度係使用股份有限公司Nikon製的數位測微計MH-15M而測定。 The thickness of the adhesive layer was measured using a digital micrometer MH-15M manufactured by Nikon Co., Ltd.
[穿刺強度的測定] [Measurement of puncture strength]
穿刺試驗係使用安裝有前端為球形(前端徑1mm 
[透濕度比的測定] [Measurement of water vapor permeability ratio]
相位差層的透濕度比係如以下測定。 The moisture permeability ratio of the retardation layer is measured as follows.
將後述黏著劑組成物A使用棒塗佈器而塗佈在基材上，來形成厚度為2至3μm的黏著劑組成物層且得到基材的透濕度評估用積層體。基材係使用Konica Minolta股份有限公司製的三乙酸纖維素膜。 The adhesive composition A described later was applied on the base material using a bar coater to form an adhesive composition layer with a thickness of 2 to 3 μm and to obtain a laminate for moisture permeability evaluation of the base material. As the base material, a cellulose triacetate membrane manufactured by Konica Minolta Co., Ltd. was used.
進一步將相位差層積層在前述基材的透濕度評估用積層體之黏著劑組成物層，得到相位差層的透濕度評估用積層體。 The retardation layer is further laminated on the adhesive composition layer of the laminate for evaluating the moisture permeability of the base material to obtain a laminate for evaluating the moisture permeability of the retardation layer.
依據JIS Z 0208：1976「防濕包裝材料的透濕度試驗方法(杯法)」在溫度40℃、濕度90%RH的條件下測定所得到的評估用積層體之透濕度。 According to JIS Z 0208: 1976 "Test method for moisture permeability of moisture-proof packaging materials (cup method)", the moisture permeability of the laminate for evaluation was measured under the conditions of temperature 40°C and humidity 90%RH.
所使用的三乙酸纖維素膜的厚度為20μm。又，與上述相同地進行而求取的三乙酸纖維素膜透濕度為1200g/m2．24h。 The thickness of the cellulose triacetate membrane used was 20 μm. Moreover, the moisture permeability of the cellulose triacetate membrane obtained in the same manner as above was 1200 g/m 2 . 24h.
前述基材的透濕度評估用積層體的透濕度為1000g/m2．24h。 The moisture permeability of the laminate used for evaluating the moisture permeability of the aforementioned base material is 1000 g/m 2 . 24h.
藉由測定相位差層的透濕度評估用積層體的透濕度，除以前述基材的透濕度評估用積層體的透濕度，算出透濕度比。 The water permeability ratio was calculated by measuring the water permeability of the laminate for water permeability evaluation of the retardation layer and dividing the water permeability of the laminate for water permeability evaluation of the base material.
[水蒸氣穿透度的測定] [Measurement of water vapor penetration]
在溫度40℃、濕度90%RH的條件，使用水蒸氣穿透度測定機(Lyssy公司製，機種名「Lyssy-L80-5000」)測定黏著劑層的水蒸氣穿透度。 Under the conditions of a temperature of 40° C. and a humidity of 90% RH, a water vapor penetration measuring machine (manufactured by Lyssy, model name "Lyssy-L80-5000") was used to measure the water vapor penetration of the adhesive layer.
[黏著劑的製造] [Manufacturing of adhesives]
黏著劑係使用以下的方法製造。 The adhesive is produced using the following method.
[黏著劑A至D的製造] [Manufacture of Adhesives A to D]
在具備攪拌機、溫度計、回流冷卻器、滴加裝置及氮氣導入管之反應容器，添加丙烯酸正丁酯95.0質量份、丙烯酸4.0質量份、丙烯酸2-羥基乙酯1.0質量份、乙酸乙酯200質量份、及2,2’-偶氮雙異丁腈0.08質量份且使用氮氣取代上述反應容器內的空氣。在氮氣環境下邊攪拌邊將反應溶液升溫至60℃，使其反應6小時後，冷卻至室溫。測定所得到的溶液的一部分之重量平均分子量時，確認生成重量平均分子量為180萬的(甲基)丙烯酸酯聚合物。 In a reaction vessel equipped with a mixer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction pipe, add 95.0 parts by mass of n-butyl acrylate, 4.0 parts by mass of acrylic acid, 1.0 parts by mass of 2-hydroxyethyl acrylate, and 200 parts by mass of ethyl acetate. parts, and 0.08 parts by mass of 2,2'-azobisisobutyronitrile, and nitrogen was used to replace the air in the above reaction vessel. The reaction solution was heated to 60°C while stirring in a nitrogen atmosphere, allowed to react for 6 hours, and then cooled to room temperature. When the weight average molecular weight of a part of the obtained solution was measured, it was confirmed that a (meth)acrylate polymer with a weight average molecular weight of 1.8 million was produced.
將上述步驟所得到的(甲基)丙烯酸酯聚合物100質量份(固體成分換算值；以下相同)、作為異氰酸酯系交聯劑之三羥甲基丙烷改質甲苯二異氰酸酯(TOSOH股份有限公司製，商品名「CORONATE(註冊商標)L」)1.5質量份、作為矽烷偶合劑之3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製，商品名「KBM403」)0.30質量份、作為紫外線硬化性化合物之乙氧基化異三聚氰酸三丙烯酸酯(新中村化學工業股份有限公司製：品名「A-9300」)7.5質量份、作為光聚合起始劑之2-甲基-1-(4-甲硫基苯基)-2-嗎啉丙烷-1-酮(BASF公司製：IRGACURE(註冊商標)907)0.5質量份混合且充分地攪拌，而且藉由使用乙酸乙酯稀釋來得到黏著劑組成物的塗佈溶液。 100 parts by mass (solid content conversion value; the same below) of the (meth)acrylate polymer obtained in the above step, trimethylolpropane-modified toluene diisocyanate (manufactured by TOSOH Co., Ltd.) as an isocyanate-based cross-linking agent , trade name "CORONATE (registered trademark) L") 1.5 parts by mass, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM403") as a silane coupling agent 0.30 7.5 parts by mass of ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: product name "A-9300") as an ultraviolet curable compound, 2 as a photopolymerization initiator -0.5 parts by mass of methyl-1-(4-methylthiophenyl)-2-morpholinpropan-1-one (manufactured by BASF: IRGACURE (registered trademark) 907) is mixed and stirred thoroughly, and by using Dilute with ethyl acetate to obtain a coating solution of the adhesive composition.
在隔離膜(LINTEC股份有限公司製：SP-PLR382190)的脫模處理面(剝離層面)，使用塗佈器將前述塗佈溶液以乾燥後的厚度各別成為5μm(黏著劑A)、15μm(黏著劑B)、20μm(黏著劑C)、或25μm(黏著劑D)之方式塗佈之後，在100℃乾燥1分鐘且在黏著劑層之與貼合有隔離膜之面的相反面，貼合另1片隔離膜(LINTEC股份有限公司製：SP-PLR381031)。使用 附輸送帶的紫外線照射裝置(Fusion UV系統公司製、燈為使用D bulb)隔著剝離片對該黏著劑層照射紫外線(照射強度500mW/cm2、累計光量500mJ/cm2)，而得到兩面附隔離膜的黏著劑層。 On the release-processed surface (peeling layer) of the release film (manufactured by LINTEC Co., Ltd.: SP-PLR382190), use an applicator to apply the aforementioned coating solution to a thickness of 5 μm (Adhesive A) and 15 μm (after drying). After applying adhesive B), 20 μm (adhesive C), or 25 μm (adhesive D), dry it at 100°C for 1 minute and stick it on the opposite side of the adhesive layer to the side where the isolation film is attached. Combined with another piece of isolation film (manufactured by LINTEC Co., Ltd.: SP-PLR381031). The adhesive layer was irradiated with ultraviolet rays (irradiation intensity 500mW/cm 2 , cumulative light amount 500mJ/cm 2 ) through the peeling sheet using an ultraviolet irradiation device with a conveyor belt (manufactured by Fusion UV Systems Co., Ltd., and a D bulb was used as the lamp). Adhesive layer with isolation film on both sides.
黏著劑A至D的儲存彈性模數G’在25℃為125,000Pa。 The storage elastic modulus G’ of adhesives A to D is 125,000 Pa at 25°C.
黏著劑A、黏著劑B、黏著劑C、黏著劑D的水蒸氣穿透度，係各別為7600g/m2．24h、5500g/m2．24h、5000g/m2．24h、4200g/m2．24h。 The water vapor penetration of adhesive A, adhesive B, adhesive C, and adhesive D is 7600g/m 2 respectively. 24h, 5500g/m 2 . 24h, 5000g/m 2 ． 24h, 4200g/m 2 ． 24h.
[黏著劑E、F的製造] [Manufacturing of Adhesives E and F]
在具備攪拌機、溫度計、回流冷卻器、滴加裝置及氮氣導入管之反應容器，添加丙烯酸正丁酯97.0質量份、丙烯酸2-羥基乙酯3.0質量份、乙酸乙酯200質量份、及2,2’-偶氮雙異丁腈0.08質量份，使用氮氣取代上述反應容器內的空氣。在氮氣環境下邊攪拌邊將反應溶液升溫至60℃，使其反應6小時後，冷卻至室溫。測定所得到的溶液的一部分之重量平均分子量時，確認生成重量平均分子量為180萬的(甲基)丙烯酸酯聚合物。 In a reaction vessel equipped with a mixer, a thermometer, a reflux cooler, a dropping device and a nitrogen introduction pipe, add 97.0 parts by mass of n-butyl acrylate, 3.0 parts by mass of 2-hydroxyethyl acrylate, 200 parts by mass of ethyl acetate, and 2, 0.08 parts by mass of 2'-azobisisobutyronitrile, and nitrogen gas was used to replace the air in the reaction container. The reaction solution was heated to 60°C while stirring in a nitrogen atmosphere, allowed to react for 6 hours, and then cooled to room temperature. When the weight average molecular weight of a part of the obtained solution was measured, it was confirmed that a (meth)acrylate polymer with a weight average molecular weight of 1.8 million was produced.
將上述步驟所得到的(甲基)丙烯酸酯聚合物100質量份(固體成分換算值；以下相同)、作為異氰酸酯系交聯劑之三羥甲基丙烷改質苯二甲基二異氰酸酯(三井化學股份有限公司製、商品名「TAKENATE(註冊商標)D-110N」)1.0質量份、作為矽烷偶合劑之3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製、商品名「KBM403」)0.30質量份混合，而且藉由充分地攪拌且使用乙酸乙酯稀釋來得到黏著劑組成物的塗佈溶液。 100 parts by mass of the (meth)acrylate polymer obtained in the above step (solid content conversion value; the same below), trimethylolpropane-modified xylylene diisocyanate (Mitsui Chemicals) as an isocyanate-based cross-linking agent Co., Ltd., trade name "TAKENATE (registered trademark) D-110N") 1.0 parts by mass, 3-glycidoxypropyltrimethoxysilane as a silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product Named "KBM403") 0.30 parts by mass was mixed, thoroughly stirred, and diluted with ethyl acetate to obtain a coating solution of the adhesive composition.
在隔離膜(LINTEC股份有限公司製：SP-PLR382190)的脫模處理面(剝離層面)，使用塗佈器將前述塗佈溶液以乾燥後的厚度各別成為15μm(黏著 劑E)、或20μm(黏著劑F)之方式塗佈之後，在100℃乾燥1分鐘且在黏著劑層之與貼合有隔離膜之面為相反面，貼合另1片隔離膜(LINTEC股份有限公司製：SP-PLR381031)而得到兩面附隔離膜的黏著劑層。 On the release-treated surface (peel-off surface) of the release film (LINTEC Co., Ltd.: SP-PLR382190), use an applicator to apply the aforementioned coating solution to a thickness of 15 μm after drying (adhesive layer). Agent E) or 20μm (Adhesive F), dry at 100°C for 1 minute and attach another piece of isolation film (LINTEC) on the opposite side of the adhesive layer to the side with the isolation film. Co., Ltd.: SP-PLR381031) to obtain an adhesive layer with isolation films on both sides.
黏著劑E、F的儲存彈性模數G’係在25℃為45,200Pa。 The storage elastic modulus G’ of adhesives E and F is 45,200 Pa at 25°C.
黏著劑E、F的水蒸氣穿透度，係各別為8200g/m2．24h、4400g/m2．24h。 The water vapor penetration of adhesives E and F is 8200g/m 2 respectively. 24h, 4400g/m 2 ． 24h.
[黏著劑G至K的製造] [Manufacturing of Adhesives G to K]
在具備攪拌機、溫度計、回流冷卻器、滴加裝置及氮氣導入管之反應容器，添加丙烯酸正丁酯97.0質量份、丙烯酸1.0質量份、丙烯酸2-羥基乙酯0.5質量份、乙酸乙酯200質量份、及2,2’-偶氮雙異丁腈0.08質量份，使用氮氣取代上述反應容器內的空氣。在氮氣環境下邊攪拌邊將反應溶液升溫至60℃，使其反應6小時後，冷卻至室溫。測定所得到的溶液的一部分之重量平均分子量時，確認生成重量平均分子量為180萬的(甲基)丙烯酸酯聚合物。 In a reaction vessel equipped with a mixer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction pipe, add 97.0 parts by mass of n-butyl acrylate, 1.0 parts by mass of acrylic acid, 0.5 parts by mass of 2-hydroxyethyl acrylate, and 200 parts by mass of ethyl acetate. parts, and 0.08 parts by mass of 2,2'-azobisisobutyronitrile, and nitrogen gas was used to replace the air in the above reaction vessel. The reaction solution was heated to 60°C while stirring in a nitrogen atmosphere, allowed to react for 6 hours, and then cooled to room temperature. When the weight average molecular weight of a part of the obtained solution was measured, it was confirmed that a (meth)acrylate polymer with a weight average molecular weight of 1.8 million was produced.
將上述步驟所得到的(甲基)丙烯酸酯聚合物100質量份(固體成分換算值；以下相同)、作為異氰酸酯系交聯劑之三羥甲基丙烷改質甲苯二異氰酸酯(TOSOH股份有限公司製、商品名「CORONATE(註冊商標)L」)0.30質量份、作為矽烷偶合劑之3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製，商品名「KBM403」)0.30質量份混合，而且藉由充分地攪拌且使用乙酸乙酯稀釋來得到黏著劑組成物的塗佈溶液。 100 parts by mass (solid content conversion value; the same below) of the (meth)acrylate polymer obtained in the above step, trimethylolpropane-modified toluene diisocyanate (manufactured by TOSOH Co., Ltd.) as an isocyanate-based cross-linking agent , trade name "CORONATE (registered trademark) L") 0.30 parts by mass, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM403") as a silane coupling agent 0.30 The mixture was mixed in parts by mass, thoroughly stirred, and diluted with ethyl acetate to obtain a coating solution of the adhesive composition.
在隔離膜(LINTEC股份有限公司製：SP-PLR382190)的脫模處理面(剝離層面)，使用塗佈器將前述塗佈溶液以乾燥後的厚度各別成為6μm(黏著 劑H)、10μm(黏著劑I)、20μm(黏著劑J)、15μm(黏著劑G)、或25μm(黏著劑K)之方式塗佈之後，在100℃乾燥1分鐘且在黏著劑層之與貼合有隔離膜之面的相反面，貼合另1片隔離膜(LINTEC股份有限公司製：SP-PLR381031)而得到兩面附隔離膜的黏著劑層。 On the release-treated surface (peel-off surface) of the release film (manufactured by LINTEC Co., Ltd.: SP-PLR382190), use an applicator to apply the aforementioned coating solution to a thickness of 6 μm after drying (adhesive layer). After coating at 10 μm (Adhesive I), 20 μm (Adhesive J), 15 μm (Adhesive G), or 25 μm (Adhesive K), dry it at 100°C for 1 minute and place it between the adhesive layer. Another piece of isolation film (SP-PLR381031 manufactured by LINTEC Co., Ltd.) was bonded to the opposite side to the side where the isolation film was bonded, thereby obtaining an adhesive layer with isolation films on both sides.
黏著劑G至K的儲存彈性模數G’在25℃為25500Pa。 The storage elastic modulus G’ of adhesives G to K is 25500Pa at 25°C.
黏著劑G至K的水蒸氣穿透度，係各別為6300g/m2．24h、8200g/m2．24h、6800g/m2．24h、4700g/m2．24h、3600g/m2．24h。 The water vapor penetration of adhesives G to K is 6300g/m 2 respectively. 24h, 8200g/m 2 . 24h, 6800g/m 2 ． 24h, 4700g/m 2 ． 24h, 3600g/m 2 . 24h.
將所調製的黏著劑A至K的厚度、及在25℃之儲存彈性模數顯示在表1。 The thickness of the prepared adhesives A to K and the storage elastic modulus at 25°C are shown in Table 1.
[偏光片(1)的製造] [Manufacturing of polarizer (1)]
將平均聚合度約2400、皂化度99.9莫耳%以上之厚度30μm的聚乙烯醇膜，在30℃的純水浸漬後，浸漬在碘：碘鉀：水的質量比為0.02：2：100之30℃的水溶液而進行碘染色(以下，亦稱為碘染色步驟)。將經過碘 染色步驟之聚乙烯醇膜，浸漬在碘化鉀：硼酸：水的質量比為12：5：100之56.5℃的水溶液而進行硼酸處理(以下，亦稱為硼酸處理步驟)。將經過硼酸處理步驟之聚乙烯醇膜使用8℃的純水洗淨之後，在65℃乾燥而得到碘吸附配向在聚乙烯醇之偏光片(延伸後的厚度12μm)。此時，在碘染色步驟及硼酸處理步驟進行延伸。在此延伸之總延伸倍率為5.3倍。 A polyvinyl alcohol film with an average degree of polymerization of about 2400 and a saponification degree of 99.9 mol% or more with a thickness of 30 μm is immersed in pure water at 30°C, and then immersed in iodine:potassium iodine:water in a mass ratio of 0.02:2:100. 30° C. aqueous solution and perform iodine staining (hereinafter also referred to as iodine staining step). will undergo iodine In the dyeing step, the polyvinyl alcohol film is immersed in an aqueous solution at 56.5°C with a mass ratio of potassium iodide: boric acid: water of 12:5:100 and subjected to boric acid treatment (hereinafter, also referred to as the boric acid treatment step). The polyvinyl alcohol film that has undergone the boric acid treatment step is washed with pure water at 8°C, and then dried at 65°C to obtain a polarizer (thickness after stretching: 12 μm) with iodine adsorbed and aligned on polyvinyl alcohol. At this time, extension is performed in the iodine staining step and the boric acid treatment step. The total stretch ratio in this stretch is 5.3 times.
將經皂化處理的三乙酸纖維素膜(Konica Minolta股份有限公司製KC4UYTAC厚度40μm)，隔著水系接著劑且使用夾輥各別貼合在所得到的偏光片之兩面。將所得到的貼合物之張力邊保持在430N/m邊於60℃乾燥2分鐘而得到在兩面具有三乙酸纖維素膜作為保護膜之偏光片(1)。又，前述水系接著劑係在水100份，添加羧基改質聚乙烯醇(股份有限公司KURARAY製KURARAYPOVAL KL318)3份、水溶性聚醯胺環氧樹脂(田岡化學工業股份有限公司製Sumirez Resin(註冊商標)650固體成分濃度30%的水溶液)1.5份而調製。 Saponified cellulose triacetate films (KC4UYTAC, thickness 40 μm, manufactured by Konica Minolta Co., Ltd.) were bonded to both sides of the obtained polarizer using nip rollers via a water-based adhesive. The obtained laminate was dried at 60° C. for 2 minutes while maintaining the tension of 430 N/m to obtain a polarizing plate (1) having a cellulose triacetate film as a protective film on both sides. In addition, the aforementioned water-based adhesive was prepared by adding 100 parts of water to 3 parts of carboxyl-modified polyvinyl alcohol (KURARAYPOVAL KL318 manufactured by KURARAY Co., Ltd.) and water-soluble polyamide epoxy resin (Sumirez Resin manufactured by Taoka Chemical Industry Co., Ltd. Registered trademark) 650 solid content concentration 30% aqueous solution) 1.5 parts and prepared.
針對所得到的偏光片(1)，使用分光光度計(V7100、日本分光股份有限公司製)而進行光學特性測定。所得到的偏光片(1)之視感度修正單體透射率為42.1%，視感度修正偏光度為99.996%，單體色相a*為-1.1，單體色相b*為3.7。 The optical properties of the obtained polarizing plate (1) were measured using a spectrophotometer (V7100, manufactured by JASCO Corporation). The obtained polarizer (1) had a sensitivity-corrected monomer transmittance of 42.1%, a sensitivity-corrected polarization degree of 99.996%, a monomer hue a* of -1.1, and a monomer hue b* of 3.7.
[第1相位差層的製造] [Manufacture of the first phase difference layer]
作為第1相位差層，係準備向列液晶化合物硬化而成之層、配向膜、及由透明基材所構成之供給λ/4的相位差之層。又，向列液晶化合物硬化而成之層與配向層的合計厚度為2μm。又，第1相位差層的透濕度比為0.48。 As the first retardation layer, a layer made of a cured nematic liquid crystal compound, an alignment film, and a layer composed of a transparent base material that provides a retardation of λ/4 are prepared. In addition, the total thickness of the layer formed by hardening the nematic liquid crystal compound and the alignment layer was 2 μm. Furthermore, the moisture permeability ratio of the first retardation layer was 0.48.
[第2相位差層的製造] [Manufacture of the second phase difference layer]
使用厚度38μm的聚對苯二甲酸乙二酯基材作為透明基材，將垂直配向層用組成物以成為膜厚3μm之方式塗佈在該透明基材的一面，照射20mJ/cm2的偏光紫外線而製造配向層。又，作為該垂直配向層用組成物，使用將丙烯酸2-苯氧基乙酯、丙烯酸四氫糠酯、二新戊四醇三丙烯酸酯、雙(2-乙烯氧基乙基)醚以1：1：4：5的比例混合且以4%的比例添加LUCIRIN(註冊商標)TPO作為聚合起始劑而成之混合物。 A polyethylene terephthalate base material with a thickness of 38 μm was used as a transparent base material, and the composition for the vertical alignment layer was coated on one side of the transparent base material so that the film thickness was 3 μm, and irradiated with polarized light of 20 mJ/cm 2 UV rays are used to create the alignment layer. Furthermore, as the composition for the vertical alignment layer, a mixture of 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, dipenterythritol triacrylate, and bis(2-vinyloxyethyl) ether was used. : Mixed in a ratio of 1:4:5 and adding LUCIRIN (registered trademark) TPO as a polymerization initiator in a ratio of 4%.
隨後，將含有光聚合性向列液晶化合物(Merck公司製，RMM28B)之液晶組成物藉由模塗佈而塗佈在所形成的配向層上。在此，在液晶組成物中係使用將甲基乙基酮(MEK)、甲基異丁基酮(MIBK)與沸點為155℃之環己酮(CHN)以質量比(MEK：MIBK：CHN)為35：30：35的比例混合而成之混合溶劑作為溶劑。而且，將以固體成分成為1至1.5g之方式調製而成之液晶組成物，以塗佈量成為4至5g(wet)之方式塗佈在配向層上。 Subsequently, a liquid crystal composition containing a photopolymerizable nematic liquid crystal compound (RMM28B manufactured by Merck Corporation) was coated on the formed alignment layer by die coating. Here, in the liquid crystal composition, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone (CHN) with a boiling point of 155°C are used in a mass ratio (MEK: MIBK: CHN ) is a mixed solvent with a ratio of 35:30:35 as the solvent. Furthermore, the liquid crystal composition prepared so that the solid content becomes 1 to 1.5 g is applied on the alignment layer so that the coating amount becomes 4 to 5 g (wet).
將液晶組成物塗佈在配向層上之後，將乾燥溫度設為75℃，將乾燥時間設為120秒鐘而施行乾燥處理。隨後，藉由照射紫外線(UV)使液晶化合物聚合，而得到光聚合性向列液晶化合物硬化而成之層、配向層、及由透明基材所構成之正C層。光聚合性向列液晶化合物硬化而成之層與配向層的合計厚度為4μm。又，第2相位差層的透濕度比為0.60。 After the liquid crystal composition was applied on the alignment layer, the drying process was performed with the drying temperature set to 75°C and the drying time set to 120 seconds. Subsequently, the liquid crystal compound is polymerized by irradiating ultraviolet (UV) to obtain a layer in which the photopolymerizable nematic liquid crystal compound is cured, an alignment layer, and a positive C layer composed of a transparent substrate. The total thickness of the layer formed by curing the photopolymerizable nematic liquid crystal compound and the alignment layer was 4 μm. Moreover, the moisture permeability ratio of the second phase difference layer was 0.60.
[相位差層的積層體(1)之製造] [Production of laminated body (1) of phase difference layer]
使用紫外線硬化型接著劑將第1相位差層2片以各自的相位差層面(與透明基材為相反側的面)為貼合面之方式貼合。其次，照射紫外線而使紫外線硬化型接著劑硬化。如此進行而製造具有2片第1相位差層之相位差層 的積層體(以下，將該積層體稱為「相位差層的積層體(1)」)。相位差層的積層體(1)的厚度為5μm。又，相位差層的積層體(1)之透濕度比為0.24。 Using an ultraviolet curable adhesive, the two first retardation layers are bonded together so that their respective retardation layers (the surface opposite to the transparent base material) are the bonding surfaces. Next, ultraviolet rays are irradiated to harden the ultraviolet curable adhesive. In this way, a retardation layer having two first retardation layers is produced. laminated body (hereinafter, this laminated body is referred to as "laminated body of phase difference layer (1)"). The thickness of the retardation layer laminate (1) is 5 μm. Furthermore, the moisture permeability ratio of the retardation layer laminate (1) was 0.24.
[相位差層的積層體(2)之製造] [Production of laminated body (2) of phase difference layer]
使用紫外線硬化型接著劑將第1相位差層與第2相位差層以各自的相位差層面(與透明基材為相反側的面)為貼合面之方式貼合。其次，照射紫外線而使紫外線硬化型接著劑硬化。如此進行而製造具有第1相位差層及第2相位差層之相位差層的積層體(以下，將該積層體稱為「相位差層的積層體(2)」)。相位差層的積層體(2)的厚度為8μm。將各別透明基材從該相位差層的積層體(2)之兩面剝離後，測定相位差層的積層體(2)之穿刺強度。相位差層的積層體(2)之穿刺強度為70gf。 The first retardation layer and the second retardation layer are bonded together using an ultraviolet curing adhesive so that the respective retardation layers (the surface opposite to the transparent base material) are the bonding surfaces. Next, ultraviolet rays are irradiated to harden the ultraviolet curable adhesive. By proceeding in this manner, a laminated body of a retardation layer having a first retardation layer and a second retardation layer is manufactured (hereinafter, this laminated body is referred to as "a laminated body of phase difference layers (2)"). The thickness of the retardation layer laminate (2) is 8 μm. After each transparent base material was peeled off from both sides of the retardation layer laminate (2), the puncture strength of the retardation layer laminate (2) was measured. The puncture strength of the retardation layer laminate (2) is 70gf.
[相位差層的積層體(3)之製造] [Production of laminated body (3) of phase difference layer]
使用紫外線硬化型接著劑將第1相位差層與第2相位差層以各自的相位差層面(與透明基材為相反側的面)為貼合面之方式貼合。其次，照射紫外線而使紫外線硬化型接著劑硬化。如此進行而製造具有第1相位差層及第2相位差層之相位差層的積層體(以下，將該積層體稱為「相位差層的積層體(3)」)。相位差層的積層體(3)的厚度為10μm。將各別透明基材從該相位差層的積層體(2)之兩面剝離後，測定相位差層的積層體(3)之穿刺強度。相位差層的積層體(3)之穿刺強度為85gf。 The first retardation layer and the second retardation layer are bonded together using an ultraviolet curing adhesive so that the respective retardation layers (the surface opposite to the transparent base material) are the bonding surfaces. Next, ultraviolet rays are irradiated to harden the ultraviolet curable adhesive. By proceeding in this manner, a laminated body of a retardation layer having a first retardation layer and a second retardation layer is manufactured (hereinafter, this laminated body is referred to as "a laminated body of phase difference layers (3)"). The thickness of the retardation layer laminate (3) is 10 μm. After peeling each transparent base material from both sides of the retardation layer laminate (2), the puncture strength of the retardation layer laminate (3) was measured. The puncture strength of the retardation layer laminate (3) is 85gf.
[實施例1] [Example 1]
將黏著劑B移轉至前述偏光片(1)的一面作為第1黏著劑層。將積層在黏著劑B之隔離膜剝下且積層在將相位差層的積層體(2)之第1相位差層側的透明基材剝下後的面。將黏著劑F積層在相位差層的積層體(2)之與積 層有偏光片之面為相反側的面作為第2黏著劑層。如此進行而製造依序包含保護膜、偏光片(1)、保護膜、第1黏著劑層、第1相位差層、接著層、第2相位差層、及第2黏著劑層之偏光板。 Transfer the adhesive B to one side of the polarizer (1) as the first adhesive layer. The separator laminated on the adhesive B is peeled off and laminated on the surface where the transparent base material on the first retardation layer side of the retardation layer laminate (2) is peeled off. The adhesive F is laminated on the laminated body (2) of the phase difference layer and The side opposite to the side with the polarizer on the layer serves as the second adhesive layer. In this manner, a polarizing plate including a protective film, a polarizing plate (1), a protective film, a first adhesive layer, a first retardation layer, an adhesive layer, a second retardation layer, and a second adhesive layer is manufactured in this order.
[實施例2至20、比較例1至2] [Examples 2 to 20, Comparative Examples 1 to 2]
除了使用表2及表3記載之物作為第1黏著劑及第2黏著劑以外，與實施例1相同地製造偏光板。 A polarizing plate was manufactured in the same manner as in Example 1, except that the substances described in Table 2 and Table 3 were used as the first adhesive agent and the second adhesive agent.
[實施例21至40及比較例3至4] [Examples 21 to 40 and Comparative Examples 3 to 4]
除了使用相位差層的積層體(3)代替相位差層的積層體(2)以外，使用與實施例2至20及比較例1至2相同的程序製造偏光板。又，第1黏著劑層係積層在相位差層的積層體(3)之將第1相位差層側的透明基材剝下後之面，第2黏著劑層係積層在相位差層的積層體(3)之將第2相位差層側的透明基材剝下後之面。 A polarizing plate was manufactured using the same procedure as Examples 2 to 20 and Comparative Examples 1 to 2, except that the retardation layer laminate (3) was used instead of the retardation layer laminate (2). In addition, the first adhesive layer is laminated on the laminate (3) of the retardation layer, and the transparent base material on the side of the first retardation layer is peeled off, and the second adhesive layer is laminated on the retardation layer. The surface of body (3) after peeling off the transparent base material on the second retardation layer side.
<在高溫、高濕的環境下之偏光板的評估> <Evaluation of polarizing plates in high temperature and high humidity environments>
將如上述製造的偏光板之第2黏著劑層的隔離膜剝下且貼合在無鹼玻璃板[Corning公司製的“Eagle-XG”]而作為評估試樣。將前述評估試樣在高壓釜中而在溫度50℃且壓力5MPa的條件下進行加壓處理20分鐘，隨後，在溫度23℃且相對濕度60%的環境下放置1天。隨後，在65℃、濕度90%的環境下放置。將評估試樣放入65℃、濕度90%的環境之後，在336小時後、504小時後、672小時後、及840小時後，目視確認試樣的外觀。 The separator of the second adhesive layer of the polarizing plate manufactured as described above was peeled off and bonded to an alkali-free glass plate ["Eagle-XG" manufactured by Corning Corporation] to prepare an evaluation sample. The evaluation sample was pressurized in an autoclave at a temperature of 50° C. and a pressure of 5 MPa for 20 minutes, and then left for 1 day in an environment of a temperature of 23° C. and a relative humidity of 60%. Then, place it in an environment of 65°C and 90% humidity. After placing the evaluation sample in an environment of 65°C and 90% humidity, the appearance of the sample was visually confirmed after 336 hours, 504 hours, 672 hours, and 840 hours.
表2至表5中，針對在840小時的時點在偏光板不產生皺紋之試樣係記載為「A」，將在840小時的時點在偏光板產生皺紋之試樣係 記載為「B」，將672小時的時點在偏光板產生皺紋之試樣係記載為「C」，將504小時的時點在偏光板產生皺紋之試樣係記載為「D」，將336小時的時點在偏光板產生皺紋之試樣係記載為「E」。表2至表5中，Log(E1/T1)係表示將第1黏著劑層的儲存彈性模數E1除以厚度T1且採用常用對數而得到的值，Log(E2/T2)係表示將第2黏著劑層的儲存彈性模數E2除以厚度T2且採用常用對數而得到的值。 In Tables 2 to 5, the sample that does not produce wrinkles on the polarizing plate at 840 hours is described as "A", and the sample that produces wrinkles on the polarizing plate at 840 hours is described as "B". The sample that produced wrinkles on the polarizing plate at 672 hours was designated as "C", the sample that produced wrinkles on the polarizing plate at 504 hours was designated as "D", and the sample that produced wrinkles on the polarizing plate at 336 hours was designated as "C". The sample is recorded as "E". In Tables 2 to 5, Log(E 1 /T 1 ) represents the value obtained by dividing the storage elastic modulus E 1 of the first adhesive layer by the thickness T 1 and using the common logarithm, Log(E 2 /T 2 ) represents the value obtained by dividing the storage elastic modulus E 2 of the second adhesive layer by the thickness T 2 and taking the common logarithm.
如表2至表5顯示，Log(E1/T1)與Log(E2/T2)的和為6.4以上之實施例的偏光板，即便在65℃、濕度90%之高溫、高濕的環境下暴露336小時，在偏光板亦未確認到有皺紋。 As shown in Tables 2 to 5, the polarizing plate of the example in which the sum of Log(E 1 /T 1 ) and Log(E 2 /T 2 ) is 6.4 or above, even under high temperature and high humidity of 65°C and 90% humidity After being exposed to the environment for 336 hours, no wrinkles were confirmed on the polarizing plate.
從以上的結果能夠顯示本發明為有用的。 From the above results, it can be shown that the present invention is useful.
因為本發明的偏光板即便在高溫、高濕的環境下，偏光板亦不產生皺紋，所以能夠應用在有可能在高溫、高濕的環境下使用之畫像顯示裝置，在產業上為有用。 Since the polarizing plate of the present invention does not produce wrinkles even in high-temperature and high-humidity environments, it can be applied to image display devices that may be used in high-temperature and high-humidity environments, which is industrially useful.
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| CN110361805B (en) * | 2018-04-11 | 2022-11-18 | 住友化学株式会社 | Polarizing plate and display device |
| JP7181260B2 (en) * | 2019-09-17 | 2022-11-30 | 住友化学株式会社 | circular polarizer |
| JP7399756B2 (en) * | 2020-03-09 | 2023-12-18 | 住友化学株式会社 | Optical laminate and its manufacturing method |
| JP2022039427A (en) * | 2020-08-28 | 2022-03-10 | 日東電工株式会社 | Retardation film, laminated retardation film, polarizing plate with retardation layer, and image display device |
| JP2023042190A (en) * | 2021-09-14 | 2023-03-27 | 日東電工株式会社 | optical laminate |
| JP2023081074A (en) * | 2021-11-30 | 2023-06-09 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device having the same |
| JP2024073940A (en) * | 2022-11-18 | 2024-05-30 | 日東電工株式会社 | Optical laminate and image display device |
| JP2024073941A (en) * | 2022-11-18 | 2024-05-30 | 日東電工株式会社 | Optical laminate and image display device |
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| JP2012073552A (en) * | 2010-09-30 | 2012-04-12 | Nippon Zeon Co Ltd | Retardation plate and liquid crystal display device |
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| JP6360821B2 (en) | 2015-07-22 | 2018-07-18 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device |
| JP6904666B2 (en) * | 2016-05-17 | 2021-07-21 | 日東電工株式会社 | Optical laminate |
| WO2018025717A1 (en) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | Laminate film |
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| JP2012068674A (en) * | 2006-12-04 | 2012-04-05 | Sumitomo Chemical Co Ltd | Elliptically polarizing plate and liquid crystal display device |
| JP2009244486A (en) * | 2008-03-31 | 2009-10-22 | Toagosei Co Ltd | Phase difference integrated type composite polarizing plate, and image display device using the same |
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| TW201934699A (en) | 2019-09-01 |
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| JP2019120950A (en) | 2019-07-22 |
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