TW202144818A - Polarizing plate and polarizing plate with retardation layer - Google Patents
Polarizing plate and polarizing plate with retardation layer Download PDFInfo
- Publication number
- TW202144818A TW202144818A TW110113258A TW110113258A TW202144818A TW 202144818 A TW202144818 A TW 202144818A TW 110113258 A TW110113258 A TW 110113258A TW 110113258 A TW110113258 A TW 110113258A TW 202144818 A TW202144818 A TW 202144818A
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- protective layer
- polarizer
- polarizing plate
- resin
- Prior art date
Links
Images
Classifications
-
- 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
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
Abstract
Description
本發明涉及偏光板及附相位差層之偏光板。The present invention relates to a polarizing plate and a polarizing plate with retardation layer.
在影像顯示裝置(例如液晶顯示裝置、有機EL顯示裝置)中,由於其影像形成方式,多數情況下會於顯示單元之至少一側配置有偏光板。近年來隨著影像顯示裝置之薄型化及撓性化發展,對於偏光板之薄型化亦有強烈需求。然而,愈將偏光板薄化,在加熱加濕環境下光學特性降低之耐久性問題便愈顯著。 先前技術文獻 專利文獻In an image display device (eg, a liquid crystal display device, an organic EL display device), a polarizing plate is usually disposed on at least one side of the display unit due to its image forming method. In recent years, with the development of thinning and flexibility of image display devices, there is also a strong demand for thinning polarizers. However, the thinner the polarizing plate is, the more serious the problem of durability is that the optical properties are degraded in a heated and humidified environment. prior art literature Patent Literature
專利文獻1:日本專利特開2015-210474號公報Patent Document 1: Japanese Patent Laid-Open No. 2015-210474
發明欲解決之課題 本發明是為了解決上述以往課題而成者,其主要目的在於提供一種即便非常薄卻耐久性優異之偏光板及附相位差層之偏光板。The problem to be solved by the invention The present invention was made in order to solve the above-mentioned conventional problems, and its main object is to provide a polarizing plate with excellent durability and a polarizing plate with retardation layer even if it is very thin.
用以解決課題之手段 本發明偏光板具有偏光件與配置於該偏光件之一側的保護層。該保護層係以具有聯苯骨架之環氧樹脂的硬化物所構成。 在一實施形態中,上述硬化物為陽離子聚合硬化物。 在一實施形態中,上述保護層更包含氧雜環丁烷樹脂。 在一實施形態中,上述保護層之厚度為10µm以下。 在一實施形態中,上述保護層之碘吸附量為10重量%以下。 在一實施形態中,上述保護層之軟化溫度為100℃以上。 在一實施形態中,上述偏光板之總厚度為10µm以下。 本發明另一面向提供一種附相位差層之偏光板。該附相位差層之偏光板於上述偏光板之未配置有上述保護層之面具有相位差層。means of solving problems The polarizing plate of the present invention has a polarizer and a protective layer disposed on one side of the polarizer. The protective layer is composed of a cured product of epoxy resin having a biphenyl skeleton. In one Embodiment, the said hardened|cured material is a cationic polymerization hardened|cured material. In one embodiment, the protective layer further contains oxetane resin. In one embodiment, the thickness of the protective layer is 10 µm or less. In one embodiment, the iodine adsorption amount of the protective layer is 10% by weight or less. In one embodiment, the softening temperature of the protective layer is 100°C or higher. In one embodiment, the total thickness of the polarizing plate is 10 µm or less. Another aspect of the present invention provides a polarizing plate with retardation layer. The polarizing plate with retardation layer has a retardation layer on the surface of the polarizing plate on which the protective layer is not arranged.
發明效果 根據本發明,藉由將配置於偏光件之保護層以具有聯苯骨架之環氧樹脂的硬化物構成,可獲得即便非常薄卻耐久性優異之偏光板。Invention effect According to the present invention, a polarizing plate excellent in durability can be obtained even if it is very thin by forming the protective layer arranged on the polarizer with a cured product of an epoxy resin having a biphenyl skeleton.
(用語及符號之定義) 本說明書中之用語及符號之定義如下。 (1)折射率(nx、ny、nz) 「nx」為面內折射率達到最大之方向(亦即慢軸方向)的折射率,「ny」為於面內與慢軸正交之方向(亦即快軸方向)的折射率,而「nz」為厚度方向的折射率。 (2)面內相位差(Re) 「Re(λ)」係於23℃下以波長λnm之光測定之面內相位差。例如,「Re(550)」係於23℃下以波長550nm之光測定之面內相位差。Re(λ)可於令層(薄膜)之厚度為d(nm)時,藉由式:Re(λ)=(nx-ny)×d求得。 (3)厚度方向之相位差(Rth) 「Rth(λ)」係於23℃下以波長λnm之光測定之厚度方向的相位差。例如,「Rth(550)」係於23℃下以波長550nm之光測定之厚度方向的相位差。Rth(λ)可於令層(薄膜)厚度為d(nm)時,藉由式:Rth(λ)=(nx-nz)×d求得。 (4)Nz係數 Nz係數可以Nz=Rth/Re求得。 (5)角度 本說明書中提及角度時,該角度包含相對於基準方向往順時針方向及逆時針方向兩者。因此,例如「45°」係指±45°。(Definition of Terms and Symbols) Definitions of terms and symbols in this specification are as follows. (1) Refractive index (nx, ny, nz) "nx" is the refractive index in the direction in which the in-plane refractive index reaches the maximum (that is, the slow axis direction), "ny" is the refractive index in the in-plane direction orthogonal to the slow axis (that is, the fast axis direction), and " nz" is the refractive index in the thickness direction. (2) In-plane phase difference (Re) "Re(λ)" is the in-plane retardation measured at 23°C with light having a wavelength of λnm. For example, "Re(550)" is an in-plane retardation measured with light having a wavelength of 550 nm at 23°C. Re(λ) can be obtained by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (film) is d(nm). (3) Phase difference in thickness direction (Rth) "Rth(λ)" is the retardation in the thickness direction measured with light having a wavelength of λ nm at 23°C. For example, "Rth(550)" is the retardation in the thickness direction measured with light having a wavelength of 550 nm at 23°C. Rth(λ) can be obtained by the formula: Rth(λ)=(nx-nz)×d when the thickness of the layer (film) is d(nm). (4) Nz coefficient The Nz coefficient can be obtained by Nz=Rth/Re. (5) Angle When referring to an angle in this specification, the angle includes both a clockwise direction and a counterclockwise direction with respect to the reference direction. Thus, for example, "45°" means ±45°.
A.偏光板之概略
圖1係本發明一實施形態之偏光板的概略截面圖。圖式例之偏光板100具有偏光件10與配置於偏光件10之一側的保護層20。偏光件10之厚度宜為8µm以下。亦可因應需求在偏光件10之與保護層20相反之側配置另一保護層(未圖示)。偏光板100應用於液晶顯示裝置時,可配置於顯示單元之視辨側,亦可配置於與視辨側相反之側(背面側)。不論在任一情況下,保護層20可配置於顯示單元側,亦可配置於與顯示單元相反之側(外側)。在一實施形態中,偏光板100配置於顯示單元(以結果而言為影像顯示裝置)之視辨側,且保護層20配置於視辨側(與顯示單元相反之側)。偏光板可為長條狀,亦可為薄片狀。當偏光板為長條狀時,宜捲繞成捲狀而製成偏光板捲材。A. Outline of polarizer
FIG. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. The polarizing
代表上,偏光板具有黏著劑層作為其中一側(代表上為偏光件10之與保護層20相反之側)之最外層,而可貼合至顯示單元。可視需求以可剝離之方式將表面保護薄膜及/或載體薄膜暫時黏著於偏光板上,以補強及/或支持偏光板。偏光板包含黏著劑層時,黏著劑層表面上以可剝離之方式暫時黏著有分離件,以至實際使用前之期間保護黏著劑層,並且可將偏光板捲狀化。Representatively, the polarizing plate has an adhesive layer as the outermost layer of one side (representatively, the side opposite to the
在本發明實施形態中,保護層20係以具有聯苯骨架之環氧樹脂之硬化物所構成。只要為所述構成,便可使保護層非常薄(例如製成為10µm以下)。並且,可將保護層直接(即不透過接著劑層或黏著劑層)形成於偏光件上。根據本發明實施形態,如上述,偏光件及保護層非常薄且可省略接著劑層或黏著劑層,故可使偏光板之總厚度極薄。且偏光件與保護層之密著性亦佳。偏光板之總厚度例如為40µm以下,宜為30µm以下,較宜為20µm以下,更宜為10µm以下,尤宜為7µm以下。偏光板之總厚度例如可為4µm以上。In the embodiment of the present invention, the
並且,藉由將保護層以具有聯苯骨架之環氧樹脂的硬化物構成,可實現即便非常薄卻耐久性優異之偏光板。具體而言,可實現即便在加熱加濕環境下光學特性之降低仍受抑制之偏光板。上述偏光板放置於85℃及85%RH之環境下120小時後,單體透射率Ts之變化量ΔTs及偏光度P的變化量ΔP各自皆非常小。單體透射率Ts係使用例如紫外線可見光分光光度計(日本分光公司製,製品名「V7100」)來測定。偏光度P係從使用紫外線可見光分光光度計測定之單體透射率(Ts)、平行透射率(Tp)及正交透射率(Tc),利用下式來算出。 偏光度(P)(%)={(Tp-Tc)/(Tp+Tc)}1 /2 ×100 此外,上述Ts、Tp及Tc係以JIS Z 8701之2度視野(C光源)進行測定並進行視感度校正所得之Y值。又,Ts及P實質上為偏光件之特性。ΔTs及ΔP各自可由下述式求得。 ΔTs(%)=Ts120 -Ts0 ΔP(%)=P120 -P0 於此,Ts0 為放置前(初始)之單體透射率,Ts120 為放置後之單體透射率,P0 為放置前(初始)之偏光度,P120 為放置後之偏光度。ΔTs宜為3.0%以下,較宜為2.7%以下,更宜為2.4%以下。ΔP宜為-0.5%~0%,較宜為-0.3%~0%,更宜為-0.1%~0%。In addition, by forming the protective layer with a cured product of an epoxy resin having a biphenyl skeleton, a polarizing plate excellent in durability can be realized even if it is very thin. Specifically, it is possible to realize a polarizing plate in which the decrease in optical properties is suppressed even in a heated and humidified environment. After the polarizing plate was placed in an environment of 85° C. and 85% RH for 120 hours, the change amount ΔTs of the single transmittance Ts and the change amount ΔP of the polarization degree P were each very small. The monomer transmittance Ts is measured using, for example, an ultraviolet-visible light spectrophotometer (manufactured by JASCO Corporation, product name "V7100"). The degree of polarization P is calculated by the following formula from the single transmittance (Ts), parallel transmittance (Tp), and orthogonal transmittance (Tc) measured using an ultraviolet-visible light spectrophotometer. Degree of polarization (P)(%)={(Tp-Tc)/(Tp+Tc)} 1 /2 ×100 In addition, the above-mentioned Ts, Tp and Tc are measured by the 2-degree field of view (C light source) of JIS Z 8701 And the Y value obtained by the visual sensitivity correction. In addition, Ts and P are substantially the characteristics of a polarizer. Each of ΔTs and ΔP can be obtained by the following equation. ΔTs(%)=Ts 120 -Ts 0 ΔP(%)=P 120 -P 0 Here, Ts 0 is the transmittance of the monomer before placing (initial), Ts 120 is the transmittance of the monomer after placing, P 0 is the polarization degree before (initial) placement, and P 120 is the polarization degree after placement. ΔTs is preferably 3.0% or less, more preferably 2.7% or less, and more preferably 2.4% or less. ΔP should be -0.5%~0%, preferably -0.3%~0%, more preferably -0.1%~0%.
在本發明實施形態中偏光板之厚度可極薄。因此,可適宜應用於撓性之影像顯示裝置。較佳為影像顯示裝置具有彎曲的形狀(實質上為彎曲的顯示畫面),及/或可撓曲或可彎折。影像顯示裝置的具體例可舉液晶顯示裝置、電致發光(EL)顯示裝置(例如有機EL顯示裝置、無機EL顯示裝置)。當然,上述說明並不妨礙本發明偏光板應用於一般的影像顯示裝置。In the embodiment of the present invention, the thickness of the polarizing plate can be extremely thin. Therefore, it can be suitably applied to a flexible image display device. Preferably, the image display device has a curved shape (substantially a curved display), and/or is flexible or bendable. Specific examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (eg, an organic EL display device and an inorganic EL display device). Of course, the above description does not prevent the polarizing plate of the present invention from being applied to general image display devices.
以下針對偏光件及保護層進行詳細說明。The polarizer and the protective layer are described in detail below.
B.偏光件 偏光件可採用任意適當的偏光件。偏光件在代表上可使用兩層以上之積層體來製作。關於偏光件之製造方法係以偏光板之製造方法而後於D項中說明。B. Polarizer Any suitable polarizer can be used as the polarizer. The polarizer can be typically produced by using a laminate of two or more layers. The manufacturing method of the polarizer is explained in the section D after the manufacturing method of the polarizing plate.
偏光件之厚度宜為1µm~8µm,1µm~7µm較佳,2µm~5µm更佳。The thickness of the polarizer is preferably 1µm~8µm, preferably 1µm~7µm, and more preferably 2µm~5µm.
偏光件之硼酸含量宜為10重量%以上,較宜為13重量%~25重量%。只要偏光件之硼酸含量在所述範圍內,便可藉由與後述碘含量之加乘效果,來良好維持調整貼合時之捲曲的容易性且良好抑制加熱時之捲曲,同時改善加熱時之外觀耐久性。硼酸含量例如可由中和法使用下述式以每單位重量之偏光件所含硼酸量來算出。 [數學式1] The content of boric acid in the polarizer is preferably 10% by weight or more, more preferably 13% by weight to 25% by weight. As long as the boric acid content of the polarizer is within the above-mentioned range, the easiness of adjusting the curling during lamination can be well maintained, and the curling during heating can be suppressed, and the curling during heating can be improved at the same time due to the synergistic effect with the iodine content described later. Appearance durability. The boric acid content can be calculated by the amount of boric acid per unit weight of the polarizer by the neutralization method using the following formula, for example. [Mathematical formula 1]
偏光件之碘含量宜為2重量%以上,較宜為2重量%~10重量%。只要偏光件之碘含量在所述範圍內,便可藉由與上述硼酸含量之加乘效果,來良好維持調整貼合時之捲曲的容易性且良好抑制加熱時之捲曲,同時改善加熱時之外觀耐久性。本說明書中之「碘含量」意指偏光件(PVA系樹脂薄膜)中所含之所有碘的量。更具體而言,碘在偏光件中以碘離子(I- )、碘分子(I2 )、多碘離子(I3 - 、I5 - )等形態存在,而本說明書中之碘含量意指包含所有該等形態之碘的量。碘含量可利用例如X射線螢光分析之檢量曲線法來算出。另,多碘離子在偏光件中係在形成有PVA-碘錯合物之狀態下存在。藉由形成所述錯合物,可在可見光之波長範圍中展現吸收二色性。具體而言,PVA與三碘化物離子之錯合物(PVA・I3 - )在470nm附近具有吸光峰,而PVA與五碘化物離子之錯合物(PVA・I5 - )在600nm附近具有吸光峰。結果,多碘離子可根據其形態在可見光之寬廣範圍中吸收光。另一方面,碘離子(I- )在230nm附近具有吸光峰,其實質上與可見光之吸收無關聯。因此,在與PVA之錯合物之狀態下存在的多碘離子,才主要與偏光件之吸收性能有關。The iodine content of the polarizer is preferably 2 wt % or more, more preferably 2 wt % to 10 wt %. As long as the iodine content of the polarizer is within the above-mentioned range, the easiness of adjusting the curling during lamination can be well maintained, the curling during heating can be suppressed, and the curling during heating can be improved at the same time due to the synergistic effect of the above-mentioned boric acid content. Appearance durability. The "iodine content" in this specification means the total amount of iodine contained in the polarizer (PVA-based resin film). More specifically, iodine exists in the polarizer in the form of iodide ions (I − ), iodine molecules (I 2 ), polyiodide ions (I 3 − , I 5 − ), etc., and the iodine content in this specification means Contains the amount of iodine in all such forms. The iodine content can be calculated by a calibration curve method such as X-ray fluorescence analysis. In addition, polyiodide ions exist in a state in which a PVA-iodine complex is formed in the polarizer. By forming the complex, absorption dichroism can be exhibited in the wavelength range of visible light. Specifically, the complex of PVA and triiodide ion (PVA·I 3 - ) has an absorption peak near 470 nm, while the complex of PVA and pentaiodide ion (PVA·I 5 - ) has an absorption peak near 600 nm absorbance peak. As a result, polyiodide ions can absorb light in a wide range of visible light according to their morphology. On the other hand, iodide ion (I − ) has an absorption peak around 230 nm, which is not substantially related to the absorption of visible light. Therefore, the polyiodide ions existing in the complex state with PVA are mainly related to the absorption performance of the polarizer.
偏光件宜在波長380nm~780nm的任一波長下顯示吸收二色性。偏光件之單體透射率Ts宜為40%~48%,較宜為41%~46%。偏光件之偏光度P以97.0%以上為佳,99.0%以上較佳,99.9%以上更佳。The polarizer should exhibit absorption dichroism at any wavelength from 380nm to 780nm. The single transmittance Ts of the polarizer is preferably 40% to 48%, preferably 41% to 46%. The degree of polarization P of the polarizer is preferably above 97.0%, preferably above 99.0%, and even more preferably above 99.9%.
C.保護層 保護層如上述係以具有聯苯骨架之環氧樹脂的硬化物所構成。藉由保護層包含具有聯苯骨架之環氧樹脂,可更提升保護層之耐久性。保護層宜為具有聯苯骨架之環氧樹脂的陽離子聚合硬化物。藉由為陽離子聚合硬化物,可獲得即便非常薄卻耐久性優異之偏光板。以下,針對保護層之構成成分進行具體說明,接著說明保護層之特性。C. Protective layer The protective layer is formed of a cured product of an epoxy resin having a biphenyl skeleton as described above. The durability of the protective layer can be further enhanced by including the epoxy resin with biphenyl skeleton in the protective layer. The protective layer is preferably a cationic polymerized hardened product of an epoxy resin having a biphenyl skeleton. By being a cationic polymer cured product, a polarizing plate excellent in durability can be obtained even if it is very thin. Hereinafter, the constituent components of the protective layer will be specifically described, and then the characteristics of the protective layer will be described.
C-1.具有聯苯骨架之環氧樹脂 在一實施形態中,具有聯苯骨架之環氧樹脂係包含以下結構之環氧樹脂。具有聯苯骨架之環氧樹脂可僅使用1種,亦可組合2種以上來使用。 [化學式1] (式中,R1 ~R8 分別獨立表示氫原子、碳數1~12之直鏈狀或支鏈狀之取代或非取代的烴基、或鹵素元素)。C-1. Epoxy resin having biphenyl skeleton In one embodiment, the epoxy resin having biphenyl skeleton includes epoxy resins having the following structures. The epoxy resin which has a biphenyl skeleton may be used only by 1 type, and may be used in combination of 2 or more types. [Chemical formula 1] (In the formula, R 1 to R 8 each independently represent a hydrogen atom, a linear or branched substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, or a halogen element).
R1 ~R8 分別獨立表示氫原子、碳數1~12之直鏈狀或支鏈狀之取代或非取代的烴基、或鹵素元素。碳數1~12之直鏈狀或支鏈狀之取代或非取代的烴基可舉例如:甲基、乙基、正丙基、異丙基、正丁基、二級丁基、三級丁基、正戊基、異戊基、新戊基、三級戊基、環戊基、正己基、異己基、環己基、正庚基、環庚基、甲基環己基、正辛基、環辛基、正壬基、3,3,5-三甲基環己基、正癸基、環癸基、正十一基、正十二基、環十二基、苯基、苄基、甲基苄基、二甲基苄基、三甲基苄基、萘基甲基、苯乙基、2-苯基異丙基等。碳數1~12之直鏈狀或支鏈狀之取代或非取代的烴基宜為甲基、乙基、正丙基、異丙基、正丁基等碳數1~4烷基。鹵素元素可舉氟及溴。R 1 to R 8 each independently represent a hydrogen atom, a linear or branched substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, or a halogen element. The linear or branched substituted or unsubstituted hydrocarbon groups of carbon number 1-12 include, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, tertiary butyl base, n-pentyl, isopentyl, neopentyl, tertiary pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclohexyl Octyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, phenyl, benzyl, methyl Benzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, 2-phenylisopropyl, etc. The linear or branched substituted or unsubstituted hydrocarbon group with 1 to 12 carbon atoms is preferably an alkyl group with 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl and the like. The halogen element includes fluorine and bromine.
在一實施形態中,具有聯苯骨架之環氧樹脂為下式所示環氧樹脂。 [化學式2] (式中,R1 ~R8 如上述,n表示0~6之整數)。In one embodiment, the epoxy resin having a biphenyl skeleton is an epoxy resin represented by the following formula. [Chemical formula 2] (wherein, R 1 to R 8 are as described above, and n represents an integer of 0 to 6).
在一實施形態中,具有聯苯骨架之環氧樹脂為僅具有聯苯骨架之環氧樹脂。藉由使用僅具有聯苯骨架之環氧樹脂,可更提升所得保護層之耐久性。In one embodiment, the epoxy resin having a biphenyl skeleton is an epoxy resin having only a biphenyl skeleton. By using an epoxy resin having only a biphenyl skeleton, the durability of the resulting protective layer can be further enhanced.
在一實施形態中,具有聯苯骨架之環氧樹脂亦可包含有聯苯骨架以外之化學結構。聯苯骨架以外之化學結構可舉例如雙酚骨架、脂環式結構、芳香族環結構等。在該實施形態中,聯苯骨架以外之化學結構的比率(莫耳比)宜少於聯苯骨架。In one embodiment, the epoxy resin having a biphenyl skeleton may contain chemical structures other than the biphenyl skeleton. As a chemical structure other than a biphenyl skeleton, a bisphenol skeleton, an alicyclic structure, an aromatic ring structure, etc. are mentioned, for example. In this embodiment, the ratio (molar ratio) of chemical structures other than the biphenyl skeleton is preferably smaller than that of the biphenyl skeleton.
具有聯苯骨架之環氧樹脂亦可使用市售物。市售物可舉例如Mitsubishi Chemical Co.製,商品名:jER YX4000、jER YX4000H、jER YL6121、jER YL664、jER YL6677、jER YL6810、jER YL7399等。The epoxy resin which has a biphenyl skeleton can also use a commercial item. Commercially available products include, for example, the Mitsubishi Chemical Co. product, trade names: jER YX4000, jER YX4000H, jER YL6121, jER YL664, jER YL6677, jER YL6810, jER YL7399, and the like.
具有聯苯骨架之環氧樹脂宜玻璃轉移溫度(Tg)為100℃以上。結果,保護層之軟化溫度亦幾乎成為100℃以上。具有聯苯骨架之環氧樹脂的Tg只要為100℃以上,包含所得保護層之偏光板便容易成為耐久性優異者。具有聯苯骨架之環氧樹脂的Tg宜為110℃以上,較宜為120℃以上,更宜為125℃以上。另一方面,具有聯苯骨架之環氧樹脂的Tg宜為300℃以下,較宜為250℃以下,更宜為200℃以下,尤宜為160℃以下。具有聯苯骨架之環氧樹脂的Tg只要在所述範圍內,成形性及加工性便佳。The glass transition temperature (Tg) of the epoxy resin having a biphenyl skeleton is preferably 100°C or higher. As a result, the softening temperature of the protective layer is almost 100°C or higher. As long as the Tg of the epoxy resin having a biphenyl skeleton is 100° C. or higher, the polarizing plate including the obtained protective layer tends to be excellent in durability. The Tg of the epoxy resin having a biphenyl skeleton is preferably 110°C or higher, more preferably 120°C or higher, and more preferably 125°C or higher. On the other hand, the Tg of the epoxy resin having a biphenyl skeleton is preferably 300°C or lower, more preferably 250°C or lower, more preferably 200°C or lower, and particularly preferably 160°C or lower. As long as the Tg of the epoxy resin having a biphenyl skeleton is within the above range, the moldability and workability are good.
具有聯苯骨架之環氧樹脂的環氧當量宜為100g/當量以上,較宜為150g/當量以上,更宜為200g/當量以上。又,具有聯苯骨架之環氧樹脂的環氧當量宜為3000g/當量以下,較宜為2500g/當量以下,更宜為2000g/當量以下。藉由具有聯苯骨架之環氧當量為上述範圍,可獲得更穩定之保護層(殘留單體少且已充分硬化之保護層)。另,在本說明書中,「環氧當量」意指「包含1當量環氧基之環氧樹脂的質量」,可依循JIS K7236進行測定。The epoxy equivalent of the epoxy resin having a biphenyl skeleton is preferably 100 g/equivalent or more, more preferably 150 g/equivalent or more, and more preferably 200 g/equivalent or more. In addition, the epoxy equivalent of the epoxy resin having a biphenyl skeleton is preferably 3000 g/equivalent or less, more preferably 2500 g/equivalent or less, and more preferably 2000 g/equivalent or less. When the epoxy equivalent having a biphenyl skeleton is in the above-mentioned range, a more stable protective layer (a protective layer with less residual monomer and sufficiently hardened) can be obtained. In addition, in this specification, "epoxy equivalent" means "the mass of the epoxy resin containing 1 equivalent of an epoxy group", and it can measure based on JISK7236.
在本發明實施形態中,亦可併用具有聯苯骨架之環氧樹脂與其他樹脂。即,亦可將具有聯苯骨架之環氧樹脂與其他樹脂之摻合物供於保護層之成形。其他樹脂可舉例如苯乙烯系樹脂、聚乙烯、聚丙烯、聚醯胺、聚伸苯硫醚、聚醚醚酮、聚酯、聚碸、聚伸苯醚、聚縮醛、聚醯亞胺、聚醚醯亞胺等熱塑性樹脂、丙烯酸系樹脂及氧雜環丁烷系樹脂等硬化型樹脂。較佳可使用丙烯酸系樹脂及氧雜環丁烷系樹脂。併用之樹脂的種類及摻混量可按目的及所得薄膜所期望之特性等來適當設定。舉例而言,苯乙烯系樹脂可作為相位差控制劑來併用。In the embodiment of the present invention, an epoxy resin having a biphenyl skeleton and other resins may be used in combination. That is, a blend of an epoxy resin having a biphenyl skeleton and other resins may be used for forming the protective layer. Other resins include, for example, styrene-based resins, polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polystyrene, polyphenylene ether, polyacetal, and polyimide , thermoplastic resins such as polyetherimide, hardening resins such as acrylic resins and oxetane resins. Preferably, an acrylic resin and an oxetane-based resin can be used. The type and blending amount of the resin to be used in combination can be appropriately set according to the purpose, desired properties of the obtained film, and the like. For example, a styrene resin can be used together as a retardation control agent.
丙烯酸系樹脂可使用任意適當之丙烯酸系樹脂。例如(甲基)丙烯酸系化合物可舉例如分子內具有一個(甲基)丙烯醯基之(甲基)丙烯酸系化合物(以下亦稱「單官能(甲基)丙烯酸系化合物」)、分子內具有二個以上(甲基)丙烯醯基之(甲基)丙烯酸系化合物(以下亦稱「多官能(甲基)丙烯酸系化合物」)。該等(甲基)丙烯酸系化合物可單獨使用,亦可組合2種以上來使用。關於該等丙烯酸系樹脂例如記載於日本專利特開2019-168500號公報中。本說明書中係援用該公報整體之記載作為參考。As the acrylic resin, any appropriate acrylic resin can be used. For example, the (meth)acrylic compound includes a (meth)acrylic compound having one (meth)acryloyl group in the molecule (hereinafter also referred to as "monofunctional (meth)acrylic compound"), (Meth)acrylic-type compound (henceforth "polyfunctional (meth)acrylic-type compound") of two or more (meth)acryloyl groups. These (meth)acrylic compounds may be used alone or in combination of two or more. About these acrylic resins, for example, it describes in Unexamined-Japanese-Patent No. 2019-168500. In this specification, the entire description of this gazette is incorporated by reference.
氧雜環丁烷樹脂可使用分子內具有1個以上氧雜環丁烷基之任意適當的化合物。可舉例如:3-乙-3-羥甲基氧雜環丁烷、3-乙-3-(2-乙基己基氧基甲基)氧雜環丁烷、3-乙-3-(苯氧基甲基)氧雜環丁烷、3-乙-3-(環己基氧基甲基)氧雜環丁烷、3-乙-3-(環氧乙烷基甲氧基)氧雜環丁烷、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯等分子內具有1個氧雜環丁烷基之氧雜環丁烷化合物;3-乙-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷、1,4-雙[(3-乙-3-氧雜環丁烷基)甲氧基甲基]苯、4,4'-雙[(3-乙-3-氧雜環丁烷基)甲氧基甲基]聯苯等分子內具有2個以上氧雜環丁烷基之氧雜環丁烷化合物等。該等氧雜環丁烷樹脂可僅使用1種亦可組合2種以上。As the oxetane resin, any appropriate compound having one or more oxetane groups in the molecule can be used. For example: 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(benzene Oxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, 3-ethyl-3-(oxiranylmethoxy)oxetane Butane, (3-ethyloxetan-3-yl)methyl (meth)acrylate and other oxetane compounds with one oxetanyl group in the molecule; 3-ethyl-3 {[(3-Ethyloxetan-3-yl)methoxy]methyl}oxetane, 1,4-bis[(3-ethyl-3-oxetanyl) Methoxymethyl]benzene, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, etc. having 2 or more oxetanyl groups in the molecule oxetane compounds, etc. These oxetane resins may be used alone or in combination of two or more.
宜使用3-乙-3-羥甲基氧雜環丁烷、1,4-雙[(3-乙-3-氧雜環丁烷基)甲氧基甲基]苯、3-乙-3-(2-乙基己基氧基甲基)氧雜環丁烷、3-乙-3-(環氧乙烷基甲氧基)氧雜環丁烷、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、3-乙-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷等。該等氧雜環丁烷樹脂可輕易取得,且稀釋性(低黏度)、相溶性佳。It is suitable to use 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3 -(2-Ethylhexyloxymethyl)oxetane, 3-Ethane-3-(oxiranylmethoxy)oxetane, (3-ethyl)(meth)acrylic acid oxetan-3-yl) methyl ester, 3-ethane-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, etc. These oxetane resins can be easily obtained, and have good diluting properties (low viscosity) and good compatibility.
在一實施形態中,由相溶性或接著性之觀點來看,宜使用分子量500以下且在室溫(25℃)下呈液態的氧雜環丁烷樹脂。在一實施形態中,宜使用分子內含有2個以上氧雜環丁烷基之氧雜環丁烷化合物、分子內含有1個氧雜環丁烷基與1個(甲基)丙烯醯基或1個環氧基之氧雜環丁烷化合物,較宜使用3-乙-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷、3-乙-3-(環氧乙烷基甲氧基)氧雜環丁烷、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯。藉由使用該等氧雜環丁烷樹脂,可提升保護層之硬化性及耐久性。In one embodiment, from the viewpoint of compatibility or adhesiveness, it is preferable to use an oxetane resin having a molecular weight of 500 or less and a liquid state at room temperature (25° C.). In one embodiment, an oxetane compound containing two or more oxetanyl groups in the molecule, one oxetanyl group and one (meth)acryloyl group in the molecule, or An oxetane compound with one epoxy group, preferably 3-ethane-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane , 3-ethyl-3-(oxiranylmethoxy)oxetane, (3-ethyloxetan-3-yl)methyl (meth)acrylate. By using these oxetane resins, the hardenability and durability of the protective layer can be improved.
氧雜環丁烷樹脂亦可使用市售物。具體上,可使用ARON OXETANE OXT-101、ARON OXETANE OXT-121、ARON OXETANE OXT-212、ARON OXETANE OXT-221(皆為東亞合成公司製)。較佳可使用ARON OXETANE OXT-101及ARON OXETANE OXT-221。A commercially available thing can also be used for oxetane resin. Specifically, ARON OXETANE OXT-101, ARON OXETANE OXT-121, ARON OXETANE OXT-212, and ARON OXETANE OXT-221 (all manufactured by Toagosei Corporation) can be used. Preferably, ARON OXETANE OXT-101 and ARON OXETANE OXT-221 can be used.
併用具有聯苯骨架之環氧樹脂與其他樹脂時,具有聯苯骨架之環氧樹脂與其他樹脂之摻合物中,具有聯苯骨架之環氧樹脂之含量宜為50重量%~100重量%,較宜為60重量%~100重量%,更宜為70重量%~100重量%,尤宜為80重量%~100重量%。當含量小於50重量%時,恐無法獲得保護層之耐熱性及與偏光件之充分密著性。When an epoxy resin having a biphenyl skeleton and other resins are used together, the content of the epoxy resin having a biphenyl skeleton in the blend of the epoxy resin having a biphenyl skeleton and other resins is preferably 50% by weight to 100% by weight , preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and particularly preferably 80% by weight to 100% by weight. When the content is less than 50% by weight, the heat resistance of the protective layer and the sufficient adhesion to the polarizer may not be obtained.
當併用具有聯苯骨架之環氧樹脂與氧雜環丁烷樹脂時,相對於具有聯苯骨架之環氧系樹脂與氧雜環丁烷樹脂之合計量100重量份,氧雜環丁烷樹脂之含量宜為1重量份~50重量份,較宜為5重量份~45重量份,更宜為10重量份~40重量份。藉由設為上述範圍,可提升硬化性,亦可提升保護層與偏光件之密著性。When an epoxy resin having a biphenyl skeleton and an oxetane resin are used in combination, the oxetane resin is 100 parts by weight of the total amount of the epoxy resin having a biphenyl skeleton and the oxetane resin. The content is preferably 1 to 50 parts by weight, preferably 5 to 45 parts by weight, more preferably 10 to 40 parts by weight. By setting it as the said range, sclerosis|hardenability can be improved, and the adhesiveness of a protective layer and a polarizer can also be improved.
C-2.硬化劑 具有聯苯骨架之環氧樹脂可藉由與任意適當之硬化劑一同使用而成為硬化物。硬化劑可使用可使環氧樹脂硬化之任意適當之硬化劑。在一實施形態中,硬化劑包含光陽離子聚合引發劑。藉由包含光陽離子聚合引發劑,可形成陽離子聚合硬化物,即保護層。光陽離子聚合引發劑可使用可藉由紫外線等光照射而使具有聯苯骨架之環氧樹脂硬化的任意適當之化合物。光陽離子聚合引發劑可僅使用1種,亦可組合2種以上來使用。C-2. Hardener The epoxy resin which has a biphenyl skeleton can be hardened|cured by using together with any suitable hardening|curing agent. As the hardener, any suitable hardener that can harden the epoxy resin can be used. In one embodiment, the hardener contains a photocationic polymerization initiator. By including a photocationic polymerization initiator, a cationic polymerization cured product, that is, a protective layer can be formed. As a photocationic polymerization initiator, any appropriate compound which can harden the epoxy resin which has a biphenyl skeleton by light irradiation, such as an ultraviolet-ray, can be used. The photocationic polymerization initiator may be used alone or in combination of two or more.
光陽離子聚合引發劑可舉例如三苯基鋶六氟銻酸鹽、三苯基鋶六氟磷酸鹽、對(苯硫基)苯基二苯基鋶六氟銻酸鹽、對(苯硫基)苯基二苯基鋶六氟磷酸鹽、4-氯苯基二苯基鋶六氟磷酸鹽、4-氯苯基二苯基鋶六氟銻酸鹽、雙[4-(二苯基鋶基)苯基]硫醚雙六氟磷酸鹽、雙[4-(二苯基鋶基)苯基]硫醚雙六氟銻酸鹽、(2,4-環戊二烯-1-基)[(1-甲基乙基)苯]-Fe-六氟磷酸鹽、二苯基碘鎓六氟銻酸鹽等。較宜係使用三苯基鋶鹽系六氟銻酸鹽型之光陽離子聚合引發劑、二苯基碘鎓鹽系六氟銻酸鹽型之光陽離子聚合引發劑。Examples of the photocationic polymerization initiator include triphenyl perylene hexafluoroantimonate, triphenyl perylene hexafluorophosphate, p-(phenylthio)phenyldiphenyl perylene hexafluoroantimonate, p-(phenylthio) ) Phenyl diphenyl hexafluorophosphate, 4-chlorophenyl diphenyl hexafluorophosphate, 4-chlorophenyl diphenyl hexafluoroantimonate, bis[4-(diphenyl perionate) (2,4-Cyclopentadien-1-yl) [(1-methylethyl)benzene]-Fe-hexafluorophosphate, diphenyliodonium hexafluoroantimonate, etc. It is preferable to use a photocationic polymerization initiator of triphenyl perionium salt type hexafluoroantimonate type, and a photocationic polymerization initiator of diphenyliodonium salt type hexafluoroantimonate type.
光陽離子聚合引發劑亦可使用市售物。市售物可舉三苯基鋶鹽系六氟銻酸鹽型之SP-170(ADEKA公司製)、CPI-101A(SAN-APRO公司製)、WPAG-1056(和光純藥工業公司製)、二苯基碘鎓鹽系六氟銻酸鹽型之WPI-116(和光純藥工業公司製)等。Commercially available ones can also be used as the photocationic polymerization initiator. Commercially available products include SP-170 (manufactured by ADEKA), CPI-101A (manufactured by SAN-APRO), WPAG-1056 (manufactured by Wako Pure Chemical Industries, Ltd.) The diphenyliodonium salt is WPI-116 (manufactured by Wako Pure Chemical Industries, Ltd.) of the hexafluoroantimonate type, and the like.
相對於具有聯苯骨架之環氧樹脂100重量份,光陽離子聚合引發劑之含量宜為0.1重量份~3重量份,較宜為0.25重量份~2重量份。當光陽離子聚合引發劑之含量小於0.1重量份時,有即便照射光(紫外線)仍未充分硬化之情形。The content of the photocationic polymerization initiator is preferably 0.1 to 3 parts by weight, preferably 0.25 to 2 parts by weight, relative to 100 parts by weight of the epoxy resin having a biphenyl skeleton. When the content of the photocationic polymerization initiator is less than 0.1 part by weight, there may be cases where it is not sufficiently cured even if it is irradiated with light (ultraviolet rays).
C-3.保護層之構成及特性 保護層如上述係以具有聯苯骨架之環氧樹脂的硬化物所構成。只要為所述硬化物,便可使其厚度較擠製成形薄膜薄上甚多。保護層之厚度宜為10µm以下,7µm以下較佳,5µm以下更佳,3µm以下尤佳。保護層之厚度例如可為1µm以上。相較於水溶液或水分散體這類水系塗佈膜的固化物,具有聯苯骨架之環氧樹脂的硬化物其吸濕性及透濕性更小,因此具有加濕耐久性優異之優點。結果,可實現即便在加熱加濕環境下,仍可維持光學特性的耐久性優異之偏光板。又,具有聯苯骨架之環氧樹脂的硬化物,即保護層,其與偏光件之密著性優異。因此,即便為如上述之厚度,仍可與使用以往之薄膜的保護層相同程度地保護偏光件。且,即便為上述之厚度,仍可防止偏光件發生褪色等不良情況。C-3. Composition and characteristics of protective layer The protective layer is formed of a cured product of an epoxy resin having a biphenyl skeleton as described above. As long as it is the hardened product, the thickness can be much thinner than that of an extruded film. The thickness of the protective layer is preferably 10µm or less, preferably 7µm or less, more preferably 5µm or less, and even more preferably 3µm or less. The thickness of the protective layer may be, for example, 1 µm or more. Compared with the cured products of aqueous coating films such as aqueous solutions or aqueous dispersions, the cured products of epoxy resins having a biphenyl skeleton have lower hygroscopicity and moisture permeability, and thus have the advantage of being excellent in humidification durability. As a result, a polarizing plate excellent in durability that can maintain optical properties even in a heated and humidified environment can be realized. Moreover, the hardened|cured material of the epoxy resin which has a biphenyl skeleton, ie, a protective layer, is excellent in the adhesiveness with a polarizer. Therefore, even with the above-mentioned thickness, the polarizer can be protected to the same extent as the protective layer using a conventional thin film. In addition, even if the thickness is as described above, the polarizer can still be prevented from occurrence of defects such as fading.
保護層之軟化溫度宜為100℃以上。保護層之軟化溫度只要在100℃以上,包含所得保護層之偏光板便容易成為耐久性優異者。保護層之軟化溫度宜為110℃以上,較宜為120℃以上,更宜為125℃以上。另一方面,保護層之軟化溫度宜為300℃以下,較宜為250℃以下,更宜為200℃以下,尤宜為160℃以下。保護層之軟化點只要在所述範圍內,成形性及加工性便佳。The softening temperature of the protective layer is preferably above 100°C. As long as the softening temperature of the protective layer is 100° C. or higher, the polarizing plate including the obtained protective layer is likely to be excellent in durability. The softening temperature of the protective layer is preferably 110°C or higher, more preferably 120°C or higher, and more preferably 125°C or higher. On the other hand, the softening temperature of the protective layer is preferably 300°C or lower, more preferably 250°C or lower, more preferably 200°C or lower, and particularly preferably 160°C or lower. As long as the softening point of the protective layer is within the above range, the formability and workability are good.
保護層之碘吸附量宜為10重量%以下,較宜為6.0重量%以下,更宜為3.0重量%以下,尤宜為2.0重量%以下。碘吸附量越小越佳。只要碘吸附量在所述範圍內,便可獲得具有更優異耐久性之偏光板。碘吸附量可以下述方法測定。 將保護層形成用組成物以灑佈器塗佈於基材(PET薄膜),形成保護層(厚度約3µm)。將所得附保護層之PET薄膜裁切成1cm×1cm(1cm2 )做成試料,採取到頂空小瓶(20mL容量)並秤量。接著,將裝有碘溶液1mL(碘濃度1重量%、碘化鉀濃度7重量%)的螺口瓶(1.5mL容量)亦放入該頂空小瓶中並蓋緊。之後,將頂空小瓶放入65℃之乾燥機中加溫6小時。藉此使氣體狀態之I2 吸附於試料上。之後,將試料採取到陶瓷舟皿並使用自動試料燃燒裝置使其燃燒,再將所產生之氣體採集至吸收液10mL中。收集後,將該吸收液以純水調製為15mL,並針對原液或適當稀釋後之液體進行IC定量分析。另,僅以PET薄膜進行相同測定時之碘吸附量幾乎為0。根據經IC定量分析所得碘重量與保護層單體之重量(「附保護層之PET薄膜之重量」-「PET薄膜之重量」),從以下式算出碘吸附量(重量%)。 碘吸附量(重量%)=IC定量分析所得碘重量/保護層單體之重量×100 分析例如可使用以下測定裝置。 [測定裝置] 自動試料燃燒裝置:Mitsubishi Chemical Analytech公司製,「AQF-2100H」 IC(陰離子):Thermo Fisher Scientific公司製,「ICS-3000」The iodine adsorption amount of the protective layer is preferably 10% by weight or less, more preferably 6.0% by weight or less, more preferably 3.0% by weight or less, particularly preferably 2.0% by weight or less. The smaller the amount of iodine adsorbed, the better. As long as the amount of iodine adsorption is within the range, a polarizing plate having more excellent durability can be obtained. The amount of iodine adsorption can be measured by the following method. The composition for forming a protective layer was applied to a substrate (PET film) with a sprayer to form a protective layer (thickness of about 3 µm). The obtained PET film with a protective layer was cut into 1 cm×1 cm (1 cm 2 ) to prepare a sample, which was collected into a headspace vial (20 mL capacity) and weighed. Next, a screw-top vial (1.5 mL capacity) containing 1 mL of an iodine solution (1 wt % iodine concentration, 7 wt % potassium iodide concentration) was also placed in the headspace vial and capped tightly. Afterwards, the headspace vial was warmed in a desiccator at 65°C for 6 hours. Thereby, I 2 in gaseous state is adsorbed on the sample. After that, the sample was collected in a ceramic boat and burned using an automatic sample burning device, and the generated gas was collected into 10 mL of the absorbing liquid. After the collection, the absorbing solution was prepared to 15 mL with pure water, and IC quantitative analysis was performed on the stock solution or the appropriately diluted solution. In addition, the iodine adsorption amount was almost zero when the same measurement was performed only with the PET film. Based on the weight of iodine obtained by IC quantitative analysis and the weight of the protective layer monomer ("weight of PET film with protective layer" - "weight of PET film"), the iodine adsorption amount (% by weight) was calculated from the following formula. Iodine adsorption amount (% by weight)=Iodine weight obtained by IC quantitative analysis/weight of protective layer monomer×100 For the analysis, the following measuring apparatus can be used, for example. [Measuring device] Automatic sample combustion device: "AQF-2100H" manufactured by Mitsubishi Chemical Analytech Co., Ltd. IC (anion): "ICS-3000" manufactured by Thermo Fisher Scientific Co., Ltd.
保護層宜實質上在光學上具有各向同性。本說明書中,「實質上在光學上具有各向同性」意指在波長550nm下之相位差為-50nm~+50nm。面內相位差Re(550)較宜為-30nm~+30nm,更宜為-10nm~+10nm,尤宜為0nm~2nm。厚度方向之相位差Rth(550)較宜為-5nm~5nm,更宜為-3nm~3nm,尤宜為-2nm~2nm。只要保護層之Re(550)及Rth(550)在所述範圍內,在將包含該保護層之偏光板應用於影像顯示裝置時,便可防止對顯示特性帶來不良影響。此外,Re(550)係在23℃下以波長550nm之光測定之薄膜的面內相位差。Re(550)可藉由式:Re(550)=(nx-ny)×d求得。Rth(550)係在23℃下以波長550nm之光測定之薄膜之厚度方向的相位差。Rth(550)可藉由式:Rth(550)=(nx-nz)×d求得。在此,nx為面內折射率達到最大之方向(亦即慢軸方向)的折射率,ny為於面內與慢軸正交之方向(亦即快軸方向)的折射率,nz為厚度方向的折射率,d為薄膜之厚度(nm)。The protective layer is preferably substantially optically isotropic. In the present specification, "substantially optically isotropic" means that the retardation at a wavelength of 550 nm is -50 nm to +50 nm. The in-plane retardation Re(550) is preferably -30 nm to +30 nm, more preferably -10 nm to +10 nm, and particularly preferably 0 nm to 2 nm. The retardation Rth(550) in the thickness direction is preferably -5 nm to 5 nm, more preferably -3 nm to 3 nm, and particularly preferably -2 nm to 2 nm. As long as the Re(550) and Rth(550) of the protective layer are within the above-mentioned ranges, when the polarizing plate including the protective layer is applied to an image display device, adverse effects on display characteristics can be prevented. In addition, Re(550) is the in-plane retardation of the thin film measured at 23 degreeC with the light of wavelength 550nm. Re(550) can be obtained by the formula: Re(550)=(nx-ny)×d. Rth(550) is the retardation in the thickness direction of the thin film measured at 23°C with light having a wavelength of 550 nm. Rth(550) can be obtained by the formula: Rth(550)=(nx-nz)×d. Here, nx is the refractive index in the direction where the in-plane refractive index reaches the maximum (that is, the slow axis direction), ny is the refractive index in the in-plane direction orthogonal to the slow axis (that is, the fast axis direction), and nz is the thickness The refractive index in the direction, d is the thickness (nm) of the film.
保護層在厚度3µm時之在380nm下之光線透射率愈高愈佳。具體而言,光線透射率宜為85%以上,較宜為88%以上,更宜為90%以上。只要光線透射率在所述範圍內,便可確保所期望之透明性。光線透射率例如可以根據ASTM-D-1003之方法來測定。When the thickness of the protective layer is 3µm, the light transmittance at 380nm is as high as possible. Specifically, the light transmittance is preferably 85% or more, more preferably 88% or more, and more preferably 90% or more. As long as the light transmittance is within the range, desired transparency can be ensured. The light transmittance can be measured according to the method of ASTM-D-1003, for example.
保護層之霧度越低越佳。具體而言霧度宜為5%以下,較宜為3%以下,更宜為1.5%以下,尤宜為1%以下。霧度若為5%以下,便可賦予薄膜良好的透明感。並且,即便用於影像顯示裝置之視辨側偏光板之情況下,仍可良好視辨顯示內容。The lower the haze of the protective layer, the better. Specifically, the haze is preferably 5% or less, more preferably 3% or less, more preferably 1.5% or less, and particularly preferably 1% or less. When the haze is 5% or less, it is possible to impart a good sense of transparency to the film. Moreover, even if it is used for the polarizing plate on the viewing side of the image display device, the displayed content can be well viewed.
保護層在厚度3µm時之YI宜為1.27以下,1.25以下較佳,1.23以下更佳,1.20以下尤佳。當YI大於1.3時,有光學上透明性不足之情形。另,YI例如可從使用高速積分球式分光透射率測定機(商品名DOT-3C:村上色彩技術研究所製)測定而得之色彩三刺激值(X,Y,Z),利用下式求出。 YI=[(1.28X-1.06Z)/Y]×100When the thickness of the protective layer is 3µm, the YI is preferably 1.27 or less, preferably 1.25 or less, more preferably 1.23 or less, and even more preferably 1.20 or less. When YI is more than 1.3, the optical transparency may be insufficient. In addition, YI can be obtained from the color tristimulus values (X, Y, Z) measured using a high-speed integrating sphere spectroscopic transmittance measuring machine (trade name DOT-3C: manufactured by Murakami Color Technology Laboratory), for example, by the following formula out. YI=[(1.28X-1.06Z)/Y]×100
保護層在厚度3µm時之b值(依循亨特(Hunter)表色系統之色相尺度)宜小於1.5,且1.0以下較佳。當b值為1.5以上時,有出現非期望之色調之情形。另,b值例如可依以下方式獲得:將構成保護層之薄膜的試樣裁切成3cm見方,使用高速積分球式分光透射率測定機(商品名DOT-3C:村上色彩技術研究所製)測定色相,並依循亨特表色系統評估該色相。When the thickness of the protective layer is 3µm, the b value (according to the hue scale of the Hunter color system) should preferably be less than 1.5, and preferably less than 1.0. When the b value is 1.5 or more, an undesired color tone may appear. In addition, the b value can be obtained, for example, by cutting a sample of the film constituting the protective layer into a 3 cm square, and using a high-speed integrating sphere type spectroscopic transmittance measuring machine (trade name DOT-3C: manufactured by Murakami Color Institute) Hue is measured and evaluated according to the Hunter Color System.
保護層(具有聯苯骨架之環氧樹脂的硬化物)可按目的包含有任意適當之添加劑。添加劑之具體例可舉:紫外線吸收劑;調平劑;受阻酚系、磷系、硫系等抗氧化劑;耐光穩定劑、耐候穩定劑、熱穩定劑等穩定劑;玻璃纖維、碳纖維等補強材;近紅外線吸收劑;參(二溴化丙基)磷酸酯、三烯丙基磷酸酯、氧化銻等阻燃劑;陰離子系、陽離子系、非離子系界面活性劑等抗靜電劑;無機顏料、有機顏料、染料等著色劑;有機填料或無機填料;樹脂改質劑;有機填充劑或無機填充劑;塑化劑;滑劑;抗靜電劑;阻燃劑等。添加劑通常係於保護層形成時添加於溶液中。添加劑之種類、數量、組合、添加量等可按目的適當設定。The protective layer (hardened product of an epoxy resin having a biphenyl skeleton) may contain any appropriate additives according to the purpose. Specific examples of additives include: ultraviolet absorbers; leveling agents; antioxidants such as hindered phenols, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers. ;Near-infrared absorbers; ginseng (dibromopropyl) phosphate, triallyl phosphate, antimony oxide and other flame retardants; anionic, cationic, nonionic surfactants and other antistatic agents; inorganic pigments , organic pigments, dyes and other colorants; organic fillers or inorganic fillers; resin modifiers; organic fillers or inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants, etc. Additives are usually added to the solution when the protective layer is formed. The type, quantity, combination, addition amount, etc. of the additives can be appropriately set according to the purpose.
保護層之偏光件側亦可形成有易接著層。易接著層例如包含水系聚胺甲酸酯與㗁唑啉系交聯劑。藉由形成所述易接著層,可提升保護層與偏光件之密著性。易接著層可利用任意適當之方法與偏光件積層。例如亦可直接形成於偏光件上,或可透過任意適當之黏著劑層或接著劑層積層。且,保護層上亦可形成有硬塗層。硬塗層可於當將保護層用作視辨側偏光板之視辨側的保護層時形成。當形成易接著層及硬塗層兩者時,代表上該等可分別形成於保護層之不同側。An easily bonding layer may also be formed on the polarizer side of the protective layer. The easily bonding layer contains, for example, a water-based polyurethane and an oxazoline-based crosslinking agent. By forming the easy bonding layer, the adhesion between the protective layer and the polarizer can be improved. The easy-bond layer can be laminated with the polarizer by any suitable method. For example, it can also be formed directly on the polarizer, or can be passed through any suitable adhesive layer or adhesive layer. In addition, a hard coat layer may be formed on the protective layer. The hard coat layer can be formed when the protective layer is used as the protective layer on the viewing side of the viewing-side polarizing plate. When both the easy-bond layer and the hard coat layer are formed, it means that these can be formed on different sides of the protective layer, respectively.
D.偏光板之製造方法 D-1.偏光件之製造方法 上述B項記載之偏光件之製造方法包含以下步驟:於長條狀熱塑性樹脂基材之單側形成包含鹵化物與聚乙烯醇系樹脂(PVA系樹脂)之聚乙烯醇系樹脂層(PVA系樹脂層),而製成積層體;及,對積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理及乾燥收縮處理,該乾燥收縮處理係一邊將上述積層體沿長邊方向輸送一邊進行加熱,藉此使其於寬度方向收縮2%以上。PVA系樹脂層中之鹵化物含量相對於PVA系樹脂100重量份宜為5重量份~20重量份。乾燥收縮處理宜使用加熱輥進行處理,且加熱輥溫度宜為60℃~120℃。根據所述製造方法可獲得如上述之偏光件。尤其是製作包含含鹵化物之PVA系樹脂層的積層體後,將上述積層體之延伸進行包含空中輔助延伸及水中延伸的多階段延伸,再將延伸後之積層體以加熱輥進行加熱,藉此可獲得具有優異光學特性(代表上為單體透射率及偏光度)並且光學特性之參差經抑制的偏光件。具體而言,藉由在乾燥收縮處理步驟中使用加熱輥,可一邊輸送積層體一邊使積層體整體全部均勻收縮。藉此不僅可提升所得偏光件的光學特性,還可穩定生產光學特性優異的偏光件,而可抑制偏光件之光學特性(尤其是單體透射率)的參差。以下就鹵化物及乾燥收縮處理加以說明。該等以外之製造方法的詳細內容例如記載於日本專利特開2012-73580號公報及日本專利第6470455號中。本說明書中係援用該公報整體之記載作為參考。D. Manufacturing method of polarizing plate D-1. Manufacturing method of polarizer The manufacturing method of the polarizer described in the above item B includes the following steps: forming a polyvinyl alcohol-based resin layer (PVA-based resin) comprising a halide and a polyvinyl-alcohol-based resin (PVA-based resin) on one side of an elongated thermoplastic resin substrate resin layer) to produce a layered product; and the layered product is subjected to air-assisted stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment in this order while conveying the above-mentioned layered product in the longitudinal direction. By heating, it shrinks by 2% or more in the width direction. The halide content in the PVA-based resin layer is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin. The drying shrinkage treatment should be carried out with a heating roller, and the temperature of the heating roller should be 60℃~120℃. According to the manufacturing method, the above-mentioned polarizer can be obtained. In particular, after a laminate containing a halide-containing PVA-based resin layer is produced, the above-mentioned laminate is stretched by multi-stage stretching including air-assisted stretching and underwater stretching, and then the stretched laminate is heated with a heating roller. This makes it possible to obtain a polarizer having excellent optical properties (representatively, single transmittance and degree of polarization) and suppressed variations in optical properties. Specifically, by using a heating roll in the drying shrinkage treatment step, the entire layered body can be uniformly shrunk while conveying the layered body. In this way, not only the optical properties of the obtained polarizer can be improved, but also the polarizer with excellent optical properties can be stably produced, and the variation in the optical properties (especially the transmittance of a single unit) of the polarizer can be suppressed. The halide and drying shrinkage treatment will be described below. Details of production methods other than these are described in, for example, Japanese Patent Laid-Open No. 2012-73580 and Japanese Patent No. 6470455 . In this specification, the entire description of this gazette is incorporated by reference.
D-1-1.鹵化物 包含鹵化物與PVA系樹脂之PVA系樹脂層可藉由將包含鹵化物與PVA系樹脂之塗佈液塗佈於熱塑性樹脂基材上並將塗佈膜乾燥來形成。塗佈液代表上係使上述鹵化物及上述PVA系樹脂溶解於溶劑而成之溶液。作為溶劑,可舉例如水、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、各種甘醇類、三羥甲丙烷等多元醇類、伸乙二胺、二伸乙三胺等胺類。該等可單獨使用亦可組合2種以上來使用。該等中又以水為佳。溶液之PVA系樹脂濃度相對於溶劑100重量份宜為3重量份~20重量份。只要為所述樹脂濃度,便可形成密著於熱塑性樹脂基材且均勻的塗佈膜。D-1-1. Halide The PVA-based resin layer containing the halide and the PVA-based resin can be formed by coating a coating liquid containing the halide and the PVA-based resin on a thermoplastic resin substrate and drying the coating film. The coating liquid represents a solution obtained by dissolving the above-mentioned halide and the above-mentioned PVA-based resin in a solvent. Examples of the solvent include water, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, etc. Amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, water is preferred. The PVA-based resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight relative to 100 parts by weight of the solvent. As long as it is the said resin density|concentration, a uniform coating film which adheres to a thermoplastic resin base material can be formed.
鹵化物可採用任意適當之鹵化物。可舉例如碘化物及氯化鈉。碘化物可舉例如碘化鉀、碘化鈉及碘化鋰。該等之中又以碘化鉀為佳。As the halide, any suitable halide can be used. For example, iodide and sodium chloride are mentioned. Examples of the iodide include potassium iodide, sodium iodide, and lithium iodide. Among them, potassium iodide is preferred.
塗佈液中之鹵化物量相對於PVA系樹脂100重量份宜為5重量份~20重量份,較佳為10重量份~15重量份。若鹵化物量過多,則有鹵化物溢出而使最後所得偏光件變白濁之情形。The amount of the halide in the coating liquid is preferably 5 parts by weight to 20 parts by weight, preferably 10 parts by weight to 15 parts by weight, relative to 100 parts by weight of the PVA resin. If the amount of the halide is too large, the halide may overflow and the polarizer finally obtained may become cloudy.
一般而言,PVA系樹脂層經延伸,PVA樹脂層中之聚乙烯醇分子之定向性會變高,但若將延伸後之PVA系樹脂層浸漬於含水之液體中,則有聚乙烯醇分子之定向紊亂而定向性降低之情形。尤其是在對熱塑性樹脂基材與PVA系樹脂層之積層體進行硼酸水中延伸時,為了使熱塑性樹脂基材之延伸穩定而在相對較高溫度下在硼酸水中將上述積層體進行延伸時,上述定向度降低之傾向很明顯。舉例而言,PVA薄膜單體在硼酸水中之延伸一般而言係在60℃下進行,相對於此,A-PET(熱塑性樹脂基材)與PVA系樹脂層之積層體之延伸係在70℃前後之溫度的較高溫度下進行,此時,延伸初始之PVA的定向性會在藉由水中延伸而上升之前的階段便降低。對此,藉由製作包含鹵化物之PVA系樹脂層與熱塑性樹脂基材之積層體,並將積層體在硼酸水中進行延伸前,在空氣中進行高溫延伸(輔助延伸),可促進輔助延伸後之積層體之PVA系樹脂層中的PVA系樹脂之結晶化。結果,在將PVA系樹脂層浸漬於液體中時,相較於PVA系樹脂層不含鹵化物之情況,更能抑制聚乙烯醇分子之定向紊亂及定向性降低。藉此,可提升經由染色處理及水中延伸處理等將積層體浸漬於液體中來進行的處理步驟而得之偏光件的光學特性。Generally speaking, when the PVA-based resin layer is stretched, the orientation of the polyvinyl alcohol molecules in the PVA-based resin layer will become higher, but if the stretched PVA-based resin layer is immersed in a water-containing liquid, there will be polyvinyl alcohol molecules A situation in which the orientation is disordered and the orientation is reduced. In particular, when the laminate of the thermoplastic resin base material and the PVA-based resin layer is stretched in boric acid water, the above-mentioned laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin base material. The tendency to decrease the degree of orientation is obvious. For example, the extension of the PVA film monomer in boric acid water is generally carried out at 60°C, while the extension of the laminate of A-PET (thermoplastic resin substrate) and the PVA-based resin layer is performed at 70°C At this time, the orientation of the PVA at the beginning of the stretching is reduced at a stage before it rises by the stretching in water. In this regard, by fabricating a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate, and performing high temperature stretching (assisted stretching) in air before stretching the laminated body in boric acid water, the post-assisted stretching can be accelerated. Crystallization of the PVA-based resin in the PVA-based resin layer of the laminate. As a result, when the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in the orientation can be suppressed more than when the PVA-based resin layer does not contain a halide. Thereby, the optical characteristics of the polarizer obtained by the process steps of immersing the laminated body in liquid, such as dyeing process and underwater stretching process, can be improved.
D-1-2.乾燥收縮處理 乾燥收縮處理可透過將區域整體加熱所進行之區域加熱來進行,亦可透過將輸送輥加熱(所謂使用加熱輥)來進行(加熱輥乾燥方式)。較佳為使用這兩者。藉由使用加熱輥使其乾燥,可有效率地抑制積層體之加熱捲曲,而製造出外觀優異的偏光件。具體而言,藉由在使積層體沿附加熱輥之狀態下進行乾燥,可有效率地促進上述熱塑性樹脂基材之結晶化而增加結晶度,即使是在相對較低的乾燥溫度下,仍可良好增加熱塑性樹脂基材之結晶度。結果熱塑性樹脂基材之剛性增加而成為得以承受PVA系樹脂層因乾燥而收縮的狀態,從而捲曲受到抑制。又,藉由使用加熱輥,可在將積層體維持平坦狀態的同時進行乾燥,因此不只能抑制捲曲還能抑制起皺的產生。此時,積層體可透過乾燥收縮處理使其於寬度方向收縮,來提升光學特性。其係因可有效提升PVA及PVA/碘錯合物之定向性之故。積層體進行乾燥收縮處理所得寬度方向之收縮率宜為2%~10%,較宜為2%~8%,尤宜為4%~6%。藉由使用加熱輥,可在輸送積層體的同時使其連續於寬度方向收縮,而可實現高生產性。D-1-2. Drying shrinkage treatment The drying shrinkage treatment can be performed by area heating by heating the entire area, or by heating a conveying roller (so-called using a heating roller) (heating roller drying method). It is preferable to use both. By drying it using a heating roll, the heating curl of the laminated body can be effectively suppressed, and a polarizer having an excellent appearance can be produced. Specifically, by drying the layered body in a state where a heated roll is attached, the crystallization of the thermoplastic resin substrate can be effectively promoted to increase the degree of crystallinity, and even at a relatively low drying temperature, the It can improve the crystallinity of thermoplastic resin substrates. As a result, the rigidity of the thermoplastic resin base material increases, and the PVA-based resin layer is in a state of being able to withstand shrinkage due to drying, and curling is suppressed. Moreover, since the laminated body can be dried while maintaining a flat state by using a heating roll, not only the curling but also the generation of wrinkles can be suppressed. At this time, the layered body can be shrunk in the width direction by drying shrinkage treatment to improve optical properties. This is because it can effectively improve the orientation of PVA and PVA/iodine complexes. The shrinkage rate in the width direction of the laminated body obtained by drying shrinkage treatment is preferably 2% to 10%, more preferably 2% to 8%, especially 4% to 6%. By using a heating roll, the laminated body can be continuously shrunk in the width direction while being conveyed, and high productivity can be realized.
圖2係顯示乾燥收縮處理之一例的概略圖。在乾燥收縮處理中,係利用已加熱至預定溫度的輸送輥R1~R6與導輥G1~G4來一邊輸送積層體200一邊使其乾燥。在圖式例中,係將輸送輥R1~R6配置成可交替連續加熱PVA樹脂層之面與熱塑性樹脂基材之面,但例如亦可將輸送輥R1~R6配置成僅連續加熱積層體200的其中一面(例如熱塑性樹脂基材面)。FIG. 2 is a schematic diagram showing an example of drying shrinkage treatment. In the drying shrinkage treatment, the
藉由調整輸送輥之加熱溫度(加熱輥之溫度)、加熱輥之數量及與加熱輥的接觸時間等,可控制乾燥條件。加熱輥之溫度宜為60℃~120℃,更宜為65℃~100℃,尤宜為70℃~80℃。可在可良好地增加熱塑性樹脂之結晶度而良好地抑制捲曲的同時,製造出耐久性極優異的光學積層體。另,加熱輥之溫度可以接觸式溫度計來測定。在圖式例中設置有6個輸送輥,惟輸送輥只要為複數個即無特別限制。輸送輥通常為2個~40個,較佳為設置4個~30個。積層體與加熱輥之接觸時間(總接觸時間)以1秒~300秒為宜,以1~20秒較佳,以1~10秒更佳。Drying conditions can be controlled by adjusting the heating temperature of the conveying rollers (the temperature of the heating rollers), the number of heating rollers, and the contact time with the heating rollers. The temperature of the heating roller is preferably 60°C to 120°C, more preferably 65°C to 100°C, and particularly preferably 70°C to 80°C. The crystallinity of the thermoplastic resin can be favorably increased, and curling can be favorably suppressed, and an optical laminate having extremely excellent durability can be produced. In addition, the temperature of the heating roller can be measured with a contact thermometer. In the illustrated example, six conveying rollers are provided, but there is no particular limitation as long as the number of conveying rollers is plural. The number of conveying rollers is usually 2 to 40, preferably 4 to 30. The contact time (total contact time) between the laminated body and the heating roller is preferably 1 to 300 seconds, preferably 1 to 20 seconds, and more preferably 1 to 10 seconds.
加熱輥可設置於加熱爐(例如烘箱)內,亦可設置於一般的製造產線(室溫環境下)。宜設置於具備送風機構的加熱爐內。藉由併用以加熱輥進行之乾燥與熱風乾燥,可抑制在加熱輥間急遽的溫度變化,而可容易控制寬度方向之收縮。熱風乾燥之溫度宜為30℃~100℃。且,熱風乾燥時間宜為1秒~300秒。熱風之風速宜為10m/s~30m/s左右。另,該風速係在加熱爐內之風速,可以迷你扇葉型數位風速計來測定。The heating roller can be installed in a heating furnace (eg, an oven), or can be installed in a general manufacturing line (at room temperature). It should be installed in a heating furnace with an air supply mechanism. The rapid temperature change between the heating rollers can be suppressed by combining the drying with the heating roller and the hot air drying, and the shrinkage in the width direction can be easily controlled. The temperature of hot air drying should be 30℃~100℃. In addition, the hot air drying time is preferably 1 second to 300 seconds. The wind speed of the hot air should be about 10m/s~30m/s. In addition, the wind speed is the wind speed in the heating furnace, which can be measured by a miniature fan-blade digital anemometer.
宜在水中延伸處理之後且在乾燥收縮處理之前,施行洗淨處理。上述洗淨處理代表上可藉由使PVA系樹脂層浸漬於碘化鉀水溶液中來進行。It is preferable to perform a washing treatment after the stretching treatment in water and before the drying shrinkage treatment. The above-mentioned cleaning treatment can be typically performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
依上述方式可獲得熱塑性樹脂基材/偏光件之積層體。In the above manner, a laminate of thermoplastic resin substrate/polarizer can be obtained.
D-2.偏光板之製造方法 可於上述D-1項所得積層體表面(例如偏光件表面)塗佈包含具有聯苯骨架之環氧樹脂及硬化劑之組成物而形成塗膜,並使該塗膜硬化藉此形成保護層。在一實施形態中,保護層為陽離子聚合硬化物。在該實施形態中,可使用光陽離子聚合引發劑作為硬化劑。可將包含具有聯苯骨架之環氧樹脂與光陽離子聚合引發劑之組成物塗佈於積層體表面(例如偏光件表面)而形成塗膜,再對該塗膜照射光(例如紫外線)藉此形成保護層。D-2. Manufacturing method of polarizing plate A coating film can be formed by coating a composition comprising an epoxy resin having a biphenyl skeleton and a hardener on the surface of the laminate obtained in the above item D-1 (eg, the surface of a polarizer), and curing the coating film to form a protective layer . In one embodiment, the protective layer is a cationic polymer cured product. In this embodiment, a photocationic polymerization initiator can be used as a hardener. A composition comprising an epoxy resin having a biphenyl skeleton and a photocationic polymerization initiator can be coated on the surface of the laminate (such as the surface of the polarizer) to form a coating film, and then the coating film can be irradiated with light (such as ultraviolet rays) to thereby form a protective layer.
上述組成物中所含溶劑可使用可將具有聯苯骨架之環氧樹脂及硬化劑溶解或均勻分散之任意適當之溶劑。溶劑之具體例可舉乙酸乙酯、甲苯、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、環戊酮、環己酮。Any appropriate solvent that can dissolve or uniformly disperse the epoxy resin having a biphenyl skeleton and the hardener can be used as the solvent contained in the above-mentioned composition. Specific examples of the solvent include ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone.
溶液之環氧樹脂濃度相對於溶劑100重量份宜為10重量份~30重量份。只要為所述樹脂濃度,便可形成密著於偏光件且均勻的塗佈膜。又,硬化劑之含量如上述C項所述。The epoxy resin concentration of the solution is preferably 10 parts by weight to 30 parts by weight relative to 100 parts by weight of the solvent. As long as it is the said resin density|concentration, a uniform coating film which adheres to a polarizer can be formed. In addition, the content of the hardener is as described in the above-mentioned item C.
溶液可塗佈於任意適當之基材上,亦可塗佈於偏光件上。當將溶液塗佈於基材時,形成於基材上之塗佈膜的硬化物會轉印至偏光件上。當將溶液塗佈於偏光件時,例如藉由光照射使塗佈膜硬化,藉此於偏光件上直接形成保護層。較佳為溶液塗佈於偏光件上,而於偏光件上直接形成保護層。只要為所述構成,便可省略轉印所需之接著劑層或黏著劑層,故可使偏光板更薄。溶液之塗佈方法可採用任意適當的方法。具體例可列舉輥塗法、旋塗法、線棒塗佈法、浸塗法、模塗法、簾塗法、噴塗法、刮刀塗佈法(缺角輪塗佈法等)。The solution can be coated on any suitable substrate, and can also be coated on the polarizer. When the solution is applied to the substrate, the cured product of the coating film formed on the substrate is transferred to the polarizer. When the solution is applied to the polarizer, for example, the coating film is hardened by light irradiation, whereby a protective layer is directly formed on the polarizer. Preferably, the solution is coated on the polarizer, and the protective layer is directly formed on the polarizer. With the above-described configuration, the adhesive layer or the adhesive layer required for transfer can be omitted, so that the polarizing plate can be made thinner. Any appropriate method can be adopted for the coating method of the solution. Specific examples thereof include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and blade coating (cut-off wheel coating, etc.).
藉由光照射使塗佈膜硬化時,可使用任意適當之光源以成為任意適當之照射量之方式對塗佈膜照射光(代表上為紫外線)。紫外線之光源例如可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、無電極燈、鹵素燈、碳弧燈、氙燈、金屬鹵素燈、化學燈、黑光燈、LED燈等。紫外線之照射量例如為2mJ/cm2 ~3000mJ/cm2 ,宜為10mJ/cm2 ~2000mJ/cm2 。具體上,在使用高壓水銀燈作為光源時,照射量通常係在5mJ/cm2 ~3000mJ/cm2 、較宜在50mJ/cm2 ~2000mJ/cm2 之條件下進行。使用無電極燈作為光源時,照射量通常係在2mJ/cm2 ~2000mJ/cm2 、較宜在10mJ/cm2 ~1000mJ/cm2 之條件下進行。When hardening the coating film by light irradiation, light (representatively ultraviolet rays) can be irradiated to the coating film so as to have any appropriate irradiation amount using any appropriate light source. As the light source of ultraviolet rays, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, halogen lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, black light lamps, and LED lamps can be used. For example, the amount of ultraviolet radiation 2mJ / cm 2 ~ 3000mJ / cm 2, is suitably 10mJ / cm 2 ~ 2000mJ / cm 2. Specifically, when a high pressure mercury lamp as a light source, the irradiation dose is usually based 5mJ / cm 2 ~ 3000mJ / cm 2, more suitably carried out at 50mJ / cm 2 ~ 2000mJ / cm 2 of conditions. When using electrodeless lamp as a light source, the irradiation dose is usually based 2mJ / cm 2 ~ 2000mJ / cm 2, more suitably carried out at 10mJ / cm 2 ~ 1000mJ / cm 2 of conditions.
照射時間可因應光源之種類、光源與塗佈面之距離、塗佈厚度及其他條件設定成任意適當之值。照射時間通常為數秒~數十秒,亦可為數分之1秒。光之照射可從任意適當之方向照射。由防止不均勻硬化之觀點下,宜從保護層形成用組成物之塗敷面側照射。The irradiation time can be set to any appropriate value according to the type of the light source, the distance between the light source and the coating surface, the coating thickness and other conditions. The irradiation time is usually several seconds to several tens of seconds, and may also be a fraction of a second. The irradiation of light may be irradiated from any suitable direction. From the viewpoint of preventing uneven hardening, it is preferable to irradiate from the coating surface side of the composition for forming a protective layer.
利用紫外線照射等光照射進行曝光後,為了使光反應進行之硬化結束,亦可進一步施行加熱處理。加熱處理可在任意適當之溫度及時間下進行。加熱溫度例如為80℃~250℃,宜為100℃~150℃。加熱時間例如為10秒~2小時,宜為5分鐘~1小時。After exposure by light irradiation such as ultraviolet irradiation, a heat treatment may be further performed in order to complete curing by photoreaction. The heat treatment can be performed at any appropriate temperature and time. The heating temperature is, for example, 80°C to 250°C, preferably 100°C to 150°C. The heating time is, for example, 10 seconds to 2 hours, preferably 5 minutes to 1 hour.
依以上方式形成保護層,結果可獲得熱塑性樹脂基材/偏光件/保護層之積層體。藉由從該積層體剝離熱塑性樹脂基材,可獲得如圖1所示之具有偏光件10與保護層20之偏光板。或者,亦可於熱塑性樹脂基材/偏光件之積層體的偏光件表面貼合構成另一保護層之樹脂薄膜,接著剝離熱塑性樹脂基材,並於該剝離面形成保護層。此時,可獲得更具有另一保護層之偏光板。As a result of forming the protective layer in the above manner, a laminate of thermoplastic resin substrate/polarizer/protective layer can be obtained. By peeling the thermoplastic resin base material from the laminate, a polarizing plate having the
E.附相位差層之偏光板
E-1.附相位差層之偏光板的概要
本發明一實施形態中,可提供一種附相位差層之偏光板。該附相位差層之偏光板於上述偏光板之未配置有保護層之面更具有相位差層。圖3係本發明一實施形態之附相位差層之偏光板的概略截面圖。圖式例之附相位差層之偏光板110具有:偏光件10、配置於偏光件10之一側的保護層20與配置於偏光件10之另一側的相位差層40。偏光件10與保護層20係構成上述偏光板。因此,附相位差層之偏光板具有偏光板與相位差層,該偏光板包含偏光件與配置於該偏光件之一側的保護層,而該相位差層配置於該偏光板之與該保護層相反之側。偏光板亦可因應需求在偏光件10之與保護層20相反之側更包含有另一保護層(未圖示)。換言之,附相位差層之偏光板110亦可於偏光件10與相位差層40之間更包含有另一保護層(未圖示)。如上述,亦可於保護層之偏光件側形成有易接著層。易接著層可利用任意適當之方法與偏光件積層。例如亦可直接形成於偏光件上,或可透過任意適當之黏著劑層或接著劑層積層。E. Polarizing plate with retardation layer
E-1. Outline of polarizing plate with retardation layer
In one embodiment of the present invention, a polarizing plate with a retardation layer can be provided. The polarizing plate with retardation layer further has a retardation layer on the surface of the polarizing plate that is not provided with the protective layer. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. The
圖3所示實施形態中,相位差層40為單一層。此時,相位差層40之Re(550)例如為100nm~190nm,相位差層40的慢軸與偏光件10的吸收軸形成之角度例如為40°~50°。此時,較佳為於相位差層40之外側(與偏光件10相反之側)設置另一相位差層(未圖示)。另一相位差層代表上折射率特性展現nz>nx=ny之關係。或是如圖4所示,另一實施形態之附相位差層之偏光板111中,相位差層40具有第1層41與第2層42的積層結構。此時,第1層41之Re(550)例如為200nm~300nm,且第1層41的慢軸與偏光件10的吸收軸形成之角度例如為10°~20°;第2層42之Re(550)例如為100nm~190nm,且第2層42的慢軸與偏光件10的吸收軸形成之角度為例如70°~80°。不論為何種實施形態,相位差層40可為樹脂薄膜,亦可為液晶化合物之定向固化層。相位差層40具有積層結構時,代表上第1層41及第2層42分別為樹脂薄膜或液晶化合物之定向固化層。In the embodiment shown in FIG. 3, the
E-2.以單一層構成之相位差層
相位差層以單一層構成時,該相位差層如上述其Re(550)例如為100nm~190nm,且相位差層40的慢軸與偏光件10的吸收軸形成之角度例如為40°~50°。相位差層代表上係為了賦予偏光板抗反射特性而設置,在一實施形態中可作為λ/4板發揮功能。相位差層如上述可為樹脂薄膜,亦可為液晶化合物之定向固化層。E-2. A retardation layer composed of a single layer
When the retardation layer is composed of a single layer, the Re(550) of the retardation layer is, for example, 100 nm to 190 nm as described above, and the angle formed by the slow axis of the
相位差層較佳為折射率特性展現nx>ny≧nz之關係。相位差層之面內相位差Re(550)如上述例如為100nm~190nm,宜為110nm~170nm,較宜為130nm~160nm。此外,在此「ny=nz」不只ny與nz完全相同之情況,還包含實質上相同之情況。因此,在不損及本發明效果之範圍下可有成為ny<nz之情形。The retardation layer preferably exhibits the relationship of nx>ny≧nz in refractive index characteristics. As mentioned above, the in-plane retardation Re(550) of the retardation layer is, for example, 100 nm to 190 nm, preferably 110 nm to 170 nm, and more preferably 130 nm to 160 nm. In addition, "ny=nz" here includes not only the case where ny and nz are completely identical, but also the case where they are substantially the same. Therefore, in the range which does not impair the effect of this invention, there may be a case where ny<nz is satisfied.
相位差層之Nz係數宜為0.9~3,較宜為0.9~2.5,更宜為0.9~1.5,0.9~1.3尤佳。藉由滿足所述關係,在將所得附相位差層之偏光板使用於影像顯示裝置時,可達成非常優異之反射色相。The Nz coefficient of the retardation layer is preferably 0.9~3, more preferably 0.9~2.5, more preferably 0.9~1.5, preferably 0.9~1.3. By satisfying the above relationship, when the obtained polarizing plate with retardation layer is used in an image display device, a very excellent reflection hue can be achieved.
相位差層40的慢軸與偏光件10的吸收軸形成之角度θ如上述例如為40°~50°,宜為42°~48°,更宜為約45°。只要角度θ在所述範圍內,藉由將相位差層製成λ/4板,可獲得具有非常優異圓偏光特性(以結果而言為非常優異的抗反射特性)的附相位差層之偏光板。The angle θ formed by the slow axis of the
相位差層可展現相位差值隨測定光之波長變大的逆分散波長特性,亦可展現相位差值隨測定光之波長變小的正波長分散特性,又可展現相位差值幾乎不隨測定光之波長變化的平坦的波長分散特性。在一實施形態中,相位差層展現逆分散波長特性。此時,相位差層之Re(450)/Re(550)宜為0.8以上且小於1,較宜為0.8以上且0.95以下。只要為所述構成,便可實現非常優異的抗反射特性。The retardation layer can exhibit a reverse dispersion wavelength characteristic in which the retardation value increases with the wavelength of the measurement light, and a positive wavelength dispersion characteristic in which the retardation value becomes smaller with the wavelength of the measurement light, and can also exhibit a retardation value that hardly changes with the measurement light. Flat wavelength dispersion characteristics of light wavelength variation. In one embodiment, the retardation layer exhibits reverse dispersion wavelength characteristics. At this time, Re(450)/Re(550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With the above-described configuration, very excellent antireflection properties can be achieved.
相位差層包含光彈性係數的絕對值宜為2.0×10-11 m2 /N以下、較宜為2.0×10-13 m2 /N~1.5×10-11 m2 /N、更宜為1.0×10-12 m2 /N~1.2×10-11 m2 /N之樹脂。光彈性係數的絕對值只要在所述範圍內,加熱時產生收縮應力時便不易產生相位差變化。結果,可良好地防止所得影像顯示裝置的熱不均。The absolute value of the photoelastic coefficient contained in the retardation layer is preferably 2.0×10 -11 m 2 /N or less, preferably 2.0×10 -13 m 2 /N~1.5×10 -11 m 2 /N, more preferably 1.0 Resin of ×10 -12 m 2 /N~1.2×10 -11 m 2 /N. As long as the absolute value of the photoelastic coefficient is within the above-mentioned range, a change in phase difference hardly occurs when shrinkage stress is generated during heating. As a result, thermal unevenness of the resulting image display device can be well prevented.
E-2-1.樹脂薄膜 相位差層為樹脂薄膜時,該樹脂薄膜代表上為延伸薄膜。此時,相位差層之厚度宜為60µm以下,較宜為30µm~55µm。相位差層之厚度只要在所述範圍內,便可良好地抑制加熱時之捲曲,同時可良好地調整貼合時之捲曲。E-2-1. Resin film When the retardation layer is a resin film, the resin film is typically a stretched film. At this time, the thickness of the retardation layer is preferably 60µm or less, preferably 30µm~55µm. As long as the thickness of the retardation layer is within the above-mentioned range, the curl at the time of heating can be suppressed favorably, and the curl at the time of lamination can be adjusted favorably.
相位差層可以可滿足上述特性之任意適當之樹脂薄膜構成。所述樹脂之代表例可舉聚碳酸酯系樹脂、聚酯碳酸酯系樹脂、聚酯系樹脂、聚乙烯縮醛系樹脂、聚芳酯系樹脂、環狀烯烴系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚醚系樹脂、聚苯乙烯系樹脂、丙烯酸系樹脂。該等樹脂可單獨使用,亦可組合(例如摻合、共聚)來使用。相位差層以顯示逆分散波長特性之樹脂薄膜構成時,可適宜使用聚碳酸酯系樹脂或聚酯碳酸酯系樹脂(以下有僅稱作聚碳酸酯系樹脂之情形)。The retardation layer may be composed of any appropriate resin film that can satisfy the above-mentioned properties. Representative examples of the resins include polycarbonate-based resins, polyester carbonate-based resins, polyester-based resins, polyvinyl acetal-based resins, polyarylate-based resins, cyclic olefin-based resins, cellulose-based resins, Polyvinyl alcohol-based resin, polyamide-based resin, polyimide-based resin, polyether-based resin, polystyrene-based resin, and acrylic resin. These resins may be used alone or in combination (eg, blending, copolymerization). When the retardation layer is formed of a resin film exhibiting reverse dispersion wavelength characteristics, a polycarbonate-based resin or a polyester-carbonate-based resin (hereinafter referred to only as a polycarbonate-based resin) can be suitably used.
只要可獲得本發明之效果,上述聚碳酸酯系樹脂便可使用任意適當之聚碳酸酯系樹脂。例如,聚碳酸酯系樹脂包含源自茀系二羥基化合物之結構單元、源自異山梨醇系二羥基化合物之結構單元及源自選自於由脂環式二醇、脂環式二甲醇、二、三或聚乙二醇、以及伸烷基二醇或螺甘油所構成群組中之至少1種二羥基化合物之結構單元。聚碳酸酯系樹脂宜包含源自茀系二羥基化合物之結構單元、源自異山梨醇系二羥基化合物之結構單元、源自脂環式二甲醇之結構單元以及/或是源自二、三或聚乙二醇之結構單元;更宜包含源自茀系二羥基化合物之結構單元、源自異山梨醇系二羥基化合物之結構單元與源自二、三或聚乙二醇之結構單元。聚碳酸酯系樹脂亦可因應需要包含有源自其他二羥基化合物之結構單元。此外,本發明可適宜使用之聚碳酸酯系樹脂的詳細內容例如記載於日本專利特開2014-10291號公報、日本專利特開2014-26266號公報、日本專利特開2015-212816號公報、日本專利特開2015-212817號公報、日本專利特開2015-212818號公報中,而本說明書即援用該記載作為參考。As long as the effect of the present invention can be obtained, any appropriate polycarbonate-based resin can be used as the above-mentioned polycarbonate-based resin. For example, the polycarbonate-based resin contains a structural unit derived from a perylene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from the group consisting of alicyclic diol, alicyclic dimethanol, A structural unit of at least one dihydroxy compound in the group consisting of di-, tri- or polyethylene glycol, and alkylene glycol or spiroglycerol. The polycarbonate resin preferably contains a structural unit derived from a perylene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, a structural unit derived from alicyclic dimethanol, and/or a structural unit derived from di- or tri-dihydroxyl compounds. or a structural unit of polyethylene glycol; more preferably, it includes a structural unit derived from a perylene dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from di-, tri- or polyethylene glycol. The polycarbonate-based resin may also contain structural units derived from other dihydroxy compounds as required. In addition, the details of the polycarbonate-based resin that can be suitably used in the present invention are described in, for example, Japanese Patent Laid-Open No. 2014-10291, Japanese Patent Laid-Open No. 2014-26266, Japanese Patent Laid-Open No. 2015-212816, In Unexamined-Japanese-Patent No. 2015-212817 and Unexamined-Japanese-Patent No. 2015-212818, the description is incorporated herein by reference.
上述聚碳酸酯系樹脂的玻璃轉移溫度宜為110℃以上且150℃以下,較宜為120℃以上且140℃以下。玻璃轉移溫度若過低,耐熱性有變差之傾向,而有在薄膜成形後造成尺寸變化之可能性,或有降低所得有機EL面板之影像品質的情況。玻璃轉移溫度若過高,有薄膜成形時之成形穩定性變差之情況,或有損及薄膜之透明性之情況。此外,玻璃轉移溫度可依循JIS K 7121(1987)求得。The glass transition temperature of the polycarbonate-based resin is preferably 110°C or higher and 150°C or lower, and more preferably 120°C or higher and 140°C or lower. If the glass transition temperature is too low, the heat resistance tends to be deteriorated, and there is a possibility of dimensional change after film forming, or the image quality of the obtained organic EL panel may be lowered. If the glass transition temperature is too high, the forming stability of the film may be deteriorated, or the transparency of the film may be impaired. In addition, the glass transition temperature can be calculated|required according to JIS K 7121 (1987).
上述聚碳酸酯系樹脂的分子量可以比濃黏度表示。比濃黏度係用二氯甲烷作為溶劑,將聚碳酸酯濃度精密調製成0.6g/dL後,在溫度20.0℃±0.1℃下用烏氏黏度管進行測定。比濃黏度通常宜為0.30dL/g以上,較宜為0.35dL/g以上。又,還原黏度通常宜為1.20dL/g以下,較宜為1.00dL/g以下,更宜為0.80dL/g以下。比濃黏度若小於0.30dL/g,有產生成形品之機械強度變小之問題的情形。另一方面,比濃黏度若大於1.20dL/g,有成形時之流動性降低,而產生生產性或成形性降低之問題的情形。The molecular weight of the above-mentioned polycarbonate resin can be represented by a reduced viscosity. The reduced viscosity was measured with an Ubbelohde viscometer at a temperature of 20.0°C ± 0.1°C after precisely adjusting the polycarbonate concentration to 0.6 g/dL using dichloromethane as a solvent. The reduced viscosity should normally be above 0.30dL/g, preferably above 0.35dL/g. In addition, the reduced viscosity is usually preferably 1.20 dL/g or less, more preferably 1.00 dL/g or less, and more preferably 0.80 dL/g or less. If the reduced viscosity is less than 0.30 dL/g, there may be a problem that the mechanical strength of the molded product is reduced. On the other hand, if the reduced viscosity exceeds 1.20 dL/g, the fluidity at the time of molding may be lowered, and the productivity or formability may be lowered.
聚碳酸酯系樹脂薄膜亦可使用市售薄膜。市售品之具體例可舉帝人公司製之商品名「PURE-ACE WR-S」、「PURE-ACE WR-W」、「PURE-ACE WR-M」、日東電工公司製之商品名「NRF」。A commercially available film can also be used for the polycarbonate-based resin film. Specific examples of commercially available products include "PURE-ACE WR-S", "PURE-ACE WR-W", "PURE-ACE WR-M" manufactured by Teijin Corporation, and "NRF" manufactured by Nitto Denko Corporation. ".
相位差層40例如可藉由將由上述聚碳酸酯系樹脂形成之薄膜延伸而得。由聚碳酸酯系樹脂形成薄膜之方法可採用任意適當之成形加工法。具體例可舉:壓縮成形法、轉注成形法、射出成形法、擠製成形法、吹氣成形法、粉末成形法、FRP成形法、澆鑄塗敷法(例如流延法)、砑光成形法、熱壓法等。而宜為擠製成形法或澆鑄塗敷法。其係因可提高所得薄膜之平滑性,從而可獲得良好的光學均一性。成形條件可因應使用之樹脂的組成或種類、對相位差層所期望之特性等來適當設定。此外,如上述,聚碳酸酯系樹脂在市面上販售有很多薄膜製品,故可將該市售薄膜直接供於延伸處理。The
樹脂薄膜(未延伸薄膜)的厚度可因應相位差層所期望的厚度、所期望的光學特性、後述延伸條件等設定成任意適當之值。宜為50µm~300µm。The thickness of the resin film (unstretched film) can be set to any appropriate value according to the desired thickness of the retardation layer, desired optical properties, stretching conditions described later, and the like. It should be 50µm~300µm.
上述延伸可採用任意適當之延伸方法、延伸條件(例如延伸溫度、延伸倍率、延伸方向)。具體而言,可單獨使用自由端延伸、固定端延伸、自由端收縮、固定端收縮等各種延伸方法,亦可同時或逐次使用。關於延伸方向,亦可沿長度方向、寬度方向、厚度方向、斜向等各種方向或維度進行。延伸的溫度相對於樹脂薄膜的玻璃轉移溫度(Tg)宜為Tg-30℃~Tg+60℃,較宜為Tg-10℃~Tg+50℃。Any appropriate stretching method and stretching conditions (eg, stretching temperature, stretching ratio, stretching direction) can be used for the above-mentioned stretching. Specifically, various extension methods such as free-end extension, fixed-end extension, free-end shrinkage, and fixed-end shrinkage can be used alone, or they can be used simultaneously or sequentially. The extending direction may be carried out in various directions or dimensions such as the longitudinal direction, the width direction, the thickness direction, and the diagonal direction. The stretching temperature is preferably Tg-30°C to Tg+60°C, preferably Tg-10°C to Tg+50°C, relative to the glass transition temperature (Tg) of the resin film.
藉由適當選擇上述延伸方法、延伸條件,可獲得具有上述所期望之光學特性(例如折射率特性、面內相位差、Nz係數)的相位差薄膜。By appropriately selecting the above-described stretching method and stretching conditions, a retardation film having the above-described desired optical properties (eg, refractive index properties, in-plane retardation, and Nz coefficient) can be obtained.
在一實施形態中,相位差薄膜可藉由將樹脂薄膜進行單軸延伸或固定端單軸延伸來製作。固定端單軸延伸之具體例,可舉一邊使樹脂薄膜在長邊方向上移動,一邊往寬度方向(橫向)進行延伸之方法。延伸倍率宜為1.1倍~3.5倍。In one embodiment, the retardation film can be produced by uniaxially extending a resin film or by uniaxially extending a fixed end. A specific example of the uniaxial stretching at the fixed end includes a method of stretching the resin film in the width direction (horizontal direction) while moving the resin film in the longitudinal direction. The extension ratio should be 1.1 times to 3.5 times.
在另一實施形態中,相位差薄膜可藉由將長條狀樹脂薄膜往相對於長邊方向呈上述角度θ之方向連續進行斜向延伸來製作。藉由採用斜向延伸,可獲得相對於薄膜之長邊方向具有角度θ之定向角(於角度θ之方向上具有慢軸)的長條狀延伸薄膜,例如在與偏光件積層時,可進行捲對捲,從而可簡化製造步驟。此外,角度θ可為附相位差層之偏光板中偏光件的吸收軸與相位差層的慢軸形成之角度。角度θ如上述,宜為40°~50°,較宜為42°~48°,更宜為約45°。In another embodiment, the retardation film can be produced by continuously extending the elongated resin film obliquely in the direction of the above-mentioned angle θ with respect to the longitudinal direction. By adopting oblique stretching, a long stretched film with an orientation angle of angle θ (with a slow axis in the direction of angle θ) can be obtained with respect to the longitudinal direction of the film. For example, when laminating with a polarizer, it can be Roll-to-roll, which simplifies manufacturing steps. In addition, the angle θ may be the angle formed by the absorption axis of the polarizer and the slow axis of the retardation layer in the polarizing plate with retardation layer. As mentioned above, the angle θ is preferably 40° to 50°, more preferably 42° to 48°, and more preferably about 45°.
斜向延伸所用延伸機可舉拉幅式延伸機,其係例如對橫向及/或縱向附加左右相異之速度的輸送力或是拉伸力或拉抽力者。拉幅式延伸機有橫式單軸延伸機、同時雙軸延伸機等,只要可將長條狀樹脂薄膜連續地進行斜向延伸,便可使用任意適當的延伸機。The stretching machine used for the oblique stretching can be a tenter-type stretching machine, which is, for example, adding a conveying force, a stretching force, or a pulling force to the transverse direction and/or the longitudinal direction with different speeds on the left and right. As tenter stretching machines, there are horizontal uniaxial stretching machines, simultaneous biaxial stretching machines, and the like, and any appropriate stretching machine can be used as long as the elongated resin film can be continuously stretched obliquely.
藉由將上述延伸機中之左右速度分別適當控制,可獲得具有上述所期望之面內相位差且於上述所期望之方向上具有慢軸之相位差層(實質上為長條狀相位差薄膜)。By appropriately controlling the left and right speeds in the above-mentioned stretching machine, a retardation layer (substantially an elongated retardation film) having the above-mentioned desired in-plane retardation and having a slow axis in the above-mentioned desired direction can be obtained. ).
上述薄膜的延伸溫度可因應對相位差層期望之面內相位差值及厚度、所使用之樹脂的種類、所使用之薄膜的厚度、延伸倍率等變化。具體而言,延伸溫度宜為Tg-30℃~Tg+30℃,更宜為Tg-15℃~Tg+15℃,最宜為Tg-10℃~Tg+10℃。藉由以所述溫度延伸,可獲得具有適於本發明之特性的相位差層。此外,Tg係薄膜之構成材料的玻璃轉移溫度。The stretching temperature of the film can be changed according to the desired in-plane retardation value and thickness of the retardation layer, the type of resin used, the thickness of the film used, the stretching ratio, and the like. Specifically, the extension temperature is preferably Tg-30°C to Tg+30°C, more preferably Tg-15°C to Tg+15°C, and most preferably Tg-10°C to Tg+10°C. By extending at the above temperature, a retardation layer having characteristics suitable for the present invention can be obtained. In addition, Tg is the glass transition temperature of the constituent material of the thin film.
E-2-2.液晶化合物之定向固化層 相位差層為液晶化合物之定向固化層時,藉由使用液晶化合物,可使所得相位差層的nx與ny之差比非液晶材料大上甚多,因此可使用以獲得期望之面內相位差之相位差層的厚度小上甚多。結果可實現附相位差層之偏光板進一步之薄型化。本說明書中所謂「定向固化層」係指液晶化合物在層內於預定方向定向,且其定向狀態已受固定之層。另外,「定向固化層」之概念包含如後述使液晶單體硬化而得的定向硬化層。在本實施形態中,代表上係棒狀液晶化合物在相位差層之慢軸方向上排列之狀態下定向(沿面定向)。E-2-2. Directionally cured layer of liquid crystal compound When the retardation layer is a directionally cured layer of liquid crystal compound, by using the liquid crystal compound, the difference between nx and ny of the obtained retardation layer can be much larger than that of the non-liquid crystal material, so it can be used to obtain the desired in-plane retardation The thickness of the retardation layer is much smaller. As a result, further thinning of the polarizing plate with retardation layer can be realized. The term "orientation-cured layer" in this specification refers to a layer in which the liquid crystal compound is oriented in a predetermined direction within the layer, and the orientation state thereof has been fixed. In addition, the concept of "orientation hardening layer" includes the orientation hardening layer obtained by hardening a liquid crystal monomer as mentioned later. In the present embodiment, the upper rod-like liquid crystal compound is aligned in the state of alignment in the slow axis direction of the retardation layer (grain alignment).
液晶化合物可舉例如液晶相為向列相之液晶化合物(向列型液晶)。這種液晶化合物例如可使用液晶聚合物或液晶單體。液晶化合物之液晶性的表現機構可為溶致亦可為熱致。液晶聚合物及液晶單體各自可單獨使用,亦可組合使用。As a liquid crystal compound, the liquid crystal compound (nematic liquid crystal) whose liquid crystal phase is a nematic phase is mentioned, for example. As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The expression mechanism of the liquid crystallinity of the liquid crystal compound may be lyotropic or thermotropic. Each of the liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
液晶化合物為液晶單體時,該液晶單體宜為聚合性單體及交聯性單體。其係因藉由使液晶單體聚合或交聯(亦即硬化)可固定液晶單體的定向狀態之故。在使液晶單體定向之後,例如只要使液晶單體彼此聚合或交聯,便可藉此固定上述定向狀態。在此係藉由聚合來形成聚合物,藉由交聯來形成3維網目結構,而該等為非液晶性。因此,所形成之相位差層例如不會發生液晶性化合物特有之因溫度變化而轉變為液晶相、玻璃相、結晶相之情形。結果相位差層會成為不受溫度變化影響而穩定性極優異的相位差層。When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the orientation state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (ie, hardening) the liquid crystal monomer. After the liquid crystal monomers are aligned, for example, the above-mentioned alignment state can be fixed by polymerizing or crosslinking the liquid crystal monomers with each other. Here, a polymer is formed by polymerization, a 3-dimensional mesh structure is formed by cross-linking, and these are non-liquid crystalline. Therefore, the formed retardation layer does not change into a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change, which is peculiar to a liquid crystal compound, for example. As a result, the retardation layer becomes a retardation layer which is not affected by temperature changes and has excellent stability.
液晶單體展現液晶性之溫度範圍會因其種類而異。具體來說,該溫度範圍宜為40℃~120℃,更宜為50℃~100℃,最宜為60℃~90℃。The temperature range in which the liquid crystal monomer exhibits liquid crystallinity varies depending on the type. Specifically, the temperature range is preferably 40°C to 120°C, more preferably 50°C to 100°C, and most preferably 60°C to 90°C.
上述液晶單體可採用任意適當之液晶單體。例如可使用日本專利特表2002-533742(WO00/37585)、EP358208(US5211877)、EP66137(US4388453)、WO93/22397、EP0261712、DE19504224、DE4408171及GB2280445等所記載之聚合性液晶原化合物等。所述聚合性液晶原化合物之具體例可舉例如BASF公司之商品名LC242、Merck公司之商品名E7、Wacker-Chem公司之商品名LC-Sillicon-CC3767。液晶單體宜為例如向列性液晶單體。Any appropriate liquid crystal monomer can be used as the above-mentioned liquid crystal monomer. For example, polymerizable mesogenic compounds described in Japanese Patent Application Laid-Open No. 2002-533742 (WO00/37585), EP358208 (US5211877), EP66137 (US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445 and the like can be used. Specific examples of the polymerizable mesogen compound include BASF's trade name LC242, Merck's trade name E7, and Wacker-Chem's trade name LC-Silicon-CC3767. The liquid crystal monomer is preferably, for example, a nematic liquid crystal monomer.
液晶化合物之定向固化層可藉由以下方式來形成:對預定基材之表面施行定向處理,並於該表面塗敷含液晶化合物的塗敷液,使該液晶化合物於對應上述定向處理之方向定向,並固定該定向狀態。在一實施形態中,基材為任意適當之樹脂薄膜,而形成於該基材上的定向固化層可轉印至偏光件10之表面。在另一實施形態中,基材可為另一保護層。此時會省略轉印步驟,而可在形成定向固化層(相位差層)後接續以捲對捲方式進行積層,因此可更提升生產性。The alignment curing layer of the liquid crystal compound can be formed by the following method: performing alignment treatment on the surface of a predetermined substrate, and coating the surface with a coating liquid containing the liquid crystal compound, so that the liquid crystal compound is aligned in the direction corresponding to the above alignment treatment , and fix the orientation state. In one embodiment, the base material is any suitable resin film, and the orientation cured layer formed on the base material can be transferred to the surface of the
上述定向處理可採用任意適當之定向處理。具體可舉機械性定向處理、物理性定向處理、化學性定向處理。機械性定向處理的具體例可舉磨擦處理、延伸處理。物理性定向處理的具體例可舉磁場定向處理、電場定向處理。化學性定向處理的具體例可舉斜向蒸鍍法、光定向處理。各種定向處理的處理條件可按目的採用任意適當之條件。The above-mentioned orientation process can adopt any suitable orientation process. Specifically, a mechanical orientation treatment, a physical orientation treatment, and a chemical orientation treatment can be mentioned. Specific examples of the mechanical orientation treatment include rubbing treatment and stretching treatment. Specific examples of the physical alignment treatment include magnetic field alignment treatment and electric field alignment treatment. Specific examples of the chemical alignment treatment include oblique vapor deposition and photo alignment treatment. The treatment conditions for the various orientation treatments can be any appropriate conditions according to the purpose.
液晶化合物的定向可因應液晶化合物的種類於可展現液晶相之溫度下進行處理來進行。藉由進行所述溫度處理,液晶化合物會變為液晶狀態,而該液晶化合物會因應基材表面之定向處理方向而定向。The alignment of the liquid crystal compound can be performed by processing at a temperature at which a liquid crystal phase can be exhibited according to the type of the liquid crystal compound. By performing the temperature treatment, the liquid crystal compound becomes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the surface of the substrate.
在一實施形態中,定向狀態之固定係藉由冷卻依上述方式定向之液晶化合物來進行。當液晶化合物為聚合性單體或交聯性單體時,定向狀態之固定係藉由對依上述方式定向之液晶化合物施行聚合處理或交聯處理來進行。In one embodiment, the fixation of the alignment state is performed by cooling the liquid crystal compound aligned in the above-described manner. When the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the orientation state is fixed by subjecting the liquid crystal compound oriented in the above-described manner to a polymerization treatment or a crosslinking treatment.
液晶化合物之具體例及定向固化層的形成方法的詳細內容記載於日本專利特開2006-163343號公報中。本說明書中係援用該公報之記載作為參考。Specific examples of the liquid crystal compound and details of the method for forming the alignment cured layer are described in Japanese Patent Laid-Open No. 2006-163343. In this specification, the description of this gazette is used as a reference.
定向固化層之另一例可舉盤狀液晶化合物在垂直定向、混合定向及傾斜定向之任一狀態下定向之形態。盤狀液晶化合物在代表上係盤狀液晶化合物之圓盤面相對於相位差層之薄膜面實質上垂直定向。所謂盤狀液晶化合物實質上垂直意指薄膜面與盤狀液晶化合物之圓盤面形成之角度的平均值宜為70°~90°,較宜為80°~90°,更宜為85°~90°。所謂盤狀液晶化合物一般而言係指一種具有圓盤狀分子結構的液晶化合物,該圓盤狀分子結構是將如苯、1,3,5-三𠯤、杯芳烴等之環狀母核配置於分子中心,且直鏈烷基、烷氧基、取代苄醯氧基等作為其側鏈呈放射狀取代者。盤狀液晶之代表例可舉:C.Destrade等人之研究報告,Mol.Cryst.Liq.Cryst.第71期第111頁(1981年)所記載之苯衍生物、聯伸三苯衍生物、參茚并苯衍生物、酞青素衍生物;B.Kohne等人之研究報告,Angew.Chem.第96期第70頁(1984年)所記載之環己烷衍生物;以及J.M.Lehn等人之研究報告,J.Chem.Soc.Chem.Commun.第1794頁(1985年)、J.Zhang等人之研究報告,J.Am.Chem.Soc.第116期第2655頁(1994年)所記載之氮雜冠醚系或苯乙炔系的大環。盤狀液晶化合物的更多具體例可舉例如日本專利特開2006-133652號公報、日本專利特開2007-108732號公報、日本專利特開2010-244038號公報所記載之化合物。本說明書中係援用上述文獻及公報之記載作為參考。Another example of the alignment cured layer includes a form in which the discotic liquid crystal compound is aligned in any state of vertical alignment, hybrid alignment, and oblique alignment. The discotic liquid crystalline compound is oriented substantially perpendicularly with respect to the film surface of the retardation layer on the surface of the disk representing the upper discotic liquid crystalline compound. The so-called discotic liquid crystal compound is substantially vertical means that the average value of the angle formed by the film surface and the disc surface of the discotic liquid crystal compound is preferably 70°~90°, more preferably 80°~90°, more preferably 85°~ 90°. The so-called discotic liquid crystal compound generally refers to a liquid crystal compound with a discotic molecular structure, and the discotic molecular structure is configured by cyclic cores such as benzene, 1,3,5-tris-arene, calixarene, etc. In the center of the molecule, straight-chain alkyl, alkoxy, substituted benzyloxy, etc. are radially substituted as their side chains. Representative examples of discotic liquid crystals include: the research report of C. Destrade et al., Mol. Cryst. Liq. Cryst. No. 71, p. 111 (1981), the benzene derivatives, triphenyl derivatives, and reference Indenacene derivatives, phthalocyanin derivatives; research reports by B. Kohne et al., Angew. Chem. No. 96, p. 70 (1984) cyclohexane derivatives; and JMLehn et al. Research report, J.Chem.Soc.Chem.Commun. p. 1794 (1985), J. Zhang et al. research report, J.Am.Chem.Soc. No. 116 p. 2655 (1994) Recorded The macrocycle of the azacrown ether system or phenylacetylene system. More specific examples of the discotic liquid crystal compound include compounds described in JP 2006-133652 A, JP 2007-108732 A, and JP 2010-244038 A. In the present specification, the descriptions of the above-mentioned documents and gazettes are incorporated by reference.
相位差層為液晶化合物之定向固化層時,其厚度宜為0.5µm~7µm,較宜為1µm~5µm。藉由使用液晶化合物,可以較樹脂薄膜薄上甚多的厚度實現與樹脂薄膜同等的面內相位差。When the retardation layer is a directional solidification layer of a liquid crystal compound, its thickness is preferably 0.5µm~7µm, more preferably 1µm~5µm. By using the liquid crystal compound, the in-plane retardation equivalent to that of the resin film can be realized at a thickness much thinner than that of the resin film.
E-2-3.另一相位差層 如上述,相位差層以單一層構成時,較佳為設置另一相位差層。另一相位差層如上述,可為折射率特性展現nz>nx=ny之關係的所謂正C板(Positive C-plate)。藉由使用正C板作為另一相位差層,可良好地防止斜向之反射,而可使抗反射功能廣視角化。此時,另一相位差層之厚度方向的相位差Rth(550)宜為-50nm~-300nm,較宜為-70nm~-250nm,更宜為-90nm~-200nm,尤宜為-100nm~-180nm。在此,「nx=ny」不僅包含nx與ny嚴格上相等之情況,還包含nx與ny實質上相等之情況。即,另一相位差層的面內相位差Re(550)可小於10nm。E-2-3. Another retardation layer As described above, when the retardation layer is constituted by a single layer, it is preferable to provide another retardation layer. The other retardation layer can be a so-called positive C-plate which exhibits the relation of nz>nx=ny in the refractive index characteristic as described above. By using the positive C plate as another retardation layer, the oblique reflection can be prevented well, and the anti-reflection function can be widened. At this time, the retardation Rth(550) in the thickness direction of the other retardation layer is preferably -50nm~-300nm, more preferably -70nm~-250nm, more preferably -90nm~-200nm, especially -100nm~ -180nm. Here, "nx=ny" includes not only the case where nx and ny are strictly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re(550) of the other retardation layer may be less than 10 nm.
具有nz>nx=ny之折射率特性的另一相位差層可以任意適當之材料形成。另一相位差層宜由包含固定為垂面排列定向之液晶材料的薄膜構成。可使垂面排列定向的液晶材料(液晶化合物)可為液晶單體亦可為液晶聚合物。該液晶化合物及該相位差層之形成方法的具體例可舉日本專利特開2002-333642號公報中段落[0020]~[0028]記載之液晶化合物及相位差層之形成方法。此時,另一相位差層之厚度宜為0.5µm~10µm,較宜為0.5µm~8µm,更宜為0.5µm~5µm。The other retardation layer having the refractive index characteristic of nz>nx=ny can be formed of any suitable material. The other retardation layer is preferably composed of a thin film comprising a liquid crystal material fixed in a homeotropic orientation. The liquid crystal material (liquid crystal compound) that can orient the homeotropic alignment can be either a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the retardation layer include the methods for forming the liquid crystal compound and the retardation layer described in paragraphs [0020] to [0028] of Japanese Patent Laid-Open No. 2002-333642. At this time, the thickness of the other retardation layer is preferably 0.5µm~10µm, more preferably 0.5µm~8µm, more preferably 0.5µm~5µm.
E-3.2層結構之相位差層
相位差層40為具有第1層41與第2層42之積層結構時,第1層41及第2層42中之任一者可作為λ/4板發揮功能,另一者可作為λ/2板發揮功能。例如,第1層41作為λ/2板發揮功能、第2層42作為λ/4板發揮功能時,第1層之面內相位差Re(550)如上述例如為200nm~300nm,宜為230nm~290nm,較宜為250nm~280nm。第2層之面內相位差Re(550)如上述例如為100nm~190nm,宜為110nm~170nm,較宜為130nm~160nm。第1層的慢軸與偏光件的吸收軸形成之角度如上述例如為10°~20°,宜為12°~18°,較宜為約15°。第2層的慢軸與偏光件的吸收軸形成之角度如上述例如為70°~80°,宜為72°~78°,較宜為約75°。只要為所述構成,便可獲得接近理想之逆波長分散特性的特性,結果可實現非常優異之抗反射特性。Phase difference layer of E-3.2 layer structure
When the
第1層41及第2層42可為其中一者是樹脂薄膜而另一者是液晶化合物之定向固化層,亦可兩者為樹脂薄膜,亦可兩者為液晶化合物之定向固化層。較佳為第1層41及第2層42兩者為樹脂薄膜或液晶化合物之定向固化層。One of the
第1層41及第2層42之厚度可為了獲得λ/4板或λ/2板的期望面內相位差而進行調整。例如,第1層41作為λ/2板發揮功能、第2層42作為λ/4板發揮功能,且第1層41及第2層42為樹脂薄膜時,第1層41之厚度例如為40µm~75µm,第2層42之厚度例如為30µm~55µm。第1層41及第2層42為液晶化合物之定向固化層時,第1層41之厚度例如為2.0µm~3.0µm,第2層42之厚度例如為1.0µm~2.0µm。The thicknesses of the
關於構成第1層及第2層之樹脂薄膜、液晶化合物、第1層及第2層之形成方法、光學特性等,如有關單一層在上述所說明。The resin films constituting the first layer and the second layer, the liquid crystal compound, the method for forming the first layer and the second layer, the optical properties, and the like are as described above for the single layer.
實施例 以下,以實施例來具體說明本發明,惟本發明不受該等實施例限定。各特性之測定方法如以下所述。此外,只要無特別註記,實施例中之「份」及「%」即為重量基準。Example Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. The measurement method of each characteristic is as follows. In addition, unless otherwise noted, "parts" and "%" in the examples are based on weight.
(1)褪色及保護層之收縮 從實施例及比較例所得偏光板裁切出試驗片(50mm×50mm),該試驗片形成分別與垂直於偏光件之吸收軸方向之方向及吸收軸方向相對向之兩邊。以使保護層成為內側,並利用黏著劑將試驗片貼合於玻璃板而製成試驗試樣,將該試驗試樣放置於85℃及85%RH之烘箱內120小時進行加熱加濕,並配置成與標準偏光板成正交偏光之狀態後,以肉眼調查加濕後之偏光板之褪色狀態,並依以下基準進行評估。又,亦以肉眼確認加熱加濕後之保護層有無收縮。 無問題:未觀察到褪色 部分褪色:於端部觀察到褪色 整體褪色:偏光板整體明顯褪色 (2)單體透射率及偏光度 針對褪色評估非為整體褪色者,測定單體透射率及偏光度。從實施例及比較例所得偏光板裁切出試驗片(50mm×50mm),該試驗片形成分別與垂直於偏光件之吸收軸方向之方向及吸收軸方向相對向之兩邊。以使保護層成為外側,並利用黏著劑將試驗片貼合於無鹼玻璃板,而製成試驗試樣,對該試驗試樣使用紫外線可見光分光光度計(日本分光公司製,製品名「V7100」)測定單體透射率(Ts)、平行透射率(Tp)及正交透射率(Tc),並利用下式求出偏光度(P)。此時,使測定光從保護層側入射。 偏光度(P)(%)={(Tp-Tc)/(Tp+Tc)}1 /2 ×100 此外,上述Ts、Tp及Tc係以JIS Z 8701之2度視野(C光源)進行測定並進行視感度校正所得之Y值。又,Ts及P實質上為偏光件之特性。 然後,將偏光板放置於85℃及85%RH之烘箱內120小時進行加熱加濕後(加熱試驗),從加熱試驗前之單體透射率Ts0 及加熱試驗後之單體透射率Ts120 用下述式求出單體透射率變化量ΔTs。 ΔTs(%)=Ts120 -Ts0 同樣地,從加熱試驗前之偏光度P0 及加熱試驗後之偏光度P120 用下述式求出偏光度變化量ΔP。 ΔP(%)=P120 -P0 另,加熱試驗係依與上述褪色時相同方式製作試驗試樣而進行。(1) Fading and shrinkage of protective layer Test pieces (50 mm×50 mm) were cut out from the polarizing plates obtained in the examples and comparative examples, and the test pieces were formed to face the direction perpendicular to the absorption axis direction and the absorption axis direction of the polarizer, respectively. to both sides. So that the protective layer becomes the inner side, the test piece is attached to the glass plate with an adhesive to make a test sample, and the test sample is placed in an oven at 85°C and 85% RH for 120 hours for heating and humidifying, and After arranging in a state of orthogonal polarization with the standard polarizing plate, the fading state of the polarizing plate after humidification was checked with the naked eye, and the evaluation was performed according to the following criteria. In addition, the presence or absence of shrinkage of the protective layer after heating and humidifying was also confirmed with the naked eye. No problem: no fading was observed. Partial fading: fading was observed at the end. Overall fading: the polarizing plate was obviously faded as a whole (2) Transmittance and polarization degree of monomers For the evaluation of fading, the transmittance and polarized light were measured for those who were not overall faded Spend. Test pieces (50 mm×50 mm) were cut out from the polarizing plates obtained in the examples and comparative examples, and the test pieces were formed on two sides opposite to the direction perpendicular to the absorption axis direction and the absorption axis direction of the polarizer, respectively. With the protective layer on the outside, the test piece was attached to an alkali-free glass plate with an adhesive to prepare a test sample, and an ultraviolet-visible light spectrophotometer (manufactured by JASCO Corporation, product name "V7100" was used for the test sample. ") to measure the single transmittance (Ts), parallel transmittance (Tp), and orthogonal transmittance (Tc), and obtain the degree of polarization (P) by the following formula. At this time, the measurement light was made incident from the protective layer side. Degree of polarization (P)(%)={(Tp-Tc)/(Tp+Tc)} 1 /2 ×100 In addition, the above-mentioned Ts, Tp and Tc are measured by the 2-degree field of view (C light source) of JIS Z 8701 And the Y value obtained by the visual sensitivity correction. In addition, Ts and P are substantially the characteristics of a polarizer. Then, the polarizing plate was placed in an oven at 85°C and 85% RH for 120 hours for heating and humidification (heating test), and the transmittance of the monomer before the heating test Ts 0 and the monomer transmittance after the heating test Ts 120 The individual transmittance change amount ΔTs was obtained by the following formula. ΔTs(%)=Ts 120 −Ts 0 Similarly, the polarization degree change amount ΔP was obtained from the polarization degree P 0 before the heating test and the polarization degree P 120 after the heating test by the following formula. ΔP(%)=P 120 -P 0 In addition, the heating test was performed in the same manner as in the case of discoloration described above to prepare a test sample.
(3)碘吸附量 依與各實施例及比較例中之保護層之形成相同方式,於PET薄膜之單面形成保護層(厚度:約3µm)。將所得附保護層之PET薄膜裁切成1cm×1cm(1cm2 )做成試料,採取到頂空小瓶(20mL容量)並秤量。接著,將裝有碘溶液1mL(碘濃度1重量%、碘化鉀濃度7重量%)的螺口瓶(1.5mL容量)亦放入該頂空小瓶中並蓋緊。之後,將頂空小瓶放入65℃之乾燥機中加溫6小時(藉此,氣體狀態之I2 會吸附於試料上)。之後,將試料採取到陶瓷舟皿並使用自動試料燃燒裝置使其燃燒,再將所產生之氣體採集至吸收液10mL中。收集後,將該吸收液以純水調製成15mL,並針對原液或適當稀釋後之液體進行IC定量分析。此外,僅以PET薄膜進行相同測定後之碘吸附量幾乎為0,故根據經IC定量分析所得碘重量與保護層單體之重量(「附保護層之PET薄膜之重量」-「PET薄膜之重量」),從以下式算出碘吸附量(重量%)。 碘吸附量(重量%)=IC定量分析所得碘重量/保護層單體之重量×100 又,測定裝置及測定條件如下述。 [測定裝置] 自動試料燃燒裝置:Mitsubishi Chemical Analytech公司製,「AQF-2100H」 IC(陰離子):Thermo Fisher Scientific公司製,「ICS-3000」(3) The amount of iodine adsorption A protective layer (thickness: about 3 µm) was formed on one side of the PET film in the same manner as the protective layer in each Example and Comparative Example. The obtained PET film with a protective layer was cut into 1 cm×1 cm (1 cm 2 ) to prepare a sample, which was collected into a headspace vial (20 mL capacity) and weighed. Next, a screw-top vial (1.5 mL capacity) containing 1 mL of an iodine solution (1 wt % iodine concentration, 7 wt % potassium iodide concentration) was also placed in the headspace vial and capped tightly. After that, the headspace vial was placed in a desiccator at 65°C for 6 hours (thereby, I 2 in gaseous state was adsorbed on the sample). After that, the sample was collected in a ceramic boat and burned using an automatic sample burning device, and the generated gas was collected into 10 mL of the absorbing liquid. After the collection, the absorption solution was prepared to 15 mL with pure water, and IC quantitative analysis was performed on the stock solution or the appropriately diluted solution. In addition, the iodine adsorption amount was almost 0 after the same measurement was carried out only with the PET film, so the iodine weight and the weight of the protective layer monomer obtained by the IC quantitative analysis ("The weight of the PET film with the protective layer" - "The weight of the PET film" The iodine adsorption amount (% by weight) was calculated from the following formula. Iodine adsorption amount (% by weight)=Iodine weight obtained by IC quantitative analysis/weight of protective layer monomer×100 Also, the measuring apparatus and measuring conditions are as follows. [Measuring device] Automatic sample combustion device: "AQF-2100H" manufactured by Mitsubishi Chemical Analytech Co., Ltd. IC (anion): "ICS-3000" manufactured by Thermo Fisher Scientific Co., Ltd.
(4)保護層之軟化溫度 針對實施例及比較例所得偏光板的保護層表面進行局部熱分析(Nano-TA測定),算出保護層之軟化溫度。測定裝置及測定條件如下述。 測定裝置:Hitachi High-Tech Science Co.製,製品名「AFM5300E//Nano-TA2」 測定模式:接觸模式 探針:AN2-200 測定面積:8µm□ 掃描 測定氣體環境:大氣壓(4) Softening temperature of protective layer Local thermal analysis (Nano-TA measurement) was performed on the surface of the protective layer of the polarizing plates obtained in Examples and Comparative Examples, and the softening temperature of the protective layer was calculated. The measurement apparatus and measurement conditions are as follows. Measuring device: Hitachi High-Tech Science Co., product name "AFM5300E//Nano-TA2" Measurement Mode: Contact Mode Probe: AN2-200 Measurement area: 8µm Scanning Measurement gas environment: atmospheric pressure
(5)判定 針對所得偏光板,按以下基準進行判定。 佳:ΔP之值為0%至-4.0% 可:ΔP之值大於-4.0%且為-10.0% 不佳:ΔP之值大於-10%且為-99.9%(完全脫色)(5) Judgment The obtained polarizing plate was judged according to the following criteria. Good: The value of ΔP is 0% to -4.0% Yes: The value of ΔP is greater than -4.0% and -10.0% Poor: The value of ΔP is greater than -10% and -99.9% (complete decolorization)
<實施例1> 1.偏光件/樹脂基材之積層體之製作 樹脂基材是使用長條狀且吸水率0.75%、Tg約75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯薄膜(厚度:100µm)。並對樹脂基材之單面施行了電暈處理。 在以9:1混合聚乙烯醇(聚合度4200,皂化度99.2莫耳%)及乙醯乙醯基改質PVA(Mitsubishi Chemical Co.製,商品名「GOHSEFIMER Z410」)而成之PVA系樹脂100重量份中,添加碘化鉀13重量份,而調製出PVA水溶液(塗佈液)。 於樹脂基材之電暈處理面塗佈上述PVA水溶液並在60℃下乾燥,藉此形成厚度13µm之PVA系樹脂層,而製作出積層體。 將所得積層體於130℃之烘箱內在周速相異之輥間沿縱方向(長邊方向)進行自由端單軸延伸成2.4倍(空中輔助延伸處理)。 接著,使積層體浸漬於液溫40℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒鐘(不溶解處理)。 接著,一邊調整液溫30℃的染色浴(相對於水100重量份,以1:7之重量比摻混碘與碘化鉀而獲得之碘水溶液)之濃度一邊浸漬於其中60秒鐘,以使最後所得偏光件的單體透射率(Ts)成為41.5%±0.1%(染色處理)。 接著,使其浸漬於液溫40℃的交聯浴(相對於水100重量份摻混3重量份的碘化鉀並摻混5重量份的硼酸而得之硼酸水溶液)中30秒鐘(交聯處理)。 然後,一邊使積層體浸漬於液溫70℃的硼酸水溶液(硼酸濃度4.0重量%,碘化鉀5重量%)中,一邊在周速相異的輥間沿縱方向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸處理)。 之後,使積層體浸漬於液溫20℃的洗淨浴(相對於水100重量份摻混4重量份的碘化鉀而得之水溶液)中(洗淨處理)。 之後,一邊在保持於90℃之烘箱中乾燥,一邊使其接觸表面溫度保持於75℃之SUS製加熱輥約2秒(乾燥收縮處理)。積層體進行乾燥收縮處理所得寬度方向之收縮率為5.2%。 依上述方式,於樹脂基材上形成了厚度5µm之偏光件,而製作出偏光件/樹脂基材之積層體。偏光件之單體透射率(初始單體透射率)Ts0為42.0%,偏光度(初始偏光度)P0為99.996%。<Example 1> 1. Fabrication of polarizer/resin base laminate The resin substrate is a long strip of amorphous isophthalic acid copolymer polyethylene terephthalate film (thickness: 100µm) with a water absorption rate of 0.75% and a Tg of about 75°C. Corona treatment was performed on one side of the resin substrate. PVA-based resin obtained by mixing polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetylacetate modified PVA (manufactured by Mitsubishi Chemical Co., trade name "GOHSEFIMER Z410") at a ratio of 9:1 To 100 parts by weight, 13 parts by weight of potassium iodide was added to prepare an aqueous PVA solution (coating liquid). The above-mentioned PVA aqueous solution was coated on the corona-treated surface of the resin substrate and dried at 60° C. to form a PVA-based resin layer with a thickness of 13 μm, thereby producing a laminate. The obtained layered body was uniaxially stretched by 2.4 times the free end in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130°C (aerial-assisted stretching treatment). Next, the layered body was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insolubility treatment). Next, it was immersed for 60 seconds in a dyeing bath with a liquid temperature of 30° C. (an aqueous iodine solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) for 60 seconds so that the final The single transmittance (Ts) of the obtained polarizer was 41.5%±0.1% (dyeing treatment). Next, it was immersed in a cross-linking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (cross-linking treatment) at a liquid temperature of 40° C. ). Then, while immersing the layered body in a boric acid aqueous solution (boric acid concentration 4.0 wt %, potassium iodide 5 wt %) at a liquid temperature of 70° C., uniaxial stretching was performed in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds. so that the total extension ratio was 5.5 times (in water extension treatment). Then, the layered body was immersed in a cleaning bath (aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 20°C (cleaning treatment). After that, while drying in an oven maintained at 90° C., the contact surface temperature was maintained at 75° C. with a heating roll made of SUS for about 2 seconds (drying shrinkage treatment). The shrinkage rate in the width direction of the laminate obtained by drying shrinkage treatment was 5.2%. In the above-described manner, a polarizer with a thickness of 5 µm was formed on the resin substrate to produce a polarizer/resin substrate laminate. The single transmittance (initial single transmittance) Ts0 of the polarizer was 42.0%, and the polarization degree (initial polarization degree) P0 was 99.996%.
2.偏光板之製作 透過紫外線硬化型接著劑,將環烯烴系薄膜(日本Zeon公司製,ZT-12,厚度23µm)作為構成第2保護層之薄膜貼合於上述所得偏光件之表面。具體而言,是塗敷成硬化型接著劑之總厚度成為1.0µm,並使用輥軋機進行貼合。之後,從薄膜側照射UV光線使接著劑硬化。接著,剝離樹脂基材,而獲得具有第2保護層(ZT-12)/偏光件之構成的偏光板。2. Production of polarizing plate A cycloolefin-based film (ZT-12, 23 µm in thickness, manufactured by Japan Zeon Co., Ltd.) was attached to the surface of the polarizer obtained above as a film constituting the second protective layer through an ultraviolet curable adhesive. Specifically, it was applied so that the total thickness of the hardening adhesive was 1.0 µm, and was bonded using a rolling mill. After that, UV light is irradiated from the film side to harden the adhesive. Next, the resin base material was peeled off, and the polarizing plate which has the structure of a 2nd protective layer (ZT-12)/polarizer was obtained.
3.保護層之製作 將具有聯苯骨架之環氧樹脂(Mitsubishi Chemical Co.製,商品名:jER(註冊商標) YX4000)15份溶解於甲基乙基酮83.8份中,而獲得環氧樹脂溶液。於所得環氧樹脂溶液中添加光陽離子聚合引發劑(San-Apro Ltd.,商品名:CPI(註冊商標)-100P)1.2份,而獲得保護層形成組成物。將所得保護層形成組成物以線棒塗佈於上述所得偏光板的偏光件表面,並將塗佈膜在60℃下乾燥3分鐘。接著,使用高壓水銀燈以使累積光量為600mJ/cm2 之方式照射紫外線,形成保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於上述(1)~(4)之評估。3. Production of protective layer 15 parts of an epoxy resin having a biphenyl skeleton (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) YX4000) was dissolved in 83.8 parts of methyl ethyl ketone to obtain an epoxy resin solution. To the obtained epoxy resin solution, 1.2 parts of a photocationic polymerization initiator (San-Apro Ltd., trade name: CPI (registered trademark)-100P) was added to obtain a protective layer forming composition. The obtained protective layer-forming composition was applied to the polarizer surface of the above-obtained polarizing plate with a wire bar, and the coated film was dried at 60° C. for 3 minutes. Next, ultraviolet rays were irradiated using a high-pressure mercury lamp so that the accumulated light amount would be 600 mJ/cm 2 to form a protective layer. The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the evaluation of the above-mentioned (1)-(4).
<實施例2> 將具有聯苯骨架之環氧樹脂(Mitsubishi Chemical Co.製,商品名:jER(註冊商標) YX4000)15份與氧雜環丁烷樹脂(東亞合成公司製,商品名:ARON OXETANE(註冊商標) OXT-221)10份溶解於甲基乙基酮73份中,而獲得環氧樹脂溶液。於所得環氧樹脂溶液中添加光陽離子聚合引發劑(San-Apro Ltd.,商品名:CPI(註冊商標)-100P)2份,而獲得保護層形成組成物。使用該環氧樹脂溶液來獲得保護層形成組成物,除此之外依與實施例1相同方式而形成保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於上述(1)~(4)之評估。<Example 2> 15 parts of epoxy resin having a biphenyl skeleton (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) YX4000) and oxetane resin (manufactured by Toagosei Co., Ltd., trade name: ARON OXETANE (registered trademark)) 10 parts of OXT-221) were dissolved in 73 parts of methyl ethyl ketone to obtain an epoxy resin solution. To the obtained epoxy resin solution, 2 parts of a photocationic polymerization initiator (San-Apro Ltd., trade name: CPI (registered trademark)-100P) was added to obtain a protective layer forming composition. A protective layer was formed in the same manner as in Example 1, except that the epoxy resin solution was used to obtain a protective layer-forming composition. The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the evaluation of the above-mentioned (1)-(4).
(比較例1) 使用氫化雙酚型環氧樹脂(Mitsubishi Chemical Co.製,商品名:jER(註冊商標) YX8000)取代具有聯苯骨架之環氧樹脂,除此之外依與實施例1相同方式而形成保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 1) A protective layer was formed in the same manner as in Example 1, except that a hydrogenated bisphenol-type epoxy resin (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) YX8000) was used in place of the epoxy resin having a biphenyl skeleton . The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例2) 使用氫化雙酚型環氧樹脂(Mitsubishi Chemical Co.製,商品名:jER(註冊商標) YX8000)來取代具有聯苯骨架之環氧樹脂,除此之外依與實施例2相同方式而形成保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 2) A protection was formed in the same manner as in Example 2, except that a hydrogenated bisphenol-type epoxy resin (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) YX8000) was used in place of the epoxy resin having a biphenyl skeleton Floor. The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例3) 使用雙酚型環氧樹脂(Mitsubishi Chemical Co.製,商品名:jER(註冊商標) 828)來取代具有聯苯骨架之環氧樹脂,除此之外依與實施例1相同方式而形成保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 3) A protective layer was formed in the same manner as in Example 1, except that a bisphenol-type epoxy resin (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) 828) was used in place of the epoxy resin having a biphenyl skeleton . The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例4) 使用雙酚型環氧樹脂(Mitsubishi Chemical Co.製,商品名:jER(註冊商標) 828)來取代具有聯苯骨架之環氧樹脂,除此之外依與實施例2相同方式而形成保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 4) A protective layer was formed in the same manner as in Example 2, except that a bisphenol-type epoxy resin (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) 828) was used in place of the epoxy resin having a biphenyl skeleton . The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例5) 將聚酯系樹脂(日本合成化學工業公司製,商品名:Nichigo-POLYESTER WR905)20份溶解於純水80份中,而獲得塗敷用樹脂溶液(20%)。將該塗敷用樹脂溶液使用線棒塗佈於實施例所用偏光板的偏光件表面,並將塗佈膜在60℃下乾燥5分鐘,而形成以塗佈膜之固化物構成之保護層。保護層之厚度為2µm~3µm。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 5) 20 parts of polyester-based resins (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Nichigo-POLYESTER WR905) were dissolved in 80 parts of pure water to obtain a coating resin solution (20%). The coating resin solution was coated on the surface of the polarizer of the polarizing plate used in the examples using a wire bar, and the coating film was dried at 60° C. for 5 minutes to form a protective layer composed of a cured product of the coating film. The thickness of the protective layer is 2µm~3µm. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例6) 除了使用胺甲酸酯系樹脂(第一工業製藥公司製,商品名:SUPERFLEX 210)取代聚酯系樹脂外,依與比較例5相同方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 6) A protective layer/polarizer/another protective layer ( ZT-12) of the composition of the polarizing plate. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例7) 於具有第2保護層(ZT-12)/偏光件之構成的偏光板之偏光件面,將聚胺甲酸酯系水系分散樹脂(第一工業製藥公司製,製品名:SUPERFLEX SF210)塗佈成厚度成為0.1µm作為易接著層,而形成易接著層。另外,將甲基丙烯酸甲酯/甲基丙烯酸丁酯(莫耳比35/65)之共聚物的丙烯酸系樹脂(楠本化成公司製,製品名「B-734」)20份溶解於甲基乙基酮80份中,而獲得丙烯酸系樹脂溶液(20%)。接著,將該丙烯酸系樹脂溶液用線棒塗佈於易接著層上,並將塗佈膜在60℃下乾燥5分鐘後,形成以塗佈膜的固化物構成之保護層。保護層之厚度為3µm,軟化溫度為80.4℃,碘吸附量為30.4重量%。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 7) Polyurethane-based water-based dispersion resin (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., product name: SUPERFLEX SF210) was coated on the polarizer surface of the polarizing plate having the second protective layer (ZT-12)/polarizer An easy-adhesion layer was formed as a thickness of 0.1 µm as an easy-adhesion layer. Separately, 20 parts of an acrylic resin (manufactured by Kusumoto Chemical Co., Ltd., product name "B-734") of a copolymer of methyl methacrylate/butyl methacrylate (mol ratio 35/65) was dissolved in methyl ethyl acetate. In 80 parts of base ketones, an acrylic resin solution (20%) was obtained. Next, this acrylic resin solution was coated on the easily bonding layer with a wire bar, and the coating film was dried at 60° C. for 5 minutes to form a protective layer composed of a cured product of the coating film. The thickness of the protective layer was 3 µm, the softening temperature was 80.4°C, and the iodine adsorption amount was 30.4% by weight. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
(比較例8) 除了使用甲基丙烯酸甲酯/丙烯酸乙酯(莫耳比55/45)之共聚物的丙烯酸系樹脂(楠本化成公司製,製品名「B-722」)外,依與比較例8相同方式而形成保護層。保護層之厚度為3µm,軟化溫度為57.2℃,碘吸附量為1.3重量%。依上述方式而獲得具有保護層/偏光件/另一保護層(ZT-12)之構成的偏光板。將所得偏光板供於與實施例相同之評估。將結果列於表1。(Comparative Example 8) The same procedure as in Comparative Example 8 was carried out except that an acrylic resin (manufactured by Kusumoto Chemical Co., Ltd., product name "B-722") of a copolymer of methyl methacrylate/ethyl acrylate (mol ratio 55/45) was used. form a protective layer. The thickness of the protective layer was 3 µm, the softening temperature was 57.2°C, and the amount of iodine adsorption was 1.3% by weight. In the above manner, a polarizing plate having a configuration of protective layer/polarizer/another protective layer (ZT-12) was obtained. The obtained polarizing plate was used for the same evaluation as in Examples. The results are listed in Table 1.
[表1] [Table 1]
<評估> 由表1清楚可知,實施例所得偏光板為即便非常薄,在加熱加濕環境下光學特性之降低仍受到抑制而耐久性優異者。<Assessment> As is clear from Table 1, even if the polarizing plates obtained in the examples are very thin, the decrease in optical properties is suppressed in a heating and humidifying environment, and they are excellent in durability.
產業上之可利用性 本發明偏光板可適合使用於影像顯示裝置。影像顯示裝置可舉例如:攜帶型資訊終端機(PDA)、智慧型手機、行動電話、時鐘、數位相機、可攜式遊戲機等攜帶型機器;電腦螢幕、筆記型電腦、複印機等OA機器;視訊攝影機、電視、微波爐等家庭用電氣機器;後照監測器、汽車導航系統用監測器、汽車音響等車載用機器;數位標牌、商業店鋪用資訊導覽用螢幕等展示機器;監視用螢幕等警報機器;看護用監測器、醫療用監測器等看護醫療機器等。industrial availability The polarizing plate of the present invention can be suitably used in an image display device. Examples of image display devices include portable devices such as portable information terminals (PDAs), smart phones, mobile phones, clocks, digital cameras, and portable game consoles; OA devices such as computer monitors, notebook computers, and copiers; Video cameras, televisions, microwave ovens and other household electrical appliances; rear-light monitors, monitors for car navigation systems, car audio and other in-vehicle appliances; digital signage, display devices such as information guide screens for commercial stores; monitors, etc. Alarm equipment; nursing care monitors, medical monitors and other nursing care medical equipment.
10:偏光件 20:保護層 40:相位差層 41:第1層 42:第2層 100:偏光板 110,111:附相位差層之偏光板 200:積層體 G1~G4:導輥 R1~R6:輸送輥10: Polarizer 20: Protective layer 40: retardation layer 41: Tier 1 42: Tier 2 100: polarizer 110,111: Polarizing plate with retardation layer 200: Laminate G1~G4: Guide roller R1~R6: Conveying roller
圖1係本發明一實施形態之偏光板的概略截面圖。 圖2係顯示本發明一實施形態之偏光板之製造方法中,利用加熱輥之乾燥收縮處理一例的概略圖。 圖3係本發明一實施形態之附相位差層之偏光板的概略截面圖。 圖4為本發明之另一實施形態之附相位差層之偏光板的概略截面圖。FIG. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. FIG. 2 is a schematic diagram showing an example of drying shrinkage treatment using a heating roller in the method for producing a polarizing plate according to an embodiment of the present invention. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. 4 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention.
10:偏光件10: Polarizer
20:保護層20: Protective layer
100:偏光板100: polarizer
Claims (8)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-080489 | 2020-04-30 | ||
JP2020080489 | 2020-04-30 | ||
JP2020110540A JP2021177230A (en) | 2020-04-30 | 2020-06-26 | Polarizing plate and polarizing plate with retardation layer |
JP2020-110540 | 2020-06-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW202144818A true TW202144818A (en) | 2021-12-01 |
Family
ID=78331518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW110113258A TW202144818A (en) | 2020-04-30 | 2021-04-13 | Polarizing plate and polarizing plate with retardation layer |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR20230002505A (en) |
CN (1) | CN115485592A (en) |
TW (1) | TW202144818A (en) |
WO (1) | WO2021220741A1 (en) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007297604A (en) * | 2006-04-03 | 2007-11-15 | Showa Denko Kk | Thermosetting resin composition |
JP5076763B2 (en) * | 2007-09-12 | 2012-11-21 | 大日本印刷株式会社 | Optical laminate manufacturing method, optical laminate, polarizing plate, and image display device |
TWI494359B (en) * | 2009-12-07 | 2015-08-01 | Dainippon Ink & Chemicals | A cellulose ester resin composition, an optical film using the same, and a polarizing plate for a liquid crystal display device |
JP2015210474A (en) | 2014-04-30 | 2015-11-24 | 株式会社カネカ | Polarizer protection film and polarizing plate |
JP7178776B2 (en) * | 2017-09-15 | 2022-11-28 | 日東電工株式会社 | Method for manufacturing polarizing film |
WO2020066830A1 (en) * | 2018-09-28 | 2020-04-02 | 住友化学株式会社 | Optical laminate, polarizing plate composite, and image display device |
JP6748279B2 (en) * | 2018-11-29 | 2020-08-26 | 日東電工株式会社 | Liquid crystal panel with touch sensing function, liquid crystal display device, and polarizing film with adhesive layer |
JP7372824B2 (en) * | 2018-11-29 | 2023-11-01 | 日東電工株式会社 | Polarizing film with adhesive layer and image display device |
-
2021
- 2021-04-07 WO PCT/JP2021/014707 patent/WO2021220741A1/en active Application Filing
- 2021-04-07 CN CN202180031610.6A patent/CN115485592A/en active Pending
- 2021-04-07 KR KR1020227037389A patent/KR20230002505A/en unknown
- 2021-04-13 TW TW110113258A patent/TW202144818A/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN115485592A (en) | 2022-12-16 |
WO2021220741A1 (en) | 2021-11-04 |
KR20230002505A (en) | 2023-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI613470B (en) | Polarizing plate with a retardation layer and image display apparatus | |
KR102577635B1 (en) | Optical laminate and image display device using the optical laminate | |
WO2021220729A1 (en) | Polarizing plate and polarizing plate with optical functional layer | |
JP2021177230A (en) | Polarizing plate and polarizing plate with retardation layer | |
TWI835966B (en) | Polarizing plates and polarizing plate coils | |
JP7513594B2 (en) | Polarizer | |
TW202144818A (en) | Polarizing plate and polarizing plate with retardation layer | |
JP2021177229A (en) | Polarizing plate and polarizing plate with optical function layer | |
TWI839433B (en) | Polarizing plate with phase difference layer | |
TW202146240A (en) | Polarizing plate and polarizing plate with optical functional layer | |
JP7412972B2 (en) | Polarizing plate and polarizing plate roll | |
TW202016579A (en) | Polarizing plate with phase difference layer and image display device using the same which is thin, excellent in handleability, and excellent in optical characteristics | |
JP7412973B2 (en) | Polarizing plate and polarizing plate roll | |
WO2021261276A1 (en) | Polarizing plate, retardation-layer-equipped polarizing plate, and image display device | |
TW202039255A (en) | Polarizing plate and polarizing plate roll | |
TW202043045A (en) | Laminate for polarizer protection, and polarizing plate using said laminate |