TW202128416A - Polarizing plate, liquid crystal display device and organic electroluminescence display device - Google Patents

Polarizing plate, liquid crystal display device and organic electroluminescence display device Download PDF

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TW202128416A
TW202128416A TW110112956A TW110112956A TW202128416A TW 202128416 A TW202128416 A TW 202128416A TW 110112956 A TW110112956 A TW 110112956A TW 110112956 A TW110112956 A TW 110112956A TW 202128416 A TW202128416 A TW 202128416A
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protective film
polarizer
change rate
dimensional change
polarizing plate
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TWI751939B (en
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白石貴志
呂宜樺
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日商住友化學股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

An object of the present invention is to provide a thin polarizing plate excellent in strength which does not occur light leakage even when exposed to high temperature and humidity conditions, and further suppresses occurrence of poor appearance such as cracking in the polarizer under an environment where high temperature and low temperature are repeated.
The polarizing plate having a polarizer, a protective film and an adhesive layer, wherein the absolute value of the difference between the dimensional change rate (85℃) of the protective film and the dimensional change rate (30℃) of the protective film is 0.02 to 0.50, with the dimensional change rate of the protective film after one hour under the condition of 85℃ and 5% relative humidity in the direction parallel to the transmission axis direction of the polarizer being defined as the dimensional change rate (85℃) of the protective film, and the dimensional change rate of the protective film after 0.5 hours under conditions of 30℃ and 95% relative humidity in the direction parallel to the transmission axis direction of the polarizer being defined as the dimensional change rate (30 ℃) of the protective film.

Description

偏光板、液晶顯示裝置及有機電激發光顯示裝置 Polarizing plate, liquid crystal display device and organic electroluminescent display device

本發明係關於可使用於各種光學用途之偏光板。而且本發明係關於具備該偏光板之液晶顯示裝置及有機電激發光顯示裝置。 The present invention relates to a polarizing plate that can be used for various optical applications. Furthermore, the present invention relates to a liquid crystal display device and an organic electroluminescent display device provided with the polarizing plate.

偏光板被廣泛使用作為液晶顯示裝置等顯示裝置之偏光的供應元件，而且作為偏光的感測元件。於如此的偏光板，適合採用將聚乙烯醇膜延伸、染色而成之偏光片(polarizer)。 The polarizing plate is widely used as a supply element for polarized light of display devices such as liquid crystal display devices, and as a sensor element for polarized light. For such a polarizing plate, it is suitable to use a polarizer formed by stretching and dyeing a polyvinyl alcohol film.

於專利文獻1(日本特開2012-145645)，揭露一種偏光板，其中，保護膜的線膨脹若越比偏光片的穿透軸方向的線膨脹小，則偏光片的破裂(龜裂)越少。根據專利文獻1，藉由將偏光板在-40℃至85℃之間重複進行單純升溫及降溫的步驟的測試(熱衝擊加速測試)，評價關於偏光片的破裂(龜裂)。如此根據專利文獻1記載的線膨脹的評價，一般為溫度依存性的參數。 Patent Document 1 (Japanese Patent Laid-Open No. 2012-145645) discloses a polarizing plate in which the more the linear expansion of the protective film is smaller than the linear expansion in the direction of the transmission axis of the polarizer, the more the polarizer will break (crack). few. According to Patent Document 1, the polarizer is evaluated for cracking (cracking) of the polarizer by repeating a test (thermal shock acceleration test) of a simple heating and cooling step between -40°C and 85°C. In this way, the evaluation of linear expansion described in Patent Document 1 is generally a temperature-dependent parameter.

而且，近年要求薄型的偏光板，偏光片也 被要求薄化。 Moreover, in recent years, thin polarizers are required, and polarizers are also Was required to be thinner.

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2012-145645號公報 [Patent Document 1] JP 2012-145645 A

但是，經延伸所製作的偏光片，係有沿著延伸軸方向而容易發生破裂(龜裂)的問題點，例如若將偏光板暴露在有劇烈溫度變化的環境時，偏光片會發生龜裂，而發生外觀上的缺陷及漏光等光學上的缺陷。伴隨著近年的偏光板的薄型化，變得更容易發生偏光片的破裂，故尋求解決方案。 However, the polarizer produced by stretching has the problem that it is prone to cracking (cracking) along the direction of the extension axis. For example, if the polarizer is exposed to an environment with drastic temperature changes, the polarizer may crack. , And optical defects such as appearance defects and light leakage occur. With the thinning of the polarizing plate in recent years, cracking of the polarizing plate is more likely to occur, so a solution is sought.

再者，包含聚乙烯醇的偏光片，係因對濕度的耐性低，故在高濕度條件下之使用是有所限制。 Furthermore, polarizers containing polyvinyl alcohol have low resistance to humidity, so their use under high humidity conditions is limited.

例如，於專利文獻1記載的發明中，根據線膨脹而進行評價。但是，一般根據線膨脹而進行的評價方法是以溫度依存性的參數來表示，故於引用文獻1中，沒有考慮到偏光片的破裂(龜裂)與濕度的關係。 For example, in the invention described in Patent Document 1, evaluation is made based on linear expansion. However, the general evaluation method based on linear expansion is expressed by a temperature-dependent parameter. Therefore, in Cited Document 1, the relationship between cracking (cracking) of the polarizer and humidity is not considered.

而且，為了滿足使偏光板薄化的要求，在將偏光片予以薄化時，例如於保護膜的表面產生刮傷的情況下，薄膜狀的偏光片也會發生破裂。 In addition, in order to meet the requirements for thinning the polarizer, when the polarizer is thinned, for example, when scratches are generated on the surface of the protective film, the thin-film polarizer may also be cracked.

本發明之目的係提供即使暴露於高溫高濕的條件下亦不發生漏光的偏光板。再者，本發明之目的係 提供在重複高溫與低溫的環境下抑制偏光片破裂等外觀不良的發生之偏光板。 The object of the present invention is to provide a polarizing plate that does not leak light even when exposed to high-temperature and high-humidity conditions. Furthermore, the purpose of the present invention is Provides a polarizing plate that suppresses appearance defects such as cracking of the polarizer under repeated high and low temperature environments.

本發明包含以下。 The present invention includes the following.

[1]一種偏光板，其具備偏光片、保護膜及黏著劑層；其中，當前述保護膜的在與前述偏光片的穿透軸方向呈平行的方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率係設為保護膜的尺寸變化率(85℃)，並且前述保護膜的在與前述偏光片的穿透軸方向呈平行的方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率係設為保護膜的尺寸變化率(30℃)時， [1] A polarizing plate comprising a polarizer, a protective film, and an adhesive layer; wherein, when the protective film is in a direction parallel to the direction of the penetration axis of the polarizer, the condition of a relative humidity of 5% at 85°C The rate of dimensional change after 1 hour is the rate of dimensional change of the protective film (85°C), and the relative humidity of the protective film is 95% at 30°C in a direction parallel to the direction of the transmission axis of the polarizer. The dimensional change rate after 0.5 hours under the conditions is the dimensional change rate of the protective film (30°C),

前述保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差的絕對值為0.02至0.50。 The absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is 0.02 to 0.50.

[2]如[1]記載之偏光板，其中，前述偏光片的在穿透軸方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率係設為偏光片的尺寸變化率(85℃)， [2] The polarizing plate according to [1], wherein the dimensional change rate of the polarizer in the direction of the transmission axis at 85°C and 5% relative humidity after 1 hour is defined as the dimensional change of the polarizer Rate (85℃),

前述偏光片的在穿透軸方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率係設為偏光片的尺寸變化率(30℃)， The dimensional change rate of the aforementioned polarizer in the direction of the transmission axis at a relative humidity of 95% at 30°C for 0.5 hours is taken as the dimensional change rate of the polarizer (30°C),

前述偏光片的尺寸變化率(85℃)與前述偏光片的尺寸變化率(30℃)的差的絕對值係設為FPZ， The absolute value of the difference between the dimensional change rate (85°C) of the polarizer and the dimensional change rate (30°C) of the polarizer is F PZ ,

前述保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差的絕對值係設為FPF， The absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is F PF ,

從前述FPZ減去前述FPF之差係設為△FTD，以及 The difference between the aforementioned F PZ and the aforementioned F PF is set as △F TD , and

△FTD相對於FPZ的比例(△FTD/FPZ)為0.5至0.95的範圍。 The ratio of ΔF TD to F PZ (ΔF TD /F PZ ) is in the range of 0.5 to 0.95.

[3]如[1]或[2]記載之偏光板，其中，前述偏光片、前述保護膜及前述黏著劑層係依此順序配置。 [3] The polarizing plate according to [1] or [2], wherein the polarizer, the protective film, and the adhesive layer are arranged in this order.

[4]如[1]或[2]記載之偏光板，其中，前述保護膜、前述偏光片及前述黏著劑層係依此順序配置。 [4] The polarizing plate according to [1] or [2], wherein the protective film, the polarizer, and the adhesive layer are arranged in this order.

[5]如[1]至[4]中任一項記載之偏光板，其中，前述保護膜係由纖維素酯系樹脂、聚酯系樹脂、聚碳酸酯系樹脂、(甲基)丙烯酸系樹脂、或該等的至少2種以上的混合物所構成的透明樹脂膜。 [5] The polarizing plate according to any one of [1] to [4], wherein the protective film is made of cellulose ester resin, polyester resin, polycarbonate resin, and (meth)acrylic resin. A transparent resin film composed of a resin or a mixture of at least two or more of these.

[6]一種液晶顯示裝置，其係藉由將前述[1]至[5]中任一項記載之偏光板隔著前述黏著劑層而積層於液晶單元(liquid crystal cell)所成者。 [6] A liquid crystal display device, which is formed by laminating the polarizing plate described in any one of [1] to [5] in a liquid crystal cell via the adhesive layer.

[7]一種有機電激發光顯示裝置，其係藉由將前述[1]至[5]中任一項記載之偏光板隔著前述黏著劑層而積層於有機電激發光顯示器所成者。 [7] An organic electroluminescent display device, which is formed by stacking the polarizing plate described in any one of [1] to [5] on an organic electroluminescent display via the adhesive layer.

根據本發明，提供即使於高溫條件、高濕度條件下亦抑制偏光片發生破裂及龜裂而為耐久性佳的偏光板。而且，於重複高溫及低溫的環境下，又即使於發生結露的環境下，本發明的偏光板也不會發生漏光、偏光片破裂等，可顯示良好的偏光特性。所以，本發明的偏光板，即使於傳統不適用的高溫條件、高濕度條件等各種條件下，也可不發生漏光、破裂等而適於使用。 According to the present invention, there is provided a polarizing plate that suppresses cracks and cracks of the polarizer even under high-temperature conditions and high-humidity conditions, and has excellent durability. Moreover, even in an environment where high and low temperatures are repeated, and even in an environment where condensation occurs, the polarizing plate of the present invention does not cause light leakage, polarizer cracking, etc., and can exhibit good polarization characteristics. Therefore, the polarizing plate of the present invention is suitable for use without light leakage, cracking, etc., even under various conditions such as high temperature conditions and high humidity conditions that are not conventionally applicable.

再者，根據本發明，可將偏光片予以薄化，並且即使在保護膜的表面即使發生刮傷時亦可抑制偏光片的破裂。所以，本發明的偏光板為薄型且強度、耐久性佳的偏光板。 Furthermore, according to the present invention, the polarizer can be thinned, and even when the surface of the protective film is scratched, the polarizer can be prevented from breaking. Therefore, the polarizing plate of the present invention is a thin polarizing plate with excellent strength and durability.

11:偏光片 11: Polarizer

12:保護膜(第1保護膜) 12: Protective film (the first protective film)

13:黏著劑層(第1黏著劑層) 13: Adhesive layer (1st adhesive layer)

22:第2保護膜 22: 2nd protective film

23:第2黏著劑層 23: The second adhesive layer

40:玻璃基板 40: Glass substrate

100、110:偏光板 100, 110: Polarizing plate

第1圖(a)係表示本發明的偏光板的層構成之一例的概略剖面圖，第1圖(b)係表示本發明的偏光板的層構成之另一例的概略剖面圖。 Fig. 1(a) is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate of the present invention, and Fig. 1(b) is a schematic cross-sectional view showing another example of the layer structure of the polarizing plate of the present invention.

第2圖(a)係表示在寬度方向具有穿透軸(實線)的偏光板中之穿透軸與吸收軸的軸角度之概略平面圖，第2圖(b)係表示在長度方向具有穿透軸(實線)的偏光板中之穿透軸與吸收軸的軸角度之概略平面圖。 Figure 2 (a) is a schematic plan view showing the axis angle between the transmission axis and the absorption axis in a polarizing plate having a transmission axis (solid line) in the width direction, and Figure 2 (b) shows that there is a penetration axis (solid line) in the length direction. A schematic plan view of the axis angle between the transmission axis and the absorption axis in the polarizing plate of the transmission axis (solid line).

第3圖係表示本發明的偏光板及貼合有偏光板之玻璃基板的層構成之一例的概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate of the present invention and the glass substrate to which the polarizing plate is bonded.

以下，雖然使用適宜的圖說明關於本發明的偏光板，本發明不限於該等實施態樣。 Hereinafter, although appropriate figures are used to describe the polarizing plate of the present invention, the present invention is not limited to these embodiments.

第1圖係表示本發明的偏光板的較佳層構成之例的概略剖面圖。於第1圖(a)中，偏光板100係由偏光片11、保護膜12及黏著劑層13所積層而成者。同樣地，於第1圖(b)中，偏光板110係由保護膜12、偏光片11及黏著劑層13所積層而成者。如此，於本發明中，沒有特別限制偏光片、保護膜及黏著劑層的積層順序。 Fig. 1 is a schematic cross-sectional view showing an example of a preferable layer structure of the polarizing plate of the present invention. In FIG. 1(a), the polarizing plate 100 is formed by stacking a polarizer 11, a protective film 12, and an adhesive layer 13. Similarly, in FIG. 1(b), the polarizing plate 110 is formed by stacking the protective film 12, the polarizer 11, and the adhesive layer 13. In this way, in the present invention, the stacking order of the polarizer, the protective film, and the adhesive layer is not particularly limited.

本發明的偏光板係具有將自然光等光轉換為直線偏光的功能之構件，偏光片一般具有穿透軸及吸收軸。如此的偏光片的穿透軸方向，係被理解為在使自然光穿透偏光片時的穿透光的振動方向。另一方面，偏光片的吸收軸係與偏光片的穿透軸垂直。再者，偏光片一般可為延伸膜，偏光片的吸收軸方向係與其延伸方向一致。 The polarizing plate of the present invention is a member having the function of converting natural light and other light into linear polarized light, and the polarizing plate generally has a transmission axis and an absorption axis. The direction of the transmission axis of such a polarizer is understood as the vibration direction of the transmitted light when natural light is transmitted through the polarizer. On the other hand, the absorption axis of the polarizer is perpendicular to the transmission axis of the polarizer. Furthermore, the polarizer can generally be a stretched film, and the direction of the absorption axis of the polarizer is consistent with its extension direction.

於本發明中，「與偏光片的穿透軸方向呈平行的方向」的用語，係表示與上述偏光片的穿透軸方向呈平行或略平行(所成角度為±7度以內)的方向。 In the present invention, the term "a direction parallel to the direction of the transmission axis of the polarizer" means a direction that is parallel or slightly parallel to the direction of the transmission axis of the above-mentioned polarizer (the angle is within ±7 degrees) .

於本發明中，在85℃相對濕度5%的條件下經過1小時後的尺寸變化率，係根據以下的式測定。再者，在85℃相對濕度5%的條件下經過1小時後的尺寸變化率，有記載為尺寸變化率(85℃)的情況。 In the present invention, the dimensional change rate after 1 hour under the condition of 85°C and 5% relative humidity is measured according to the following formula. In addition, the dimensional change rate after 1 hour under the condition of 85°C and 5% relative humidity is sometimes described as the dimensional change rate (85°C).

例如，於本發明中，保護膜的在與偏光片的穿透軸方向呈平行的方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率，係記載為保護膜的尺寸變化率(85℃)。 For example, in the present invention, the dimensional change rate of the protective film in a direction parallel to the direction of the transmission axis of the polarizer after 1 hour under the condition of 85°C and 5% relative humidity is described as the size of the protective film Change rate (85°C).

而且，偏光片的穿透軸的方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率，係記載為偏光片的尺寸變化率(85℃)。 In addition, the dimensional change rate after 1 hour in the direction of the transmission axis of the polarizer under the condition of 85°C and 5% relative humidity is described as the dimensional change rate of the polarizer (85°C).

以下，為了說明，保護膜的尺寸變化率(85℃)及偏光片的尺寸變化率(85℃)有只記載為尺寸變化率(85℃)的情況。 Hereinafter, for the purpose of explanation, the dimensional change rate (85°C) of the protective film and the dimensional change rate (85°C) of the polarizer may only be described as the dimensional change rate (85°C).

尺寸變化率(85℃)=[(L0-L85)/L0]×100 [式中，L0表示在與偏光片的穿透軸方向呈平行的方向(長度方向或寬度方向)之經裁切之膜的膜尺寸， Dimensional change rate (85℃)=[(L0-L85)/L0]×100 [In the formula, L0 represents the film size of the cut film in a direction parallel to the transmission axis direction of the polarizer (length direction or width direction),

L85表示在85℃相對濕度5%的條件下經過1小時後，在與偏光片的穿透軸方向呈平行的方向(長度方向或寬度方向)之膜尺寸。] L85 represents the film size in the direction parallel to the transmission axis of the polarizer (length direction or width direction) after 1 hour under the condition of 85°C and 5% relative humidity. ]

例如，在已測定經裁切之膜的寬度方向的尺寸(L0)的情況下，在85℃相對濕度5%的條件下靜置1小時後亦測定膜的寬度方向的尺寸(L85)，而算出尺寸變化率。並且，在製造偏光板後，在已測定從偏光板除去偏光片等所得的保護膜之在與偏光片的穿透軸方向呈平行的方向之尺寸(L0)的情況下，在85℃相對濕度5%的條件下靜置1小時後亦測定在與偏光片的穿透軸方向呈平行的方向之尺寸(L85)，而算出尺寸變化率。 For example, in the case where the widthwise dimension (L0) of the cut film has been measured, the widthwise dimension (L85) of the film is also measured after standing for 1 hour under the condition of 85°C and 5% relative humidity, and Calculate the dimensional change rate. In addition, after manufacturing the polarizing plate, after measuring the dimension (L0) of the protective film obtained by removing the polarizer from the polarizing plate in a direction parallel to the direction of the transmission axis of the polarizer (L0), the relative humidity is 85°C. After standing for 1 hour under the condition of 5%, the dimension (L85) in the direction parallel to the transmission axis of the polarizer was also measured, and the dimensional change rate was calculated.

如此所算出的尺寸變化率(85℃)，可表示為正的值(亦即收縮)或負的值(亦即膨脹)之任一者。尺寸變化率(85℃)為正值之保護膜，係例如由下述者所構成：選自鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂之聚烯烴系樹脂；選自纖維素三乙酸酯及纖維素二乙酸酯之纖維素酯系樹脂；選自聚甲基丙烯酸甲酯樹脂(PMMA樹脂)等之(甲基)丙烯酸系樹脂等。 The dimensional change rate (85°C) calculated in this way can be expressed as either a positive value (that is, shrinkage) or a negative value (that is, expansion). The protective film whose dimensional change rate (85°C) is a positive value is composed of, for example, the following: polyolefin resin selected from chain polyolefin resins and cyclic polyolefin resins; selected from cellulose triethyl Cellulose ester resins of acid esters and cellulose diacetate; (meth)acrylic resins selected from polymethyl methacrylate resins (PMMA resins) and the like.

與上述同樣地，於本發明中，在30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率的計算，係針對已測定尺寸變化率(85℃)後的膜，根據以下的式進行測定。此外，在30℃相對濕度95%的條件下經過0.5小 時後的尺寸變化率，有記載為尺寸變化率(30℃)的情況。 In the same way as above, in the present invention, the calculation of the dimensional change rate after 0.5 hours under the conditions of 30°C and 95% relative humidity is based on the film whose dimensional change rate (85°C) has been measured according to the following formula Perform the measurement. In addition, after 0.5 hours at 30°C and 95% relative humidity The dimensional change rate after time is sometimes described as the dimensional change rate (30°C).

例如，於本發明中，保護膜的在與偏光片的穿透軸方向呈平行的方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率，係有記載為保護膜的尺寸變化率(30℃)的情況。另一方面，在與偏光片的穿透軸方向呈平行的方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率，係有記載為偏光片的尺寸變化率(30℃)的情況。 For example, in the present invention, the dimensional change rate of the protective film in a direction parallel to the direction of the transmission axis of the polarizer after 0.5 hours at 30°C and 95% relative humidity is described as a protective film In the case of dimensional change rate (30°C). On the other hand, in the direction parallel to the transmission axis of the polarizer, the dimensional change rate after 0.5 hours at 30°C and 95% relative humidity is described as the dimensional change rate of the polarizer (30°C )Case.

以下，為了說明，保護膜的尺寸變化率(30℃)及偏光片的尺寸變化率(30℃)，有只記載為尺寸變化率(30℃)的情況。 Hereinafter, for the purpose of explanation, the dimensional change rate (30°C) of the protective film and the dimensional change rate (30°C) of the polarizer may be described only as the dimensional change rate (30°C).

尺寸變化率(30℃)=[(L030-L30)/L0]×100[式中，L030表示在與偏光片的穿透軸方向呈平行的方向(長度方向或寬度方向)之在測定尺寸變化率(85℃)後的膜的尺寸， Dimensional change rate (30℃)=[(L030-L30)/L0]×100[In the formula, L030 represents the measured dimensional change in the direction parallel to the transmission axis of the polarizer (length direction or width direction) The size of the film after the rate (85℃),

L30表示在30℃相對濕度95%的條件下經過0.5小時後的在與偏光片的穿透軸方向呈平行的方向(長度方向或寬度方向)的膜的尺寸。] L30 represents the size of the film in a direction (length direction or width direction) parallel to the transmission axis direction of the polarizer after 0.5 hours under the condition of 30° C. and 95% relative humidity. ]

例如，在測定尺寸變化率(85℃)後，於溫度23℃、濕度55%放置15分鐘後，可測定L030。 For example, after measuring the dimensional change rate (85°C) and leaving it at a temperature of 23°C and a humidity of 55% for 15 minutes, L030 can be measured.

如此所算出的尺寸變化率(30℃)，可表示為正的值(亦即收縮)或負的值(亦即膨脹)之任一者。尺寸變化率(30℃)為正值之保護膜，係例如由下述者所構成：鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等聚烯烴系樹脂；聚酯系樹脂； 例如聚對苯二甲酸乙二酯。 The dimensional change rate (30°C) calculated in this way can be expressed as either a positive value (that is, shrinkage) or a negative value (that is, expansion). The protective film whose dimensional change rate (30°C) is a positive value is composed of, for example, polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins; polyester resins; For example, polyethylene terephthalate.

另一方面，尺寸變化率(30℃)為負值(膨脹)之保護膜，係例如由下述者所構成：纖維素三乙酸酯及纖維素二乙酸酯等纖維素酯系樹脂、以及例如聚甲基丙烯酸甲酯樹脂(PMMA樹脂)等(甲基)丙烯酸系樹脂。 On the other hand, a protective film with a negative dimensional change rate (30°C) (expansion) is composed of, for example, cellulose ester resins such as cellulose triacetate and cellulose diacetate, And, for example, (meth)acrylic resins such as polymethyl methacrylate resin (PMMA resin).

本發明的保護膜，只要尺寸變化率(85℃)與尺寸變化率(30℃)的差之絕對值在本發明的範圍內，則尺寸變化率(85℃)的符號與尺寸變化率(30℃)的符號可皆為相同的符號(正、負或零)，亦可為不同的符號。 As long as the absolute value of the difference between the dimensional change rate (85°C) and the dimensional change rate (30°C) of the protective film of the present invention is within the scope of the present invention, the symbol of the dimensional change rate (85°C) and the dimensional change rate (30 The signs of °C) can all be the same sign (positive, negative or zero), or different signs.

於本發明中，保護膜係保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差之絕對值為0.02至0.50者。較佳為保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差之絕對值為0.03至0.30，更佳為0.03至0.20。 In the present invention, the absolute value of the difference between the dimensional change rate (85° C.) of the protective film-based protective film and the dimensional change rate (30° C.) of the protective film is 0.02 to 0.50. Preferably, the absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is 0.03 to 0.30, and more preferably 0.03 to 0.20.

本發明的偏光板，藉由在如此的範圍具有尺寸變化率的差之絕對值，即可提供於高溫條件、高濕度條件下抑制偏光片發生破裂並可抑制漏光而為耐久性佳的偏光板。而且，即使於重複高溫與低溫的環境下，本發明的偏光板亦不會發生漏光、破裂等，可顯示良好的偏光特性。 The polarizing plate of the present invention, by having the absolute value of the difference in the dimensional change rate in such a range, can provide a polarizing plate with excellent durability under high temperature conditions and high humidity conditions, which can suppress the cracking of the polarizer and suppress light leakage. . Moreover, even in environments where high and low temperatures are repeated, the polarizing plate of the present invention does not leak light, breaks, etc., and can exhibit good polarization characteristics.

再者，具備具有如此特性之保護膜之偏光板，可將偏光片予以薄化，並且即使於保護膜的表面發生刮傷時亦可抑制偏光片的破裂。 Furthermore, a polarizing plate provided with a protective film with such characteristics can reduce the thickness of the polarizer and prevent the polarizer from breaking even when the surface of the protective film is scratched.

於較佳的實施態樣中，本發明的偏光板， In a preferred embodiment, the polarizing plate of the present invention,

前述偏光片的在穿透軸方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率係設為偏光片的尺寸變化率(85℃)， The dimensional change rate of the aforementioned polarizer in the direction of the transmission axis at a relative humidity of 5% at 85°C after 1 hour is taken as the dimensional change rate of the polarizer (85°C),

前述偏光片的在穿透軸方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率係設為偏光片的尺寸變化率(30℃)， The dimensional change rate of the aforementioned polarizer in the direction of the transmission axis at a relative humidity of 95% at 30°C for 0.5 hours is taken as the dimensional change rate of the polarizer (30°C),

前述偏光片的尺寸變化率(85℃)與前述偏光片的尺寸變化率(30℃)的差的絕對值係設為FPZ， The absolute value of the difference between the dimensional change rate (85°C) of the polarizer and the dimensional change rate (30°C) of the polarizer is F PZ ,

前述保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差的絕對值係設為FPF， The absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is F PF ,

當從前述FPZ減去前述FPF之差係設為△FTD時， When the difference between the aforementioned F PZ and the aforementioned F PF is set as ΔF TD ,

以△FTD=FPZ-FPF表示， Expressed by △F TD =F PZ -F PF,

尺寸變化率的算出方法係可根據上述內容而算出。 The calculation method of the dimensional change rate can be calculated based on the above.

△FTD相對於FPZ的比例(△FTD/FPZ)較佳為0.5至0.95的範圍。更佳為△FTD/FPZ為0.55至0.95，又更佳為0.60至0.95。 The ratio of ΔF TD to F PZ (ΔF TD /F PZ ) is preferably in the range of 0.5 to 0.95. More preferably, ΔF TD /F PZ is 0.55 to 0.95, and still more preferably 0.60 to 0.95.

當△FTD/FPZ超過0.95時，保護膜的收縮及/或膨脹現象係比聚乙烯醇膜的收縮‧膨脹現象小，由於聚乙烯醇膜與保護膜間的變形，而導致可能發生聚乙烯醇膜的破裂。 When △F TD /F PZ exceeds 0.95, the shrinkage and/or expansion of the protective film is smaller than that of the polyvinyl alcohol film. Due to the deformation between the polyvinyl alcohol film and the protective film, polymerization may occur. Rupture of vinyl alcohol film.

因偏光片與保護膜具有如此的關係，故可提供於高溫條件、高濕度條件下不會發生漏光、破裂等而為耐久性佳的偏光板。而且，即使於重複高溫與低溫的環境下，本發明的偏光板亦不會發生漏光、破裂等，可顯示良好的偏光特性。再者，具備具有如此特性之保護膜之偏 光板，可將偏光片予以薄化，且即使於保護膜的表面發生刮傷時亦可抑制偏光片的破裂。 Since the polarizer and the protective film have such a relationship, it is possible to provide a polarizing plate with high durability without light leakage, cracking, etc. under high temperature conditions and high humidity conditions. Moreover, even in environments where high and low temperatures are repeated, the polarizing plate of the present invention does not leak light, breaks, etc., and can exhibit good polarization characteristics. Furthermore, the bias of a protective film with such characteristics The light plate can thin the polarizer, and even when the surface of the protective film is scratched, the polarizer can be prevented from breaking.

於較佳的實施態樣中，本發明的偏光板，係由偏光片、保護膜及黏著劑層依此順序配置而成的偏光板。於其他較佳的實施態樣中，本發明的偏光板，係由保護膜、偏光片及黏著劑層依此順序配置而成的偏光板。於較佳的實施態樣中，本發明的偏光片與保護膜係隔著接著劑層而貼合。接著劑層的厚度係例如為0.01μm至5μm。接著劑層可使用該技術領域習知者。 In a preferred embodiment, the polarizing plate of the present invention is a polarizing plate composed of a polarizer, a protective film, and an adhesive layer arranged in this order. In other preferred embodiments, the polarizing plate of the present invention is a polarizing plate in which a protective film, a polarizer, and an adhesive layer are arranged in this order. In a preferred embodiment, the polarizer and the protective film of the present invention are attached via the adhesive layer. The thickness of the adhesive layer is, for example, 0.01 μm to 5 μm. As the adhesive layer, those skilled in the art can be used.

例如本發明的偏光板，係如第2圖所示，可具有偏光片的吸收軸及穿透軸。 For example, the polarizing plate of the present invention, as shown in Fig. 2, may have the absorption axis and the transmission axis of the polarizer.

例如第2圖(a)係表示在寬度方向具有偏光片的穿透軸11a且在長度方向具有偏光片的吸收軸11b之偏光板100中之穿透軸11a與吸收軸11b的軸角度之概略平面圖。第2圖(b)係表示在長度方向具有偏光片的穿透軸11a且在寬度方向具有偏光片的吸收軸11b之偏光板100中之穿透軸11a與吸收軸11b的軸角度之概略平面圖。 For example, Figure 2(a) shows the outline of the axis angles between the transmission axis 11a and the absorption axis 11b in the polarizer 100 having the transmission axis 11a of the polarizer in the width direction and the absorption axis 11b of the polarizer in the length direction. Floor plan. Fig. 2(b) is a schematic plan view showing the axis angles of the transmission axis 11a and the absorption axis 11b in the polarizing plate 100 having the transmission axis 11a of the polarizer in the longitudinal direction and the absorption axis 11b of the polarizer in the width direction .

於較佳的實施態樣中，如第2圖(a)所示，偏光板100的外形形狀係可為例如具有長邊與短邊的長方形形狀。於該情況時，偏光板100(偏光片11)的穿透軸11a與偏光板100的短邊可呈平行或略平行(所成的角度為±7度以內)。另一方面，吸收軸11b係與穿透軸11a呈垂直。 In a preferred embodiment, as shown in FIG. 2(a), the outer shape of the polarizing plate 100 may be, for example, a rectangular shape with long sides and short sides. In this case, the transmission axis 11a of the polarizer 100 (the polarizer 11) and the short side of the polarizer 100 may be parallel or slightly parallel (the angle formed is within ±7 degrees). On the other hand, the absorption axis 11b is perpendicular to the penetration axis 11a.

而且，於其他較佳的實施態樣中，如第2圖(b)所示，偏光板100(偏光片11)的穿透軸11a與偏光板 100的長邊可呈平行或略平行(所成的角度為±7度以內)。另一方面，吸收軸11b係與穿透軸11a呈垂直。 Moreover, in other preferred embodiments, as shown in Figure 2(b), the transmission axis 11a of the polarizer 100 (the polarizer 11) and the polarizer The long sides of 100 can be parallel or slightly parallel (the angle formed is within ±7 degrees). On the other hand, the absorption axis 11b is perpendicular to the penetration axis 11a.

[偏光片] [Polarizer]

偏光片，係可為使二色性色素吸附配向於一軸延伸的聚乙烯醇系樹脂層而成者。偏光片，通常其厚度若為20μm以下時，即可實現偏光板的薄膜化。於本發明中，可採用例如厚度為10μm以下之偏光片，較佳為8μm以下之偏光片。而且，本發明之偏光片通常具有2μm以上的厚度。 The polarizer may be formed by adsorbing and aligning a dichroic dye to a polyvinyl alcohol-based resin layer extending uniaxially. Generally, if the thickness of the polarizer is 20 μm or less, the thin film of the polarizer can be realized. In the present invention, for example, a polarizer with a thickness of 10 μm or less, preferably a polarizer with a thickness of 8 μm or less can be used. Moreover, the polarizer of the present invention usually has a thickness of 2 μm or more.

聚乙烯醇系樹脂係可使用將聚乙酸乙烯酯系樹脂皂化者。聚乙酸乙烯酯系樹脂，除了可例示如屬於乙酸乙烯酯的均聚物之聚乙酸乙烯酯以外，亦可例示如由乙酸乙烯酯及可與其共聚合之其他單體所成的共聚物。可與乙酸乙烯酯共聚合之其他單體，係可舉例如不飽和羧酸、烯烴、乙烯醚、不飽和磺酸、具有銨基的丙烯醯胺等。 As the polyvinyl alcohol-based resin, those obtained by saponifying a polyvinyl acetate-based resin can be used. The polyvinyl acetate-based resin may be exemplified by polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as a copolymer of vinyl acetate and other monomers copolymerizable therewith. Other monomers that can be copolymerized with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamide having an ammonium group.

聚乙烯醇系樹脂的皂化度可為80莫耳%以上的範圍，較佳為90莫耳%以上，更佳為95莫耳%以上的範圍。聚乙烯醇系樹脂可為一部分被改性之改性聚乙烯醇，可舉例如使聚乙烯醇被下述等所改性者：乙烯及丙烯等烯烴；丙烯酸、甲基丙烯酸及巴豆酸等不飽和羧酸；不飽和羧酸的烷酯及丙烯醯胺等。聚乙烯醇系樹脂的平均聚合度，較佳為100至10000，更佳為1500至8000，又更佳為2000至5000。 The degree of saponification of the polyvinyl alcohol-based resin may be in the range of 80 mol% or more, preferably 90 mol% or more, and more preferably in the range of 95 mol% or more. The polyvinyl alcohol-based resin may be modified polyvinyl alcohol partially modified. Examples include those modified by polyvinyl alcohol: olefins such as ethylene and propylene; acrylic acid, methacrylic acid, and crotonic acid. Saturated carboxylic acid; alkyl ester of unsaturated carboxylic acid and acrylamide, etc. The average degree of polymerization of the polyvinyl alcohol-based resin is preferably 100 to 10,000, more preferably 1,500 to 8,000, and still more preferably 2,000 to 5,000.

偏光片，係例如可藉由將由聚乙烯醇系樹 脂所構成的原料膜進行一軸延伸，以二色性色素染色(染色處理)，然後以硼酸水溶液處理(硼酸處理)，並且予以水洗(水洗處理)，最後使其乾燥而製造。 Polarizers, for example, can be made of polyvinyl alcohol The raw film made of grease is stretched uniaxially, dyed with a dichroic dye (dyeing treatment), then treated with an aqueous solution of boric acid (boric acid treatment), washed with water (washed treatment), and finally dried to manufacture.

聚乙烯醇系樹脂膜的一軸延伸，可在二色性色素的染色前進行，亦可與二色性色素的染色同時進行，也可在二色性色素的染色後進行。在二色性色素的染色後進行一軸延伸時，該一軸延伸可在硼酸處理前進行，亦可在硼酸處理中進行。當然，亦可在該等複數個階段中進行一軸延伸。若要實施一軸延伸，可通過轉速不同的滾輪間進行延伸，亦可藉由以熱滾輪夾住的方法進行延伸。而且，可為在大氣中進行延伸的乾式延伸，亦可為因溶劑而膨脹的狀態下進行延伸的濕式延伸。聚乙烯醇系樹脂膜的最終延伸倍率通常為4至8倍左右。 The uniaxial stretching of the polyvinyl alcohol-based resin film may be performed before the dyeing of the dichroic dye, may be performed simultaneously with the dyeing of the dichroic dye, or may be performed after the dyeing of the dichroic dye. When performing uniaxial stretching after dyeing of the dichroic dye, the uniaxial stretching may be performed before the boric acid treatment or may be performed during the boric acid treatment. Of course, one-axis extension can also be performed in these plural stages. To implement one-axis extension, it can be extended between rollers with different rotation speeds, or it can be extended by a method of clamping by hot rollers. Furthermore, it may be dry stretching in which it is stretched in the atmosphere, or wet stretching in which it is stretched in a state swollen by a solvent. The final stretching ratio of the polyvinyl alcohol-based resin film is usually about 4 to 8 times.

於染色處理中，係將聚乙烯醇系樹脂膜以二色性色素染色，使二色性色素吸附於膜。染色處理，係只要例如將聚乙烯醇系樹脂膜浸漬於含有二色性色素的水溶液即可。二色性色素係具體上是使用碘或二色性染料。 In the dyeing process, the polyvinyl alcohol-based resin film is dyed with a dichroic dye to adsorb the dichroic dye to the film. For the dyeing treatment, for example, the polyvinyl alcohol-based resin film may be immersed in an aqueous solution containing a dichroic dye. Specifically, the dichroic dye system uses iodine or a dichroic dye.

當使用碘作為二色性色素時，通常採用將聚乙烯醇系樹脂膜浸漬於含有碘及碘化鉀的水溶液而染色的方法。該水溶液中的碘的含量，相對於水100重量份，通常為0.01至0.5重量份左右；碘化鉀的含量，相對於水100重量份，通常為0.5至10重量份左右。該水溶液的溫度通常為20至40℃左右，而且對該水溶液的浸漬時間通常為30至300秒左右。 When iodine is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide for dyeing is usually adopted. The content of iodine in the aqueous solution is usually about 0.01 to 0.5 parts by weight relative to 100 parts by weight of water; the content of potassium iodide is usually about 0.5 to 10 parts by weight relative to 100 parts by weight of water. The temperature of the aqueous solution is usually about 20 to 40°C, and the immersion time for the aqueous solution is usually about 30 to 300 seconds.

另一方面，當使用二色性染料作為二色性色素時，通常採用將聚乙烯醇系樹脂膜浸漬於含有水溶性二色性染料的水溶液而染色的方法。該水溶液中的二色性染料的含量，相對於水100重量份，通常為1×10-3至1×10-2重量份左右。該水溶液亦可含有硫酸鈉等無機鹽。該水溶液的溫度通常為20至80℃左右，而且對該水溶液的浸漬時間通常為30至300秒左右。 On the other hand, when a dichroic dye is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye for dyeing is usually adopted. The content of the dichroic dye in the aqueous solution is usually about 1×10 -3 to 1×10 -2 parts by weight with respect to 100 parts by weight of water. The aqueous solution may contain inorganic salts such as sodium sulfate. The temperature of the aqueous solution is usually about 20 to 80°C, and the immersion time for the aqueous solution is usually about 30 to 300 seconds.

硼酸處理，係例如將經染色的聚乙烯醇系樹脂膜浸漬於硼酸水溶液而進行。硼酸水溶液中的硼酸的含量，相對於水100重量份，通常為2至15重量份左右，較佳為5至12重量份。當使用碘作為二色性色素時，該硼酸水溶液係以含有碘化鉀為佳。硼酸水溶液中的碘化鉀的含量，相對於水100重量份，通常為2至20重量份左右，較佳為5至15重量份。對硼酸水溶液的浸漬時間通常為100至1200秒左右，較佳為150秒以上，更佳為200秒以上，而且較佳為600秒以下，更佳為400秒以下。硼酸水溶液的溫度通常為50℃以上，較佳為50至85℃。於硼酸水溶液中，可添加硫酸、鹽酸、乙酸、抗壞血酸等作為pH調整劑。 The boric acid treatment is performed, for example, by immersing the dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. The content of boric acid in the boric acid aqueous solution is usually about 2 to 15 parts by weight, preferably 5 to 12 parts by weight, relative to 100 parts by weight of water. When iodine is used as the dichroic pigment, the boric acid aqueous solution preferably contains potassium iodide. The content of potassium iodide in the boric acid aqueous solution is usually about 2 to 20 parts by weight, and preferably 5 to 15 parts by weight with respect to 100 parts by weight of water. The immersion time for the boric acid aqueous solution is usually about 100 to 1200 seconds, preferably 150 seconds or more, more preferably 200 seconds or more, and preferably 600 seconds or less, more preferably 400 seconds or less. The temperature of the boric acid aqueous solution is usually 50°C or higher, preferably 50 to 85°C. In the boric acid aqueous solution, sulfuric acid, hydrochloric acid, acetic acid, ascorbic acid, etc. can be added as a pH adjusting agent.

硼酸處理後的聚乙烯醇系樹脂膜，通常經實施水洗處理。水洗處理，係例如將經硼酸處理過的聚乙烯醇系樹脂膜浸漬於水而進行。水洗後實施乾燥，得到偏光片。水洗處理的水的溫度通常為5至40℃左右，浸漬時間通常為2至120秒左右。其後進行的乾燥，通常是使用 熱風乾燥機、遠紅外線加熱器進行。其乾燥溫度通常為40至100℃，乾燥時間通常為120至600秒左右。 The polyvinyl alcohol-based resin film after the boric acid treatment is usually subjected to water washing treatment. The water washing treatment is performed, for example, by immersing a polyvinyl alcohol-based resin film treated with boric acid in water. After washing with water, drying was performed to obtain a polarizer. The temperature of the water to be washed is usually about 5 to 40°C, and the immersion time is usually about 2 to 120 seconds. The subsequent drying is usually done using Hot air dryer, far-infrared heater. The drying temperature is usually 40 to 100°C, and the drying time is usually about 120 to 600 seconds.

[保護膜] [Protective Film]

如上所述，本發明的保護膜，係保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差之絕對值為0.02至0.50者。 As described above, the protective film of the present invention is one in which the absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is 0.02 to 0.50.

保護膜係積層於偏光片的至少一面。再者，亦可於偏光片的單面積層保護膜(第1保護膜)，並於另一面積層其他保護膜(第2保護膜)。較佳為於偏光片的單面積層保護膜(第1保護膜)。第1保護膜與第2保護膜，可為單層，亦可為將複數片膜藉由黏著劑或接著劑而積層者。 The protective film is laminated on at least one side of the polarizer. Furthermore, a single-area protective film (first protective film) of the polarizer may be layered, and another protective film (second protective film) may be layered on another area. Preferably, it is a single-area layer protective film (first protective film) of a polarizer. The first protective film and the second protective film may be a single layer, or a plurality of films laminated by an adhesive or an adhesive.

保護膜(第1保護膜)及第2保護膜，分別可為由熱塑性樹脂所構成的透明樹脂膜。熱塑性樹脂係可舉例如：以聚丙烯系樹脂為例的鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等聚烯烴系樹脂；纖維素三乙酸酯及纖維素二乙酸酯等纖維素酯系樹脂；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯及聚對苯二甲酸丁二酯等聚酯系樹脂；聚碳酸酯系樹脂；選自聚甲基丙烯酸甲酯樹脂之(甲基)丙烯酸系樹脂；或該等的至少2種以上的混合物等。而且，亦可使用構成上述樹脂的至少2種以上的單體的共聚物。 The protective film (first protective film) and the second protective film may each be a transparent resin film made of a thermoplastic resin. Examples of thermoplastic resins include: polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins such as polypropylene resins; cellulose such as cellulose triacetate and cellulose diacetate Ester resins; polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; polycarbonate resins; selected from polymethyl methacrylate resins (Meth)acrylic resin; or a mixture of at least two or more of these. Furthermore, a copolymer of at least two or more monomers constituting the above-mentioned resin may also be used.

環狀聚烯烴系樹脂，通常係以環狀烯烴作為聚合單元而聚合成的樹脂的總稱，可舉例如日本特開平 1-240517號公報、特開平3-14882號公報、特開平3-122137號公報等記載的樹脂。若要列舉環狀聚烯烴系樹脂的具體例，則為環狀烯烴的開環(共)聚合物、環狀烯烴的加成聚合物、由乙烯及丙烯等鏈狀烯烴與環狀烯烴所成的共聚物(代表例為無規共聚物)、及將該等以不飽和羧酸或其衍生物改性的接枝共聚物、以及該等的氫化物等。其中，使用降莰烯或多環降莰烯系單體等降莰烯系單體作為環狀烯烴之降莰烯系樹脂係較適用。 Cyclic polyolefin resins are generally a general term for resins polymerized with cyclic olefins as polymerization units. For example, Japanese Patent Application Laid-Open 1-240517, Japanese Patent Application Publication No. 3-14882, Japanese Patent Application Publication No. 3-122137, etc. Specific examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, and cyclic olefins such as ethylene and propylene. (A representative example is a random copolymer), graft copolymers modified with unsaturated carboxylic acid or derivatives thereof, and hydrogenated products thereof. Among them, a norbornene-based resin system that uses a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer as a cyclic olefin is more suitable.

環狀聚烯烴系樹脂有各種市售品販售。環狀聚烯烴系樹脂的市售品的例子，以商品名表示，有由TOPAS ADVANCED POLYMERS GmbH公司生產且於日本由Polyplastics股份有限公司販售的“TOPAS”(註冊商標)、JSR股份有限公司販售的“ARTON”(註冊商標)、日本ZEON股份有限公司販售的“ZEONOR”(註冊商標)及“ZEONEX”(註冊商標)、三井化學股份有限公司製販售的“APEL”(註冊商標)等。 Cyclic polyolefin resins are sold in various commercial products. Examples of commercially available products of cyclic polyolefin resins are represented by trade names. There are "TOPAS" (registered trademark) produced by TOPAS ADVANCED POLYMERS GmbH and sold in Japan by Polyplastics Co., Ltd., and JSR Co., Ltd. "ARTON" (registered trademark) sold by Japan, "ZEONOR" (registered trademark) and "ZEONEX" (registered trademark) sold by ZEON Co., Ltd., "APEL" (registered trademark) sold by Mitsui Chemicals Co., Ltd., etc. .

而且，可使用經製膜的環狀聚烯烴系樹脂膜作為保護膜。其市售品的例子，以商品名表示，有JSR股份有限公司販售的“ARTON FILM”(「ARTON」為該公司的註冊商標)、積水化學工業股份有限公司販售的“ESCENA”(註冊商標)及“SCA40”、日本ZEON股份有限公司販售的“ZEONOR FILM”(註冊商標)等。 Furthermore, the formed cyclic polyolefin resin film can be used as a protective film. Examples of commercially available products are represented by product names, such as "ARTON FILM" sold by JSR Co., Ltd. ("ARTON" is a registered trademark of the company), and "ESCENA" sold by Sekisui Chemical Industry Co., Ltd. (registered Trademark) and "SCA40", "ZEONOR FILM" (registered trademark) sold by ZEON Co., Ltd., etc.

纖維素酯系樹脂，通常為纖維素與脂肪酸的酯。纖維素酯系樹脂的具體例，可舉例如纖維素三乙酸 酯、纖維素二乙酸酯、纖維素三丙酸酯、纖維素二丙酸酯等。而且，可使用該等的共聚物、或羥基的一部分經其他取代基修飾者。該等之中，特佳為纖維素三乙酸酯(三乙醯基纖維素：TAC)。纖維素三乙酸酯有許多製品市售，從取得容易性、成本的觀點來看也為有利。纖維素三乙酸酯的市售品的例子，以商品名表示，例如富士軟片股份有限公司販售的“Fujitac(註冊商標)TD80”、“Fujitac(註冊商標)TD80UF”、“Fujitac(註冊商標)TD80UZ”及“Fujitac(註冊商標)TD40UZ”、柯尼卡美能達股份有限公司製的TAC膜“KC8UX2M”、“KC2UA”及“KC4UY”等。 The cellulose ester resin is usually an ester of cellulose and fatty acid. Specific examples of cellulose ester resins include cellulose triacetic acid Ester, cellulose diacetate, cellulose tripropionate, cellulose dipropionate, etc. Furthermore, these copolymers, or a part of the hydroxyl group modified with other substituents can be used. Among them, cellulose triacetate (triacetyl cellulose: TAC) is particularly preferred. Many products of cellulose triacetate are commercially available, and they are also advantageous from the viewpoint of ease of acquisition and cost. Examples of commercially available products of cellulose triacetate are represented by trade names, such as "Fujitac (registered trademark) TD80", "Fujitac (registered trademark) TD80UF", "Fujitac (registered trademark) sold by Fuji Film Co., Ltd. ) TD80UZ" and "Fujitac (registered trademark) TD40UZ", TAC films "KC8UX2M", "KC2UA" and "KC4UY" manufactured by Konica Minolta Co., Ltd.

聚甲基丙烯酸酯及聚丙烯酸酯(以下，有將聚甲基丙烯酸酯及聚丙烯酸酯合併稱為(甲基)丙烯酸系樹脂之情形)可容易地從市場上取得。 Polymethacrylate and polyacrylate (hereinafter, polymethacrylate and polyacrylate may be collectively referred to as (meth)acrylic resin) are easily available on the market.

(甲基)丙烯酸系樹脂係可舉例如甲基丙烯酸烷酯或丙烯酸烷酯的均聚物、或是甲基丙烯酸烷酯與丙烯酸烷酯的共聚物等。就甲基丙烯酸烷酯而言，具體上可列舉如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯等；而且，就丙烯酸烷酯而言，具體上可列舉如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯等。而且，如此的(甲基)丙烯酸系樹脂係可使用市售之泛用(甲基)丙烯酸系樹脂，(甲基)丙烯酸系樹脂亦可使用被稱為耐衝擊(甲基)丙烯酸樹脂者。 The (meth)acrylic resin system includes, for example, a homopolymer of alkyl methacrylate or alkyl acrylate, or a copolymer of alkyl methacrylate and alkyl acrylate. For alkyl methacrylates, specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc.; and, for alkyl acrylates, specific examples include methyl acrylate. , Ethyl acrylate, Propyl acrylate, etc. In addition, a commercially available general-purpose (meth)acrylic resin can be used for such a (meth)acrylic resin, and what is called an impact-resistant (meth)acrylic resin can also be used for the (meth)acrylic resin.

(甲基)丙烯酸系樹脂，通常係以甲基丙烯酸酯為主體的聚合物。甲基丙烯酸酯，可為1種甲基丙烯酸 酯的均聚物，亦可為甲基丙烯酸酯與其他甲基丙烯酸酯或丙烯酸酯等的共聚物。就甲基丙烯酸酯而言，可舉例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等甲基丙烯酸烷酯，其烷基的碳數通常為1至4左右。而且，亦可使用：甲基丙烯酸環戊酯、甲基丙烯酸環己酯等甲基丙烯酸環烷酯；甲基丙烯酸苯酯等甲基丙烯酸芳基酯；甲基丙烯酸環己基甲酯等甲基丙烯酸環烷基烷酯；甲基丙烯酸苯甲酯等甲基丙烯酸芳烷酯。 The (meth)acrylic resin is usually a polymer mainly composed of methacrylate. Methacrylate, can be 1 type of methacrylic acid The homopolymer of ester may also be a copolymer of methacrylate and other methacrylate or acrylate. Examples of methacrylates include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. The number of carbon atoms in the alkyl group is usually about 1 to 4. Moreover, cycloalkyl methacrylates such as cyclopentyl methacrylate and cyclohexyl methacrylate; aryl methacrylates such as phenyl methacrylate; methyl methacrylates such as cyclohexyl methyl methacrylate can also be used. Cycloalkyl alkyl acrylate; aralkyl methacrylate such as benzyl methacrylate.

可構成(甲基)丙烯酸系樹脂的上述其他聚合性單體，係可舉例如丙烯酸酯、或是甲基丙烯酸酯及丙烯酸酯以外的聚合性單體。丙烯酸酯係可使用丙烯酸烷酯，其具體例包括：丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸2-乙基己酯、丙烯酸環己酯、丙烯酸2-羥基乙酯等烷基的碳數為1至8之丙烯酸烷酯。烷基的碳數較佳為1至4。於(甲基)丙烯酸系樹脂中，丙烯酸酯可使用單獨1種，亦可併用2種以上。 The above-mentioned other polymerizable monomers that can constitute the (meth)acrylic resin include, for example, acrylate, or polymerizable monomers other than methacrylate and acrylate. Acrylate series can use alkyl acrylate, and specific examples include: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic acid 2 -Ethylhexyl, cyclohexyl acrylate, 2-hydroxyethyl acrylate and other alkyl acrylates with the alkyl group of 1 to 8 carbon atoms. The carbon number of the alkyl group is preferably 1 to 4. In (meth)acrylic resin, acrylate may be used individually by 1 type, and may use 2 or more types together.

甲基丙烯酸酯及丙烯酸酯以外的聚合性單體，可舉例如分子內具有1個聚合性碳-碳雙鍵的單官能基單體、或分子內具有至少2個聚合性碳-碳雙鍵的多官能基單體，並且以使用單官能基單體為較佳。單官能基單體的具體例係包括：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、鹵化苯乙烯、羥基苯乙烯等苯乙烯系單體；丙烯腈、甲基丙烯腈等氰化乙烯；丙烯酸、甲基丙烯酸、順丁烯二酸酐、 亞甲基丁二酸酐等不飽和酸；N-甲基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等順丁烯二醯亞胺；甲基丙烯醇(methacryl alcohol)、烯丙醇(allyl alcohol)等烯丙醇；乙酸乙烯酯、氯化乙烯、乙烯、丙烯、4-甲基-1-戊烯、2-羥基甲基-1-丁烯、甲基乙烯基酮、N-乙烯基吡咯烷酮、N-乙烯基咔唑等其他單體。 Examples of polymerizable monomers other than methacrylate and acrylate include monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule, or at least two polymerizable carbon-carbon double bonds in the molecule Monofunctional monomers are preferred, and monofunctional monomers are preferred. Specific examples of monofunctional monomers include: styrene-based monomers such as styrene, α-methylstyrene, vinyl toluene, halogenated styrene, and hydroxystyrene; vinyl cyanide such as acrylonitrile and methacrylonitrile ; Acrylic acid, methacrylic acid, maleic anhydride, Unsaturated acids such as methylene succinic anhydride; N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, etc. Diimine; Allyl alcohols such as methacryl alcohol and allyl alcohol; Vinyl acetate, vinyl chloride, ethylene, propylene, 4-methyl-1-pentene, 2- Hydroxymethyl-1-butene, methyl vinyl ketone, N-vinylpyrrolidone, N-vinylcarbazole and other monomers.

而且，多官能基單體的具體例係包括：乙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯等多元醇的聚不飽和羧酸酯；丙烯酸烯丙酯、甲基丙烯酸烯丙酯、肉桂酸烯丙酯等不飽和羧酸的烯酯；鄰苯二甲酸二烯丙酯、順丁烯二酸二烯丙酯、三聚氰酸三烯丙酯、三聚異氰酸三烯丙酯等多元酸的聚烯酯、二乙烯基苯等芳香族聚烯基化合物。甲基丙烯酸酯及丙烯酸酯以外的聚合性單體，可使用單獨1種，亦可併用2種以上。 Furthermore, specific examples of multifunctional monomers include: polyunsaturated carboxylic acids of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, etc. Esters; allyl acrylate, allyl methacrylate, allyl cinnamate and other unsaturated carboxylic acid esters; diallyl phthalate, diallyl maleate, cyanuric acid Polyalkenyl esters of polybasic acids such as triallyl acid and triallyl isocyanate, and aromatic polyalkenyl compounds such as divinylbenzene. Polymerizable monomers other than methacrylate and acrylate may be used alone or in combination of two or more.

(甲基)丙烯酸系樹脂的較佳單體的組成，係以全部單體量為基準，甲基丙烯酸烷酯為50至100重量%，丙烯酸烷酯為0至50重量%，該等以外的聚合性單體為0至50重量%者；更佳為甲基丙烯酸烷酯為50至99.9重量%，丙烯酸烷酯為0.1至50重量%，該等以外的聚合性單體為0至49.9重量%者。 The composition of the preferred monomers of the (meth)acrylic resin is based on the total amount of monomers, the alkyl methacrylate is 50 to 100% by weight, the alkyl acrylate is 0 to 50% by weight, other than those The polymerizable monomer is from 0 to 50% by weight; more preferably, the alkyl methacrylate is from 50 to 99.9% by weight, the alkyl acrylate is from 0.1 to 50% by weight, and the polymerizable monomers other than these are from 0 to 49.9% by weight. %By.

而且，(甲基)丙烯酸系樹脂，係由於可提高膜的耐久性，故可在高分子主鏈具有環構造。環構造較佳為環狀酸酐構造、環狀醯亞胺構造、內酯環構造等雜環構 造。具體上可舉例如：戊二酸酐構造、丁二酸酐等環狀酸酐構造；戊二醯亞胺構造、丁二醯亞胺構造等環狀醯亞胺構造；丁內酯、戊內酯等內酯環構造。主鏈中的環構造的含量越多，越可提高(甲基)丙烯酸系樹脂的玻璃轉化溫度。環狀酸酐構造及環狀醯亞胺構造，係可藉由將具有順丁烯二酸或順丁烯二醯亞胺等環狀構造的單體予以共聚合而導入的方法、以聚合後脫水‧脫甲醇縮合反應而導入環狀酸酐構造的方法、使胺基化合物反應導入環狀醯亞胺構造的方法等來導入。具有內酯環構造的樹脂(聚合物)，可藉由調製在高分子鏈具有羥基及酯基的聚合物後，將所得之聚合物之羥基及酯基依需要在有機磷化合物等觸媒之存在下以加熱進行環化縮合來形成內酯環構造的方法而得之。 In addition, the (meth)acrylic resin can improve the durability of the film, so it can have a ring structure in the polymer main chain. The ring structure is preferably a heterocyclic structure such as a cyclic anhydride structure, a cyclic imine structure, and a lactone ring structure. make. Specifically, for example, cyclic acid anhydride structures such as glutaric anhydride structure and succinic anhydride; cyclic acid imine structures such as glutaric anhydride structure and succinimide structure; internal butyrolactone, valerolactone, etc. Ester ring structure. The more the content of the ring structure in the main chain, the higher the glass transition temperature of the (meth)acrylic resin. The cyclic acid anhydride structure and the cyclic imine structure can be introduced by copolymerizing monomers having a cyclic structure such as maleic acid or maleimide, and dehydrating after polymerization. ‧Introduction is a method of introducing a cyclic acid anhydride structure by a demethanol condensation reaction, a method of introducing a cyclic imine structure by reacting an amine-based compound, etc. A resin (polymer) with a lactone ring structure can be prepared by preparing a polymer having a hydroxyl group and an ester group in the polymer chain. It is obtained by the method of forming a lactone ring structure by heating and performing cyclization and condensation in the presence of the present.

在高分子鏈具有羥基及酯基的聚合物，可藉由例如使用2-(羥基甲基)丙烯酸甲酯、2-(羥基甲基)丙烯酸乙酯、2-(羥基甲基)丙烯酸異丙酯、2-(羥基甲基)丙烯酸正丁酯、2-(羥基甲基)丙烯酸第三丁酯等具有羥基及酯基的(甲基)丙烯酸酯作為單體的一部分而得之。具有內酯環構造的聚合物的更具體的調製方法，係記載於例如日本特開2007-254726號公報。 For polymers having hydroxyl and ester groups in the polymer chain, for example, methyl 2-(hydroxymeth)acrylate, ethyl 2-(hydroxymeth)acrylate, isopropyl 2-(hydroxymeth)acrylate can be used. A (meth)acrylate having a hydroxyl group and an ester group, such as an ester, n-butyl 2-(hydroxymeth)acrylate, and tertiary butyl 2-(hydroxymeth)acrylate, is obtained as a part of the monomer. A more specific method of preparing a polymer having a lactone ring structure is described in, for example, Japanese Patent Application Laid-Open No. 2007-254726.

藉由將包含上述單體之單體組成物進行自由基聚合，而可調製(甲基)丙烯酸系樹脂。單體組成物係可依需要而包含溶劑或聚合起始劑。 The (meth)acrylic resin can be prepared by radically polymerizing a monomer composition containing the above-mentioned monomers. The monomer composition system may contain a solvent or a polymerization initiator as needed.

(甲基)丙烯酸系樹脂，亦可包含上述(甲基) 丙烯酸系樹脂以外的其他樹脂。該其他樹脂的含有比例，較佳為0至70重量%，更佳為0至50重量%，又更佳為0至30重量%。該樹脂可為例如：聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚(4-甲基-1-戊烯)等烯烴系聚合物；氯化乙烯、氯化乙烯樹脂等含鹵素系聚合物；聚苯乙烯、苯乙烯-甲基丙烯酸甲酯共聚物、苯乙烯-丙烯腈共聚物等苯乙烯系聚合物；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯；由芳香族二醇與芳香族二羧酸所構成的聚芳酯；聚乳酸、聚丁二酸丁二酯等生物分解性聚酯；聚碳酸酯；尼龍6、尼龍66、尼龍610等聚醯胺；聚縮醛；聚苯醚；聚苯硫醚；聚醚醚酮；聚醚腈；聚碸；聚醚碸；聚氧苯甲酯(polyoxybenzylene)；聚醯胺醯亞胺等。 (Meth)acrylic resins may also include the above (meth) Resins other than acrylic resins. The content of the other resin is preferably 0 to 70% by weight, more preferably 0 to 50% by weight, and still more preferably 0 to 30% by weight. The resin may be, for example, olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly(4-methyl-1-pentene), etc.; halogen-containing polymers such as chlorinated ethylene and chlorinated vinyl resins ; Polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer and other styrene polymers; polyethylene terephthalate, polybutylene terephthalate, polynaphthalene Polyesters such as ethylene dicarboxylate; polyarylate composed of aromatic diols and aromatic dicarboxylic acids; biodegradable polyesters such as polylactic acid and polybutylene succinate; polycarbonate; nylon 6 , Nylon 66, nylon 610 and other polyamides; polyacetal; polyphenylene ether; polyphenylene sulfide; polyether ether ketone; polyether nitrile; Amide and imine etc.

從提高膜的耐衝擊性、製膜性的觀點來看，(甲基)丙烯酸系樹脂亦可含有橡膠粒子。橡膠粒子，可為只由顯示橡膠彈性的層所構成的粒子，亦可為具有顯示橡膠彈性的層與其他層的多層構造的粒子。橡膠彈性體係可舉例如烯烴系彈性聚合物、二烯系彈性聚合物、苯乙烯-二烯系彈性聚合物、丙烯酸系彈性聚合物等。其中，從耐光性及透明性的觀點來看，以使用丙烯酸系彈性聚合物為較佳。 From the viewpoint of improving the impact resistance and film forming properties of the film, the (meth)acrylic resin may contain rubber particles. The rubber particles may be particles composed of only a layer exhibiting rubber elasticity, or particles having a multilayer structure of a layer exhibiting rubber elasticity and other layers. Examples of the rubber elastic system include olefin-based elastic polymers, diene-based elastic polymers, styrene-diene-based elastic polymers, and acrylic-based elastic polymers. Among them, from the viewpoint of light resistance and transparency, it is preferable to use an acrylic elastic polymer.

丙烯酸系彈性聚合物係以丙烯酸烷酯為主體，亦即，以全部單體量為基準，可為包含50重量%以上的來自丙烯酸烷酯的構成單元的聚合物。丙烯酸系彈性聚合物，可為丙烯酸烷酯的均聚物，亦可為包含50重量%以 上的來自丙烯酸烷酯的構成單元與50重量%以下的來自其他聚合性單體的構成單元之共聚物。 The acrylic elastic polymer system is mainly composed of alkyl acrylate, that is, based on the total monomer amount, it may be a polymer containing 50% by weight or more of structural units derived from alkyl acrylate. The acrylic elastic polymer may be a homopolymer of alkyl acrylate, or may contain more than 50% by weight A copolymer of the above structural units derived from alkyl acrylate and 50% by weight or less of structural units derived from other polymerizable monomers.

構成丙烯酸系彈性聚合物的丙烯酸烷酯，通常係使用烷基的碳數為4至8者。若要列舉上述其他聚合性單體的例子，則為例如：甲基丙烯酸甲酯、甲基丙烯酸乙酯等甲基丙烯酸烷酯；苯乙烯、烷基苯乙烯等苯乙烯系單體；丙烯腈、甲基丙烯腈等不飽和腈等單官能基單體；再者，(甲基)丙烯酸烯丙酯、(甲基)丙烯酸甲基丙烯酯等不飽和羧酸的烯酯；順丁烯二酸二烯丙酯等二元酸的二烯酯；烷二醇二(甲基)丙烯酸酯等二醇的不飽和羧酸二酯等多官能基單體。 The alkyl acrylate constituting the acrylic elastic polymer is usually one having 4 to 8 carbon atoms in the alkyl group. If the examples of other polymerizable monomers mentioned above are mentioned, for example, alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; styrene monomers such as styrene and alkyl styrene; acrylonitrile Monofunctional monomers such as unsaturated nitriles such as methacrylonitrile and methacrylonitrile; in addition, allyl (meth)acrylate and methacrylate (meth)acrylate and other unsaturated carboxylic acid alkenes; maleic Diene esters of dibasic acids such as diallyl acid; multifunctional monomers such as unsaturated carboxylic acid diesters of glycols such as alkanediol di(meth)acrylate.

包含丙烯酸系彈性聚合物的橡膠粒子，較佳為具有丙烯酸系彈性聚合物的層之多層構造的粒子。具體上，可舉例如：於丙烯酸系彈性聚合物的層之外側具有以甲基丙烯酸烷酯為主體的硬質聚合物層的2層構造者，或是再於丙烯酸系彈性聚合物的層之內側具有以甲基丙烯酸烷酯為主體的硬質聚合物層的3層構造者。 The rubber particles containing an acrylic elastic polymer are preferably particles having a multilayer structure of acrylic elastic polymer layers. Specifically, for example, a two-layer structure having a hard polymer layer mainly composed of alkyl methacrylate on the outer side of the acrylic elastic polymer layer, or on the inner side of the acrylic elastic polymer layer It has a three-layer structure with a hard polymer layer mainly composed of alkyl methacrylate.

構成「在丙烯酸系彈性聚合物的層的外側或內側所形成之硬質聚合物層」之以甲基丙烯酸烷酯為主體的聚合物之單體組成的例子，係與作為(甲基)丙烯酸系樹脂的例子而列舉的以甲基丙烯酸烷酯為主體的聚合物的單體組成的例子相同，特別是以甲基丙烯酸甲酯為主體的單體組成係為較適用。如此的多層構造的丙烯酸系橡膠彈性體粒子，例如可藉由日本特公昭55-27576號公報記載的 方法製造。 An example of the monomer composition of a polymer mainly composed of alkyl methacrylate that constitutes the "hard polymer layer formed on the outside or inside of the acrylic elastic polymer layer" is the same as that of (meth)acrylic The examples of the resin are the same as the examples of the monomer composition of the polymer mainly composed of alkyl methacrylate, and the monomer composition system mainly composed of methyl methacrylate is more suitable. Such a multilayer structure of acrylic rubber elastomer particles can be described in Japanese Patent Publication No. 55-27576, for example. Method of manufacturing.

從(甲基)丙烯酸系樹脂的製膜性、膜的耐衝擊性、膜表面的光滑性的觀點來看，橡膠粒子較佳係到其中所含的橡膠彈性體層(丙烯酸系彈性聚合物的層)為止的平均粒徑為10至350nm的範圍者。該平均粒徑更佳為30nm以上，再更佳為50nm以上，而且更佳為300nm以下，再更佳為280nm以下。 From the viewpoints of (meth)acrylic resin film forming properties, film impact resistance, and film surface smoothness, the rubber particles are preferably connected to the rubber elastomer layer (acrylic elastic polymer layer) contained therein. The average particle size up to) is in the range of 10 to 350 nm. The average particle size is more preferably 30 nm or more, still more preferably 50 nm or more, more preferably 300 nm or less, and still more preferably 280 nm or less.

橡膠粒子中到的到橡膠彈性體層(丙烯酸系彈性聚合物的層)為止的平均粒徑，係藉由以下方式測定。亦即，將如此的橡膠粒子混合於(甲基)丙烯酸系樹脂而使其薄膜化，將其剖面用氧化釕的水溶液染色時，只有橡膠彈性體層著色，觀察到略圓形狀，但母層的甲基丙烯酸系樹脂沒有被染色。然後，從如此染色的膜剖面，使用切片機等調製薄片，以電子顯微鏡觀察。繼而，隨機抽選100個經染色的橡膠粒子，算出各自之粒徑(到橡膠彈性體層為止的直徑)後，以其數量平均值作為上述平均粒徑。因用如此的方法測定，故所得的上述平均粒徑為數量平均粒徑。 The average particle diameter of the rubber particles to the rubber elastomer layer (acrylic elastic polymer layer) was measured in the following manner. That is, when such rubber particles are mixed with (meth)acrylic resin to make the film thin, and the cross section is dyed with an aqueous solution of ruthenium oxide, only the rubber elastomer layer is colored, and a slightly round shape is observed, but the base layer The methacrylic resin is not dyed. Then, from the cross-section of the film dyed in this way, a slice is prepared using a microtome or the like, and it is observed with an electron microscope. Next, 100 dyed rubber particles were randomly selected, and their particle diameters (diameters up to the rubber elastomer layer) were calculated, and the number average value was used as the average particle diameter. Because of the measurement by this method, the average particle size obtained above is the number average particle size.

當橡膠粒子是最外層為以甲基丙烯酸甲酯為主體的硬質聚合物且於其中包裹有橡膠彈性體層(丙烯酸系彈性聚合物的層)的橡膠粒子時，若將其混合於母體的甲基丙烯酸系樹脂，則橡膠粒子的最外層會與母體的甲基丙烯酸系樹脂混合。因此，將其剖面用氧化釕的水溶液染色並以電子顯微鏡觀察時，會觀察到橡膠粒子為除去最外層的狀態的粒子。具體上，當橡膠粒子是內層為丙烯酸系 彈性聚合物且外層為以甲基丙烯酸甲酯為主體的硬質聚合物之2層構造的橡膠粒子時，內層的丙烯酸系彈性聚合物部分會被染色，而觀察到單層構造的粒子。而且，當橡膠粒子是最內層為以甲基丙烯酸甲酯為主體的硬質聚合物、中間層為丙烯酸系彈性聚合物、且最外層為以甲基丙烯酸甲酯為主體的硬質聚合物之3層構造的橡膠粒子時，最內層的粒子中心部分不會被染色，只有中間層的丙烯酸系彈性聚合物部分被染色，而觀察到2層構造的粒子。 When the rubber particles are rubber particles whose outermost layer is a hard polymer with methyl methacrylate as the main body and a rubber elastomer layer (acrylic elastic polymer layer) is wrapped in it, if it is mixed with the methyl group of the matrix Acrylic resin, the outermost layer of the rubber particles will be mixed with the methacrylic resin of the matrix. Therefore, when the cross section is dyed with an aqueous solution of ruthenium oxide and observed with an electron microscope, it is observed that the rubber particles are particles with the outermost layer removed. Specifically, when the rubber particles are the inner layer of acrylic When the outer layer is a two-layer rubber particle composed of an elastic polymer and a hard polymer mainly composed of methyl methacrylate, the acrylic elastic polymer part of the inner layer is dyed, and particles of a single layer structure are observed. Moreover, when the rubber particles are the innermost layer of a hard polymer mainly composed of methyl methacrylate, the middle layer is composed of an acrylic elastic polymer, and the outermost layer is the third of a hard polymer composed mainly of methyl methacrylate. In the case of rubber particles with a layer structure, the center part of the innermost layer of particles is not dyed, and only the acrylic elastic polymer part of the middle layer is dyed, and particles with a two-layer structure are observed.

從(甲基)丙烯酸系樹脂的製膜性、膜的耐衝擊性、膜表面的光滑性的觀點來看，橡膠粒子之調配比例，係以與構成(甲基)丙烯酸系樹脂膜之(甲基)丙烯酸系樹脂的合計量為基準，較佳為以3重量%以上、60重量%以下的比例來調配，更佳為45重量%以下，又更佳為35重量%以下。橡膠彈性體粒子變得比60重量%多時，膜的尺寸變化變大，耐熱性降低。另一方面，橡膠彈性體粒子比3重量%少時，雖然膜的耐熱性良好，但製膜時之捲取性差、生產性低。再者，於本發明中，當橡膠彈性體粒子係使用具有顯示橡膠彈性的層及其他層的多層構造的粒子時，是將由顯示橡膠彈性的層及其內側的層所構成的部分的重量視為橡膠彈性體粒子的重量。例如，當使用上述3層構造的丙烯酸系橡膠彈性體粒子時，是將中間層的丙烯酸系彈性聚合物部分與最內層的以甲基丙烯酸甲酯為主體的硬質聚合物部分的合計重量視為橡膠彈性體粒子的重量。將上述3層構造的丙烯酸系橡膠彈性體粒子溶解於丙酮時，因 中間層的丙烯酸系彈性聚合物部分與最內層的以甲基丙烯酸甲酯為主體的硬質聚合物部分係以作為不溶成分而殘留，故可容易地求得3層構造的丙烯酸系橡膠粒子中所佔的中間層與最內層的合計重量比例。 From the viewpoints of (meth)acrylic resin film forming properties, film impact resistance, and film surface smoothness, the blending ratio of rubber particles is based on the ratio of (A) which constitutes the (meth)acrylic resin film. Based on the total amount of the acrylic resin, it is preferably formulated in a ratio of 3% by weight or more and 60% by weight or less, more preferably 45% by weight or less, and still more preferably 35% by weight or less. When the amount of rubber elastomer particles exceeds 60% by weight, the dimensional change of the film increases, and the heat resistance decreases. On the other hand, when the amount of rubber elastomer particles is less than 3% by weight, although the heat resistance of the film is good, the coilability during film formation is poor and the productivity is low. Furthermore, in the present invention, when the rubber elastomer particles are particles having a multilayer structure of a layer exhibiting rubber elasticity and other layers, the weight of the part composed of the layer exhibiting rubber elasticity and the inner layer is regarded as the weight. Is the weight of the rubber elastomer particles. For example, when the acrylic rubber elastomer particles with the above three-layer structure are used, the total weight of the acrylic elastic polymer part of the middle layer and the hard polymer part mainly composed of methyl methacrylate in the innermost layer is regarded as the weight. Is the weight of the rubber elastomer particles. When the acrylic rubber elastomer particles with the above three-layer structure are dissolved in acetone, The acrylic elastic polymer part of the middle layer and the hard polymer part mainly composed of methyl methacrylate in the innermost layer remain as insoluble components, so it can be easily determined in the acrylic rubber particles with a three-layer structure The total weight ratio of the middle layer to the innermost layer.

當(甲基)丙烯酸系樹脂膜包含橡膠粒子時，在製作該膜時所使用的含有橡膠粒子的(甲基)丙烯酸系樹脂組成物，係可藉由將(甲基)丙烯酸系樹脂與橡膠粒子以熔融混練等進行混合而得之，此外，亦可藉由先製作橡膠粒子，於其存在下，使成為甲基丙烯酸系樹脂的原料之單體組成物進行聚合的方法而得之。 When the (meth)acrylic resin film contains rubber particles, the (meth)acrylic resin composition containing rubber particles used in the production of the film can be obtained by combining (meth)acrylic resin and rubber The particles are obtained by mixing by melt kneading or the like, and it can also be obtained by a method of first preparing rubber particles and, in the presence of them, polymerizing a monomer composition that becomes a raw material of the methacrylic resin.

於保護膜中亦可含有通常的添加劑，例如紫外線吸收劑、有機系染料、顏料、無機系色素、抗氧化劑、抗靜電劑、界面活性劑等。其中，紫外線吸收劑係因會提高耐候性而為較佳。紫外線吸收劑的例子，可舉例如：2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯並***-2-基)酚]、2-(5-甲基-2-羥基苯基)-2H-苯並***、2-[2-羥基-3,5-雙(α,α-二甲基苯甲基)苯基]-2H-苯並***、2-(3,5-二第三丁基-2-羥基苯基)-2H-苯並***、2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯-2H-苯並***、2-(3,5-二第三丁基-2-羥基苯基)-5-氯-2H-苯並***、2-(3,5-二第三戊基-2-羥基苯基)-2H-苯並***、2-(2’-羥基-5’-第三辛基苯基)-2H-苯並***等苯並***系紫外線吸收劑；2-羥基-4-甲氧基二苯基甲酮、2-羥基-4-辛氧基二苯基甲酮、2,4-二羥基二苯基甲酮、2-羥基-4-甲氧基-4’-氯二苯基甲酮、 2,2’-二羥基-4-甲氧基二苯基甲酮、2,2’-二羥基-4,4’-二甲氧基二苯基甲酮等2-羥基二苯基甲酮系紫外線吸收劑；水楊酸對-第三丁基苯酯、水楊酸對-辛基苯酯等水楊酸苯酯系紫外線吸收劑；2,4-二苯基-6-(2-羥基-4-甲氧基苯基)-1,3,5-三嗪(triazine)、2,4-二苯基-6-(2-羥基-4-乙氧基苯基)-1,3,5-三嗪、2,4-二苯基-(2-羥基-4-丙氧基苯基)-1,3,5-三嗪、2,4-二苯基-(2-羥基-4-丁氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-丁氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-己氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-辛氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-十二烷氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-苯甲氧基苯基)-1,3,5-三嗪、2-(2-羥基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三嗪、4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三嗪、2-[4-[2-羥基-3-(2’-乙基)己氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-羥基苯基、2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛氧基)酚、2-[2,6-二(2,4-二甲苯基)-1,3,5-三嗪-2-基]-5-辛氧基酚、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己醯基)乙氧基]酚、2,4,6-三(2-羥基-4-己氧基-3-甲氧基苯基)-1,3,5-三嗪等三嗪系紫外線吸收劑等。可依需要而使用該等的2種以上。 The protective film may also contain usual additives, such as ultraviolet absorbers, organic dyes, pigments, inorganic pigments, antioxidants, antistatic agents, surfactants, and the like. Among them, ultraviolet absorbers are preferred because they improve weather resistance. Examples of ultraviolet absorbers include: 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2- Yl)phenol], 2-(5-methyl-2-hydroxyphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl) )Phenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5 -Methyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzo Triazole, 2-(3,5-ditertiary pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)-2H -Benzotriazole-based ultraviolet absorbers such as benzotriazole; 2-hydroxy-4-methoxy diphenyl ketone, 2-hydroxy-4-octyloxy diphenyl ketone, 2,4-bis Hydroxy diphenyl ketone, 2-hydroxy-4-methoxy-4'-chloro diphenyl ketone, 2,2'-Dihydroxy-4-methoxydiphenyl ketone, 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone and other 2-hydroxy diphenyl ketones UV absorbers; Phenyl salicylate UV absorbers such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate; 2,4-Diphenyl-6-(2- Hydroxy-4-methoxyphenyl)-1,3,5-triazine (triazine), 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3 ,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy- 4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine , 2,4-Diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-Diphenyl-6-(2-hydroxy-4 -Octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-tris Oxazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxy Carbonyl ethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 4-bis[2-hydroxy-4-butoxyphenyl]- 6-(2,4-Dibutoxyphenyl)-1,3,5-triazine, 2-[4-[2-hydroxy-3-(2'-ethyl)hexyloxy]-2- Hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6-bis(2,4-dimethylphenyl) -1,3,5-triazin-2-yl)-5-hydroxyphenyl, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine- 2-yl]-5-(octyloxy)phenol, 2-[2,6-bis(2,4-xylenyl)-1,3,5-triazin-2-yl]-5-octyloxy Phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexyl)ethoxy]phenol, 2, Triazine-based ultraviolet absorbers such as 4,6-tris(2-hydroxy-4-hexyloxy-3-methoxyphenyl)-1,3,5-triazine, etc. Two or more of these can be used as needed.

紫外線吸收劑係可使用市售品，例如三嗪系紫外線吸收劑係有CHEMPRO化成股份有限公司製的 "Kemisorb 102"(註冊商標)、ADEKA股份有限公司製的"ADEKA STAB(註冊商標)LA46"、"ADEKA STAB(註冊商標)LAF70"、BASF公司製的"TINUVIN(註冊商標)460"、"TINUVIN(註冊商標)405"、"TINUVIN(註冊商標)400"及"TINUVIN(註冊商標)477"、Sun Chemical股份有限公司製的"CYASORB(註冊商標)UV-1164"(以上皆為商品名)等。苯並***系紫外線吸收劑則有例如ADEKA股份有限公司製的"ADEKA STAB LA31"及"ADEKA STAB LA36"、住化Chemtex股份有限公司製的"SUMISORB(註冊商標)200"、"SUMISORB(註冊商標)250"、"SUMISORB(註冊商標)300"、"SUMISORB(註冊商標)340"及"SUMISORB(註冊商標)350"、CHEMPRO化成股份有限公司製的"Kemisorb 74"(註冊商標)、"Kemisorb 79"(註冊商標)及"Kemisorb 279"(註冊商標)、BASF公司製的"TINUVIN(註冊商標)99-2"、"TINUVIN(註冊商標)900"及"TINUVIN(註冊商標)928"(以上皆為商品名)等。當(甲基)丙烯酸系樹脂膜包含紫外線吸收劑時，其量相對於(甲基)丙烯酸系樹脂100重量%而言，通常為0.1重量%以上，較佳為0.3重量%以上，又，較佳為3重量%以下。 Commercially available UV absorbers can be used. For example, triazine UV absorbers are manufactured by CHEMPRO Chemical Co., Ltd. "Kemisorb 102" (registered trademark), "ADEKA STAB (registered trademark) LA46", "ADEKA STAB (registered trademark) LAF70" manufactured by ADEKA Co., Ltd., "TINUVIN (registered trademark) 460", "TINUVIN manufactured by BASF Corporation" (Registered trademark) 405", "TINUVIN (registered trademark) 400" and "TINUVIN (registered trademark) 477", "CYASORB (registered trademark) UV-1164" made by Sun Chemical Co., Ltd. (all the above are trade names), etc. . Benzotriazole-based ultraviolet absorbers include, for example, "ADEKA STAB LA31" and "ADEKA STAB LA36" manufactured by ADEKA Co., Ltd., "SUMISORB (registered trademark) 200" manufactured by Sumika Chemtex Co., Ltd., and "SUMISORB (registered Trademark) 250", "SUMISORB (registered trademark) 300", "SUMISORB (registered trademark) 340" and "SUMISORB (registered trademark) 350", "Kemisorb 74" (registered trademark) manufactured by CHEMPRO Chemical Co., Ltd., and "Kemisorb 79" (registered trademark) and "Kemisorb 279" (registered trademark), BASF "TINUVIN (registered trademark) 99-2", "TINUVIN (registered trademark) 900" and "TINUVIN (registered trademark) 928" (above All are product names) and so on. When the (meth)acrylic resin film contains an ultraviolet absorber, the amount is usually 0.1% by weight or more, preferably 0.3% by weight or more, relative to 100% by weight of the (meth)acrylic resin. It is preferably 3% by weight or less.

在製作(甲基)丙烯酸系樹脂膜時，可採用傳統習知的製膜方法。(甲基)丙烯酸系樹脂膜可具有多層構造，多層構造的(甲基)丙烯酸系樹脂膜可採用使用進料模組(feed block)的方法、使用多歧管模具(multi-manifold die)的方法等的一般習知的各種方法。其中，例如隔著進料模組而積層並從T型模具進行多層熔融擠出成形使所得之積 層膜狀物的至少單面接觸滾輪或皮帶而製膜的方法，係因可得到表面性質形狀良好的膜，而為較佳。特別是從提高(甲基)丙烯酸系樹脂膜的表面平滑性及表面光澤性的觀點來看，較佳係使上述多層熔融擠出成形所得之積層膜狀物的兩面接觸滾輪表面或皮帶表面而予以薄膜化的方法。此時所使用的滾輪或皮帶，其與(甲基)丙烯酸系樹脂膜接觸的滾輪表面或皮帶表面，為了對(甲基)丙烯酸系樹脂膜表面賦予平滑性，係以該表面成為鏡面者為較佳。 When the (meth)acrylic resin film is made, a conventionally known film making method can be used. The (meth)acrylic resin film may have a multilayer structure, and the (meth)acrylic resin film of the multilayer structure may adopt a method using a feed block or a method using a multi-manifold die. Various methods of general knowledge such as methods. Among them, for example, laminated layers are laminated via a feed module, and multilayer melt-extrusion molding is performed from a T-die to make the resulting product The method of forming a film by contacting at least one side of the layered film-like substance with a roller or a belt is preferable because a film with good surface properties and shape can be obtained. In particular, from the viewpoint of improving the surface smoothness and surface gloss of the (meth)acrylic resin film, it is preferable that both sides of the laminated film obtained by the above-mentioned multi-layer melt extrusion molding contact the surface of the roller or the surface of the belt. The method of thinning. For the roller or belt used at this time, the surface of the roller or belt which is in contact with the (meth)acrylic resin film, in order to impart smoothness to the surface of the (meth)acrylic resin film, the surface is a mirror surface Better.

(甲基)丙烯酸系樹脂膜，可為對依以上方式製作的膜實施延伸處理後所得者。為了得到具有所期望的光學特性、機械特性的膜，有時需要延伸處理。延伸處理係可舉例如一軸延伸、二軸延伸等。延伸方向係可舉例如未延伸膜的機械流動方向(MD)、與其垂直的方向(TD)、與機械流動方向(MD)斜交的方向等。二軸延伸，可為往2個延伸方向同時延伸的同時二軸延伸，亦可為往指定方向延伸後再往其他方向延伸之逐次二軸延伸。 The (meth)acrylic resin film may be obtained by subjecting the film produced in the above manner to stretching treatment. In order to obtain a film having desired optical and mechanical properties, stretching treatment may be necessary. Examples of the stretching treatment system include one-axis stretching and two-axis stretching. Examples of the stretching direction include the machine flow direction (MD) of the unstretched film, the direction perpendicular to it (TD), the direction oblique to the machine flow direction (MD), and the like. The two-axis extension can be two-axis extension while simultaneously extending in two extension directions, or it can be a sequential two-axis extension after extending in a specified direction and then extending in other directions.

第1保護膜及第2保護膜，只要是在包含於本發明的範圍限制下，可為兼具相位差膜及增亮膜等光學功能的保護膜。例如，可藉由將由上述材料所構成的透明樹脂膜進行延伸(一軸延伸或二軸延伸等)、或於該膜上形成液晶層等，而賦予任意的相位差值以製成相位差膜。 As long as the first protective film and the second protective film are included in the scope of the present invention, they may be protective films that have both optical functions such as a retardation film and a brightness enhancement film. For example, a transparent resin film made of the above-mentioned material can be stretched (uniaxially stretched or biaxially stretched, etc.), or a liquid crystal layer is formed on the film, and an arbitrary retardation value can be given to produce a retardation film.

第1保護膜及第2保護膜，係可在與偏光片為相反側的表面，形成硬塗層、防眩層、抗反射層、抗靜電層及防污層等表面處理層(塗佈層)。於保護膜的表面形 成表面處理層的方法，可使用習知的方法。 The first protective film and the second protective film can form surface treatment layers (coating layer ). For the surface shape of the protective film As the method of forming the surface treatment layer, a conventional method can be used.

第1保護膜及第2保護膜，互相可為相同的保護膜，亦可為不同的保護膜。保護膜不同的情況之例子，係有下述組合：構成保護膜的熱塑性樹脂的種類至少不同的組合；保護膜的光學功能的有無或其種類至少不同的組合；形成於表面的表面處理層的有無或其種類至少不同的組合等。 The first protective film and the second protective film may be the same protective film or different protective films. Examples of cases where the protective film is different include the following combinations: a combination of at least different types of thermoplastic resins constituting the protective film; presence or absence of the optical function of the protective film or combinations of at least different types; a combination of the surface treatment layer formed on the surface The presence or absence or the combination of at least different types, etc.

第1保護膜及第2保護膜的厚度，從偏光板的薄膜化的觀點來看，係以薄者較佳，但太薄時會強度降低且加工性變差。所以，第1保護膜及第2保護膜的厚度係以5至90μm以下較佳，更佳為60μm以下，又更佳為50μm以下，特佳為30μm以下。 The thickness of the first protective film and the second protective film is preferably thinner from the viewpoint of thinning of the polarizing plate, but if it is too thin, the strength will decrease and the workability will deteriorate. Therefore, the thickness of the first protective film and the second protective film is preferably 5 to 90 μm or less, more preferably 60 μm or less, still more preferably 50 μm or less, particularly preferably 30 μm or less.

保護膜(第1保護膜)，只要是藉由吸水而有適度的尺寸變化者，即可容易地得到本發明的效果。較佳為由纖維素酯系樹脂、聚酯系樹脂、聚碳酸酯系樹脂、(甲基)丙烯酸系樹脂或該等的至少2種以上的混合物所構成的透明樹脂膜，更佳為由纖維素酯系樹脂、(甲基)丙烯酸系樹脂或該等的至少2種以上的混合物所構成的透明樹脂膜。 The protective film (first protective film) can easily obtain the effects of the present invention as long as it has a moderate dimensional change due to water absorption. It is preferably a transparent resin film composed of cellulose ester resin, polyester resin, polycarbonate resin, (meth)acrylic resin, or a mixture of at least two or more of these, and more preferably fiber A transparent resin film composed of a plain ester resin, a (meth)acrylic resin, or a mixture of at least two of these.

(黏著劑) (Adhesive)

形成黏著劑層的黏著劑，只要適當選擇以往習知者即可，並且只要是於偏光板所暴露的高溫環境、濕熱環境或重複高溫與低溫的環境下具有不會發生剝離等的程度之接 著性者即可。具體上，可舉例如丙烯酸系黏著劑、聚矽氧(silicone)系黏著劑、橡膠系黏著劑等，從透明性、耐候性、耐熱性、加工性的觀點來看，以丙烯酸系黏著劑為特佳。 The adhesive to form the adhesive layer can be appropriately selected from those known in the past, as long as it has a level of adhesion that does not cause peeling, etc., in the high-temperature environment, humid environment, or repeated high-temperature and low-temperature environments to which the polarizing plate is exposed. Those who have sex are fine. Specifically, for example, acrylic adhesives, silicone adhesives, rubber adhesives, etc., from the viewpoint of transparency, weather resistance, heat resistance, and processability, acrylic adhesives are Especially good.

於黏著劑中，可依需要而適當地調配黏著賦予劑、可塑劑、玻璃纖維、玻璃珠、金屬粉、由其他無機粉末等所構成的填充劑、顏料、著色劑、填充劑、抗氧化劑、紫外線吸收劑、抗靜電劑、矽烷偶合劑等各種添加劑。 In the adhesive, an adhesive agent, plasticizer, glass fiber, glass beads, metal powder, filler composed of other inorganic powders, pigments, colorants, fillers, antioxidants, etc. can be appropriately formulated as needed. Various additives such as ultraviolet absorbers, antistatic agents, silane coupling agents, etc.

黏著劑層，通常是藉由將黏著劑的溶液塗佈於脫模片上並使其乾燥而形成。朝脫模片上的塗佈，例如可採用反轉塗佈法(reverse coating)、凹版塗佈法等滾輪塗佈法、旋轉塗佈法、網版塗佈法、噴泉塗佈法、浸塗法、噴塗法等。設有黏著劑層的脫模片，係藉由將其轉印的方法等而被利用。黏著劑層的厚度，通常為3至100μm左右，較佳為5至50μm。 The adhesive layer is usually formed by applying an adhesive solution on the release sheet and drying it. For coating on the release sheet, for example, roll coating methods such as reverse coating and gravure coating, spin coating, screen coating, fountain coating, and dip coating can be used. , Spraying method, etc. The release sheet provided with the adhesive layer is used by a method of transferring it. The thickness of the adhesive layer is usually about 3 to 100 μm, preferably 5 to 50 μm.

黏著劑層的於23℃的儲存彈性模數係以0.01MPa至1MPa為較佳。黏著劑層的儲存彈性模數未達0.01MPa時，無法抑制高溫測試時之偏光板的收縮，有容易發生剝離等外觀不良的傾向。而且，黏著劑層的儲存彈性模數大於1MPa時，在冷熱衝擊測試時，黏著劑無法緩和玻璃與偏光板之間產生的變形，偏光板有容易發生龜裂的傾向。 The storage elastic modulus of the adhesive layer at 23° C. is preferably 0.01 MPa to 1 MPa. When the storage elastic modulus of the adhesive layer is less than 0.01 MPa, the shrinkage of the polarizing plate during the high temperature test cannot be suppressed, and there is a tendency for appearance defects such as peeling to easily occur. Moreover, when the storage elastic modulus of the adhesive layer is greater than 1 MPa, the adhesive cannot alleviate the deformation between the glass and the polarizing plate during the thermal shock test, and the polarizing plate tends to crack.

於較佳的實施態樣中，黏著劑層的於80℃的儲存彈性模數為0.01MPa至1MPa。 In a preferred embodiment, the storage elastic modulus of the adhesive layer at 80° C. is 0.01 MPa to 1 MPa.

藉由隔著黏著劑層而將偏光板貼合於液晶單元，可得到液晶面板。而且，藉由隔著黏著劑層而將偏光板貼合於有機電激發光顯示器，可得到有機電激發光顯示裝置。例如，液晶面板及有機電激發光顯示器，係如第3圖所示，可具有玻璃基板40、第1黏著劑層13、第1保護膜12、偏光片11、第2黏著劑層23、第2保護膜22的構成。 By bonding the polarizing plate to the liquid crystal cell via the adhesive layer, a liquid crystal panel can be obtained. Furthermore, by bonding the polarizing plate to the organic electroluminescent display through the adhesive layer, an organic electroluminescent display device can be obtained. For example, a liquid crystal panel and an organic electroluminescent display, as shown in Figure 3, may have a glass substrate 40, a first adhesive layer 13, a first protective film 12, a polarizer 11, a second adhesive layer 23, and a second adhesive layer. 2The composition of the protective film 22.

根據本發明的偏光板，可提供薄且強度佳的偏光板。 According to the polarizing plate of the present invention, a thin and strong polarizing plate can be provided.

(實施例) (Example)

以下，列示實施例，更具體地說明本發明，但本發明不限於該等例。例中，表示含量或使用量的%及份，在無特別記述下即為重量基準。 Hereinafter, examples are listed to explain the present invention more specifically, but the present invention is not limited to these examples. In the examples, the% and parts of the content or usage amount are shown, and they are based on weight unless otherwise stated.

[偏光片的製造] [Manufacturing of Polarizer]

將厚度20μm的聚乙烯醇膜(平均聚合度2,400、平均皂化度99.9莫耳%以上)藉由乾式延伸進行一軸延伸至約5倍，再於保持緊張狀態下浸漬於60℃的純水1分鐘後，在碘/碘化鉀/水的重量比為0.05/5/100的水溶液中於28℃浸漬60秒。然後，在碘化鉀/硼酸/水的重量比為8.5/8.5/100的水溶液中於72℃浸漬300秒。繼而，用26℃的純水洗淨20秒後，於65℃乾燥，得到碘吸附配向於聚乙烯醇膜而成之厚度7μm的偏光片。 A polyvinyl alcohol film with a thickness of 20μm (average degree of polymerization of 2,400, average degree of saponification of 99.9 mol% or more) is stretched uniaxially to about 5 times by dry stretching, and then immersed in pure water at 60°C for 1 minute under tension. Then, it was immersed in an aqueous solution with a weight ratio of iodine/potassium iodide/water of 0.05/5/100 at 28°C for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide/boric acid/water of 8.5/8.5/100 at 72°C for 300 seconds. Then, after washing with pure water at 26° C. for 20 seconds, it was dried at 65° C. to obtain a 7 μm-thick polarizer in which iodine was adsorbed and aligned on the polyvinyl alcohol film.

[第1黏著劑] [First Adhesive]

使用市售之黏著劑片，其係在經實施脫模處理的厚度38μm的聚對苯二甲酸乙二酯膜(脫模膜)的脫模處理面積層有厚度20μm的丙烯酸系黏著劑層者。於丙烯酸系黏著劑中，不調配胺酯丙烯酸酯寡聚物(urethane acrylate oligomer)。從黏著劑片除去脫模膜後之黏著劑層的儲存彈性模數，於23℃為0.05MPa，於80℃為0.04MPa。 Use a commercially available adhesive sheet, which has an acrylic adhesive layer with a thickness of 20 μm on the release treatment area of a 38 μm thick polyethylene terephthalate film (release film) that has undergone a release treatment . In acrylic adhesives, urethane acrylate oligomers are not formulated. The storage elastic modulus of the adhesive layer after removing the release film from the adhesive sheet was 0.05 MPa at 23°C and 0.04 MPa at 80°C.

[第2黏著劑層] [Second Adhesive Layer]

將對於丙烯酸丁酯與丙烯酸的共聚物添加胺酯丙烯酸酯寡聚物及異氰酸酯系交聯劑而成的有機溶劑溶液，藉由刮刀塗佈機塗佈於經實施脫模處理的厚度38μm的聚對苯二甲酸乙二酯膜(脫模膜)的脫模處理面，以使乾燥後的厚度成為5μm之方式使其乾燥，得到積層有黏著劑層的黏著劑片。從黏著劑片除去脫模膜後之黏著劑層的儲存彈性模數，於23℃為0.40MPa，於80℃為0.18MPa。 An organic solvent solution prepared by adding urethane acrylate oligomer and isocyanate-based crosslinking agent to the copolymer of butyl acrylate and acrylic acid was applied by a knife coater to the 38μm thick poly The release-treated surface of the ethylene terephthalate film (release film) was dried so that the thickness after drying became 5 μm to obtain an adhesive sheet on which an adhesive layer was laminated. The storage elastic modulus of the adhesive layer after removing the release film from the adhesive sheet was 0.40 MPa at 23°C and 0.18 MPa at 80°C.

[第1保護膜-1] [第1保护膜-1]

使用柯尼卡美能達股份有限公司製的三乙醯基纖維素膜(厚度20μm、於波長590nm之面內相位差值=1.2nm、於波長590nm之厚度方向相位差值=1.3nm)。 A triacetyl cellulose film manufactured by Konica Minolta Co., Ltd. (thickness 20 μm, in-plane retardation value at a wavelength of 590 nm = 1.2 nm, thickness direction retardation value at a wavelength of 590 nm = 1.3 nm) was used.

[第1保護膜-2] [第1保护膜-2]

使用柯尼卡美能達股份有限公司製的商品名"KC2UA"、 厚度25μm的未延伸的TAC膜。 Use the trade name "KC2UA" manufactured by Konica Minolta Co., Ltd., Unstretched TAC film with a thickness of 25 μm.

[第1保護膜-3] [第1保护膜-3]

使用厚度13μm的環烯烴樹脂膜(日本ZEON股份有限公司製)。於波長590nm之面內相位差值(Re(590))=0.8nm，於波長590nm之厚度方向相位差值(Rth(590))=3.4nm，於波長483nm之厚度方向相位差值(Rth(483))=3.5nm，於波長755nm之厚度方向相位差值(Rth(755))=2.8nm。 A 13 μm thick cycloolefin resin film (manufactured by ZEON Co., Ltd., Japan) was used. The in-plane retardation value at a wavelength of 590nm (Re(590))=0.8nm, the thickness direction retardation value at a wavelength of 590nm (Rth(590))=3.4nm, and the thickness direction retardation value at a wavelength of 483nm (Rth( 483))=3.5nm, the thickness direction retardation value at a wavelength of 755nm (Rth(755))=2.8nm.

[第1保護膜-4] [第1保护膜-4]

使用日本ZEON股份有限公司製的商品名"ZEONOR FILM(註冊商標)ZF14-023"、厚度23μm的環狀聚烯烴系樹脂膜。 A cyclic polyolefin-based resin film with a trade name of "ZEONOR FILM (registered trademark) ZF14-023" and a thickness of 23 μm manufactured by Japan ZEON Co., Ltd. was used.

[第1保護膜-5] [第1保护膜-5]

使用表面經硬塗處理(厚度7μm)的三乙醯基纖維素膜(Toppan TOMOEGAWA optical film股份有限公司製、25KCHC-TC、厚度32μm)。 A triacetyl cellulose film (manufactured by Toppan TOMOEGAWA Optical Film Co., Ltd., 25KCHC-TC, thickness 32 μm) whose surface was hard-coated (thickness 7 μm) was used.

[第1保護膜-6] [第1保护膜-6]

將第1保護膜-1溶解於1,3-二氧雜環戊烷(1,3-dioxolane)，調製成12wt%，使用棒塗器(號數：60)塗佈於玻璃基板上，以使乾燥後厚度成為10μm之方式在60℃的烤箱乾燥3分鐘後，將塗膜從玻璃剝離，得到第1保護膜-6。 Dissolve the first protective film-1 in 1,3-dioxolane (1,3-dioxolane) to prepare 12wt%, and use a bar coater (number: 60) to coat it on the glass substrate to After drying for 3 minutes in an oven at 60°C so that the thickness after drying became 10 μm, the coating film was peeled off from the glass to obtain the first protective film-6.

[第2保護膜] [Second protective film]

使用厚度26μm的增亮膜(3M公司製、商品名Advanced Polarized Film,Version 3)。 A brightness enhancement film with a thickness of 26 μm (manufactured by 3M, trade name Advanced Polarized Film, Version 3) was used.

[水系接著劑的調製] [Preparation of water-based adhesive]

相對於水100份，使經羧基改性的聚乙烯醇(Kuraray股份有限公司製的KL-318)3份溶解，於該水溶液中添加屬於水溶性環氧化合物之聚醯胺環氧系添加劑(住化CHEMTEX股份有限公司製的SUMIREZ RESIN(註冊商標)650(30)、固體成分濃度30%的水溶液)1.5份，作成水系接著劑。 With respect to 100 parts of water, 3 parts of carboxyl-modified polyvinyl alcohol (KL-318 manufactured by Kuraray Co., Ltd.) was dissolved, and the water-soluble epoxy compound polyamide epoxy additive ( 1.5 parts of SUMIREZ RESIN (registered trademark) 650 (30), 30% solid content concentration aqueous solution) manufactured by Sumika CHEMTEX Co., Ltd., as a water-based adhesive.

[偏光板前驅物A的製作] [Production of Polarizing Plate Precursor A]

於上述偏光片的單面，隔著水系接著劑而積層第1保護膜-1。積層後，藉由在80℃乾燥5分鐘，而貼合第1保護膜-1與偏光片。在偏光片之與第1保護膜-1的貼合面為相反側的面，貼合積層於脫模膜上的第2黏著劑層。在第1保護膜-1之與偏光片的貼合面為相反側的面，貼合積層於脫模膜上的第1黏著劑層。 On one side of the above-mentioned polarizer, the first protective film-1 was laminated with the water-based adhesive interposed therebetween. After the lamination, the first protective film-1 and the polarizer were bonded by drying at 80°C for 5 minutes. The second adhesive layer laminated on the release film was bonded to the surface of the polarizer on the opposite side to the bonding surface of the first protective film-1. On the surface on the opposite side to the bonding surface of the polarizer of the first protective film-1, the first adhesive layer laminated on the release film was bonded.

再者，係以使偏光片的穿透軸方向與保護膜的寬度方向呈平行之方式貼合。 In addition, it is bonded so that the transmission axis direction of the polarizer is parallel to the width direction of the protective film.

如此，製作由第1黏著劑層、保護膜、偏光片及第2黏著劑層依此順序積層而成的偏光板前驅物A-1。 In this way, a polarizing plate precursor A-1 was produced by laminating the first adhesive layer, the protective film, the polarizer, and the second adhesive layer in this order.

同樣地，使用第1保護膜-2取代第1保護膜-1，將作成偏光板前驅物作為偏光板前驅物A-2。針對其他保護膜，也同樣地作成偏光板前驅物。 Similarly, the first protective film-2 is used instead of the first protective film-1, and the polarizing plate precursor is made as the polarizing plate precursor A-2. For other protective films, the polarizing plate precursors were also made in the same way.

[偏光板A的製作] [Production of Polarizing Plate A]

將上述偏光板前驅物之第2黏著劑層上的脫模膜剝離。將偏光板前驅物A之第2黏著劑層與增亮膜貼合，得到由第1黏著劑層、保護膜(第1保護膜)、偏光片、第2黏著劑層、增亮膜(第2保護膜)依此順序積層而成的偏光板A。例如使用第1保護膜-1作成的偏光板則為偏光板A1。同樣地，使用第1保護膜-2作成的具有如此構造之偏光板則為偏光板A2。 The release film on the second adhesive layer of the polarizing plate precursor is peeled off. The second adhesive layer of the polarizer precursor A and the brightness enhancement film are bonded together to obtain a first adhesive layer, a protective film (first protective film), a polarizer, a second adhesive layer, and a brightness enhancement film (the first 2 Protective film) Polarizing plate A laminated in this order. For example, the polarizing plate made using the first protective film-1 is the polarizing plate A1. Similarly, the polarizing plate with such a structure made using the first protective film-2 is the polarizing plate A2.

[偏光板B的製作] [Production of Polarizing Plate B]

除了上述偏光板前驅物A-1中之偏光片與保護膜的積層位置互換以外，與上述偏光板A1同樣地製作偏光板B1。所得之偏光板B1，係由第1黏著劑層、偏光片、保護膜(第1保護膜)、第2黏著劑層及增亮膜(第2保護膜)依此順序積層而成的偏光板。 A polarizing plate B1 was produced in the same manner as the above-mentioned polarizing plate A1 except that the positions of the polarizer and the protective film in the above-mentioned polarizing plate precursor A-1 were interchanged. The obtained polarizing plate B1 is a polarizing plate formed by laminating the first adhesive layer, polarizer, protective film (first protective film), second adhesive layer, and brightness enhancement film (second protective film) in this order .

[偏光板C的製作] [Production of Polarizing Plate C]

於上述偏光片的單面，隔著水系接著劑而積層第1保護膜-1。積層後，藉由在80℃乾燥5分鐘，將第1保護膜與偏光片貼合。在偏光片之與第1保護膜的貼合面為相反 側的面，貼合積層於脫模膜上的第1黏著劑層，然後剝離脫模膜，得到偏光板C。所得之偏光板係由第1黏著劑層、偏光片、保護膜(第1保護膜)依此順序積層而成的偏光板。再者，關於偏光板C，使用第1保護膜-1之偏光板則為偏光板C1，例如使用第1保護膜-5之偏光板則為偏光板C5。 On one side of the above-mentioned polarizer, the first protective film-1 was laminated with the water-based adhesive interposed therebetween. After the lamination, the first protective film and the polarizer were bonded together by drying at 80°C for 5 minutes. The bonding surface of the polarizer and the first protective film is opposite On the side surface, the first adhesive layer laminated on the release film was bonded, and then the release film was peeled off, and a polarizing plate C was obtained. The obtained polarizing plate is a polarizing plate formed by laminating a first adhesive layer, a polarizer, and a protective film (first protective film) in this order. Furthermore, regarding the polarizing plate C, the polarizing plate using the first protective film-1 is the polarizing plate C1, and for example, the polarizing plate using the first protective film-5 is the polarizing plate C5.

[尺寸變化率的算出] [Calculation of Dimensional Change Rate]

對於上述保護膜，用以下的方法測定尺寸變化率差。 For the above-mentioned protective film, the difference in the dimensional change rate was measured by the following method.

再者，於實施例、比較例所使用的保護膜，寬度方向係與偏光片的穿透軸方向呈平行的方向。 Furthermore, the width direction of the protective films used in the examples and comparative examples is parallel to the direction of the transmission axis of the polarizer.

首先，將長條的各保護膜裁切為長度方向100mm×寬度方向100mm的正方形。在裁切保護膜後，寬度方向的尺寸(L0)係使用二維測定器"NEXIV VMR-12072"(尼康股份有限公司製)進行測定。同樣地，也測定長度方向的尺寸。 First, each long protective film is cut into a square of 100 mm in the length direction×100 mm in the width direction. After cutting the protective film, the dimension (L0) in the width direction was measured using a two-dimensional measuring device "NEXIV VMR-12072" (manufactured by Nikon Co., Ltd.). Similarly, the dimensions in the longitudinal direction are also measured.

然後，將保護膜在85℃環境下靜置1小時(濕度：5%)。該步驟後，與上述同樣地測定保護膜的寬度方向的尺寸(L85)及長度方向的尺寸。 Then, the protective film was left to stand in an environment of 85° C. for 1 hour (humidity: 5%). After this step, the widthwise dimension (L85) and the longitudinal dimension of the protective film were measured in the same manner as described above.

由以下的式求得尺寸變化率(%)，算出保護膜的寬度方向的尺寸變化率(85℃)及長度方向的尺寸變化率。 The dimensional change rate (%) was obtained from the following formula, and the dimensional change rate (85° C.) in the width direction of the protective film and the dimensional change rate in the longitudinal direction were calculated.

尺寸變化率(85℃)=[(L0-L85)/L0]×100 Dimensional change rate (85℃)=[(L0-L85)/L0]×100

再者，算出在85℃環境下之尺寸變化率後，將同一樣品，於溫度23℃、濕度55%下放置15分鐘後，於30℃相對濕度95%的條件下靜置0.5小時。該步驟後，與上述同樣地測定保護膜的寬度方向的尺寸(L30)及長 度方向的尺寸。由以下的式求得尺寸變化率(%)，算出保護膜的寬度方向的尺寸變化率及長度方向的尺寸變化率。再者，「L030」係指在與偏光片的穿透軸方向呈平行的方向(長度方向或寬度方向)測定尺寸變化率(85℃)後，於溫度23℃、濕度55%下放置15分鐘後的膜的尺寸。 In addition, after calculating the dimensional change rate in an environment of 85°C, the same sample was placed at a temperature of 23°C and a humidity of 55% for 15 minutes, and then placed at 30°C and a relative humidity of 95% for 0.5 hours. After this step, measure the width (L30) and length of the protective film in the same manner as above. Dimensions in degrees. The dimensional change rate (%) was obtained from the following formula, and the dimensional change rate in the width direction and the dimensional change rate in the longitudinal direction of the protective film were calculated. Furthermore, "L030" refers to the measurement of the dimensional change rate (85°C) in the direction parallel to the transmission axis of the polarizer (length direction or width direction), and then leave it at 23°C and 55% humidity for 15 minutes The size of the back film.

尺寸變化率(30℃)=[(L030-L30)/L0]×100 Dimensional change rate (30℃)=[(L030-L30)/L0]×100

算出所求得之尺寸變化率(85℃)與尺寸變化率(30℃)的差的絕對值。該等的結果係表示於表1。再者，表中之「FTD」係表示尺寸變化率(85℃)與尺寸變化率(30℃)的差的絕對值的簡稱。再者，偏光片的FPZ也藉由與上述相同的方法進行測定。 Calculate the absolute value of the difference between the obtained dimensional change rate (85°C) and the dimensional change rate (30°C). These results are shown in Table 1. In addition, "F TD " in the table is an abbreviation that represents the absolute value of the difference between the dimensional change rate (85°C) and the dimensional change rate (30°C). Furthermore, the F PZ of the polarizer was also measured by the same method as described above.

而且，算出△FTD(偏光片的尺寸變化率的差的絕對值FPZ與保護膜的尺寸變化率的差的絕對值FPF之差)。再者，算出△FTD相對於FPZ的比例(△FTD/FPZ)。結果表示於表1。 Then, ΔF TD (the difference between the absolute value F PZ of the difference in the dimensional change rate of the polarizer and the absolute value F PF of the difference in the dimensional change rate of the protective film) was calculated. Furthermore, the ratio of ΔF TD to F PZ (ΔF TD /F PZ ) is calculated. The results are shown in Table 1.

[表1]

Figure 110112956-A0101-12-0037-1
[Table 1]
Figure 110112956-A0101-12-0037-1

[冷熱衝擊環境測試及結露冷熱衝擊環境測試] [Cold and heat shock environmental test and condensation heat and cold shock environmental test]

將如上述作成的附黏著劑層的偏光板裁切為100mm×60mm，從該第1黏著劑層側剝離脫模膜，隔著露出的黏著劑層而貼合於玻璃板。將所得之評價用樣品進行後述的冷熱衝擊環境測試及結露冷熱衝擊環境測試。 The polarizing plate with the adhesive layer prepared as described above was cut into a size of 100 mm×60 mm, the release film was peeled from the first adhesive layer side, and the adhesive layer was exposed to be bonded to the glass plate. The obtained evaluation samples were subjected to the thermal shock environmental test and the condensation thermal shock environmental test described later.

[冷熱衝擊環境測試] [Cold and heat shock environmental test]

冷熱衝擊環境測試，係在將偏光板貼合於玻璃板的狀態下，使用冷熱衝擊測試裝置(ESPEC股份有限公司販售的製品名「TSA-71L-A-3」)，以高溫條件(85℃)保持時間30分鐘及低溫條件(-40℃)保持時間30分鐘為一循環而進行。再者，溫度移行時間設為1分鐘，溫度移行時的溫度移行時間為0分鐘時，設定成不導入外氣且不使光學構件發生結露的條件。實施將該循環重複400循環的測試。 The thermal shock environment test is based on the state where the polarizing plate is attached to the glass plate, and the thermal shock test device (product name "TSA-71L-A-3" sold by ESPEC Co., Ltd.) is used under high temperature conditions (85 ℃) hold time of 30 minutes and low temperature condition (-40°C) hold time of 30 minutes as one cycle. In addition, the temperature transition time is set to 1 minute, and when the temperature transition time at the time of temperature transition is 0 minutes, the conditions are set so that no outside air is introduced and no condensation occurs on the optical member. A test in which this cycle is repeated 400 cycles is performed.

[結露冷熱衝擊環境測試] [Condensation thermal shock environmental test]

結露冷熱衝擊環境測試，係於上述冷熱衝擊環境測試中，在溫度移行時藉由將外氣導入裝置內5分鐘而意圖使光學構件發生結露的條件下進行。實施將該循環重複40循環的測試。 The condensation heat and cold shock environment test is performed in the above cold and heat shock environment test, under the condition that the optical components are intended to be dew by introducing external air into the device for 5 minutes when the temperature is shifted. A test in which this cycle is repeated for 40 cycles is performed.

於該測試中，外氣的溫度為23℃，相對濕度為55%。 In this test, the temperature of the outside air is 23°C and the relative humidity is 55%.

[判定] [determination]

進行冷熱衝擊環境測試(循環次數：400次)以及結露冷熱衝擊環境測試(循環次數：400次)後，以目視確認龜裂的有無。測試前無變化，測試後在交叉尼柯爾(crossed Nichol)下不發生漏光者為「○」；測試後在交叉尼柯爾下發生漏光者為「X」。 After conducting a thermal shock environment test (cycle number: 400 times) and a condensation thermal shock environment test (cycle number: 400 times), the presence or absence of cracks was visually confirmed. There is no change before the test. After the test, there is no light leakage under the crossed Nichol, it is "○"; the light leakage under the crossed Nichol after the test is "X".

而且，在進行結露冷熱衝擊環境測試後的樣品，將樣品發生的龜裂的最大長度在交叉尼柯爾下測定。於冷熱衝擊環境測試及結露冷熱衝擊環境測試所得之結果係表示於表2。 In addition, the maximum length of the cracks in the sample after the condensation thermal shock environment test was measured under the cross Nicol. The results obtained in the thermal shock environment test and the condensation thermal shock environment test are shown in Table 2.

[表2]

Figure 110112956-A0101-12-0039-2
[Table 2]
Figure 110112956-A0101-12-0039-2

由該結果可知，本發明的偏光板不論是在冷熱衝擊環境測試及結露冷熱衝擊環境測試皆具有良好的效果。亦即，根據本發明，可提供於高溫條件、高濕度條件下偏光片不發生漏光且耐久性佳的偏光板。而且，即使 於重複高溫與低溫的環境下，本發明的偏光板亦不會發生漏光、破裂等，而可顯示良好的偏光特性。 It can be seen from this result that the polarizing plate of the present invention has good effects in both the cold and heat shock environment test and the condensation cold and heat shock environment test. That is, according to the present invention, it is possible to provide a polarizing plate that does not leak light from the polarizer under high temperature conditions and high humidity conditions and has good durability. And even though Under repeated high and low temperature environments, the polarizing plate of the present invention will not leak light, crack, etc., and can show good polarization characteristics.

而且，本發明的偏光板，因結露冷熱衝擊環境測試而發生的龜裂的最大長度，相較於比較例的偏光板，係為顯著地短。所以，本發明的偏光板，即使於發生結露的高濕度條件下，亦可抑制偏光片的龜裂的成長，可維持良好的偏光特性。 Moreover, in the polarizing plate of the present invention, the maximum length of the cracks caused by the condensation thermal shock environment test is significantly shorter than that of the polarizing plate of the comparative example. Therefore, the polarizing plate of the present invention can suppress the growth of cracks in the polarizer even under high humidity conditions where condensation occurs, and can maintain good polarization characteristics.

[突刺後的冷熱衝擊環境測試] [Environmental test of thermal shock after stab]

於偏光板的表面形成壓傷，將該偏光板進行冷熱衝擊環境測試，確認偏光片的破裂之有無。具體上係經由以下的步驟進行評價。 A pressure mark is formed on the surface of the polarizing plate, and the polarizing plate is subjected to a cold and heat shock environment test to confirm whether the polarizer is broken. Specifically, it is evaluated through the following steps.

將如上述作成的偏光板裁切為100mm×60mm，將第1黏著劑層上的脫模膜剝離，隔著第1黏著劑層而將偏光板貼合於無鹼玻璃(康寧股份有限公司製、EAGLE XG(註冊商標))。在貼合於該玻璃的偏光板的從端部算起1.0mm處，藉由刮傷式硬度計(德國Erichsen公司製、型號318、球直徑0.75mm)，施加3N的負重於偏光板的表面，賦予壓傷。壓傷的深度為1μm以下，大小為直徑0.2mm。 The polarizing plate prepared as described above was cut into 100mm×60mm, the release film on the first adhesive layer was peeled off, and the polarizing plate was bonded to alkali-free glass via the first adhesive layer (made by Corning Co., Ltd.) , EAGLE XG (registered trademark)). At 1.0mm from the end of the polarizing plate attached to the glass, a scratch-type hardness tester (manufactured by Erichsen, Germany, model 318, ball diameter 0.75mm) was used to apply a 3N load on the surface of the polarizing plate , Give crush. The depth of the crush is 1 μm or less, and the size is 0.2 mm in diameter.

而且，在貼合於該玻璃的其他偏光板的從端部算起1.0mm處，藉由刮傷式硬度計施加5N，再於其他偏光板施加10N的負重於表面，作成樣品。 In addition, at 1.0 mm from the end of the other polarizing plate attached to the glass, 5N was applied by a scratch-type hardness tester, and a 10N load was applied to the surface of the other polarizing plate to make a sample.

藉由所謂賦予負重於偏光板表面之操作而得之負傷，可假設為通常在將積層於偏光板的保護膜用鑷 子等銳利器具剝離時、或在將背光源與偏光板貼合時以異物咬合的狀態貼合時等所發生的傷者。 The injury caused by the so-called operation of applying a load to the surface of the polarizer can be assumed to be the tweezers usually used for the protective film laminated on the polarizer. Injuries that occur when sharp instruments such as children are peeled off, or when the backlight is attached to the polarizing plate in a state where foreign matter bites.

針對藉由施加3N、5N或10N的負重而對表面形成壓傷之偏光板，實施溫度85℃及-40℃(以各30分鐘為1循環)的冷熱衝擊環境測試(250循環)。判定係如以下進行。結果表示於表3。 For the polarizing plate that is crushed on the surface by applying a load of 3N, 5N or 10N, a thermal shock environment test (250 cycles) at a temperature of 85°C and -40°C (each 30 minutes is a cycle) is performed. The judgment is performed as follows. The results are shown in Table 3.

[判定] [determination]

在施加任一種負重時，於冷熱衝擊環境測試後，在交叉尼柯爾下沒有發生偏光片的漏光的情況為「○」。在施加任一種負重時，冷熱衝擊環境測試後，偏光片破裂，在交叉尼柯爾下或目視可確認漏光的情況為「X」。 When any load is applied, after the thermal shock environment test, there is no light leakage of the polarizer under the cross Nicol, which is "○". When any load is applied, after the thermal shock environment test, the polarizer is broken, and the light leakage can be confirmed as "X" under the cross Nicol or by visual inspection.

[表3]

Figure 110112956-A0101-12-0042-3
[table 3]
Figure 110112956-A0101-12-0042-3

(產業上的利用可能性) (Industrial use possibility)

根據本發明，提供即使於高溫條件、高濕度條件下亦不易發生漏光且耐久性佳的偏光板。而且，即 使於重複高溫及低溫的環境下，本發明的偏光板亦不發生漏光、破裂等，可顯示良好的偏光特性。再者，根據本發明，可將偏光片予以薄化，且即使於保護膜的表面發生刮傷的情況，亦可抑制偏光片的破裂。 According to the present invention, there is provided a polarizing plate that is less prone to light leakage and has good durability even under high-temperature conditions and high-humidity conditions. And, that is Under repeated high and low temperature environments, the polarizing plate of the present invention does not leak light, cracks, etc., and can show good polarization characteristics. Furthermore, according to the present invention, the polarizer can be thinned, and even if the surface of the protective film is scratched, the polarizer can be prevented from breaking.

本案係主張基於2015年11月13日所申請的日本特願2015-223443及2016年4月12日所申請的日本特願2016-079655之優先權，其記載內容的全部參考援用於本說明書。 This case claims priority based on Japanese Patent Application No. 2015-223443 filed on November 13, 2015 and Japanese Patent Application No. 2016-079655 filed on April 12, 2016, and the entire contents of the description are used in this specification by reference.

11:偏光片 11: Polarizer

12:保護膜(第1保護膜) 12: Protective film (the first protective film)

13:黏著劑層(第1黏著劑層) 13: Adhesive layer (1st adhesive layer)

100、110:偏光板 100, 110: Polarizing plate

Claims (11)

一種偏光板， A kind of polarizer, 其具備偏光片、保護膜及黏著劑層； It has a polarizer, a protective film and an adhesive layer; 其中，前述偏光片、前述保護膜及前述黏著劑層係依此順序配置， Wherein, the aforementioned polarizer, the aforementioned protective film and the aforementioned adhesive layer are arranged in this order, 當前述保護膜的在與前述偏光片的穿透軸方向呈平行的方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率係設為保護膜的尺寸變化率(85℃)，並且前述保護膜的在與前述偏光片的穿透軸方向呈平行的方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率係設為保護膜的尺寸變化率(30℃)時， When the dimensional change rate of the protective film in the direction parallel to the transmission axis of the polarizer and the relative humidity of 5% at 85°C after 1 hour is set as the dimensional change rate of the protective film (85°C ), and the dimensional change rate of the protective film after 0.5 hours under the conditions of 30°C and 95% relative humidity in a direction parallel to the direction of the transmission axis of the polarizer is taken as the dimensional change rate of the protective film ( 30℃), 前述保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差的絕對值為0.02至0.50。 The absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is 0.02 to 0.50. 一種偏光板， A kind of polarizer, 其具備偏光片、保護膜及黏著劑層； It has a polarizer, a protective film and an adhesive layer; 其中，前述保護膜、前述偏光片及前述黏著劑層係依此順序配置， Wherein, the protective film, the polarizer and the adhesive layer are arranged in this order, 當前述保護膜的在與前述偏光片的穿透軸方向呈平行的方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率係設為保護膜的尺寸變化率(85℃)，並且前述保護膜的在與前述偏光片的穿透軸方向呈平行的方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率係設為保護膜的尺寸變化率(30℃)時， When the dimensional change rate of the protective film in the direction parallel to the transmission axis of the polarizer and the relative humidity of 5% at 85°C after 1 hour is set as the dimensional change rate of the protective film (85°C ), and the dimensional change rate of the protective film after 0.5 hours under the conditions of 30°C and 95% relative humidity in a direction parallel to the direction of the transmission axis of the polarizer is taken as the dimensional change rate of the protective film ( 30℃), 前述保護膜的尺寸變化率(85℃)與前述保護膜的 尺寸變化率(30℃)的差的絕對值為0.02至0.50。 The dimensional change rate (85℃) of the aforementioned protective film is the same as that of the aforementioned protective film The absolute value of the difference in the dimensional change rate (30°C) is 0.02 to 0.50. 如申請專利範圍第1或2項所述之偏光板，其中，前述偏光片的在穿透軸方向之於85℃相對濕度5%的條件下經過1小時後的尺寸變化率係設為偏光片的尺寸變化率(85℃)， The polarizing plate described in item 1 or 2 of the scope of patent application, wherein the dimensional change rate of the aforementioned polarizer in the direction of the transmission axis at 85°C relative humidity of 5% after 1 hour is set as the polarizer Dimensional change rate (85℃), 前述偏光片的在穿透軸方向之於30℃相對濕度95%的條件下經過0.5小時後的尺寸變化率係設為偏光片的尺寸變化率(30℃)， The dimensional change rate of the aforementioned polarizer in the direction of the transmission axis at a relative humidity of 95% at 30°C for 0.5 hours is taken as the dimensional change rate of the polarizer (30°C), 前述偏光片的尺寸變化率(85℃)與前述偏光片的尺寸變化率(30℃)的差的絕對值係設為FPZ， The absolute value of the difference between the dimensional change rate (85°C) of the polarizer and the dimensional change rate (30°C) of the polarizer is F PZ , 前述保護膜的尺寸變化率(85℃)與前述保護膜的尺寸變化率(30℃)的差的絕對值係設為FPF， The absolute value of the difference between the dimensional change rate (85°C) of the protective film and the dimensional change rate (30°C) of the protective film is F PF , 從前述FPZ減去前述FPF之差係設為△FTD，以及 The difference between the aforementioned F PZ and the aforementioned F PF is set as △F TD , and △FTD相對於FPZ的比例(△FTD/FPZ)為0.5至0.95的範圍。 The ratio of ΔF TD to F PZ (ΔF TD /F PZ ) is in the range of 0.5 to 0.95. 如申請專利範圍第1或2項所述之偏光板，其中，前述偏光片與前述保護膜係僅隔著接著劑層而積層。 The polarizing plate described in claim 1 or 2, wherein the polarizer and the protective film are laminated only through the adhesive layer. 如申請專利範圍第1項所述之偏光板，其中，在前述偏光片之與前述保護膜反對之側隔著第2黏著劑層積層有第2保護膜。 The polarizing plate described in claim 1, wherein a second protective film is laminated on the side of the polarizer opposite to the protective film via a second adhesive layer. 如申請專利範圍第5項所述之偏光板，其中，在前述偏光片中，前述第2保護膜係僅隔著前述第2黏著劑層而積層。 The polarizing plate according to claim 5, wherein, in the polarizer, the second protective film is laminated only through the second adhesive layer. 如申請專利範圍第5項所述之偏光板，其中，前述第2 保護膜為增亮膜。 The polarizing plate described in item 5 of the scope of patent application, wherein the second The protective film is a brightness enhancement film. 如申請專利範圍第1或2項所述之偏光板，其中，前述偏光片具有10μm以下的厚度。 The polarizing plate described in item 1 or 2 of the scope of patent application, wherein the aforementioned polarizing plate has a thickness of 10 μm or less. 如申請專利範圍第1或2項所述之偏光板，其中，前述保護膜係由纖維素酯系樹脂、聚酯系樹脂、聚碳酸酯系樹脂、(甲基)丙烯酸系樹脂、或該等的至少2種以上的混合物所構成的透明樹脂膜。 The polarizing plate described in item 1 or 2 of the scope of patent application, wherein the protective film is made of cellulose ester resin, polyester resin, polycarbonate resin, (meth)acrylic resin, or the like A transparent resin film composed of a mixture of at least two or more of. 一種液晶顯示裝置，其係將如申請專利範圍第1項至第9項中任一項所述之偏光板隔著前述黏著劑層而積層於液晶單元所成者。 A liquid crystal display device, which is formed by laminating the polarizing plate described in any one of items 1 to 9 of the scope of patent application on a liquid crystal cell via the adhesive layer. 一種有機電激發光顯示裝置，其係將如申請專利範圍第1項至第9項中任一項所述之偏光板隔著前述黏著劑層而積層於有機電激發光顯示器所成者。 An organic electroluminescent display device, which is formed by laminating the polarizing plate described in any one of items 1 to 9 of the scope of patent application on an organic electroluminescent display via the adhesive layer.
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