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TW202122839A - Polarizing film laminate with adhesive layer and optical display panel in which said polarizing film laminate with adhesive layer is used - Google Patents

Polarizing film laminate with adhesive layer and optical display panel in which said polarizing film laminate with adhesive layer is used Download PDF

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Publication number
TW202122839A
TW202122839A TW109129209A TW109129209A TW202122839A TW 202122839 A TW202122839 A TW 202122839A TW 109129209 A TW109129209 A TW 109129209A TW 109129209 A TW109129209 A TW 109129209A TW 202122839 A TW202122839 A TW 202122839A
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polarizing film
coordinate point
film laminate
adhesive layer
iodine concentration
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TW109129209A
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Chinese (zh)
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TWI858119B (en
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木村智之
小野寬大
外山雄祐
竹田哲郎
高田勝則
木村啓介
山下智弘
杉野洋一郎
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日商日東電工股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/023Optical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/03Layered 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 with respect to the orientation of features
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/06Interconnection of layers permitting easy separation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating 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
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • B32B2307/4023Coloured on the layer surface, e.g. ink
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/42Polarizing, birefringent, filtering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514Oriented
    • B32B2307/516Oriented mono-axially
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80Constructional details
    • H10K59/8791Arrangements for improving contrast, e.g. preventing reflection of ambient light

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides: a polarizing film laminate which is capable of comprehensively solving the problems of polyene formation, decoloration and red discoloration by heating; and the like. A polarizing film laminate with an adhesive layer comprising a polarizing film that contains a polyvinyl alcohol resin and an adhesive layer that is provided on at least one surface of the polarizing film directly or with an optically transparent polarizing film protection film being interposed therebetween, wherein: the adhesive layer contains an adhesive polymer; the adhesive polymer has a copolymerized acid component; and the amount of the acid component in all monomer components in the adhesive polymer is 5% by weight or less. In an x-y rectangular coordinate system in which the iodine concentration in the polarizing film is taken on the x-axis and the moisture content in the polarizing film laminate is taken on the y-axis, this polarizing film laminate with an adhesive layer has an iodine concentration and a moisture content within the region bounded by: a first line segment that connects a first coordinate point where the iodine concentration is 7.0 wt% and the moisture content is 0.7 g/m2 and a second coordinate point where the iodine concentration is 2.2 wt% and the moisture content is 3.2 g/m2; a second line segment that connects the second coordinate point and a third coordinate point where the iodine concentration is 2.2 wt% and the moisture content is 4.0 g/m2; a third line segment that connects the third coordinate point and a fourth coordinate point where the iodine concentration is 3.0 wt% and the moisture content is 4.0 g/m2; a fourth line segment that connects the fourth coordinate point and a fifth coordinate point where the iodine concentration is 10.0 wt% and the moisture content is 0.7 g/m2; and a fifth line segment that connects the first coordinate point and the fifth coordinate point.

Description

附黏著劑層之偏光薄膜積層體、及使用該附黏著劑層之偏光薄膜積層體之光學顯示面板Adhesive layer-attached polarizing film laminate, and optical display panel using the adhesive layer-attached polarizing film laminate

本發明涉及附黏著劑層之偏光薄膜積層體、及使用該附黏著劑層之偏光薄膜積層體之光學顯示面板。The present invention relates to a polarizing film laminate with an adhesive layer and an optical display panel using the polarizing film laminate with the adhesive layer.

近年來,液晶面板及有機EL面板等光學性顯示面板除了可用於智慧型手機、個人電腦等電子設備、IoT家電等電器製品之外,還發現可用於汽車、電車、飛機等動力行進車輛的各種可能性。例如有在考慮於汽車之擋風玻璃、儀表板、外裝、其他各種車體部分搭載光學顯示面板,提供駕駛人各種資訊或對外部傳送各種資訊。In recent years, optical display panels such as liquid crystal panels and organic EL panels can be used in electronic devices such as smartphones, personal computers, and electrical appliances such as IoT home appliances, as well as various types of power vehicles such as automobiles, trams, and airplanes. possibility. For example, it is considered that the windshield, dashboard, exterior, and other various parts of the car body are equipped with optical display panels to provide various information to the driver or to transmit various information to the outside.

然而,與智慧型手機等不同,動力行進車輛多使用於戶外之嚴酷環境下,舉例而言,高溫或高濕這類使用環境會使光學顯示面板、尤其是用於光學顯示面板之偏光薄膜積層體(偏光板)、以及用於偏光薄膜積層體之偏光膜(偏光件)的性能劣化,而在最壞的情況下還有可能變得無法使用。However, unlike smartphones, powered vehicles are mostly used in harsh outdoor environments. For example, use environments such as high temperature or high humidity will cause optical display panels, especially polarizing film laminates for optical display panels. The performance of the polarizing film (polarizing plate) and the polarizing film (polarizing member) used for the polarizing film laminate is deteriorated, and in the worst case, it may become unusable.

專利文獻1中揭示了已提高於高溫或高濕環境下之耐久性的偏光件、使用該偏光件之偏光板、以及使用偏光板之液晶顯示裝置之一例。在耐久性上,在此其問題為放置於高溫條件下時會產生在正交偏光下的透紅光(長波長光之偏光透光),為了解決該問題提出了使其含有鋅,並將該鋅含量按照與碘含量之關係調整成預定範圍。Patent Document 1 discloses an example of a polarizer that has improved durability in a high temperature or high humidity environment, a polarizer using the polarizer, and a liquid crystal display device using the polarizer. In terms of durability, the problem here is that when placed under high temperature conditions, red light (polarized light transmission of long-wavelength light) will be generated under cross-polarized light. In order to solve this problem, it is proposed to make it contain zinc. The zinc content is adjusted to a predetermined range according to the relationship with the iodine content.

同樣地,專利文獻2係有關於已提高於高溫或高濕環境下之耐久性的車載用影像顯示裝置所用之偏光板,在此著眼於偏光板之水分量及保護薄膜之飽和吸水量。對於車載用之偏光板係要求高溫耐久性,但在高溫環境下,偏光板會有因多烯化而透射率顯著降低之情形,為了解決該問題,在專利文獻2中提出了使用飽和吸水量在預定範圍內者作為與偏光件貼合之透明保護薄膜、並且減少偏光板之水分量的方法。Similarly, Patent Document 2 relates to a polarizing plate used in an in-vehicle image display device that has improved durability in a high-temperature or high-humidity environment, and focuses on the moisture content of the polarizing plate and the saturated water absorption of the protective film. Polarizers for automotive use require high-temperature durability. However, under high-temperature environments, polarizers may have a significant decrease in transmittance due to polyolefinization. In order to solve this problem, Patent Document 2 proposes the use of saturated water absorption. Those within a predetermined range are used as a transparent protective film attached to the polarizer and a method to reduce the moisture content of the polarizer.

專利文獻3亦有關於已提高於高溫或高濕下之耐久性的偏光板,在此係著眼於偏光板之水分率及保護薄膜之透濕度。在高溫環境下等,偏光板之內部會成為高溫高濕狀態,結果會使光線透射率、偏光度、影像之色相等的變化量變大,而使作為偏光板之可靠性變低,因此提出了在已極力壓低偏光件之水分率的狀態下貼合透濕性低的保護薄膜之方法。 先前技術文獻 專利文獻Patent Document 3 also relates to a polarizing plate that has improved durability under high temperature or high humidity, and here focuses on the moisture content of the polarizing plate and the moisture permeability of the protective film. In high temperature environments, etc., the inside of the polarizing plate will become high temperature and high humidity. As a result, the amount of change in light transmittance, polarization, and image color will increase, and the reliability of the polarizing plate will decrease. Therefore, it is proposed A method of laminating a protective film with low moisture permeability in a state where the moisture content of the polarizer has been reduced as much as possible. Prior art literature Patent literature

專利文獻1:日本專利特開2003-29042號公報 專利文獻2:日本專利特開2014-102353號公報 專利文獻3:日本專利特開2002-90546號公報Patent Document 1: Japanese Patent Laid-Open No. 2003-29042 Patent Document 2: Japanese Patent Laid-Open No. 2014-102353 Patent Document 3: Japanese Patent Laid-Open No. 2002-90546

發明欲解決之課題 關於光學顯示面板、尤其是用於光學顯示面板之偏光薄膜積層體或用於偏光薄膜積層體之偏光膜,已知在高溫或高濕環境下會產生之問題有「多烯化」、「褪色」、及「加熱紅變」。The problem to be solved by the invention Regarding optical display panels, especially polarizing film laminates used in optical display panels or polarizing films used in polarizing film laminates, it is known that the problems that occur under high temperature or high humidity are "polyolefinization" and "fading". ", and "Red change on heating".

一般已知所謂「多烯化」係指由於置於高溫或高濕環境下,造成偏光薄膜積層體之單體透射率降低之現象;又,所謂「褪色」及「加熱紅變」係指同樣由於置於高溫或高濕環境下,在將偏光薄膜積層體配置成正交偏光並測定波長410nm及波長700nm之正交透射率時,正交透射率上升之現象;而「褪色」特別係指約700nm之長波長側及約410nm之短波長側的透射率上升而發生在黑色顯示下褪色之現象;另一方面,「加熱紅變」特別係指約700nm之長波長側的透射率上升而使偏光膜顏色變紅之現象。It is generally known that the so-called "polyolefinization" refers to the phenomenon that the monomer transmittance of the polarizing film laminate is reduced due to the high temperature or high humidity environment; in addition, the so-called "fading" and "heating red change" refer to the same Due to the high temperature or high humidity environment, when the polarizing film laminate is arranged into cross-polarized light and the cross-transmittance at the wavelength of 410nm and 700nm is measured, the cross-transmittance increases; and "fading" especially refers to The long-wavelength side of about 700nm and the short-wavelength side of about 410nm increase in transmittance and the phenomenon of fading under black display. On the other hand, "heating red change" especially refers to the increase of transmittance on the long-wavelength side of about 700nm. The phenomenon that the color of the polarizing film turns red.

專利文獻1主要著眼於「褪色」之問題,專利文獻2主要著眼於「多烯化」之問題,專利文獻3主要著眼於「加熱紅變」之問題,而各文獻中所提出之解決手段至少對於解決個別問題是有效的。然而,各專利文獻中所記載之發明不一定足以總括性解決該等問題。 「多烯化」、「褪色」及「加熱紅變」皆會透過碘與水分、乃至透過會對水分造成影響的溫度與濕度而互相產生關聯,基於此一事實,經過反覆積極研究後,本專利申請人獲得以下見解:藉由調整偏光膜之碘濃度與偏光薄膜積層體之水分量,可總括性解決該等問題。 本發明之目的在於圖謀調整偏光膜之碘濃度與偏光薄膜積層體之水分量來總括性解決該等3個問題。Patent document 1 mainly focuses on the problem of "fading", patent document 2 mainly focuses on the problem of "polyolefinization", patent document 3 mainly focuses on the problem of "heating redness", and the solutions proposed in each document are at least It is effective for solving individual problems. However, the inventions described in various patent documents are not necessarily sufficient to solve these problems in a comprehensive manner. "Polyolefin", "fading" and "heating red change" are all related to each other through iodine and moisture, and even through the temperature and humidity that affect moisture. Based on this fact, after repeated active research, this The patent applicant obtained the following insights: By adjusting the iodine concentration of the polarizing film and the moisture content of the polarizing film laminate, these problems can be solved in a comprehensive manner. The purpose of the present invention is to attempt to adjust the iodine concentration of the polarizing film and the moisture content of the polarizing film laminate to solve these three problems in a comprehensive manner.

將偏光膜貼附於液晶單元等時,通常係使用黏著劑。又,黏著劑因具有可瞬間將偏光膜固著於液晶單元等、使偏光膜固著於液晶單元等時不需要乾燥步驟等之優點,故大多係以黏著劑層之形態預先設置於偏光膜之單面。即,貼附偏光板一般會使用附黏著劑層之偏光板。When attaching a polarizing film to a liquid crystal cell, etc., an adhesive is usually used. In addition, since the adhesive has the advantages of instantly fixing the polarizing film to the liquid crystal cell, etc., and no drying step is required when fixing the polarizing film to the liquid crystal cell, etc., most of them are pre-installed on the polarizing film in the form of an adhesive layer. The one-sided. That is, to attach a polarizing plate, a polarizing plate with an adhesive layer is generally used.

關於對黏著劑層所要求的特性,可舉:黏著性不會隨時間經過降低而耐久性高;在將偏光膜貼合至液晶單元時,即使在貼合位置有誤或貼合面有混入異物這般情況下,仍可將偏光膜從液晶面板表面剝離並再度貼合(重工)等。The characteristics required for the adhesive layer include: Adhesiveness does not decrease over time and high durability; when the polarizing film is bonded to the liquid crystal cell, even if the bonding position is wrong or the bonding surface is mixed In the case of foreign matter, the polarizing film can still be peeled from the surface of the liquid crystal panel and re-attached (heavy work), etc.

在將光學性顯示面板用於動力行進車輛時,對於用以將構成光學性顯示面板之偏光膜貼附於液晶單元等的黏著劑亦要求高溫耐久性。於所述用途上,可適宜使用黏著劑聚合物之單體成分中包含丙烯酸等酸成分者作為構成黏著劑之黏著劑組成物。When an optical display panel is used in a powered vehicle, high-temperature durability is also required for an adhesive used to attach a polarizing film constituting the optical display panel to a liquid crystal cell or the like. For the purposes described above, monomer components of the adhesive polymer containing acid components such as acrylic acid can be suitably used as the adhesive composition constituting the adhesive.

本發明人等發現,因為黏著劑聚合物中共聚之酸成分而會產生多烯化惡化之新課題。在上述先前技術中,雖然有探討有關偏光薄膜之多烯化,但關於黏著劑層之耐久性或重工並未進行研討,且對該課題亦無任何揭示。The inventors of the present invention have discovered that a new problem of deterioration of polyolefination occurs due to the acid component copolymerized in the adhesive polymer. In the above-mentioned prior art, although the polyolefinization of the polarizing film is discussed, the durability or rework of the adhesive layer has not been discussed, and there is no disclosure on the subject.

本發明之目的係針對在偏光膜直接或隔著光學上呈透明之偏光膜保護薄膜設置有黏著劑層的附黏著劑層之偏光板,可獲得光學特性之可靠性及黏著耐久性、以及重工性優異之物。The purpose of the present invention is to provide a polarizing plate with an adhesive layer with an adhesive layer on the polarizing film directly or through an optically transparent polarizing film protective film, so as to obtain the reliability of the optical characteristics, the adhesion durability, and the rework Good sex.

用以解決課題之手段 本發明人等著眼於黏著劑層所含黏著劑聚合物之單體成分中的酸成分對偏光膜之性能的影響,從而完成本發明。在以往之技術中,關於黏著劑層所含黏著劑聚合物,完全未在單體成分中之酸成分的比率、與光學特性之可靠性或黏著耐久性、重工等附黏著劑層之偏光薄膜積層體的性能之相關性的觀點上進行探討。本發明人等發現了為了獲得具有優異特性的附黏著劑層之偏光薄膜積層體所要求之黏著劑聚合物的總單體成分中之酸成分的量。Means to solve the problem The present inventors focused on the influence of the acid component in the monomer component of the adhesive polymer contained in the adhesive layer on the performance of the polarizing film, thereby completing the present invention. In the prior art, regarding the adhesive polymer contained in the adhesive layer, the ratio of the acid component that is not in the monomer component at all, the reliability of the optical properties or the adhesion durability, heavy-duty and other polarizing films attached to the adhesive layer Discuss from the viewpoint of the relevance of the performance of the laminate. The inventors of the present invention have discovered the amount of acid components in the total monomer components of the adhesive polymer required to obtain an adhesive layer-attached polarizing film laminate having excellent characteristics.

一般認為當使用黏著劑聚合物之單體成分中包含丙烯酸等酸成分者時,酸成分之COOH基的氫鍵可提升高溫耐久性,但酸成分會作為構成偏光膜之聚乙烯醇(PVA)系樹脂薄膜的脫水縮合觸媒發揮作用,而促進多烯化;惟不受任何理論限制。It is generally believed that when the monomer component of the adhesive polymer contains acid components such as acrylic acid, the hydrogen bonding of the COOH group of the acid component can improve the high temperature durability, but the acid component will serve as the polyvinyl alcohol (PVA) that constitutes the polarizing film. The dehydration condensation catalyst of the resin film plays a role to promote polyalkylene; but it is not limited by any theory.

為了解決上述課題,本發明之一態樣之偏光膜薄膜積層體係附黏著劑層之偏光薄膜積層體,其具備包含聚乙烯醇系樹脂之偏光膜、與黏著劑層,該黏著劑層係直接或隔著光學上呈透明之偏光膜保護薄膜設置在前述偏光膜之至少一面; 該偏光薄膜積層體具有以下特徵:前述黏著劑層包含黏著劑聚合物,該黏著劑聚合物中酸成分經共聚合,且構成該黏著劑聚合物之總單體成分中之酸成分的量在5重量%以下;在分別令x-軸為前述偏光膜之碘濃度(wt.%)、y-軸為前述偏光薄膜積層體之水分量(g/m2 )的x-y正交座標系中,具有包含在以下線段所包圍之區域內的碘濃度及水分量:連結碘濃度7.0wt.%及水分量0.7g/m2 之第1座標點與碘濃度2.2wt.%及水分量3.2g/m2 之第2座標點的第1線段、連結前述第2座標點與碘濃度2.2wt.%及水分量4.0g/m2 之第3座標點的第2線段、連結前述第3座標點與碘濃度3.0wt.%及水分量4.0g/m2 之第4座標點的第3線段、連結前述第4座標點與碘濃度10.0wt.%及水分量0.7g/m2 之第5座標點的第4線段、及連結前述第1座標點與前述第5座標點的第5線段。 根據該態樣之附黏著劑層之偏光膜薄膜積層體,可總括性解決「多烯化」、「褪色」、「加熱紅變」、「黏著耐久性」及「重工」之問題。In order to solve the above-mentioned problems, the polarizing film laminate of an adhesive layer with a polarizing film laminate system of one aspect of the present invention is provided with a polarizing film containing a polyvinyl alcohol-based resin, and an adhesive layer, and the adhesive layer is directly Or set on at least one side of the polarizing film through an optically transparent polarizing film protective film; the polarizing film laminate has the following characteristics: the adhesive layer contains an adhesive polymer, and the acid component in the adhesive polymer is co- Polymerization, and the amount of the acid component in the total monomer components constituting the adhesive polymer is less than 5 wt%; let the x-axis be the iodine concentration (wt.%) of the aforementioned polarizing film and the y-axis be the aforementioned In the xy orthogonal coordinate system of the moisture content (g/m 2 ) of the polarizing film laminate, there is an iodine concentration and moisture content included in the area surrounded by the following line segment: connecting the iodine concentration 7.0wt.% and the moisture content 0.7g the first line / m 2 of a first coordinate point and the iodine concentration 2.2wt.% and the amount of water 3.2g / m 2 of the second coordinate point 2, the second connecting point and the coordinate iodine concentration 2.2wt.%, and water content 4.0 the second segment g / m 2 of a third coordinate point connecting point and the third coordinate iodine concentration 3.0wt.% and the amount of water 4.0g / m 2 of a fourth coordinate point of the third line segment connecting the fourth coordinate Point and the fourth line segment of the fifth coordinate point with an iodine concentration of 10.0 wt.% and a moisture content of 0.7 g/m 2 , and a fifth line segment connecting the aforementioned first coordinate point and the aforementioned fifth coordinate point. According to this aspect, the adhesive layer-attached polarizing film film laminate can comprehensively solve the problems of "polyolefinization", "fading", "heating redness", "adhesion durability" and "heavy work".

上述態樣之偏光膜薄膜積層體中,前述黏著劑聚合物的多分散性指數(重量平均分子量(Mw)/數量平均分子量(Mn))亦可為3.0以下。此在有關本發明之(又)另一態樣亦同。In the polarizing film film laminate of the above aspect, the polydispersity index (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the adhesive polymer may be 3.0 or less. This is the same in (yet) another aspect related to the present invention.

上述態樣之偏光膜薄膜積層體中,前述偏光膜之膜厚亦可為4~20μm。In the polarizing film thin film laminate of the above aspect, the film thickness of the polarizing film may be 4-20 μm.

又,本發明之另一態樣之偏光膜薄膜積層體,係附黏著劑層之偏光薄膜積層體,其具備包含聚乙烯醇系樹脂之偏光膜、與黏著劑層,該黏著劑層係直接或隔著光學上呈透明之偏光膜保護薄膜設置在前述偏光膜之至少一面; 該偏光薄膜積層體具有以下特徵:前述黏著劑層包含黏著劑聚合物,該黏著劑聚合物中酸成分經共聚合,且構成該黏著劑聚合物之總單體成分中之酸成分的量在5重量%以下;在分別令x-軸為前述偏光膜之碘濃度(wt.%)、y-軸為前述偏光薄膜積層體之水分量(g/m2 )的x-y正交座標系中,具有包含在以下線段所包圍之區域內的碘濃度及水分量:連結碘濃度4.5wt.%及水分量2.0g/m2 之第6座標點與碘濃度2.2wt.%及水分量3.2g/m2 之第2座標點的第6線段、連結前述第2座標點與碘濃度2.2wt.%及水分量4.0g/m2 之第3座標點的第2線段、連結前述第3座標點與碘濃度3.0wt.%及水分量4.0g/m2 之第4座標點的第3線段、連結前述第4座標點與碘濃度4.5wt.%及水分量3.3g/m2 之第7座標點的第7線段、及連結前述第6座標點與前述第7座標點的第8線段。In addition, another aspect of the polarizing film laminate of the present invention is a polarizing film laminate with an adhesive layer, which includes a polarizing film containing a polyvinyl alcohol-based resin, and an adhesive layer, and the adhesive layer is directly Or set on at least one side of the polarizing film through an optically transparent polarizing film protective film; the polarizing film laminate has the following characteristics: the adhesive layer contains an adhesive polymer, and the acid component in the adhesive polymer is co- Polymerization, and the amount of the acid component in the total monomer components constituting the adhesive polymer is less than 5 wt%; let the x-axis be the iodine concentration (wt.%) of the aforementioned polarizing film and the y-axis be the aforementioned In the xy orthogonal coordinate system of the moisture content (g/m 2 ) of the polarizing film laminate, there is an iodine concentration and moisture content included in the area surrounded by the following line segment: connecting the iodine concentration 4.5wt.% and the moisture content 2.0g /m 2 of the 6th coordinate point with the iodine concentration of 2.2wt.% and the moisture content of 3.2g/m 2 of the second coordinate point of the 6th line segment connecting the aforementioned second coordinate point with the iodine concentration of 2.2wt.% and the moisture content of 4.0 the second segment g / m 2 of a third coordinate point connecting point and the third coordinate iodine concentration 3.0wt.% and the amount of water 4.0g / m 2 of a fourth coordinate point of the third line segment connecting the fourth coordinate Point and the seventh line segment of the seventh coordinate point with an iodine concentration of 4.5 wt.% and a moisture content of 3.3 g/m 2 , and the eighth line segment connecting the aforementioned sixth coordinate point and the aforementioned seventh coordinate point.

上述態樣之偏光膜薄膜積層體中,前述第6座標點亦可為碘濃度4.0wt.%及水分量2.3g/m2 之座標點,而前述第7座標點亦可為碘濃度4.0wt.%及水分量3.5g/m2 之座標點。In the polarizing film laminate of the above aspect, the sixth coordinate point may be a coordinate point with an iodine concentration of 4.0wt.% and a moisture content of 2.3g/m 2 , and the seventh coordinate point may also be a coordinate point with an iodine concentration of 4.0wt. .% and the coordinate point of the water content of 3.5g/m 2.

上述態樣之偏光膜薄膜積層體中,偏光膜之膜厚亦可為11~20μm。In the polarizing film thin film laminate of the above aspect, the film thickness of the polarizing film may also be 11-20 μm.

本發明之又另一態樣之偏光膜薄膜積層體係附黏著劑層之偏光薄膜積層體,其具備包含聚乙烯醇系樹脂之偏光膜、與黏著劑層,該黏著劑層係直接或隔著光學上呈透明之偏光膜保護薄膜設置在前述偏光膜之至少一面; 該偏光薄膜積層體具有以下特徵:前述黏著劑層包含黏著劑聚合物,該黏著劑聚合物中酸成分經共聚合,且構成該黏著劑聚合物之總單體成分中之酸成分的量在5重量%以下;在分別令x-軸為前述偏光膜之碘濃度(wt.%)、y-軸為前述偏光薄膜積層體之水分量(g/m2 )的x-y正交座標系中,具有包含在以下線段所包圍之區域內的碘濃度及水分量:連結碘濃度7.0wt.%及水分量0.7g/m2 之第1座標點與碘濃度3.0wt.%及水分量2.6g/m2 之第8座標點的第11線段、連結前述第8座標點與碘濃度6.0wt.%及水分量2.6g/m2 之第9座標點的第10線段、連結前述第9座標點與碘濃度10.0wt.%及水分量0.7g/m2 之第5座標點的第12線段、及連結前述第1座標點與前述第5座標點的第5線段。 根據該態樣之附黏著劑層之偏光膜薄膜積層體,可總括性解決「多烯化」、「褪色」、「加熱紅變」、「黏著耐久性」及「重工」之問題。In yet another aspect of the present invention, the polarizing film laminate of the polarizing film laminate system with an adhesive layer is provided with a polarizing film containing a polyvinyl alcohol-based resin, and an adhesive layer, the adhesive layer being directly or interposed An optically transparent polarizing film protective film is provided on at least one side of the polarizing film; the polarizing film laminate has the following characteristics: the adhesive layer includes an adhesive polymer, and the acid component in the adhesive polymer is copolymerized, and The amount of the acid component in the total monomer components constituting the adhesive polymer is less than 5% by weight; the x-axis is the iodine concentration (wt.%) of the aforementioned polarizing film, and the y-axis is the aforementioned polarizing film laminate. The xy orthogonal coordinate system of the water content of the body (g/m 2 ) has the iodine concentration and water content included in the area surrounded by the following line segment: connecting the iodine concentration 7.0wt.% and the water content 0.7g/m 2 the first coordinate point and the iodine concentration 3.0wt.% and the amount of water 2.6g / m 2 of the coordinate points of the eighth segment 11, connecting said first coordinate point and 8 iodine concentration 6.0wt.% and the amount of water 2.6g / m 2 The 10th line segment of the 9th coordinate point, the 12th line connecting the aforementioned 9th coordinate point with the iodine concentration of 10.0wt.% and the moisture content of 0.7g/m 2 of the 5th coordinate point, and the aforementioned first coordinate point with The 5th line segment of the aforementioned 5th coordinate point. According to this aspect, the adhesive layer-attached polarizing film film laminate can comprehensively solve the problems of "polyolefinization", "fading", "heating redness", "adhesion durability" and "heavy work".

上述態樣之偏光膜薄膜積層體中,前述第8座標點亦可為碘濃度4.5wt.%及水分量2.0g/m2 之第6座標點,而前述第9座標點亦可為碘濃度7.2wt.%及水分量2.0g/m2 之第10座標點。In the above aspect of the polarizing film laminate, the 8th coordinate point may be the 6th coordinate point with an iodine concentration of 4.5wt.% and a moisture content of 2.0g/m 2 , and the 9th coordinate point may also be the iodine concentration The 10th coordinate point of 7.2wt.% and moisture content of 2.0g/m 2.

又,上述態樣之偏光膜薄膜積層體中,前述偏光膜之膜厚亦可為4~11μm。In addition, in the polarizing film thin film laminate of the above aspect, the film thickness of the polarizing film may be 4 to 11 μm.

又,上述態樣之偏光膜薄膜積層體中,前述偏光膜宜含有鋅。In addition, in the polarizing film thin film laminate of the above aspect, the polarizing film preferably contains zinc.

並且,就上述態樣之偏光膜薄膜積層體,由偏光薄膜積層體與透過黏著劑積層於該偏光薄膜積層體之兩面的玻璃板所構成之試料,在95℃/500小時之加熱後的單體透射率宜與加熱前的單體透射率相同或較其更大。 藉此,可有效解決多烯化之問題。In addition, with regard to the polarizing film laminate of the above aspect, a sample composed of a polarizing film laminate and a glass plate laminated on both sides of the polarizing film laminate through an adhesive was heated at 95°C/500 hours. The volume transmittance is preferably the same as or greater than the monomer transmittance before heating. In this way, the problem of polyolefination can be effectively solved.

就上述態樣之偏光膜薄膜積層體,由偏光薄膜積層體與透過黏著劑積層於該偏光薄膜積層體之兩面的玻璃板所構成之試料,進行95℃/500小時之加熱處理後,在波長410nm下的正交透射率之變化量宜小於1%,且在波長700nm下的正交透射率之變化量宜小於5%。 藉此,可有效解決褪色之問題。Regarding the polarizing film laminate of the above aspect, a sample composed of a polarizing film laminate and a glass plate laminated on both sides of the polarizing film laminate with a transparent adhesive is heated at 95°C/500 hours, and the wavelength The change in orthogonal transmittance at 410nm should be less than 1%, and the change in orthogonal transmittance at a wavelength of 700nm should be less than 5%. In this way, the problem of fading can be effectively solved.

就上述態樣之偏光膜薄膜積層體,由偏光薄膜積層體與透過黏著劑積層於該偏光薄膜積層體之兩面的玻璃板所構成之試料,進行95℃/500小時之加熱處理後,在波長410nm下的正交透射率之變化量宜為1%以上,且在波長700nm下的正交透射率之變化量宜小於5%。 藉此,可有效解決加熱紅變之問題。Regarding the polarizing film laminate of the above aspect, a sample composed of a polarizing film laminate and a glass plate laminated on both sides of the polarizing film laminate with a transparent adhesive is heated at 95°C/500 hours, and the wavelength The change in the orthogonal transmittance at 410nm should be more than 1%, and the change in the orthogonal transmittance at a wavelength of 700nm should be less than 5%. In this way, the problem of heating redness can be effectively solved.

上述態樣之偏光膜薄膜積層體可於前述偏光膜之視辨側的面隔著基材設有抗反射層,且由前述基材與前述抗反射層構成之抗反射薄膜的透濕度可為15g/m2 ・24h以上。The polarizing film film laminate of the above aspect may be provided with an anti-reflection layer on the viewing side of the polarizing film via a base material, and the moisture permeability of the anti-reflection film composed of the base material and the anti-reflection layer may be 15g/m 2・24h or more.

又,上述態樣之偏光膜薄膜積層體宜具備:液晶單元,其具備液晶層且該液晶層包含在無施加電場狀態下已於面內一方向定向之液晶分子;第1偏光膜,係配置於該液晶單元之一側;及第2偏光膜,係於該液晶單元之另一側配置成吸收軸與前述第1偏光膜之吸收軸正交;並且在前述第1偏光膜與前述液晶單元之間,從該第1偏光膜之側起依序配置有第1相位差層與第2相位差層,前述第1相位差層在令面內之慢軸x方向的折射率為nx1、快軸方向之折射率為ny1、厚度z方向之折射率為nz1時,滿足nx1>ny1>nz1之關係;且前述第2相位差層在令面內之慢軸x方向的折射率為nx2、快軸方向之折射率為ny2、厚度z方向之折射率為nz2時,滿足nz2>nx2≧ny2之關係。In addition, the polarizing film thin-film laminate of the above aspect preferably includes: a liquid crystal cell having a liquid crystal layer and the liquid crystal layer contains liquid crystal molecules aligned in one direction in the plane without applying an electric field; the first polarizing film is arranged On one side of the liquid crystal cell; and a second polarizing film, arranged on the other side of the liquid crystal cell so that the absorption axis is orthogonal to the absorption axis of the first polarizing film; and on the first polarizing film and the liquid crystal cell In between, a first retardation layer and a second retardation layer are arranged in order from the side of the first polarizing film, and the refractive index of the first retardation layer in the slow axis x direction in the plane is nx1, fast When the refractive index in the axial direction is ny1 and the refractive index in the thickness z direction is nz1, the relationship of nx1>ny1>nz1 is satisfied; When the refractive index in the axial direction is ny2 and the refractive index in the thickness z direction is nz2, the relationship of nz2>nx2≧ny2 is satisfied.

又,上述態樣之偏光膜薄膜積層體宜具備:液晶單元,其具備液晶層且該液晶層包含在無施加電場狀態下已於面內一方向定向之液晶分子;第1偏光膜,係配置於該液晶單元之一側;及第2偏光膜,係於該液晶單元之另一側配置成吸收軸與前述第1偏光膜之吸收軸正交;並且在前述第1偏光膜與前述液晶單元之間,從該第1偏光膜之側起依序配置有第1相位差層與第2相位差層,前述第1相位差層在令面內之慢軸x方向的折射率為nx1、快軸方向之折射率為ny1、厚度z方向之折射率為nz1時,滿足nz1>nx1=ny1之關係;且前述第2相位差層在令面內之慢軸x方向的折射率為nx2、快軸方向之折射率為ny2、厚度z方向之折射率為nz2時,滿足nx2>ny2=nz2之關係。In addition, the polarizing film thin-film laminate of the above aspect preferably includes: a liquid crystal cell having a liquid crystal layer and the liquid crystal layer contains liquid crystal molecules aligned in one direction in the plane without applying an electric field; the first polarizing film is arranged On one side of the liquid crystal cell; and a second polarizing film, arranged on the other side of the liquid crystal cell so that the absorption axis is orthogonal to the absorption axis of the first polarizing film; and on the first polarizing film and the liquid crystal cell In between, a first retardation layer and a second retardation layer are arranged in order from the side of the first polarizing film, and the refractive index of the first retardation layer in the slow axis x direction in the plane is nx1, fast When the refractive index in the axial direction is ny1 and the refractive index in the thickness z direction is nz1, the relationship of nz1>nx1=ny1 is satisfied; When the refractive index in the axial direction is ny2 and the refractive index in the thickness z direction is nz2, the relationship nx2>ny2=nz2 is satisfied.

進而,上述態樣之偏光膜薄膜積層體宜具備:液晶單元,其具備液晶層且該液晶層包含在無施加電場狀態下已於面內一方向定向之液晶分子;與偏光膜,係配置於該液晶單元之一側;並且在前述偏光膜與前述液晶單元之間配置有相位差層,且前述相位差層在令面內之慢軸x方向的折射率為nx、快軸方向之折射率為ny、厚度z方向之折射率為nz時,滿足nx>nz>ny之關係。Furthermore, the polarizing film thin-film laminate of the above aspect preferably includes: a liquid crystal cell having a liquid crystal layer and the liquid crystal layer contains liquid crystal molecules aligned in one direction in the plane without applying an electric field; and the polarizing film is arranged in One side of the liquid crystal cell; and a retardation layer is arranged between the polarizing film and the liquid crystal cell, and the retardation layer is set such that the refractive index of the slow axis x direction in the plane is nx, the refractive index of the fast axis direction When it is ny and the refractive index in the thickness z direction is nz, the relationship of nx>nz>ny is satisfied.

並且,為了解決上述課題,本發明之一態樣之光學顯示面板之特徵在於:其具備:光學性顯示單元;如上述任一項之偏光薄膜積層體,係直接或隔著其他光學薄膜接合於前述光學性顯示單元之一面;及覆蓋板,係在光學上呈透明且於前述偏光薄膜積層體之與前述光學性顯示單元相反之側沿著前述偏光薄膜積層體配置;並且,前述光學性顯示單元、前述偏光薄膜積層體與前述透明覆蓋板係藉由透明接著層接著,且該透明接著層係以不使該等之間產生空隙之狀態充填於其中。In addition, in order to solve the above-mentioned problems, an optical display panel of one aspect of the present invention is characterized in that it includes: an optical display unit; a polarizing film laminate such as any one of the above, which is bonded directly or via another optical film One side of the optical display unit; and a cover plate, which is optically transparent and is arranged along the polarizing film laminate on the opposite side of the polarizing film laminate from the optical display unit; and, the optical display The unit, the polarizing film laminate, and the transparent cover plate are bonded by a transparent adhesive layer, and the transparent adhesive layer is filled in a state in which no gaps are generated between them.

上述態樣之光學顯示面板中,前述透明覆蓋板亦可為具有電容型觸控感測器之機能者。In the optical display panel of the above aspect, the transparent cover plate may also have the function of a capacitive touch sensor.

又,上述態樣之光學顯示面板亦可於前述透明覆蓋板與前述偏光薄膜積層體之間設有成為電容型觸控感測器之構成要素的ITO層。In addition, the optical display panel of the above aspect may also be provided with an ITO layer, which is a constituent element of a capacitive touch sensor, between the transparent cover plate and the polarizing film laminate.

發明效果 根據本發明,可總括性解決「多烯化」、「褪色」、「加熱紅變」、「黏著耐久性」及「重工」之問題。Invention effect According to the present invention, the problems of "polyolefinization", "fading", "heating redness", "adhesion durability" and "heavy industry" can be solved in a comprehensive manner.

以下邊參照添附之圖式,就本發明之較佳一實施形態予以說明。為便於說明而僅顯示較佳實施形態,但本發明理應不受此限。The following describes a preferred embodiment of the present invention with reference to the attached drawings. For the convenience of description, only the preferred embodiments are shown, but the present invention should not be limited by this.

本發明之對象為光學顯示面板、尤其是安裝於汽車、電車、飛機、其他利用動力行進之動力行進車輛的車體的光學顯示面板、及用於該光學性顯示面板的偏光薄膜積層體。在此,所謂「安裝於車體」不一定單指將光學顯示面板或偏光薄膜積層體固定於車體之情形,舉例而言亦包含如用於智慧型手機等之光學顯示面板或偏光薄膜積層體,將該等自由搭載、攜入動力行進車輛中等情形。更進一步而言,所謂「安裝於車體」係包含將光學顯示面板或偏光薄膜積層體與動力行進車輛一同使用,而有可能暴露於高溫或高濕環境下的所有狀況。The object of the present invention is an optical display panel, especially an optical display panel mounted on the body of an automobile, a tram, an airplane, and other powered vehicles that use power to travel, and a polarizing film laminate used for the optical display panel. Here, the so-called "installed in the car body" does not necessarily refer to the case where the optical display panel or the polarizing film laminate is fixed to the car body. For example, it also includes the optical display panel or the polarizing film laminate used in smartphones, etc. It can be used in such situations as freely carrying and carrying it into a powered traveling vehicle. Furthermore, the so-called "installed on the car body" includes all situations where an optical display panel or a polarizing film laminate is used together with a powered vehicle, and may be exposed to high temperature or high humidity.

1.光學顯示面板 圖1係以示意圖顯示光學性顯示面板1之層構成。光學性顯示面板1至少包含光學性顯示單元10、偏光薄膜積層體12及覆蓋板14,該偏光薄膜積層體12積層於光學性顯示單元10之一面10a側(視辨側);該覆蓋板14係於光學上呈透明且於偏光薄膜積層體12之與光學性顯示單元10相反之側亦即視辨側沿著偏光薄膜積層體12配置。而於光學性顯示單元10之另一面10b側,係透過透明接著劑16配置另一偏光薄膜積層體17。光學性顯示單元10、偏光薄膜積層體12與覆蓋板14係藉由透明接著劑11、13之層接著,且透明接著劑11、13之層係以不使該等之間產生空隙之狀態充填於其中。此外,本說明書中,若無特別指明,則「接著」一詞包含黏著(壓敏接著)。光學性顯示單元10與偏光薄膜積層體12可利用透明接著劑11直接接著,但亦可視需求隔著相位差薄膜、視角補償薄膜等其他光學薄膜(未示於圖式中)接著。1. Optical display panel FIG. 1 is a schematic diagram showing the layer structure of the optical display panel 1. The optical display panel 1 includes at least an optical display unit 10, a polarizing film laminate 12, and a cover plate 14. The polarizing film laminate 12 is laminated on one surface 10a side (viewing side) of the optical display unit 10; the cover plate 14 It is optically transparent and is arranged along the polarizing film laminate 12 on the side of the polarizing film laminate 12 opposite to the optical display unit 10, that is, the viewing side. On the other surface 10 b side of the optical display unit 10, another polarizing film laminate 17 is arranged through the transparent adhesive 16. The optical display unit 10, the polarizing film laminate 12, and the cover plate 14 are connected by layers of transparent adhesives 11, 13, and the layers of transparent adhesives 11, 13 are filled in a state that does not create gaps between them In it. In addition, in this specification, unless otherwise specified, the term "adhesive" includes adhesion (pressure-sensitive adhesive). The optical display unit 10 and the polarizing film laminate 12 can be directly bonded using a transparent adhesive 11, but can also be bonded via other optical films (not shown in the drawings) such as retardation films, viewing angle compensation films, etc., as required.

1-1.光學性顯示單元 光學性顯示單元10之例可舉液晶單元或有機EL單元。 有機EL單元可適宜使用於透明基板上依序積層有透明電極、有機發光層及金屬電極而形成發光體(有機電致發光體)者等。有機發光層係多種有機薄膜之積層體,例如可採用以下各種層構成:由三苯胺衍生物等構成之電洞注入層與由蒽等螢光性有機固體構成之發光層的積層體;該等發光層與由苝衍生物等構成之電子注入層的積層體;或電洞注入層、發光層及電子注入層之積層體等。1-1. Optical display unit Examples of the optical display unit 10 may include a liquid crystal cell or an organic EL cell. The organic EL unit can be suitably used as a light-emitting body (organic electroluminescent body) formed by sequentially layering a transparent electrode, an organic light-emitting layer, and a metal electrode on a transparent substrate. The organic light-emitting layer is a laminate of various organic thin films. For example, the following various layers can be used: a laminate of a hole injection layer composed of triphenylamine derivatives and a light-emitting layer composed of a fluorescent organic solid such as anthracene; A laminate of a light-emitting layer and an electron injection layer composed of a perylene derivative, etc.; or a laminate of a hole injection layer, a light-emitting layer, and an electron injection layer, etc.

液晶單元可使用利用外光之反射型液晶單元、利用來自背光件18等光源之光的透射型液晶單元、利用來自外部之光與來自光源之光兩者的半透射半反射型液晶單元中之任一種。在液晶單元是利用來自光源之光時,如圖1所示,亦會於光學性顯示單元(液晶單元)10之與視辨側相反之側配置偏光薄膜積層體17,並且例如會配置背光件之類的光源18。光源側之偏光薄膜積層體17與液晶單元10係利用適當之透明接著劑17之層來接著。液晶單元的驅動方式可使用例如VA模式、IPS模式、TN模式、STN模式或彎曲定向(π型)等任意型式。The liquid crystal cell can be a reflective liquid crystal cell using external light, a transmissive liquid crystal cell using light from a light source such as the backlight 18, and a semi-transmissive and semi-reflective liquid crystal cell using both external light and light from a light source. Any kind. When the liquid crystal cell uses light from a light source, as shown in FIG. 1, a polarizing film laminate 17 is also arranged on the side opposite to the viewing side of the optical display unit (liquid crystal cell) 10, and for example, a backlight is arranged Like a light source 18. The polarizing film laminate 17 on the light source side and the liquid crystal cell 10 are bonded by a layer of an appropriate transparent adhesive 17. The driving method of the liquid crystal cell may use any type such as VA mode, IPS mode, TN mode, STN mode, or bend orientation (π-type).

1-2.覆蓋板 覆蓋板14之例可舉透明板(視窗層)或觸控面板等。透明板係使用具有適當機械強度及厚度之透明板。所述透明板例如可使用丙烯酸系樹脂或聚碳酸酯系樹脂這類透明樹脂板、或玻璃板等。覆蓋板14之表面例如亦可經利用低反射薄膜(未示於圖式中)施行低反射處理。觸控面板係使用電阻膜式、靜電容式、光學式、超音波式等各種觸控面板、或具備觸控感測機能之玻璃板或透明樹脂板等。1-2. Cover plate Examples of the cover plate 14 can include a transparent plate (window layer) or a touch panel. The transparent board uses a transparent board with appropriate mechanical strength and thickness. As the transparent plate, for example, a transparent resin plate such as acrylic resin or polycarbonate resin, a glass plate, or the like can be used. The surface of the cover plate 14 can also be treated with a low reflection film (not shown in the figure), for example. The touch panel uses various touch panels such as resistive film type, electrostatic capacitance type, optical type, ultrasonic type, etc., or glass plate or transparent resin plate with touch sensing function.

在使用靜電容式觸控面板作為覆蓋板14時,宜在較觸控面板更靠視辨側設置由玻璃或透明樹脂板構成之前面透明板。又,此時,會在用以接合覆蓋板14與偏光薄膜積層體12之間的透明接著劑13,設置成為電容型觸控感測器之構成要素的ITO層(未示於圖式中)。When using a capacitive touch panel as the cover plate 14, it is advisable to provide a front transparent plate made of glass or a transparent resin plate on the side closer to the visibility than the touch panel. In addition, at this time, the transparent adhesive 13 used to join the cover plate 14 and the polarizing film laminate 12 is provided as an ITO layer (not shown in the figure) as a component of the capacitive touch sensor .

[黏著劑組成物] 說明可使用於透明接著劑11等之黏著劑組成物。[Adhesive composition] It is explained that it can be used in the adhesive composition of the transparent adhesive 11 and the like.

<黏著劑聚合物> 黏著劑組成物所含黏著劑聚合物只要是一般可作為黏著劑之基底聚合物使用之具有黏著性之聚合物即無特別限定,但基於可易取得黏著性能之平衡的理由,以Tg為0℃以下(通常為-100℃以上)之聚合物為佳。所述黏著劑聚合物中,可適宜使用聚酯系聚合物、(甲基)丙烯酸系聚合物等。 本發明所用黏著劑聚合物中,酸成分經共聚合。<Adhesive polymer> The adhesive polymer contained in the adhesive composition is not particularly limited as long as it is an adhesive polymer that can generally be used as the base polymer of the adhesive. However, for the reason that the balance of adhesive performance can be easily obtained, Tg is 0. Polymers below °C (usually above -100 °C) are preferred. Among the adhesive polymers, polyester-based polymers, (meth)acrylic-based polymers, and the like can be suitably used. In the adhesive polymer used in the present invention, the acid component is copolymerized.

聚酯系聚合物通常係使用多元醇與多元羧酸之飽和聚酯或共聚酯。Polyester-based polymers usually use saturated polyesters or copolyesters of polyols and polycarboxylic acids.

多元醇例如可舉乙二醇、丙二醇、六亞甲基二醇、新戊二醇、1,2-環己烷二甲醇、1,4-環己烷二甲醇、1,10-癸二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-雙(4-羥苯基)丙烷、雙(4-羥苯基)碸等二醇。Examples of polyols include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,10-decanediol , 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxy Diols such as phenyl) sulfite.

多元羧酸可舉例如對苯二甲酸、間苯二甲酸、鄰苯二甲酸、2,5-萘二甲酸、2,6-萘二甲酸、1,4-萘二甲酸、1,5-萘二甲酸、二苯基甲酸、二苯氧乙烷二甲酸、二苯碸甲酸、蒽二羧酸等芳香族二甲酸;1,3-環戊烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、六氫酞酸、六氫異酞酸等脂環族二羧酸;丙二酸、二甲基丙二酸、琥珀酸、3,3-二乙基琥珀酸、戊二酸、2,2-二甲基戊二酸、己二酸、2-甲基己二酸、三甲基己二酸、庚二酸、壬二酸、二體酸、癸二酸、辛二酸、十二烷二羧酸等脂肪族二羧酸等。前述多元羧酸多併用2種以上多元羧酸,譬如併用芳香族二甲酸與脂肪族二羧酸。Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalene Aromatic dicarboxylic acids such as dicarboxylic acid, diphenylcarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl sulfonic acid, anthracene dicarboxylic acid; 1,3-cyclopentane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid Alicyclic dicarboxylic acids such as carboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, and hexahydroisophthalic acid; malonic acid, dimethylmalonic acid, succinic acid, 3,3- Diethyl succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, azelaic acid, dimer Aliphatic dicarboxylic acids such as acid, sebacic acid, suberic acid, dodecane dicarboxylic acid, etc. Many of the aforementioned polycarboxylic acids are used in combination of two or more kinds of polycarboxylic acids, for example, aromatic dicarboxylic acid and aliphatic dicarboxylic acid are used in combination.

在本發明中,藉由黏著劑聚合物含有所述酸成分可提升黏著劑之耐久性,而可防止經長期而發泡或剝落等發生。以構成黏著劑聚合物之總單體成分的量為基準,酸成分量之上限值小於5重量%,宜小於3重量%,小於2重量%更佳。若酸成分量超過上限值,有會對偏光膜之多烯化造成不良影響,黏著劑層之重工性亦會降低之傾向。以構成黏著劑聚合物之總單體成分的量為基準,酸成分量之下限值宜為0.01重量%以上,0.2重量%以上較佳,0.5重量%以上更佳。酸成分量若少,有黏著劑層之耐久性降低之傾向。In the present invention, by containing the acid component in the adhesive polymer, the durability of the adhesive can be improved, and the occurrence of foaming or peeling over a long period of time can be prevented. Based on the amount of the total monomer components constituting the adhesive polymer, the upper limit of the amount of acid components is less than 5% by weight, preferably less than 3% by weight, and more preferably less than 2% by weight. If the amount of the acid component exceeds the upper limit, it will adversely affect the polyolefinization of the polarizing film, and the reworkability of the adhesive layer will tend to decrease. Based on the amount of the total monomer components constituting the adhesive polymer, the lower limit of the acid component amount is preferably 0.01% by weight or more, preferably 0.2% by weight or more, and more preferably 0.5% by weight or more. If the amount of acid is small, the durability of the adhesive layer tends to decrease.

聚酯系聚合物所用多元醇、多元羧酸可無特別限制地使用各種之物,並可使用聚碳酸酯二醇等聚合物多元醇作為多元醇。又,聚酯系聚合物可由前述二醇成分與3價以上多元醇及/或3價以上之多元羧酸獲得。聚酯系聚合物之重量平均分子量通常可使用1.1萬以上者。 (甲基)丙烯酸系聚合物通常含有(甲基)丙烯酸烷基酯為主成分作為單體單元。此外,所謂(甲基)丙烯酸酯定為意指丙烯酸酯及/或甲基丙烯酸酯。Various polyols and polycarboxylic acids used for the polyester-based polymer can be used without particular limitation, and polymer polyols such as polycarbonate diol can be used as the polyol. In addition, the polyester-based polymer can be obtained from the aforementioned diol component and a trivalent or higher polyhydric alcohol and/or a trivalent or higher polycarboxylic acid. The weight average molecular weight of the polyester-based polymer is usually 11,000 or more. The (meth)acrylic polymer usually contains an alkyl (meth)acrylate as a main component as a monomer unit. In addition, the term “(meth)acrylate” means acrylate and/or methacrylate.

構成(甲基)丙烯酸系聚合物之主骨架的(甲基)丙烯酸烷基酯,可以例示直鏈狀或支鏈狀之烷基的碳數1~18者。例如前述烷基可例示甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、己基、環己基、庚基、2-乙基己基、異辛基、壬基、癸基、異癸基、十二基、異肉豆蔻基、月桂基、十三基、十五基、十六基、十七基、十八基等。該等可單獨使用或可組合來使用。該等烷基的平均碳數宜為3~9。The (meth)acrylic acid alkyl ester constituting the main skeleton of the (meth)acrylic polymer may be a linear or branched alkyl group having 1 to 18 carbon atoms. For example, the aforementioned alkyl group can be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, Decyl, isodecyl, dodecyl, isomyristyl, lauryl, thirteen, fifteen, sixteen, seventeen, octadecyl, etc. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3-9.

又,可使用如(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苄酯等含芳香族環之(甲基)丙烯酸烷基酯。含芳香族環之(甲基)丙烯酸烷基酯可將聚合其而成之聚合物混合於前述例示之(甲基)丙烯酸系聚合物中來使用,惟從透明性的觀點來看,含芳香族環之(甲基)丙烯酸烷基酯宜與前述(甲基)丙烯酸烷基酯共聚來使用。In addition, aromatic ring-containing alkyl (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate can be used. The aromatic ring-containing alkyl (meth)acrylate can be used by mixing the polymer obtained by polymerization with the (meth)acrylic polymer exemplified above, but from the perspective of transparency, it contains aromatic The group ring alkyl (meth)acrylate is preferably used by copolymerization with the aforementioned alkyl (meth)acrylate.

為了改善接著性及耐熱性,可於前述(甲基)丙烯酸系聚合物中,藉由共聚來導入1種以上具有(甲基)丙烯醯基或乙烯基等具不飽和雙鍵之聚合性官能基的共聚單體。這類的共聚單體之具體例可舉如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯及(4-羥甲基環己基)-甲基丙烯酸酯等含羥基單體;(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸等含羧基單體;馬來酸酐、伊康酸酐等含酸酐基單體;丙烯酸之己內酯加成物;苯乙烯磺酸或烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。In order to improve adhesion and heat resistance, one or more polymerizable functions with unsaturated double bonds such as (meth)acrylic acid groups or vinyl groups can be introduced into the aforementioned (meth)acrylic polymer by copolymerization. -Based comonomers. Specific examples of such comonomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and (4-hydroxymethylcyclohexyl)-methacrylate Hydroxy-containing monomers such as acrylate; (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and other carboxyl-containing monomers ; Monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrene sulfonic acid or allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropane Sulfonic acid group-containing monomers such as sulfonic acid, (meth)acrylic acid propanesulfonic acid, (meth)acrylic acid sulfopropyl ester, (meth)acrylic acid oxynaphthalene sulfonic acid, etc.; 2-hydroxyethylacrylic acid group Phosphoric acid group-containing monomers such as phosphate esters.

上述共聚單體當中,本發明之酸成分可舉具有(甲基)丙烯醯基或乙烯基等不飽和雙鍵之聚合性官能基的共聚單體。屬酸成分之共聚單體之具體例,可舉例如丙烯酸、(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸等含羧基單體;馬來酸酐、伊康酸酐等含酸酐基單體;丙烯酸之己內酯加成物;苯乙烯磺酸或烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。Among the above-mentioned comonomers, the acid component of the present invention includes comonomers having polymerizable functional groups with unsaturated double bonds such as (meth)acrylic groups or vinyl groups. Specific examples of comonomers that are acid components include acrylic acid, (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, Carboxyl group-containing monomers such as crotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrene sulfonic acid or allyl sulfonic acid, 2-(meth)acrylic acid Amino-2-methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid and other sulfonic acid group-containing monomers; 2 -Phosphoric acid group-containing monomers such as hydroxyethyl acryloyl phosphate, etc.

當存在酸成分時,由酸所造成之不良影響的觀點來看,吾等認為宜為含羧基單體等相對較弱之弱酸系統之酸,接著亦可為含磷酸基單體、含磺酸基單體等。When there is an acid component, from the point of view of the adverse effects caused by the acid, we believe that it should be the acid of a relatively weak acid system such as a carboxyl group-containing monomer, and then it can also be a phosphoric acid group-containing monomer or a sulfonic acid system. Based monomers and so on.

作為改質目的使用之共聚單體可舉(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺或N-羥甲基(甲基)丙烯醯胺、N-羥甲丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺乙酯、(甲基)丙烯酸-N,N-二甲基胺乙酯、(甲基)丙烯酸三級丁基胺乙酯等(甲基)丙烯酸烷基胺基烷基酯系單體;(甲基)丙烯酸甲氧乙酯、(甲基)丙烯酸乙氧乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺、N-丙烯醯基嗎福林等琥珀醯亞胺系單體;N-環己基馬來醯亞胺或N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺或N-苯基馬來醯亞胺等馬來醯亞胺系單體;N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體等等。The comonomer used for the purpose of modification can include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide or N-hydroxymethyl (N-substituted) amide-based monomers such as methyl (meth)acrylamide, N-hydroxymethylpropane (meth)acrylamide, etc.; aminoethyl (meth)acrylate, (meth)acrylic acid-N, N-dimethylaminoethyl, (meth)acrylic acid tertiary butylaminoethyl and other (meth)acrylic acid alkylaminoalkyl ester monomers; (meth)acrylic acid methoxyethyl, (meth)acrylate (Meth)acrylic acid alkoxyalkyl ester monomers such as ethoxyethyl acrylate; N-(meth)acryloyloxymethylene succinimidyl or N-(meth)acryloyl -6-Oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyoctamethylene succinimide, N-acryloyl mopholin and other succinimides Monomer; N-cyclohexylmaleimide or N-isopropylmaleimide, N-laurylmaleimide or N-phenylmaleimide and other maleimides Monomers; N-methylikonimines, N-ethylikonimines, N-butylikonimines, N-octylikonimines, N-2-ethyl Iconimines such as hexyl iconimines, N-cyclohexyl iconimines, N-lauryl iconimines, etc.

並且亦可使用乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌

Figure 109129209-A0304-12-0000-4
、乙烯基吡
Figure 109129209-A0304-12-0000-4
、乙烯基吡咯、乙烯基咪唑、乙烯基
Figure 109129209-A0304-12-0059-1
唑、乙烯基嗎福林、N-乙烯基羧酸醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯基系單體;丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體;(甲基)丙烯酸環氧丙酯等含環氧基之丙烯酸系單體;聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系丙烯酸酯單體;(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯或2-甲氧基乙基丙烯酸酯等丙烯酸酯系單體等作為改質單體。更可列舉異戊二烯、丁二烯、異丁烯、乙烯基醚等。And vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidine can also be used
Figure 109129209-A0304-12-0000-4
Vinylpyridine
Figure 109129209-A0304-12-0000-4
, Vinyl pyrrole, vinyl imidazole, vinyl
Figure 109129209-A0304-12-0059-1
Vinyl monomers such as azole, vinylmorpholine, N-vinyl carboxamides, styrene, α-methylstyrene, N-vinyl caprolactam, etc.; acrylonitrile, methacrylonitrile Cyanoacrylate monomers such as glycidyl (meth)acrylate; acrylic monomers containing epoxy groups such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methacrylate Glycol acrylate monomers such as oxyethylene glycol (meth)acrylate and methoxy polypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, Acrylate-based monomers such as polysiloxane (meth)acrylate or 2-methoxyethyl acrylate are used as the modifying monomer. More examples include isoprene, butadiene, isobutylene, vinyl ether, and the like.

並且,上述以外之可共聚單體還可舉含有矽原子之矽烷系單體等。作為矽烷系單體,可列舉例如3-丙烯醯氧丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧癸基三甲氧基矽烷、10-丙烯醯氧癸基三甲氧基矽烷、10-甲基丙烯醯氧癸基三乙氧基矽烷、10-丙烯醯氧癸基三乙氧基矽烷等。In addition, the copolymerizable monomers other than the above may also include silane-based monomers containing silicon atoms. As the silane-based monomer, for example, 3-propylene oxypropyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, 4-vinyl butyl trimethoxy silane, 4- Vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propylene Oxydecyl trimethoxysilane, 10-methacrylic oxydecyl triethoxy silane, 10-acrylic oxydecyl triethoxy silane, etc.

又,作為共聚單體,也可使用三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物等具有2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵之多官能性單體,或在聚酯、環氧、胺甲酸酯等的骨架上附加2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵作為與單體成分相同的官能基的聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸酯(甲基)丙烯酸酯等。In addition, as a comonomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and bisphenol A can also be used. Diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, Neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, caprolactone modified dineopentaerythritol hexa ( (Meth)acrylic acid ester and other (meth)acrylic acid and polyhydric alcohol esterification products, etc. have two or more (meth)acrylic acid groups, vinyl groups and other unsaturated double bonds multifunctional monomers, or in polyester, ring Polyester (meth)acrylates and epoxy resins in which two or more (meth)acrylic acid groups, vinyl groups, and other unsaturated double bonds are added to the skeleton of oxygen and urethane as the same functional groups as the monomer components. (Meth)acrylate, urethane (meth)acrylate, etc.

且在該等共聚單體當中,由接著性、耐久性等觀點來看,又宜使用含羥基單體、含羧基單體。可併用含羥基單體及含羧基單體。該等共聚單體在黏著劑組成物含有交聯劑時會成為其與交聯劑的反應點。由於含羥基單體、含羧基單體等在分子間與交聯劑之反應性佳,故為了提升所得黏著劑層的凝集性及耐熱性,宜使用該等單體。就重工性之觀點而言,含羥基單體較為理想,而就可兼具耐久性與重工性之觀點而言,則以含羧基單體較為理想。 含羥基單體可以在構成黏著劑聚合物之總單體成分中為0.01~30重量%左右、宜為0.03~20重量%左右、更宜為0.05~10重量%左右之量來使用。Among these comonomers, it is also suitable to use hydroxyl group-containing monomers and carboxyl group-containing monomers from the viewpoints of adhesiveness and durability. A hydroxyl group-containing monomer and a carboxyl group-containing monomer can be used in combination. When the adhesive composition contains a cross-linking agent, these comonomers will become the reaction point of the cross-linking agent. Since hydroxyl group-containing monomers, carboxyl group-containing monomers, etc. have good reactivity with the crosslinking agent between molecules, it is preferable to use these monomers in order to improve the cohesiveness and heat resistance of the resulting adhesive layer. From the viewpoint of heavy workability, a hydroxyl group-containing monomer is preferable, and from the viewpoint of having both durability and heavy workability, a carboxyl group-containing monomer is preferable. The hydroxyl-containing monomer can be used in an amount of about 0.01 to 30% by weight, preferably about 0.03 to 20% by weight, and more preferably about 0.05 to 10% by weight in the total monomer components constituting the adhesive polymer.

除上述外,酸成分以外之共聚單體還可以在構成黏著劑聚合物之總單體成分中為0~30重量%左右、宜為0.1~20%左右、更宜為0.1~10%左右的量來使用。In addition to the above, comonomers other than acid components can also be about 0-30% by weight, preferably about 0.1-20%, and more preferably about 0.1-10% in the total monomer components constituting the adhesive polymer. Quantity to use.

本發明所用黏著劑聚合物的重量平均分子量(Mw)宜為90萬~300萬。若考慮耐久性、尤其是耐熱性,重量平均分子量較宜為120萬~250萬。若重量平均分子量小於90萬,則低分子量之聚合物成分會變多,使凝膠(黏著劑層)之交聯密度變高,而隨之黏著劑層會變硬,損害應力鬆弛性,而不佳。又,若重量平均分子量大於300萬,則會發生黏度上升及在聚合物聚合中發生凝膠化,而不佳。The weight average molecular weight (Mw) of the adhesive polymer used in the present invention is preferably 900,000 to 3 million. Considering durability, especially heat resistance, the weight average molecular weight is preferably 1.2 million to 2.5 million. If the weight average molecular weight is less than 900,000, low molecular weight polymer components will increase, which will increase the crosslinking density of the gel (adhesive layer), and consequently the adhesive layer will become harder, impairing the stress relaxation properties. Bad. In addition, if the weight average molecular weight is greater than 3 million, the viscosity will increase and gelation will occur during polymer polymerization, which is not preferable.

本發明所用黏著劑的多分散性指數(重量平均分子量(Mw)/數量平均分子量(Mn))宜為3.0以下,較宜為1.05~2.5,更宜為1.05~2.0。若多分散性指數(Mw/Mn)大於3.0,則低分子量之聚合物會變多,而為了提高黏著劑層之凝膠分率,會需要使用大量交聯劑,因此,剩餘之交聯劑會對已經凝膠化之聚合物反應,使凝膠(黏著劑層)之交聯密度變高,而隨之黏著劑層會變硬,損害應力鬆弛性,而不佳。且,吾等推測若低分子量之聚合物多,而未交聯之聚合物或寡聚物(溶膠份)變多,則在加熱及加濕條件下等,偏析至與被黏體接觸之黏著劑層界面附近的未交聯聚合物等會破壞黏著劑層,而成為黏著劑層剝落之原因。此外,重量平均分子量、多分散性指數(Mw/Mn)可利用GPC(凝膠滲透層析儀;Gel Permeation Chromatography)測定,從以苯乙烯換算所算出的數值求得。The polydispersity index (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the adhesive used in the present invention is preferably below 3.0, more preferably 1.05 to 2.5, and more preferably 1.05 to 2.0. If the polydispersity index (Mw/Mn) is greater than 3.0, there will be more low-molecular-weight polymers. In order to increase the gel fraction of the adhesive layer, a large amount of cross-linking agent will need to be used. Therefore, the remaining cross-linking agent It will react with the already gelled polymer to increase the cross-linking density of the gel (adhesive layer), and then the adhesive layer will become hard, impairing the stress relaxation, which is not good. Moreover, we speculate that if there are more low-molecular-weight polymers and more uncrosslinked polymers or oligomers (sol fraction), under heating and humidification conditions, etc., they will segregate to the adhesion of the adherend. The uncrosslinked polymer near the interface of the agent layer will damage the adhesive layer and cause the adhesive layer to peel off. In addition, the weight average molecular weight and the polydispersity index (Mw/Mn) can be measured by GPC (Gel Permeation Chromatography), and can be obtained from values calculated in terms of styrene.

本發明所用黏著劑的製造,可適當選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等公知的製造方法。又,所得黏著劑聚合物可為無規共聚物、嵌段共聚物、接枝共聚物等任一者。For the production of the adhesive used in the present invention, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. In addition, the obtained adhesive polymer may be any of random copolymers, block copolymers, graft copolymers, and the like.

此外,溶液聚合中,聚合溶劑可使用例如乙酸乙酯、甲苯等。作為具體之溶液聚合例,反應可於氮等非活性氣體氣流下添加聚合引發劑,且一般係於50~70℃左右、10分鐘~30小時左右之反應條件下進行。尤其是藉由將聚合時間縮短成30分鐘~3小時左右,可抑制於聚合後期生成之低分子量的寡聚物的生成,而可將多分散性指數(Mw/Mn)調整在3.0以下之較佳範圍。In addition, in the solution polymerization, for example, ethyl acetate, toluene, etc. can be used as the polymerization solvent. As a specific example of solution polymerization, the reaction can be carried out by adding a polymerization initiator under an inert gas flow such as nitrogen, and is generally carried out under reaction conditions of about 50 to 70°C for about 10 minutes to 30 hours. In particular, by shortening the polymerization time to about 30 minutes to 3 hours, the formation of low molecular weight oligomers formed in the late stage of the polymerization can be suppressed, and the polydispersity index (Mw/Mn) can be adjusted below 3.0. Best range.

用於自由基聚合之聚合引發劑、鏈轉移劑、乳化劑等並無特別限定,可適當選擇來使用。此外,黏著劑聚合物之重量平均分子量可藉由聚合引發劑、鏈轉移劑的使用量、反應條件來控制,並因應該等之種類來適當地調整其使用量。The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not particularly limited, and can be appropriately selected and used. In addition, the weight average molecular weight of the adhesive polymer can be controlled by the amount of polymerization initiator and chain transfer agent used, and reaction conditions, and the amount of use can be appropriately adjusted according to the type of the polymer.

作為聚合引發劑,可列舉例如2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2’-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2’-偶氮雙(N,N’-二亞甲基異丁基脒)、2,2’-偶氮雙[N-(2-羧乙基)-2-甲基丙脒]水合物(和光純藥公司製,VA-057)等偶氮系引發劑、過硫酸鉀、過硫酸銨等過硫酸鹽、二(2-乙基己基)過氧化二碳酸酯、二(4-三級丁基環己基)過氧化二碳酸酯、二-二級丁基過氧化二碳酸酯、過氧化新癸酸三級丁酯、過氧化三甲基乙酸三級己酯、過氧化三甲基乙酸三級丁酯、二月桂醯基過氧化物、二正辛醯基過氧化物、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯、二(4-甲基苯甲醯基)過氧化物、二苯甲醯基過氧化物、過異丁酸三級丁酯、1,1-二(三級己基過氧基)環己烷、三級丁基過氧化氫、過氧化氫等過氧化物系引發劑、過硫酸鹽與亞硫酸氫鈉之組合、過氧化物與抗壞血酸鈉的組合等過氧化物與還原劑組合而成之氧化還原系引發劑等,但不受限於該等。As the polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2 -(5-Methyl-2-imidazolin-2-yl)propane) dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azo Bis(N,N'-dimethylisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (Wako Pure Chemical Industries, Ltd. Manufacture, VA-057) and other azo initiators, potassium persulfate, ammonium persulfate and other persulfates, bis(2-ethylhexyl)peroxydicarbonate, bis(4-tertiarybutylcyclohexyl) Peroxydicarbonate, di-secondary butyl peroxydicarbonate, tertiary butyl peroxide neodecanoate, tertiary hexyl peroxide trimethyl acetate, tertiary butyl peroxide trimethyl acetate, Dilauryl peroxide, di-n-octyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis(4-methylbenzyl) )Peroxide, dibenzyl peroxide, tertiary butyl perisobutyrate, 1,1-di(tertiary hexylperoxy) cyclohexane, tertiary butyl hydroperoxide, peroxide Peroxide-based initiators such as hydrogen, combinations of persulfate and sodium bisulfite, combinations of peroxides and sodium ascorbate, and redox initiators combined with peroxides and reducing agents, etc., but not limited In these.

前述聚合引發劑可單獨使用,亦可將2種以上混合來使用,但整體含量相對於100重量份之單體,宜為0.005~1重量份左右,較宜為0.02~0.5重量份左右。The aforementioned polymerization initiators can be used alone or in a mixture of two or more, but the overall content relative to 100 parts by weight of the monomer is preferably about 0.005 to 1 part by weight, more preferably about 0.02 to 0.5 part by weight.

另,作為聚合引發劑,使用例如2,2'-偶氮雙異丁腈來製造前述重量平均分子量的(甲基)丙烯酸系聚合物時,聚合引發劑的使用量相對於單體成分的總量100重量份,宜設為0.06~0.2重量份左右,設為0.08~0.175重量份左右更佳。In addition, when 2,2'-azobisisobutyronitrile is used as a polymerization initiator to produce the aforementioned weight average molecular weight (meth)acrylic polymer, the amount of polymerization initiator used is relative to the total monomer components. The amount is 100 parts by weight, preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight.

作為鏈轉移劑,可列舉例如月桂基硫醇、環氧丙基硫醇、巰乙酸、2-巰基乙醇、硫代乙醇酸、硫代乙醇酸2-乙基己酯、2,3-二巰基-1-丙醇等。鏈轉移劑可單獨使用,亦可將2種以上混合來使用,但整體含量相對於單體成分的總量100重量份,為0.1重量份左右以下。As the chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, thioacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolic acid, 2,3-dimercapto -1-propanol and so on. The chain transfer agent may be used singly or in combination of two or more, but the total content is about 0.1 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components.

又,作為用於進行乳化聚合時的乳化劑,可列舉例如月桂基硫酸鈉、月桂基硫酸銨、十二基苯磺酸鈉、聚氧伸乙基烷基醚硫酸銨、聚氧伸乙基烷基苯基醚硫酸鈉等陰離子系乳化劑,聚氧伸乙基烷基醚、聚氧伸乙基烷基苯基醚、聚氧伸乙基脂肪酸酯、聚氧伸乙基-聚氧伸丙基嵌段聚合物等非離子系乳化劑等。該等乳化劑可單獨使用亦可將2種以上併用。In addition, examples of emulsifiers used for emulsification polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene sulfate. Anionic emulsifiers such as sodium alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxy Nonionic emulsifiers such as propylene block polymers. These emulsifiers may be used alone or in combination of two or more kinds.

並且,以反應性乳化劑來說,導入有丙烯基、烯丙基醚基等自由基聚合性官能基之乳化劑,具體而言可舉例如Aqualon HS-10、HS-20、KH-10、BC-05、BC-10、BC-20(以上皆為第一工業製藥公司製)、ADEKA REASOAP SE10N(旭電化工公司製)等。由於反應性乳化劑在聚合後會組入聚合物鏈,故耐水性良好而為佳。乳化劑的使用量相對於單體成分總量100重量份為0.3~5重量份,而由聚合穩定性及機械穩定性來看宜為0.5~1重量份。In addition, as reactive emulsifiers, emulsifiers introduced with radical polymerizable functional groups such as propenyl and allyl ether groups, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all made by Daiichi Kogyo Pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (made by Solectron Chemical Co., Ltd.), etc. Since the reactive emulsifier will be incorporated into the polymer chain after polymerization, it is preferred that it has good water resistance. The amount of emulsifier used is 0.3 to 5 parts by weight relative to 100 parts by weight of the total monomer components, and preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.

本發明所用黏著劑聚合物通常係使用重量平均分子量為30萬~400萬之範圍者。若考慮耐久性尤其是耐熱性,宜使用重量平均分子量為50萬~300萬之物。並以65萬~200萬更佳。重量平均分子量若小於30萬,在耐熱性觀點來看不宜。又,重量平均分子量一旦大於400萬,貼合性、接著力就會降低,故由這點來看不宜。另,重量平均分子量係指以GPC(凝膠滲透層析法;Gel Permeation Chromatography)測定,從以聚苯乙烯換算所算出之值。The adhesive polymer used in the present invention usually uses a weight average molecular weight in the range of 300,000 to 4 million. In consideration of durability, especially heat resistance, a weight average molecular weight of 500,000 to 3 million should be used. And 650,000 to 2 million is better. If the weight average molecular weight is less than 300,000, it is not suitable from the viewpoint of heat resistance. In addition, if the weight average molecular weight exceeds 4 million, the adhesion and adhesiveness will decrease, so it is unfavorable from this point of view. In addition, the weight average molecular weight means a value measured by GPC (Gel Permeation Chromatography) and calculated in terms of polystyrene.

<黏著劑組成物中之其他成分> 並且,本發明中所用黏著劑組成物中可含有交聯劑。作為交聯劑,可使用有機系交聯劑或多官能性金屬螯合物。有機系交聯劑可舉異氰酸酯系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合物是多價金屬與有機化合物共價鍵結或配位鍵結之物。多價金屬原子可列舉Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。有機化合物中可共價鍵結或配位鍵結之原子可舉氧原子等,有機化合物可舉烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。<Other components in the adhesive composition> In addition, the adhesive composition used in the present invention may contain a crosslinking agent. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include isocyanate-based crosslinking agents, peroxide-based crosslinking agents, epoxy-based crosslinking agents, and imine-based crosslinking agents. Multifunctional metal chelate is a covalent bond or coordinate bond between a multivalent metal and an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Examples of the atoms that can be covalently bonded or coordinately bonded in the organic compound include oxygen atoms, and the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.

交聯劑宜為異氰酸酯系交聯劑及/或過氧化系交聯劑。異氰酸酯系交聯劑之化合物可舉例如甲苯二異氰酸酯、氯伸苯基二異氰酸酯、四亞甲基二異氰酸酯、伸二甲苯基二異氰酸酯、二苯甲烷二異氰酸酯、經氫化之二苯甲烷二異氰酸酯等異氰酸酯單體,及該等異氰酸酯單體與三羥甲丙烷等進行加成而成的異氰酸酯化合物或三聚異氰酸酯化物、縮二脲型化合物,還有與聚醚多元醇或聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等行加成反應而成的胺甲酸酯預聚物型異氰酸酯等等。尤佳為聚異氰酸酯化合物,且為選自於由六亞甲基異氰酸酯、氫化伸二甲苯基二異氰酸酯及異佛酮二異氰酸酯所構成群組中之1種或源自於其的聚異氰酸酯化合物。在此,選自於由六亞甲基異氰酸酯、氫化伸二甲苯基二異氰酸酯及異佛酮二異氰酸酯所構成群組中之1種或源自於其的聚異氰酸酯化合物包括:六亞甲基異氰酸酯、氫化伸二甲苯基二異氰酸酯、異佛酮二異氰酸酯、多元醇改質六亞甲基異氰酸酯、多元醇改質氫化伸二甲苯基二異氰酸酯、三聚物型氫化伸二甲苯基二異氰酸酯及多元醇改質異佛酮二異氰酸酯等。所例示之聚異氰酸酯化合物因其與羥基之反應迅速進行(尤其是使聚合物中所含之酸、鹼如同觸媒般),特別有助於加速交聯而較為理想。The cross-linking agent is preferably an isocyanate-based cross-linking agent and/or a peroxide-based cross-linking agent. The compound of the isocyanate-based crosslinking agent can include, for example, isocyanates such as toluene diisocyanate, chlorophenyl diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Monomers, and isocyanate compounds or trimeric isocyanates, biuret-type compounds formed by addition of these isocyanate monomers with trimethylolpropane, etc., as well as polyether polyols, polyester polyols, and acrylic polyols. Alcohol, polybutadiene polyol, polyisoprene polyol, etc. are urethane prepolymer isocyanate formed by addition reaction, etc. Particularly preferred is a polyisocyanate compound, and is one selected from the group consisting of hexamethylene isocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate, or a polyisocyanate compound derived therefrom. Here, one selected from the group consisting of hexamethylene isocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate or polyisocyanate compounds derived therefrom include: hexamethylene isocyanate, Hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol modified hexamethylene isocyanate, polyol modified hydrogenated xylylene diisocyanate, trimer type hydrogenated xylylene diisocyanate and polyol modified iso Phosphonone diisocyanate and so on. The exemplified polyisocyanate compound is ideal because the reaction with the hydroxyl group proceeds rapidly (especially, the acid and alkali contained in the polymer are made to act like catalysts), and are particularly useful for accelerating crosslinking.

過氧化物系交聯劑只要是經加熱或光照射會產生自由基活性種而使黏著劑組成物之基底聚合物進行交聯者即可適當使用,但考慮到作業性及穩定性,宜使用1分鐘半衰期溫度在80℃~160℃之過氧化物,較宜使用在90℃~140℃之過氧化物。The peroxide-based crosslinking agent can be suitably used as long as it generates free radical active species upon heating or light irradiation to crosslink the base polymer of the adhesive composition. However, considering workability and stability, it is suitable to use Peroxides with a 1-minute half-life temperature of 80℃~160℃ are more suitable for peroxides with a temperature of 90℃~140℃.

可作為交聯劑使用之過氧化物可舉如二(2-乙基己基)過氧二碳酸酯(1分鐘半衰期溫度:90.6℃)、二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度:92.1℃)、過氧二碳酸二-二級丁酯(1分鐘半衰期溫度:92.4℃)、過氧新癸酸三級丁酯(1分鐘半衰期溫度:103.5℃)、過氧化三甲基乙酸三級己酯(1分鐘半衰期溫度:109.1℃)、過氧化三甲基乙酸三級丁酯(1分鐘半衰期溫度:110.3℃)、二月桂醯基過氧化物(1分鐘半衰期溫度:116.4℃)、二正辛醯基過氧化物(1分鐘半衰期溫度:117.4℃)、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯(1分鐘半衰期溫度:124.3℃)、二(4-甲基苯甲醯基)過氧化物(1分鐘半衰期溫度:128.2℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度:130.0℃)、過異丁酸三級丁酯(1分鐘半衰期溫度:136.1℃)、1,1-二(三級己基過氧基)環己烷(1分鐘半衰期溫度:149.2℃)等。其中,尤從交聯反應效率優異之觀點來看,有二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度:92.1℃)、二月桂醯基過氧化物(1分鐘半衰期溫度:116.4℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度:130.0℃)等。Peroxides that can be used as crosslinking agents include bis(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6℃), bis(4-tertiarybutylcyclohexyl)peroxydicarbonate Carbonate (1 minute half-life temperature: 92.1°C), peroxydicarbonate di-secondary butyl ester (1 minute half-life temperature: 92.4°C), peroxyneodecanoic acid tertiary butyl ester (1 minute half-life temperature: 103.5°C) , Trimethyl acetate tertiary hexyl peroxide (1 minute half-life temperature: 109.1 ℃), trimethyl peroxide tertiary butyl acetate (1 minute half-life temperature: 110.3 ℃), dilaurin peroxide (1 Minute half-life temperature: 116.4℃), di-n-octyl peroxide (1 minute half-life temperature: 117.4℃), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 Minute half-life temperature: 124.3°C), bis(4-methylbenzyl) peroxide (1 minute half-life temperature: 128.2°C), dibenzyl peroxide (1 minute half-life temperature: 130.0°C), Tertiary butyl perisobutyrate (1 minute half-life temperature: 136.1°C), 1,1-bis(tertiary hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2°C), etc. Among them, especially from the viewpoint of excellent crosslinking reaction efficiency, there are bis(4-tertiarybutylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1°C), dilaurin peroxide (1 One-minute half-life temperature: 116.4°C), dibenzoyl peroxide (1-minute half-life temperature: 130.0°C), etc.

此外,過氧化物之半衰期係表示過氧化物之分解速度的指標,意指過氧化物之殘存量變成一半時的時間。關於用以於任意時間達半衰期所需的分解溫度、或於任意溫度下之半衰期時間,係記載於製造商型錄等,例如係記載於日本油脂股份公司之「有機過氧化物型錄第9版(2003年5月)」等。In addition, the half-life of peroxide is an index indicating the decomposition rate of peroxide, which means the time when the residual amount of peroxide becomes half. Regarding the decomposition temperature required to reach the half-life at any time, or the half-life time at any temperature, it is recorded in the manufacturer’s catalog, for example, in the "Organic Peroxide Catalog No. 9" of NOF Corporation. Edition (May 2003)" and so on.

相對於黏著劑聚合物100重量份,交聯劑之使用量宜為0.01~20重量份,較宜為0.03~10重量份。此外,交聯劑少於0.01重量份時,黏著劑之凝集力會有不足之傾向,而有在加熱時發生發泡之虞;另一方面,若多於20重量份,則耐濕性不足,而容易在可靠性試驗等中發生剝落。Relative to 100 parts by weight of the adhesive polymer, the amount of crosslinking agent used is preferably 0.01-20 parts by weight, more preferably 0.03-10 parts by weight. In addition, when the crosslinking agent is less than 0.01 parts by weight, the cohesive force of the adhesive tends to be insufficient, and foaming may occur during heating; on the other hand, if it is more than 20 parts by weight, the moisture resistance is insufficient , And it is easy to peel off during reliability tests.

上述異氰酸酯系交聯劑可單獨使用1種,亦可將2種以上混合來使用,但整體含量相對於前述黏著劑聚合物100重量份,宜含有0.01~2重量份之前述聚異氰酸酯系化合物而成,較佳為含有0.02~2重量份而成,含有0.05~1.5重量份而成更佳。可考慮凝集力及阻止在耐久性試驗中之剝離等而適當含有交聯劑。The above-mentioned isocyanate-based crosslinking agent may be used alone or in combination of two or more, but the total content is preferably 0.01-2 parts by weight of the aforementioned polyisocyanate-based compound relative to 100 parts by weight of the aforementioned adhesive polymer. The content is preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight. A cross-linking agent can be appropriately included in consideration of cohesive force and prevention of peeling in the durability test.

前述過氧化物可單獨使用1種,亦可將2種以上混合來使用,但整體含量相對於100重量份之前述黏著劑聚合物,前述過氧化物為0.01~2重量份,並宜含有0.04~1.5重量份而成,更宜含有0.05~1重量份而成。可在此範圍內適當選擇以調整加工性、重工性、交聯穩定性、剝離性等。The aforementioned peroxide can be used alone or in a mixture of two or more. However, the total content is 0.01 to 2 parts by weight relative to 100 parts by weight of the aforementioned adhesive polymer, and preferably contains 0.04 parts by weight. ~1.5 parts by weight, more preferably 0.05~1 parts by weight. It can be appropriately selected within this range to adjust processability, reworkability, crosslinking stability, releasability, and the like.

此外,作為反應處理後殘留之過氧化物分解量之測定方法,可例如以HPLC(高效能液體層析法)來進行測定。In addition, as a method for measuring the amount of peroxide decomposition remaining after the reaction treatment, it can be measured by, for example, HPLC (High Performance Liquid Chromatography).

更具體而言,例如每次取出約0.2g的反應處理後黏著劑組成物,浸漬於乙酸乙酯10ml中,以振動機在25℃下以120rpm進行3小時振動萃取後,在室溫下靜置3天。接著,加入10ml乙腈,在25℃下以120rpm振動30分鐘,並將利用膜濾器(0.45μm)過濾所得萃取液約10μl注入HPLC進行分析,而可作為反應處理後之過氧化物量。More specifically, for example, about 0.2 g of the post-reaction adhesive composition is taken out each time, immersed in 10 ml of ethyl acetate, and subjected to shaking extraction with a shaker at 25° C. and 120 rpm for 3 hours, and then statically at room temperature. Set for 3 days. Next, add 10 ml of acetonitrile, shake at 120 rpm for 30 minutes at 25°C, and pour about 10 μl of the extract obtained by filtration with a membrane filter (0.45 μm) into HPLC for analysis, which can be used as the amount of peroxide after the reaction treatment.

添加劑以摻混矽烷耦合劑尤佳。矽烷耦合劑可列舉3-環氧丙氧基丙基三甲氧矽烷、3-環氧丙氧基丙基甲基二甲氧矽烷、2-(3,4-環氧環己基)乙基三甲氧矽烷等具有環氧結構之矽化合物;3-胺丙基三甲氧矽烷、N-(2-胺乙基)3-胺丙基三甲氧矽烷、N-(2-胺乙基)3-胺丙基甲基二甲氧矽烷等含胺基之矽化合物;3-氯丙基三甲氧矽烷;含乙醯乙醯基之三甲氧矽烷、3-丙烯醯氧基丙基三甲氧矽烷、3-甲基丙烯醯氧基丙基三乙氧矽烷等含(甲基)丙烯醯基之矽烷耦合劑;3‐異氰酸酯丙基三乙氧矽烷等含異氰酸酯基之矽烷耦合劑等。尤其,含3-環氧丙氧基丙基三甲氧矽烷、含乙醯乙醯基之三甲氧矽烷可有效抑制剝落,故適宜使用。矽烷耦合劑可賦予耐久性、尤其係在加濕環境下抑制剝落之效果。相對於黏著劑聚合物100重量份,矽烷耦合劑的使用量為1重量份以下,更宜為0.01~1重量份,又更宜為0.02~0.6重量份。矽烷耦合劑之使用量若變多,對液晶單元之接著力就會過度增大,而有對重工性等造成影響之情形。The additive is particularly preferably mixed with a silane coupling agent. Silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Silane and other silicon compounds with epoxy structure; 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropyl Amino-containing silicon compounds such as methyl dimethyl dimethyl siloxane; 3-chloropropyl trimethoxy silane; trimethoxy silyl containing acetyl acetyl group, 3-propenyl oxy propyl trimethoxy silane, 3-methyl Silane coupling agents containing (meth)acrylic acid groups such as acryloxypropyl triethoxysilane; silane coupling agents containing isocyanate groups such as 3-isocyanate propyl triethoxysilane. In particular, 3-glycidoxypropyltrimethoxysilane and trimethoxysilane containing acetylacetoxy group can effectively inhibit peeling, so it is suitable for use. Silane coupling agent can impart durability, especially the effect of inhibiting peeling in a humidified environment. Relative to 100 parts by weight of the adhesive polymer, the amount of the silane coupling agent used is 1 part by weight or less, more preferably 0.01 to 1 part by weight, and even more preferably 0.02 to 0.6 part by weight. If the amount of silane coupling agent used increases, the adhesive force to the liquid crystal cell will increase excessively, which may affect the reworkability.

並且,本發明中使用之黏著劑組成物可含有其他公知之添加劑,例如可因應使用用途於黏著劑組成物中適當添加著色劑、顏料等粉體,染料、界面活性劑、塑化劑、增黏劑、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機或有機填充劑、金屬粉、粒狀、箔狀物等。又,亦可在可控制的範圍內採用添加還原劑的氧化還原系。In addition, the adhesive composition used in the present invention may contain other well-known additives. For example, powders such as colorants, pigments, dyes, surfactants, plasticizers, and additives may be appropriately added to the adhesive composition according to the application. Adhesives, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, granules, foils, etc. In addition, it is also possible to use a redox system with a reducing agent added within a controllable range.

利用前述黏著劑組成物來形成黏著劑層,惟在形成黏著劑層時,宜調整交聯劑整體的添加量,並充分考慮交聯處理溫度及交聯處理時間之影響。The aforementioned adhesive composition is used to form the adhesive layer, but when forming the adhesive layer, it is advisable to adjust the total amount of cross-linking agent added, and fully consider the effects of the cross-linking treatment temperature and the cross-linking treatment time.

交聯處理溫度或交聯處理時間可依據所使用的交聯劑來調整。交聯處理溫度宜為170℃以下。The cross-linking treatment temperature or the cross-linking treatment time can be adjusted according to the cross-linking agent used. The cross-linking treatment temperature is preferably below 170°C.

又,所述交聯處理可在黏著劑層的乾燥步驟時之溫度下實行,也可以在乾燥步驟後另外設置交聯處理步驟來實行。In addition, the cross-linking treatment may be carried out at the temperature in the drying step of the adhesive layer, or it may be carried out by additionally providing a cross-linking treatment step after the drying step.

又,關於交聯處理時間,可考慮生產性與作業性進行設定,通常為0.2~20分鐘左右,宜為0.5~10分鐘左右。 [黏著劑層] 針對黏著劑層進行說明。In addition, the crosslinking treatment time can be set in consideration of productivity and workability, and is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes. [Adhesive layer] The adhesive layer will be described.

本發明附黏著劑層之偏光薄膜積層體係於偏光膜之至少一面直接或隔著光學上呈透明之偏光膜保護薄膜設置有黏著劑層者。The adhesive layer-attached polarizing film laminate system of the present invention is provided with an adhesive layer on at least one side of the polarizing film directly or via an optically transparent polarizing film protective film.

形成黏著劑層之方法可舉例如:將前述黏著劑組成物塗佈於經剝離處理之分離件等,並將聚合溶劑等乾燥去除而形成黏著劑層後,將其轉印至光學薄膜上之方法;或者於光學薄膜塗佈前述黏著劑組成物,並將聚合溶劑等乾燥去除而於光學薄膜上形成黏著劑層之方法等。另,黏著劑之塗佈可適當新添加聚合溶劑以外之一種以上溶劑。The method of forming the adhesive layer may include, for example, coating the aforementioned adhesive composition on a peel-off part, etc., and drying off the polymerization solvent to form an adhesive layer, and then transferring it to an optical film Method; or a method of coating the aforementioned adhesive composition on the optical film, and drying and removing the polymerization solvent, etc., to form an adhesive layer on the optical film, etc. In addition, for the application of the adhesive, one or more solvents other than the polymerization solvent can be newly added as appropriate.

經剝離處理之分離件宜使用聚矽氧剝離襯材。於所述襯材上塗佈前述黏著劑組成物並使其乾燥而形成黏著劑層的步驟中,使黏著劑乾燥之方法可視目的採用適當適切的方法。宜使用將上述塗佈膜進行過熱乾燥之方法。加熱乾燥溫度宜為40℃~200℃,更宜為50℃~180℃,尤宜為70℃~170℃。藉由將加熱溫度設定為上述範圍,可獲得具有優異黏著特性之黏著劑層。It is better to use polysilicone release liner for the separated parts after peeling treatment. In the step of coating the aforementioned adhesive composition on the lining material and drying it to form an adhesive layer, the method of drying the adhesive may adopt a suitable method depending on the purpose. It is suitable to use a method of overheating and drying the above-mentioned coated film. The heating and drying temperature should be 40℃~200℃, more preferably 50℃~180℃, especially 70℃~170℃. By setting the heating temperature to the above range, an adhesive layer with excellent adhesive properties can be obtained.

乾燥時間可採用適當適切的時間。乾燥時間宜為5秒~20分鐘,更宜為5秒~10分鐘,尤宜為10秒~5分鐘。Suitable drying time can be adopted. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

又,可於偏光膜表面形成錨固層、或施行電暈處理、電漿處理等之各種易接著處理後形成黏著劑層。亦可對黏著劑層表面施行易接著處理。In addition, an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after various easy bonding treatments such as corona treatment and plasma treatment are performed. It is also possible to perform easy bonding treatment on the surface of the adhesive layer.

關於在偏光膜表面設置黏著劑層時形成的錨固層或接著劑層,在使用該等時,亦宜設為不含酸的系。Regarding the anchor layer or the adhesive layer formed when the adhesive layer is provided on the surface of the polarizing film, it is also preferable to set it as an acid-free system when it is used.

形成錨固層之具體方法可舉以下方法等:將包含胺甲酸酯系聚合物之溶液(Nagase ChemteX Co.製:Denatron B510-C等)以水/異丙醇(容量比計65:35)混合溶液調整成固體成分成為0.2重量%,並使用線棒#5將調整後之溶液塗佈於偏光板,以50℃乾燥30秒鐘而形成厚度25nm之錨固塗覆層。The specific method of forming the anchor layer may include the following methods: a solution containing a urethane-based polymer (manufactured by Nagase ChemteX Co.: Denatron B510-C, etc.) with water/isopropanol (volume ratio 65:35) The mixed solution was adjusted to have a solid content of 0.2% by weight, and the adjusted solution was coated on a polarizing plate using wire rod #5, and dried at 50° C. for 30 seconds to form an anchor coating layer with a thickness of 25 nm.

黏著劑層之形成方法可採用各種方法。具體而言,可舉例如輥塗佈、接觸輥塗佈、凹版塗佈、逆塗佈、輥刷、噴塗佈、浸漬輥塗佈、棒塗佈、刮刀塗佈、氣刀塗佈、簾式塗佈、唇塗佈、利用模塗機等的擠壓式塗佈法等方法。Various methods can be used to form the adhesive layer. Specifically, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray cloth, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, etc. Methods such as type coating, lip coating, and extrusion coating using a die coater.

黏著劑層的厚度無特別限制,例如為1~500μm左右。且宜為1~250μm,較宜為1~100μm,更宜為1~35μm。 藉由減薄黏著劑層之厚度,可降低相對於偏光膜之黏著劑中之酸的整體量,而可減少對附黏著劑層之偏光薄膜積層體的多烯化造成影響。 又,一般來說當黏著劑層厚度變薄,黏著力就會逐漸降低,而有因偏光膜在高溫高濕下之收縮所致之偏光板的收縮應力,造成浮凸或剝落等黏著耐久性降低之傾向,故不宜減薄黏著劑層的厚度。但藉由將偏光膜薄型化可降低偏光板之收縮應力,結果即便減薄黏著劑層厚度,仍可維持或提升黏著耐久性。The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 500 μm. And it should be 1~250μm, more preferably 1~100μm, more preferably 1~35μm. By reducing the thickness of the adhesive layer, the overall amount of acid in the adhesive relative to the polarizing film can be reduced, and the impact on the polyalkenization of the polarizing film laminate with the adhesive layer can be reduced. Also, generally speaking, when the thickness of the adhesive layer becomes thinner, the adhesive force will gradually decrease, and the shrinkage stress of the polarizing plate caused by the shrinkage of the polarizing film under high temperature and humidity, resulting in embossing or peeling and other adhesion durability Therefore, it is not suitable to reduce the thickness of the adhesive layer. However, by making the polarizing film thinner, the shrinkage stress of the polarizing plate can be reduced. As a result, even if the thickness of the adhesive layer is reduced, the adhesion durability can be maintained or improved.

當前述黏著劑層露出時,可利用經剝離處理的片材(分離件)保護黏著劑層直到供實際應用前。When the aforementioned adhesive layer is exposed, the peeled-off sheet (separator) can be used to protect the adhesive layer until it is used in practice.

作為分離件的構成材料,可舉例如聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚酯薄膜等塑膠薄膜;紙、布、不織布等多孔質材料;網狀物、發泡片材、金屬箔、及其等之層合體等適當的薄片體等等,惟從表面平滑性優異此點來看,可適宜採用塑膠薄膜。Examples of constituent materials of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and non-woven fabrics; meshes and foamed sheets Appropriate sheets such as, metal foil, and laminates thereof, etc., but from the viewpoint of excellent surface smoothness, plastic films can be suitably used.

塑膠薄膜只要為可保護前述黏著劑層之薄膜即無特別限定,可舉例如聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚胺甲酸酯薄膜、乙烯-乙酸乙酯共聚物薄膜等。The plastic film is not particularly limited as long as it can protect the aforementioned adhesive layer. Examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, and polyvinyl chloride film. , Vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-ethyl acetate copolymer film, etc.

前述分離件的厚度通常為5~200μm,宜為5~100μm左右。對前述分離件亦可視需要施行利用聚矽氧系、氟系、長鏈烷基系或脂肪酸醯胺系脫模劑、矽粉等進行的脫模及防污處理、及塗佈型、捏合型、蒸鍍型等抗靜電處理。尤其,藉由對前述分離件之表面適當實施聚矽氧處理、長鏈烷基處理、氟處理等剝離處理,可更提高分離件自前述黏著劑層剝離之剝離性。The thickness of the aforementioned separator is usually 5 to 200 μm, preferably about 5 to 100 μm. The aforementioned separation parts can also be subjected to mold release and antifouling treatment, coating type, kneading type, etc., using polysiloxane-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agents, silicon powder, etc. , Evaporation type and other antistatic treatment. In particular, by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator, the peelability of the separator from the adhesive layer can be further improved.

此外,在上述附黏著劑層之偏光薄膜積層體的製作中所使用之經剝離處理的片材,可直接作為附黏著劑層之偏光薄膜積層體的分離件使用,透過所述方式可在步驟方面簡略化。In addition, the peel-off treated sheet used in the production of the above-mentioned adhesive layer-attached polarizing film laminate can be directly used as a separator for the adhesive layer-attached polarizing film laminate. Simplify the aspect.

2.偏光薄膜積層體 偏光薄膜積層體12至少包含偏光膜120與接合於偏光膜120之至少一面例如視辨側的偏光膜保護薄膜121。亦可如同本實施形態,於偏光膜120之兩面亦即偏光膜120之視辨側及與視辨側相反之側兩側,透過適當之接著劑(未示於圖式中)分別接合偏光膜保護薄膜121、122。雖無特別示於圖中,但亦可於偏光膜120與偏光膜保護薄膜121、122之間設置其他光學薄膜。2. Polarizing film laminate The polarizing film laminate 12 includes at least a polarizing film 120 and a polarizing film protective film 121 bonded to at least one surface of the polarizing film 120, such as the viewing side. It is also possible to join the polarizing film on both sides of the polarizing film 120, that is, the viewing side and the side opposite to the viewing side of the polarizing film 120, through an appropriate adhesive (not shown in the figure), respectively. Protective films 121, 122. Although not specifically shown in the figure, other optical films may be provided between the polarizing film 120 and the polarizing film protective films 121 and 122.

本發明為了總括性解決於高溫或高濕環境下所產生之問題、尤其是「多烯化」、「褪色」及「加熱紅變」之問題,特別著眼於偏光膜120之碘濃度(wt.%)與偏光薄膜積層體12之水分量(g/m2 )。該等值例如可於製造偏光膜時或製造偏光薄膜積層體時調整。In order to comprehensively solve the problems caused by high temperature or high humidity environments, the present invention particularly focuses on the iodine concentration of the polarizing film 120 (wt. %) and the moisture content of the polarizing film laminate 12 (g/m 2 ). These values can be adjusted, for example, when manufacturing a polarizing film or when manufacturing a polarizing film laminate.

2-1.偏光膜 偏光膜120係由含碘之聚乙烯醇(PVA)系樹脂薄膜構成。可適用於偏光膜之PVA系薄膜的材料,可使用PVA或其衍生物。PVA之衍生物可舉聚乙烯醇縮甲醛、聚乙烯縮醛等,其他還可舉業經乙烯、丙烯等烯烴、丙烯酸、甲基丙烯酸、巴豆酸等不飽和羧酸其烷基酯、丙烯酸醯胺等改質者。一般是使用聚合度為1000~10000左右且皂化度為80~100莫耳%左右的PVA。由該等材料所製成之PVA系薄膜具有易含有水分之傾向。2-1. Polarizing film The polarizing film 120 is composed of a polyvinyl alcohol (PVA) resin film containing iodine. PVA film materials suitable for polarizing films, PVA or its derivatives can be used. The derivatives of PVA can include polyvinyl formal, polyvinyl acetal, etc. Others can include olefins such as ethylene and propylene, acrylic acid, methacrylic acid, crotonic acid and other unsaturated carboxylic acids and their alkyl esters, and amide acrylates. Waiting for reformers. Generally, PVA with a degree of polymerization of about 1,000 to 10,000 and a degree of saponification of about 80 to 100 mole% is used. PVA-based films made from these materials tend to contain moisture.

PVA系薄膜亦可含有塑化劑等添加劑。塑化劑可舉多元醇及其縮合物等,例如可舉甘油、二甘油、三甘油、乙二醇、丙二醇、聚乙二醇等。塑化劑之使用量雖無特別限制,但宜在PVA系薄膜中佔20重量%以下。The PVA-based film may also contain additives such as plasticizers. Examples of the plasticizer include polyhydric alcohols and condensates thereof, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol. Although there is no particular limitation on the amount of plasticizer used, it should preferably account for 20% by weight or less in the PVA-based film.

2-1-1.製造偏光膜 製造膜厚6μm以上之偏光膜時,例如可施行以碘將上述PVA系薄膜染色之染色處理、及使PVA系薄膜往至少一方向延伸之延伸處理。一般係採用將上述PVA系薄膜供於包含膨潤、染色、交聯、延伸、水洗及乾燥處理的一連串處理之方式。2-1-1. Manufacture of polarizing film When manufacturing a polarizing film with a film thickness of 6 μm or more, for example, a dyeing process of dyeing the above-mentioned PVA-based film with iodine and a stretching process of extending the PVA-based film in at least one direction may be performed. Generally, the above-mentioned PVA-based film is subjected to a series of treatments including swelling, dyeing, cross-linking, stretching, water washing and drying treatments.

膨潤處理譬如可藉由將PVA系薄膜浸漬於膨潤浴(水浴)中來進行。藉由該處理,可洗淨PVA系薄膜表面的污垢及抗黏結劑,並且可使PVA系薄膜膨潤,從而防止染色參差等不均勻性。膨潤浴中亦可適當添加有甘油或碘化鉀等。膨潤浴的溫度例如為20~60℃左右,而浸漬於膨潤浴的浸漬時間例如為0.1~10分鐘左右。The swelling treatment can be performed, for example, by immersing the PVA-based film in a swelling bath (water bath). By this treatment, the dirt and anti-blocking agent on the surface of the PVA-based film can be cleaned, and the PVA-based film can be swollen, thereby preventing unevenness such as uneven dyeing. Glycerin, potassium iodide, etc. can also be appropriately added to the swelling bath. The temperature of the swelling bath is, for example, about 20 to 60°C, and the immersion time for immersion in the swelling bath is, for example, about 0.1 to 10 minutes.

染色處理譬如可將PVA系薄膜浸漬於碘溶液中來進行。碘溶液通常為碘水溶液,而含有碘及作為溶解助劑之碘化鉀。碘濃度例如為0.01~1重量%左右,且宜為0.02~0.5重量%。碘化鉀濃度例如為0.01~10重量%左右,且0.02~8重量%為佳。The dyeing treatment can be performed by immersing a PVA-based film in an iodine solution, for example. The iodine solution is usually an aqueous solution of iodine, and contains iodine and potassium iodide as a dissolution aid. The iodine concentration is, for example, about 0.01 to 1% by weight, and preferably 0.02 to 0.5% by weight. The potassium iodide concentration is, for example, about 0.01 to 10% by weight, and preferably 0.02 to 8% by weight.

染色處理中,碘溶液的溫度例如為20~50℃左右,且宜為25~40℃。浸漬時間例如為10~300秒左右,且宜為20~240秒之範圍。進行碘染色處理時,係調整碘溶液之濃度、PVA系薄膜浸漬於碘溶液之浸漬溫度、及浸漬時間等條件,以使PVA系薄膜中之碘含量及鉀含量在前述範圍內。In the dyeing process, the temperature of the iodine solution is, for example, about 20-50°C, and preferably 25-40°C. The immersion time is, for example, about 10 to 300 seconds, and preferably in the range of 20 to 240 seconds. During the iodine dyeing process, the concentration of the iodine solution, the immersion temperature of the PVA-based film in the iodine solution, and the immersion time are adjusted so that the iodine content and potassium content in the PVA-based film are within the aforementioned ranges.

交聯處理譬如可藉由將經碘染色之PVA系薄膜浸漬於含交聯劑之處理浴中來進行。交聯劑可採用任意適當之交聯劑。交聯劑之具體例可舉硼酸、硼砂等硼化合物、乙二醛、戊二醛等。該等可單獨使用或可組合使用。用於交聯浴之溶液的溶劑一般而言為水,而亦可適量添加有與水具有相溶性之有機溶劑。交聯劑可以相對於100重量份之溶劑例如為1~10重量份之比率來使用。交聯浴的溶液宜更含有碘化物等助劑。助劑的濃度宜為0.05~15重量%,且0.5~8重量%更佳。交聯浴的溫度例如為20~70℃左右,且宜為40~60℃。浸漬於交聯浴之時間例如為1秒~15分鐘左右,且宜為5秒~10分鐘。The cross-linking treatment can be performed, for example, by immersing the iodine-dyed PVA-based film in a treatment bath containing a cross-linking agent. Any appropriate cross-linking agent can be used as the cross-linking agent. Specific examples of the crosslinking agent include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. These can be used alone or in combination. The solvent of the solution used in the crosslinking bath is generally water, but an organic solvent compatible with water may be added in an appropriate amount. The crosslinking agent can be used in a ratio of, for example, 1 to 10 parts by weight with respect to 100 parts by weight of the solvent. The solution of the cross-linking bath preferably contains iodide and other auxiliary agents. The concentration of the auxiliary agent is preferably 0.05 to 15% by weight, and more preferably 0.5 to 8% by weight. The temperature of the crosslinking bath is, for example, about 20 to 70°C, and preferably 40 to 60°C. The immersion time in the crosslinking bath is, for example, about 1 second to 15 minutes, and preferably 5 seconds to 10 minutes.

延伸處理係將PVA系薄膜往至少一方向延伸之處理。一般而言,PVA系薄膜係往輸送方向(長邊方向)進行單軸延伸。延伸方法並無特別限制,可採用濕潤延伸法與乾式延伸法中之任一方法。採用濕式延伸法時,PVA系薄膜係於處理浴中延伸預定倍率。延伸浴之溶液可適宜使用於水或有機溶劑(例如乙醇)等溶劑中添加有各種處理所需之化合物等而成之溶液。乾式延伸法可舉例如輥間延伸方法、加熱輥延伸方法、壓縮延伸方法等。偏光膜之製造中,延伸處理可於任一階段進行。具體而言,可與膨潤、染色、交聯同時進行,亦可於該等各處理前後任一時機進行。且,延伸亦可以多階段進行。PVA系薄膜的累積延伸倍率例如為5倍以上,且宜為5~7倍左右。The stretching process is a process of stretching the PVA-based film in at least one direction. Generally, PVA-based films are uniaxially stretched in the conveying direction (long-side direction). The extension method is not particularly limited, and any one of the wet extension method and the dry extension method can be used. When the wet stretching method is used, the PVA-based film is stretched at a predetermined rate in the treatment bath. The solution of the extension bath can be suitably used as a solution obtained by adding various compounds required for treatment to a solvent such as water or an organic solvent (for example, ethanol). Examples of the dry stretching method include an inter-roll stretching method, a heated roll stretching method, and a compression stretching method. In the manufacture of the polarizing film, the stretching treatment can be carried out at any stage. Specifically, it can be performed simultaneously with swelling, dyeing, and crosslinking, or it can be performed at any timing before or after each of these treatments. Moreover, the extension can also be carried out in multiple stages. The cumulative stretching ratio of the PVA-based film is, for example, 5 times or more, and preferably about 5 to 7 times.

將經施行上述各處理之PVA系薄膜(延伸薄膜)依常規方法供於水洗淨處理、乾燥處理。The PVA-based film (stretched film) subjected to the above-mentioned various treatments is subjected to water washing treatment and drying treatment according to a conventional method.

水洗處理譬如可藉由將PVA系薄膜浸漬於水洗浴中來進行。水洗浴可為純水,亦可為碘化物(例如碘化鉀、碘化鈉等)之水溶液。碘化物水溶液的濃度宜為0.1~10重量%。碘化物水溶液中亦可添加有硫酸鋅、氯化鋅等助劑。The water washing treatment can be performed, for example, by immersing the PVA-based film in a water bath. The water bath can be pure water or an aqueous solution of iodide (such as potassium iodide, sodium iodide, etc.). The concentration of the iodide aqueous solution is preferably 0.1 to 10% by weight. Additives such as zinc sulfate and zinc chloride can also be added to the iodide aqueous solution.

水洗溫度例如為5~50℃,且宜為10~45℃,15~40℃之範圍更佳。浸漬時間例如為10~300秒左右,且宜為20~240秒。水洗處理可僅實施1次,亦可因應需要實施多次。實施多次水洗處理時,各處理所用之水洗浴所含添加劑之種類或濃度可適當調整。The washing temperature is, for example, 5 to 50°C, and preferably 10 to 45°C, more preferably 15 to 40°C. The immersion time is, for example, about 10 to 300 seconds, and preferably 20 to 240 seconds. The water washing treatment can be carried out only once, or it can be carried out multiple times as needed. When multiple washing treatments are performed, the type or concentration of additives contained in the water bath used for each treatment can be adjusted appropriately.

PVA系薄膜的乾燥處理可利用任意適當之方法(例如自然乾燥、送風乾燥、加熱乾燥)來進行。The drying treatment of the PVA-based film can be performed by any appropriate method (for example, natural drying, air drying, heat drying).

2-1-2.製造偏光膜 膜厚小於6μm之偏光膜例如可藉由日本專利第4751481號公報所揭示之製造方法來製造。該製造方法包含下列處理等:積層體製作處理,係將PVA系樹脂層形成於熱塑性基材上;延伸處理,係將PVA系樹脂層與熱塑性樹脂基材進行一體延伸;染色處理,係使PVA樹脂層吸附二色性物質。亦可因應需要應用PVA系樹脂層之不溶解處理及交聯處理、乾燥處理、洗淨處理等。延伸處理可於染色處理前實施,亦可於其後實施,且亦可採用空中延伸及於硼酸水溶液等水中進行之延伸中之任一延伸方式。並且,延伸可為一階段之延伸,亦可為2階段以上之多階段延伸。2-1-2. Manufacture of polarizing film A polarizing film with a film thickness of less than 6 μm can be manufactured by the manufacturing method disclosed in Japanese Patent No. 4751481, for example. The manufacturing method includes the following treatments: laminated body preparation treatment, which is to form a PVA-based resin layer on a thermoplastic substrate; stretching treatment, which is to integrally extend the PVA-based resin layer and the thermoplastic resin substrate; dyeing treatment, to make PVA The resin layer adsorbs dichroic substances. It is also possible to apply the insolubilization treatment, cross-linking treatment, drying treatment, cleaning treatment, etc. of the PVA-based resin layer according to the needs. The extension treatment can be performed before or after the dyeing treatment, and any extension method of air extension and extension in water such as boric acid aqueous solution can also be used. In addition, the extension can be a one-stage extension or a multi-stage extension with more than two stages.

參照圖2來說明偏光膜之製造方法一例。在此,係藉由將已製膜於樹脂基材上的PVA系樹脂層與前述樹脂基材進行一體延伸而製作出偏光膜。An example of a method of manufacturing a polarizing film will be described with reference to FIG. 2. Here, a polarizing film is produced by integrally extending the PVA-based resin layer formed on the resin substrate and the aforementioned resin substrate.

[積層體製作處理(A)] 首先,準備玻璃轉移溫度為75℃之具有200μm厚度的非晶性酯系熱塑性樹脂基材例如使間苯二甲酸6mol%共聚而成之間苯二甲酸共聚聚對苯二甲酸乙二酯(以下稱為「非晶性PET」)6、與將聚合度1000以上且皂化度99%以上之PVA粉末溶解於水而成之4~5重量%濃度的PVA水溶液。接著,於具備塗敷機構21與乾燥機構22及表面改質處理裝置23之積層體製作裝置20中,將PVA水溶液塗佈於該非晶性PET基材6,並於50~60℃之溫度下使其乾燥,而於PET基材6上製膜出玻璃轉移溫度為80℃之具有7μm厚度的PVA層2。藉此,製作出包含厚7μm之PVA層的積層體7。此時,藉由以表面改質處理裝置23將非晶性PET基材6之表面進行電暈處理,可提升非晶性PET基材6與製膜於其上之PVA層2的密著性。[Layered body production processing (A)] First, prepare an amorphous ester-based thermoplastic resin substrate with a thickness of 200 μm with a glass transition temperature of 75°C. For example, 6 mol% of isophthalic acid is copolymerized to form a poly(ethylene terephthalate) copolymer (hereinafter Called "amorphous PET") 6. A 4 to 5 wt% aqueous PVA solution obtained by dissolving PVA powder with a degree of polymerization of 1,000 or more and a saponification degree of 99% or more in water. Next, in a laminate manufacturing device 20 equipped with a coating mechanism 21, a drying mechanism 22, and a surface modification treatment device 23, the PVA aqueous solution is coated on the amorphous PET substrate 6, and the temperature is 50-60°C It was dried, and a PVA layer 2 having a thickness of 7 μm with a glass transition temperature of 80° C. was formed on the PET substrate 6. In this way, a laminate 7 including a PVA layer having a thickness of 7 μm was produced. At this time, by corona treatment of the surface of the amorphous PET substrate 6 with the surface modification treatment device 23, the adhesion between the amorphous PET substrate 6 and the PVA layer 2 formed on it can be improved .

接著,令包含PVA層之積層體7經過包含空中輔助延伸及硼酸水中延伸之2段延伸處理的以下處理,而最終製作成厚3μm之偏光膜。Next, the laminate 7 including the PVA layer was subjected to the following treatments including two-stage stretching treatment including aerial auxiliary stretching and boric acid water stretching, and finally a polarizing film with a thickness of 3 μm was produced.

[空中輔助延伸處理(B)] 在第1段之空中輔助延伸處理(B)中,係將包含厚7μm之PVA層2的積層體7與PET基材6進行一體延伸,而生成包含厚5μm之PVA層2的「延伸積層體8」。具體而言,係在烘箱33內配備有延伸機構31之空中輔助延伸處理裝置30中,將包含厚7μm之PVA層2的積層體7置於設定成130℃之延伸溫度環境的烘箱33的延伸機構31上,進行自由端單軸延伸成延伸倍率成為1.8倍,而生成延伸積層體8。在此階段可利用一併設置於烘箱30之捲取裝置32來製造延伸積層體8之捲材8’。[Air auxiliary extension processing (B)] In the air-assisted stretching process (B) in the first stage, the laminate 7 including the PVA layer 2 with a thickness of 7μm and the PET base material 6 are integrally extended to produce the "extended laminate" including the PVA layer 2 with a thickness of 5μm 8". Specifically, in the air-assisted stretching processing device 30 equipped with the stretching mechanism 31 in the oven 33, the laminate 7 including the PVA layer 2 with a thickness of 7 μm is placed in the oven 33 set to a stretching temperature environment of 130°C. On the mechanism 31, the free end is uniaxially stretched so that the stretch magnification becomes 1.8 times, and the stretched laminate 8 is produced. At this stage, the coiling device 32 installed in the oven 30 can be used to manufacture the coil 8'of the stretched laminate 8.

[染色處理(C)] 接著,藉由染色處理(C)而生成著色積層體9,該著色積層體9係PVA分子經定向之厚5μm的PVA層2吸附有二色性物質之碘者。具體而言,係於具備染色液41之染色浴42的染色裝置40中,從一併設置於染色裝置40之釋出裝置43釋出裝附於其上的捲材8’而得延伸積層體8,並將其於液溫30℃之含碘及碘化鉀的染色液41中浸漬任意時間以使構成最終生成之偏光膜的PVA層之單體透射率成為40~44%,藉此生成延伸積層體8之經定向的PVA層2吸附有碘之著色積層體9。[Dyeing treatment (C)] Next, by the dyeing process (C), a colored laminate 9 is produced, and the colored laminate 9 is a PVA layer 2 having a thickness of 5 μm in which PVA molecules are oriented and adsorbs iodine as a dichroic substance. Specifically, in the dyeing device 40 provided with the dyeing bath 42 of the dyeing liquid 41, the rolled material 8'attached to it is discharged from the discharging device 43 collectively provided in the dyeing device 40 to obtain the stretched laminate. 8. Immerse it in a dyeing solution 41 containing iodine and potassium iodide at a liquid temperature of 30°C for an arbitrary period of time so that the monomer transmittance of the PVA layer that constitutes the final polarizing film becomes 40~44%, thereby forming a stretched laminate The oriented PVA layer 2 of the body 8 adsorbs the colored layered body 9 of iodine.

在本處理中,染色液41為了不使延伸積層體8所含之PVA層2溶解,而以水為溶劑並將碘濃度設為0.30重量%。又,染色液41係將用於使碘溶解於水的碘化鉀濃度設為2.1重量%。碘與碘化鉀之濃度比為1比7。更詳細而言,係將延伸積層體8浸漬於碘濃度0.30重量%、碘化鉀濃度2.1重量%之染色液41中60秒,藉此生成PVA分子經定向之厚5μm的PVA層2吸附有碘之著色積層體9。In this process, in order not to dissolve the PVA layer 2 contained in the stretched laminate 8 in the dyeing solution 41, water is used as a solvent, and the iodine concentration is set to 0.30 weight%. In addition, in the dyeing solution 41, the potassium iodide concentration for dissolving iodine in water was 2.1% by weight. The concentration ratio of iodine to potassium iodide is 1:7. In more detail, the stretched laminate 8 is immersed in a dyeing solution 41 with an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, thereby generating a 5μm thick PVA layer 2 in which PVA molecules are oriented. Colored laminate 9.

[硼酸水中延伸處理(D)] 藉由第2段之硼酸水中延伸處理,進一步延伸包含碘經定向之PVA層2的著色積層體9,而生成包含厚3μm之構成偏光膜且經使碘定向之PVA層的光學薄膜積層體60。具體而言,係於具備硼酸水溶液51之硼酸浴52與延伸機構53的硼酸水中延伸處理裝置50中,將從染色裝置40連續釋出之著色積層體9浸漬於包含硼酸與碘化鉀之經設定成液溫65℃之延伸溫度環境的硼酸水溶液51中,接著將其置於硼酸水中處理裝置50所配備之延伸機構53上,並進行自由端單軸延伸成延伸倍率達3.3倍,藉此生成包含厚3μm之PVA層的光學薄膜積層體60。[Extension Treatment in Boric Acid Water (D)] By the second stage of the boric acid water extension treatment, the colored laminate 9 including the iodine-oriented PVA layer 2 is further extended to produce an optical thin film laminate 60 including a 3 μm thick polarizing film and a PVA layer oriented with iodine . Specifically, in the boric acid water extension treatment device 50 provided with the boric acid bath 52 of the boric acid aqueous solution 51 and the extension mechanism 53, the colored layered body 9 continuously released from the dyeing device 40 is immersed in a set containing boric acid and potassium iodide. In the boric acid aqueous solution 51 in an extension temperature environment of 65°C, it is then placed on the extension mechanism 53 equipped in the boric acid water treatment device 50, and the free end is uniaxially extended to a stretching magnification of 3.3 times, thereby generating Optical film laminate 60 with a thickness of 3 μm PVA layer.

[洗淨處理(G)] 接著,宜將包含偏光膜之光學薄膜積層體60直接送至洗淨處理(G)。洗淨處理(G)之目的在於利用洗淨裝置80之洗淨液81將附著在偏光膜表面之不需要的殘留物洗去。惟,亦可省略洗淨處理(G),而將取出之包含偏光膜的光學薄膜積層體60直接送入乾燥處理(H)。[Washing treatment (G)] Next, it is preferable to directly send the optical thin film laminate 60 containing the polarizing film to the cleaning process (G). The purpose of the washing treatment (G) is to use the washing liquid 81 of the washing device 80 to wash away unnecessary residues adhering to the surface of the polarizing film. However, the cleaning process (G) may be omitted, and the optical thin film laminate 60 containing the polarizing film that has been taken out may be directly sent to the drying process (H).

[乾燥處理(H)] 經洗淨之光學薄膜積層體60係送至乾燥處理(H)並於此進行乾燥。接著,經乾燥之光學薄膜積層體60係以連續帶狀之光學薄膜積層體60形式利用一併設於乾燥裝置90中之捲取裝置91進行捲取,而生成包含偏光膜之光學薄膜積層體60的捲材。乾燥處理(H)可採用任意適當之方法,如自然乾燥、送風乾燥、加熱乾燥。例如可於烘箱之乾燥裝置90中,以60℃之溫風乾燥240秒。[Drying treatment (H)] The cleaned optical film laminate 60 is sent to the drying process (H) and dried there. Next, the dried optical film laminate 60 is wound in the form of a continuous belt-shaped optical film laminate 60 with a winding device 91 integrated in the drying device 90 to produce an optical film laminate 60 including a polarizing film Of rolls. The drying treatment (H) can adopt any appropriate method, such as natural drying, air blowing drying, and heating drying. For example, it can be dried in a drying device 90 of an oven with warm air at 60°C for 240 seconds.

2-1-3.其他 偏光膜宜含有鋅。藉由偏光膜含有鋅,而有抑制加熱試驗後偏光薄膜積層體的透射率降低及色相劣化之傾向。偏光膜含有鋅時,偏光膜中之鋅含量宜為0.002~2重量%,且0.01~1重量%較佳。2-1-3. Other The polarizing film preferably contains zinc. Since the polarizing film contains zinc, there is a tendency to suppress the decrease in transmittance and hue deterioration of the polarized film laminate after the heating test. When the polarizing film contains zinc, the zinc content in the polarizing film is preferably 0.002 to 2% by weight, and preferably 0.01 to 1% by weight.

偏光膜又宜含有硫酸根離子。藉由偏光膜含有硫酸根離子,而有抑制加熱試驗後偏光薄膜積層體的透射率降低之傾向。偏光膜含有硫酸根離子時,偏光膜中之硫酸根離子含量宜為0.02~0.45重量%,且0.05~0.35重量%較佳,以0.1~0.25重量%更佳。此外,偏光膜中之硫酸根離子含量係從硫原子的含量算出。The polarizing film should also contain sulfate ions. Since the polarizing film contains sulfate ions, there is a tendency to suppress the decrease in the transmittance of the polarizing film laminate after the heating test. When the polarizing film contains sulfate ions, the sulfate ion content in the polarizing film is preferably 0.02 to 0.45% by weight, preferably 0.05 to 0.35% by weight, and more preferably 0.1 to 0.25% by weight. In addition, the sulfate ion content in the polarizing film is calculated from the sulfur atom content.

欲使偏光膜中含有鋅,宜於偏光膜之製造步驟中進行含浸鋅處理。又,為使偏光膜中含有硫酸根離子,宜於偏光膜之製造步驟中進行硫酸根離子處理。If zinc is to be contained in the polarizing film, it is advisable to impregnate zinc in the manufacturing step of the polarizing film. In addition, in order to include sulfate ions in the polarizing film, it is preferable to perform sulfate ion treatment in the manufacturing step of the polarizing film.

含浸鋅處理例如可藉由將PVA系薄膜浸漬於鋅鹽溶液中來進行。鋅鹽宜為氯化鋅、碘化鋅等鹵化鋅、硫酸鋅、乙酸鋅等水溶液之無機鹽化合物。又,含浸鋅處理中亦可使用各種鋅錯合化合物。又,鋅鹽溶液較宜使用利用碘化鉀等而含有鉀離子及碘離子之水溶液,因易使其含浸鋅離子。鋅鹽溶液中之碘化鉀濃度係設為0.5~10重量%左右,且設為1~8重量%更佳。The zinc impregnation treatment can be performed, for example, by immersing the PVA-based film in a zinc salt solution. The zinc salt is preferably an inorganic salt compound in an aqueous solution such as zinc chloride, zinc iodide, zinc halide, zinc sulfate, and zinc acetate. In addition, various zinc complex compounds can also be used in the zinc impregnation treatment. In addition, it is preferable to use an aqueous solution containing potassium ions and iodide ions using potassium iodide or the like for the zinc salt solution because it is easy to impregnate zinc ions. The potassium iodide concentration in the zinc salt solution is set to about 0.5-10% by weight, and preferably 1-8% by weight.

硫酸根離子處理例如係藉由將PVA系薄膜浸漬於含硫酸金屬鹽之水溶液中來進行。硫酸金屬鹽以易在處理液中分離成硫酸根離子與金屬離子而易將該硫酸金屬鹽以離子之狀態導入PVA系薄膜中者較為理想。例如,形成硫酸金屬鹽之金屬種類可舉:鈉、鉀等鹼金屬;鎂、鈣等鹼土族金屬;鈷、鎳、鋅、鉻、鋁、銅、錳、鐵等過渡金屬。The sulfate ion treatment is performed, for example, by immersing the PVA-based film in an aqueous solution containing a metal sulfate salt. It is preferable that the metal sulfate is easily separated into sulfate ions and metal ions in the treatment liquid, and the metal sulfate is easily introduced into the PVA-based film in the form of ions. For example, the types of metals that form the metal sulfate salt include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium; and transition metals such as cobalt, nickel, zinc, chromium, aluminum, copper, manganese, and iron.

偏光膜之製造中,上述含浸鋅處理及硫酸根離子處理可在任一階段進行。即,含浸鋅處理及硫酸根離子處理可在染色處理前進行,亦可在染色處理後進行。含浸鋅處理與硫酸根離子處理亦可同時進行。較宜為前述鋅鹽及前述硫酸金屬鹽使用硫酸鋅,並將PVA系薄膜浸漬於含有硫酸鋅之處理浴中,藉此同時進行含浸鋅處理與硫酸根離子處理。又,亦可先使前述鋅鹽或前述硫酸金屬鹽共存於染色溶液中,再與染色處理同時進行含浸鋅處理及/或硫酸根離子處理。含浸鋅處理及硫酸根離子處理亦可與延伸同時進行。In the production of the polarizing film, the above-mentioned zinc impregnation treatment and sulfate ion treatment can be performed at any stage. That is, the zinc impregnation treatment and the sulfate ion treatment may be performed before the dyeing treatment or may be performed after the dyeing treatment. Zinc impregnation treatment and sulfate ion treatment can also be carried out at the same time. Preferably, zinc sulfate is used for the zinc salt and the metal sulfate salt, and the PVA-based film is immersed in a treatment bath containing zinc sulfate, thereby simultaneously performing the zinc impregnation treatment and the sulfate ion treatment. In addition, the zinc salt or the metal sulfate salt may be first coexisted in the dyeing solution, and then the zinc impregnation treatment and/or the sulfate ion treatment may be performed simultaneously with the dyeing treatment. Zinc impregnation treatment and sulfate ion treatment can also be carried out at the same time as the extension.

2-2.偏光膜保護薄膜 構成偏光膜保護薄膜121、122之材料可舉例如透明性、機械強度及熱穩定性佳之熱塑性樹脂。熱塑性樹脂的具體例可舉三醋酸纖維素等之纖維素系樹脂、聚酯系樹脂、聚醚碸系樹脂、聚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴系樹脂(降莰烯系樹脂)、聚芳酯系樹脂、聚苯乙烯系樹脂、PVA系樹脂及該等之混合物。 偏光膜保護薄膜亦可為兼具相位差薄膜之機能者。2-2. Polarizing film protective film The material constituting the polarizing film protective films 121 and 122 may include, for example, a thermoplastic resin having excellent transparency, mechanical strength, and thermal stability. Specific examples of thermoplastic resins include cellulose resins such as cellulose triacetate, polyester resins, polyether-based resins, poly-based resins, polycarbonate-based resins, polyamide-based resins, and polyimides. Resins, polyolefin resins, (meth)acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, PVA resins, and mixtures of these . The polarizing film protective film may also have the function of a retardation film.

偏光膜保護薄膜的厚度可為了調整偏光薄膜積層體之水分量作適當調整。由強度及處置性等作業性、薄層性等觀點來看,宜為1~500μm左右,2~300μm較佳,5~200μm更佳。 偏光膜保護薄膜中亦可包含有1種以上任意的添加劑。添加劑可舉如紫外線吸收劑、抗氧化劑、滑劑、塑化劑、脫模劑、抗著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。The thickness of the polarizing film protective film can be adjusted appropriately in order to adjust the moisture content of the polarizing film laminate. From the viewpoints of workability and thin layer properties such as strength and handling properties, it is preferably about 1 to 500 μm, preferably 2 to 300 μm, and more preferably 5 to 200 μm. The polarizing film protective film may contain one or more arbitrary additives. Examples of additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, anti-colorants, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like.

2-3.其他光學薄膜 偏光膜與偏光膜保護薄膜可直接接合,但亦可與其他光學薄膜積層。其他光學薄膜並無特別限定,例如可使用相位差薄膜、視角補償薄膜等。作為其他光學薄膜之相位差薄膜可為具有作為保護薄膜之機能者。2-3. Other optical films The polarizing film and the polarizing film protective film can be directly bonded, but they can also be laminated with other optical films. Other optical films are not particularly limited, and for example, retardation films, viewing angle compensation films, etc. can be used. The retardation film as another optical film may be one having the function as a protective film.

如同上方說明,偏光膜保護薄膜亦可為兼備相位差薄膜之機能者,而此時亦可省略作為其他光學薄膜之相位差薄膜。另一方面,即使是在偏光膜保護薄膜兼備相位差薄膜之機能時,亦仍可設置相位差薄膜作為其他光學薄膜。此時,實質上會包含2個或3個以上相位差薄膜。As described above, the polarizing film protective film may also have the function of a retardation film, and at this time, it may be omitted as a retardation film of other optical films. On the other hand, even when the polarizing film protective film has the functions of a retardation film, the retardation film can still be provided as other optical films. In this case, two or more retardation films are substantially included.

2-4.接著劑 將偏光膜120與偏光膜保護薄膜121、122接合、或者將相位差薄膜等其他光學薄膜與該等接合時,例如可使用自由基聚合硬化型接著劑或陽離子聚合硬化型接著劑、水性接著劑。2-4. Adhesive When bonding the polarizing film 120 to the polarizing film protective films 121 and 122, or bonding other optical films such as retardation films to these, for example, a radical polymerization hardening type adhesive, a cation polymerization hardening type adhesive, and an aqueous adhesive can be used. .

(自由基聚合硬化型接著劑) 前述自由基聚合硬化型接著劑包含作為硬化性化合物之自由基聚合性化合物。自由基聚合性化合物可為藉由活性能量線而硬化之化合物,亦可為藉由熱而硬化之化合物。活性能量線可舉例如電子束、紫外線、可見光線等。(Free radical polymerization hardening adhesive) The aforementioned radical polymerization curable adhesive includes a radical polymerizable compound as a curable compound. The radically polymerizable compound may be a compound that is cured by active energy rays, or a compound that is cured by heat. Examples of active energy rays include electron beams, ultraviolet rays, and visible rays.

前述自由基聚合性化合物可舉例如具有(甲基)丙烯醯基、乙烯基等具碳-碳雙鍵之自由基聚合性官能基的化合物。自由基聚合性化合物宜使用多官能自由基聚合性化合物。自由基聚合性化合物可單獨僅使用1種,亦可組合2種以上來使用。又,亦可併用多官能自由基聚合性化合物與單官能自由基聚合性化合物。Examples of the aforementioned radically polymerizable compound include compounds having a radically polymerizable functional group having a carbon-carbon double bond such as a (meth)acryloyl group and a vinyl group. As the radical polymerizable compound, a polyfunctional radical polymerizable compound is preferably used. A radically polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound can also be used together.

前述聚合性化合物宜使用logP值(辛醇/水分配係數)高的化合物,自由基聚合性化合物亦宜選擇logP值高的化合物。此處,logP值表示物質親油性的指標,意指辛醇/水之分配係數的對數值。logP值高代表親油性,即意味吸水率低。logP值可進行測定(JIS-Z-7260記載之燒瓶浸透法),亦可藉由根據硬化型接著劑之構成成分(硬化性成分等)的各化合物之結構進行計算來算出(CambridgeSoft公司製之ChemDraw Ultra)。As the aforementioned polymerizable compound, it is preferable to use a compound with a high logP value (octanol/water partition coefficient), and it is also preferable to select a compound with a high logP value for the radical polymerizable compound. Here, the logP value represents an index of the lipophilicity of a substance, and means the logarithmic value of the octanol/water partition coefficient. A high logP value represents lipophilicity, which means low water absorption. The logP value can be measured (the flask permeation method described in JIS-Z-7260), or it can be calculated by calculating the structure of each compound based on the constituent components (curable components, etc.) of the hardening adhesive (made by CambridgeSoft) ChemDraw Ultra).

自由基聚合性化合物之logP值宜為2以上,3以上較佳,4以上尤佳。只要在所述範圍內,便可防止偏光件因水分而劣化,而可獲得在高溫高濕下之耐久性佳的偏光薄膜。The logP value of the radically polymerizable compound is preferably 2 or more, preferably 3 or more, and more preferably 4 or more. As long as it is within the above range, the polarizer can be prevented from being degraded by moisture, and a polarizing film with excellent durability under high temperature and high humidity can be obtained.

前述多官能自由基聚合性化合物可舉例如:三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二丙烯酸酯、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、雙酚A環氧乙烷加成物二(甲基)丙烯酸酯、雙酚A環氧丙烷加成物二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、環狀三羥甲丙烷縮甲醛(甲基)丙烯酸酯、二

Figure 109129209-A0304-12-0059-1
烷二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、EO改質二丙三醇四(甲基)丙烯酸酯等(甲基)丙烯酸酯與多元醇之酯化物;9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀;(甲基)丙烯酸環氧酯;(甲基)丙烯酸胺甲酸酯;聚酯(甲基)丙烯酸酯等。Examples of the aforementioned polyfunctional radical polymerizable compound include: tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 9-nonanediol di(meth)acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, bisphenol A bis(methyl) )Acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl ether two ( Meth) acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, two
Figure 109129209-A0304-12-0059-1
Alkyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl erythritol tri(meth)acrylate, neopentyl erythritol tetra(meth)acrylate, dineopentyl Tetraol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, EO modified diglycerol tetra(meth)acrylate and other (meth)acrylates and polyol esters ; 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]茀; (meth)acrylate epoxy; (meth)acrylate urethane; polyester (Meth)acrylate and the like.

前述多官能自由基聚合性化合物中,宜為logP值高之多官能自由基聚合性化合物。所述化合物可舉例如三環癸烷二甲醇二(甲基)丙烯酸酯(logP=3.05)、(甲基)丙烯酸異莰酯(logP=3.27)等脂環(甲基)丙烯酸酯;1,9-壬二醇二(甲基)丙烯酸酯(logP=3.68)、1,10-癸二醇二丙烯酸酯(logP=4.10)等長鏈脂肪族(甲基)丙烯酸酯;羥三甲基乙酸新戊二醇(甲基)丙烯酸加成物(logP=3.35)、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯(logP=3.92)等多支鏈(甲基)丙烯酸酯;雙酚A二(甲基)丙烯酸酯(logP=5.46)、雙酚A環氧乙烷4莫耳加成物二(甲基)丙烯酸酯(logP=5.15)、雙酚A環氧丙烷2莫耳加成物二(甲基)丙烯酸酯(logP=6.10)、雙酚A環氧丙烷4莫耳加成物二(甲基)丙烯酸酯(logP=6.43)、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀(logP=7.48)、對苯基苯酚(甲基)丙烯酸酯(logP=3.98)等含芳香環之(甲基)丙烯酸酯等。Among the aforementioned polyfunctional radical polymerizable compounds, a polyfunctional radical polymerizable compound having a high logP value is preferable. The compound includes, for example, alicyclic (meth)acrylates such as tricyclodecane dimethanol di(meth)acrylate (logP=3.05), isobornyl (meth)acrylate (logP=3.27); 1, Long-chain aliphatic (meth)acrylates such as 9-nonanediol di(meth)acrylate (logP=3.68) and 1,10-decanediol diacrylate (logP=4.10); hydroxytrimethylacetic acid Multi-branched (meth)acrylates such as neopentyl glycol (meth)acrylic acid adducts (logP=3.35), 2-ethyl-2-butylpropanediol di(meth)acrylate (logP=3.92), etc. ; Bisphenol A di(meth)acrylate (logP=5.46), bisphenol A ethylene oxide 4 mol adduct di(meth)acrylate (logP=5.15), bisphenol A propylene oxide 2 Mole adduct di(meth)acrylate (logP=6.10), bisphenol A propylene oxide 4 Mole adduct di(meth)acrylate (logP=6.43), 9,9-bis(4 -(2-(Meth)acryloyloxyethoxy)phenyl)Phenyl (logP=7.48), p-phenylphenol (meth)acrylate (logP=3.98) and other aromatic ring-containing (methyl) Acrylic etc.

併用多官能自由基聚合性化合物與單官能自由基聚合性化合物時,多官能自由基聚合性之含有比率相對於自由基聚合性化合物總量宜為20~97重量%,較宜為50~95重量%,75~92重量%更佳,80~92重量%尤佳。只要在所述範圍內,便可獲得在高溫高濕下的耐久性佳之偏光薄膜。When a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound are used together, the content ratio of the polyfunctional radical polymerizable compound relative to the total amount of the radical polymerizable compound is preferably 20 to 97% by weight, more preferably 50 to 95 Weight %, 75 to 92 weight% is more preferable, and 80 to 92 weight% is particularly preferable. As long as it is within the above range, a polarizing film with excellent durability under high temperature and high humidity can be obtained.

前述單官能自由基聚合性化合物可舉例如具有(甲基)丙烯醯胺基之(甲基)丙烯醯胺衍生物。只要使用(甲基)丙烯醯胺衍生物,便可以高生產性形成接著性佳的黏著劑層。(甲基)丙烯醯胺衍生物之具體例可舉例如N-甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺等含N-烷基之(甲基)丙烯醯胺衍生物;N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺等含N-羥烷基之(甲基)丙烯醯胺衍生物;胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺等含N-胺烷基之(甲基)丙烯醯胺衍生物;N-甲氧甲基丙烯醯胺、N-乙氧甲基丙烯醯胺等含N-烷氧基之(甲基)丙烯醯胺衍生物;巰基甲基(甲基)丙烯醯胺、巰基乙基(甲基)丙烯醯胺等含N-巰基烷基之(甲基)丙烯醯胺衍生物等。並且,(甲基)丙烯醯胺基的氮原子形成雜環之含雜環的(甲基)丙烯醯胺衍生物,可使用譬如N-丙烯醯基嗎福林、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶及N-丙烯醯基吡咯啶等。該等之中又以含N-羥烷基之(甲基)丙烯醯胺衍生物較佳,N-羥乙基(甲基)丙烯醯胺更佳。Examples of the monofunctional radical polymerizable compound include (meth)acrylamide derivatives having a (meth)acrylamide group. As long as the (meth)acrylamide derivative is used, an adhesive layer with good adhesion can be formed with high productivity. Specific examples of (meth)acrylamide derivatives include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl ( (Meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc. containing N-alkyl ( (Meth)acrylamide derivatives; N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl-N-propane (meth)acrylamide N-hydroxyalkyl-containing (meth)acrylamide derivatives such as amines; aminomethyl(meth)acrylamide, aminoethyl(meth)acrylamide, etc., containing N-aminoalkyl(form) Base) acrylamide derivatives; N-alkoxy-containing (meth)acrylamide derivatives such as N-methoxymethacrylamide, N-ethoxymethacrylamide, etc.; mercaptomethyl(formaldehyde) (Meth)acrylamide, mercaptoethyl (meth)acrylamide and other N-mercaptoalkyl-containing (meth)acrylamide derivatives. In addition, the nitrogen atom of the (meth)acrylamide group forms a heterocyclic ring-containing (meth)acrylamide derivative. For example, N-acryloyl mopholin and N-acryloyl piperidine can be used. , N-methacryloylpiperidine and N-acryloylpyrrolidine, etc. Among them, N-hydroxyalkyl-containing (meth)acrylamide derivatives are preferred, and N-hydroxyethyl (meth)acrylamide is more preferred.

又,前述單官能自由基聚合性化合物亦可使用具有(甲基)丙烯醯氧基之(甲基)丙烯酸衍生物;(甲基)丙烯酸、丙烯酸羧乙酯、丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸、異巴豆酸等含羧基單體;N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺、甲基乙烯基吡咯啶酮等內醯胺系乙烯基單體;乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌

Figure 109129209-A0304-12-0000-4
、乙烯基吡
Figure 109129209-A0304-12-0000-4
、乙烯基吡咯、乙烯基咪唑、乙烯基
Figure 109129209-A0304-12-0059-1
唑、乙烯基嗎福林等具有含氮雜環之乙烯基系單體等。In addition, the aforementioned monofunctional radical polymerizable compound can also use (meth)acrylic acid derivatives having a (meth)acryloyloxy group; (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, and itaconic acid. , Maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl-containing monomers; N-vinylpyrrolidone, N-vinyl-ε-caprolactone, methylvinylpyrrolidone and other internal amines Series vinyl monomer; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piper
Figure 109129209-A0304-12-0000-4
Vinylpyridine
Figure 109129209-A0304-12-0000-4
, Vinyl pyrrole, vinyl imidazole, vinyl
Figure 109129209-A0304-12-0059-1
Vinyl monomers with nitrogen-containing heterocycles such as azole, vinylmorphine, etc.

併用多官能自由基聚合性化合物與單官能自由基聚合性化合物時,單官能自由基聚合性之含有比率相對於自由基聚合性化合物總量宜為3~80重量%,較宜為5~50重量%,8~25重量%更佳,8~20重量%尤佳。只要在所述範圍內,便可獲得在高溫高濕下的耐久性佳之偏光薄膜。When a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound are used in combination, the content ratio of the monofunctional radical polymerizable compound relative to the total amount of the radical polymerizable compound is preferably 3 to 80% by weight, more preferably 5 to 50 % By weight, more preferably 8-25% by weight, particularly preferably 8-20% by weight. As long as it is within the above range, a polarizing film with excellent durability under high temperature and high humidity can be obtained.

前述自由基聚合硬化型接著劑可更包含其他添加劑。自由基聚合硬化型接著劑包含藉由活性能量線而硬化之硬化性化合物時,該接著劑例如可更包含光聚合引發劑、光酸產生劑、矽烷耦合劑等。又,自由基聚合硬化型接著劑包含藉由熱而硬化之硬化性化合物時,該接著劑可更包含熱聚合引發劑、矽烷耦合劑等。又,其他添加劑可舉例如聚合抑制劑、聚合引發助劑、調平劑、濕潤性改良劑、界面活性劑、塑化劑、紫外線吸收劑、無機充填劑、顏料、染料等。The aforementioned radical polymerization hardening adhesive may further contain other additives. When the radical polymerization curable adhesive includes a curable compound that is cured by active energy rays, the adhesive may further include, for example, a photopolymerization initiator, a photoacid generator, a silane coupling agent, and the like. In addition, when the radical polymerization curable adhesive includes a curable compound that is cured by heat, the adhesive may further include a thermal polymerization initiator, a silane coupling agent, and the like. In addition, examples of other additives include polymerization inhibitors, polymerization initiation aids, leveling agents, wettability modifiers, surfactants, plasticizers, ultraviolet absorbers, inorganic fillers, pigments, dyes, and the like.

(陽離子聚合硬化型接著劑) 前述陽離子聚合硬化型接著劑包含作為硬化性化合物之陽離子聚合性化合物。陽離子聚合性化合物可舉例如具有環氧基及/或氧雜環丁烷基之化合物。具有環氧基之化合物宜使用於分子內具有至少2個環氧基之化合物。具有環氧基之化合物可舉例如具有至少2個環氧基與至少1個芳香環之化合物(芳香族系環氧化合物)、分子內具有至少2個環氧基且其中至少1個係形成於構成脂環式環之2個相鄰碳原子之間的化合物(脂環式環氧化合物)等。(Cation polymerization hardening adhesive) The aforementioned cationic polymerization curable adhesive includes a cationic polymerizable compound as a curable compound. Examples of the cationically polymerizable compound include compounds having an epoxy group and/or oxetanyl group. The compound having an epoxy group is preferably used for a compound having at least two epoxy groups in the molecule. Examples of compounds having epoxy groups include compounds having at least two epoxy groups and at least one aromatic ring (aromatic epoxy compounds), and at least two epoxy groups in the molecule, and at least one of them is formed in A compound between two adjacent carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), etc.

前述陽離子聚合硬化型接著劑宜包含光陽離子聚合引發劑。光陽離子聚合引發劑藉由可見光線、紫外線、X射線、電子束等活性能量線之照射,會產生陽離子種或路易士酸,引發環氧基或氧雜環丁烷基的聚合反應。又,陽離子聚合硬化型接著劑可更包含前述添加劑。The aforementioned cationic polymerization hardening type adhesive preferably contains a photocationic polymerization initiator. The photocationic polymerization initiator is irradiated with active energy rays such as visible rays, ultraviolet rays, X-rays, electron beams, etc., to generate cationic species or Lewis acid, and initiate the polymerization reaction of epoxy groups or oxetanyl groups. In addition, the cationic polymerization curable adhesive may further contain the aforementioned additives.

(水性接著劑) 前述水性接著劑例如適宜使用異氰酸酯系接著劑、PVA系接著劑、明膠系接著劑、乙烯基系乳膠系、水系聚酯等水性接著劑之水溶液(例如固體成分濃度為0.5~60重量%)。(Aqueous adhesive) As the aforementioned aqueous adhesive, for example, an aqueous solution of an aqueous adhesive such as an isocyanate-based adhesive, PVA-based adhesive, gelatin-based adhesive, vinyl-based latex-based, water-based polyester, etc. (for example, a solid content concentration of 0.5 to 60% by weight) can be suitably used.

接著劑的塗佈可對偏光膜120、偏光膜保護薄膜121、122、其他光學薄膜中之任一者進行,亦可對該等中之任兩者進行。一般而言,宜將偏光膜浸漬於接著劑水溶液中後,利用輥層合機等與偏光膜保護薄膜121、122積層之方法。接著層的厚度並無特別限制,例如以乾燥後的厚度計為30nm~1000nm左右。The coating of the adhesive may be performed on any one of the polarizing film 120, the polarizing film protective films 121 and 122, and other optical films, or may be performed on any two of them. Generally speaking, a method of immersing the polarizing film in the adhesive aqueous solution and laminating it with the polarizing film protective films 121 and 122 using a roll laminator or the like is suitable. The thickness of the subsequent layer is not particularly limited, and for example, it is about 30 nm to 1000 nm in terms of the thickness after drying.

在將偏光膜與偏光膜保護薄膜及其他光學薄膜透過接著劑積層後,該積層體係供於乾燥處理。該積層體之乾燥步驟除了以使接著劑乾燥固化為目的之外,還以降低水分量以提升偏光薄膜積層體之初始光學特性為目的而進行。乾燥方法一般為加熱乾燥。乾燥條件宜為50~95℃之範圍,60~85℃之範圍較佳。After the polarizing film, the polarizing film protective film and other optical films are laminated through the adhesive, the laminated system is subjected to a drying process. In addition to the purpose of drying and curing the adhesive, the drying step of the laminate is performed for the purpose of reducing the moisture content and improving the initial optical properties of the polarizing film laminate. The drying method is generally heating and drying. The drying conditions are preferably in the range of 50 to 95°C, preferably in the range of 60 to 85°C.

上述積層體之乾燥條件並無特別限定,若考量處理效率或實用性時,乾燥溫度宜為50℃以上,而由使偏光薄膜積層體的光學特性均一之觀點,則宜為95℃以下。乾燥溫度亦可於上述溫度範圍內階段性升溫來實施。The drying conditions of the laminate are not particularly limited. In consideration of processing efficiency or practicality, the drying temperature is preferably 50°C or higher, and from the viewpoint of making the optical properties of the polarizing film laminate uniform, it is preferably 95°C or lower. The drying temperature can also be implemented by raising the temperature step by step within the above-mentioned temperature range.

積層體之乾燥可同偏光膜與偏光膜保護薄膜及其他光學薄膜之接合處理連續進行。且,亦可將偏光膜與偏光膜保護薄膜及其他光學薄膜之積層體暫時捲繞成捲材狀態後,將乾燥作為另一處理來進行。The drying of the laminate can be carried out continuously with the joining process of the polarizing film, the polarizing film protective film and other optical films. In addition, a laminate of a polarizing film, a polarizing film protective film, and other optical films may be temporarily wound into a roll state, and then drying may be performed as another process.

一般而言,欲減少偏光薄膜積層體之水分量,高溫、長時間之乾燥條件為必須。高溫、長時間之乾燥雖由降低偏光薄膜積層體之水分量的觀點來看屬於理想,但另一方面會有造成偏光薄膜積層體之光學特性等降低之情形。藉由使用飽和吸水量小的偏光膜保護薄膜或透濕度高的偏光膜保護薄膜,可不須採用嚴酷乾燥條件便可將偏光薄膜積層體之水分量調整至前述期望範圍內。Generally speaking, to reduce the moisture content of the polarizing film laminate, high temperature and long-term drying conditions are necessary. Drying at high temperature and long time is ideal from the viewpoint of reducing the moisture content of the polarizing film laminate, but on the other hand, the optical properties of the polarizing film laminate may decrease. By using a polarizing film protective film with small saturated water absorption or a polarizing film protective film with high moisture permeability, the moisture content of the polarizing film laminate can be adjusted to the aforementioned desired range without using severe drying conditions.

2-5.黏著劑 可同樣使用在上述「1-3.透明接著劑」所記載之黏著劑。2-5. Adhesive The adhesive described in the above "1-3. Transparent Adhesive" can be used in the same way.

3.可靠性評估項目 評估偏光薄膜積層體產生之多種現象、即多烯化、褪色、加熱紅變、黏著耐久性及重工性。產生各現象之機制雖尚未明瞭,但吾等推測大概如下。3. Reliability Evaluation Project Evaluate the various phenomena of polarized film laminates, namely polyolefinization, fading, red change on heating, adhesion durability and reworkability. Although the mechanism of each phenomenon is not yet clear, our guess is as follows.

<多烯化> 在高溫高濕環境下,偏光薄膜積層體的單體透射率會降低。吾等推測PVA的多烯化即造成該降低之原因。多烯係指-(CH=CH)n -,會在加熱下形成於偏光膜中。多烯會顯著使偏光膜之透射率降低。且,在高溫高濕環境下,PVA-多碘錯合物會被破壞而易生成I- 及I2 。 吾等推測PVA之多烯化係如以下化學式1所示,因在高溫高濕環境下生成之碘(I2 )與加熱促進脫水反應而發生。 (化學式1)

Figure 02_image001
推測是存在於偏光膜中之PVA-多碘錯合物因加熱而被破壞所產生之I2 與PVA中之OH基會形成電荷轉移錯合物(HO・・・I2 ),然後經由OI基而多烯化。吾等認為當黏著劑層中包含大量酸成分時,由酸成分產生之質子會作為PVA之脫水反應的觸媒發揮作用,故會更促進多烯化。<Polyolefinization> In a high-temperature and high-humidity environment, the monomer transmittance of the polarizing film laminate will decrease. We speculate that the polyolefination of PVA is the cause of this decrease. Polyene refers to -(CH=CH) n -, which is formed in the polarizing film under heating. Polyene will significantly reduce the transmittance of the polarizing film. Moreover, under high temperature and high humidity environment, PVA-polyiodide complexes will be destroyed and I - and I 2 are easily formed. We speculate that the polyolefination of PVA is shown in the following chemical formula 1, which occurs due to iodine (I 2 ) generated in a high temperature and high humidity environment and heating to promote the dehydration reaction. (Chemical formula 1)
Figure 02_image001
It is presumed that the PVA-polyiodide complex in the polarizing film is destroyed by heating. The I 2 produced by the heating and the OH group in the PVA will form a charge transfer complex (HO・・・I 2 ), and then pass through OI Base and polyethylenization. We believe that when the adhesive layer contains a large amount of acid components, the protons generated by the acid components will act as a catalyst for the dehydration reaction of PVA, which will further promote polyolefinization.

<褪色> 在經碘染色且延伸之PVA系薄膜(偏光膜)中,碘係以I3 - 與I5 - 之多碘離子之形態與經定向之PVA形成錯合物(PVA多碘錯合物)。此時,PVA係利用硼酸等交聯劑形成交聯點,藉此維持定向性。 然而,若將偏光膜置於高溫高濕下,硼酸交聯會發生水解,使PVA之定向性降低,造成PVA多碘錯合物崩壞。因此,PVA多碘錯合物會造成可見光吸收降低,而約700nm之長波長側及約410nm之短波長側的透射率會上升。依上所述,置於高溫高濕下之偏光膜會在黑色顯示下褪色。<Fading> In the iodine-dyed and stretched PVA-based film (polarizing film), the iodine system forms a complex with the oriented PVA in the form of I 3 - and I 5 -polyiodide ions (PVA polyiodide complex物). At this time, the PVA system uses a cross-linking agent such as boric acid to form cross-linking points, thereby maintaining the orientation. However, if the polarizing film is placed under high temperature and high humidity, the cross-linking of boric acid will undergo hydrolysis, which will reduce the orientation of PVA and cause the collapse of the PVA polyiodide complex. Therefore, the PVA polyiodide complex will cause a decrease in visible light absorption, and the transmittance of the long wavelength side of about 700 nm and the short wavelength side of about 410 nm will increase. As mentioned above, the polarizing film placed under high temperature and high humidity will fade under black display.

<加熱紅變> 在經碘染色且延伸之PVA系薄膜(偏光膜)中,碘係以I3 - 與I5 - 之多碘離子之形態與PVA形成錯合物(PVA多碘錯合物)。I3 - 在470nm附近具有寬的吸收峰,而I5 - 在600nm附近具有寬的吸收峰。亦即,PVA-I3 - 錯合物負責短波長側(藍色側)之吸收,而PVA-I5 - 錯合物負責長波長側(紅色側)之吸收。 然而,該PVA-I5 - 錯合物不耐加熱,若將偏光膜置於高溫下則PVA與I5 - 之錯合物形成會崩壞,而I5 - 會分解。 因此,置於高溫下之偏光膜中,負責長波長側之吸收的PVA-I5 - 錯合物會減少,亦即約700nm之長波長側的透射率會上升,而偏光膜顏色會變紅。 實施例<Heating red change> In the iodine-dyed and stretched PVA-based thin film (polarizing film), the iodine forms a complex with PVA in the form of I 3 - and I 5 -polyiodide ions (PVA polyiodide complex ). I 3 - has a broad absorption peak near 470 nm, and I 5 - has a broad absorption peak near 600 nm. That is, PVA-I 3 - complexes responsible absorb short wavelength side (blue side) of, the PVA-I 5 - complexes responsible for absorbing the long wavelength side (red side) of. However, the PVA-I 5 - complex is not resistant to heating. If the polarizing film is placed at a high temperature, the formation of the complex of PVA and I 5 - will collapse, and the I 5 - will decompose. Accordingly, the polarizing film was placed under the high temperature, it is responsible for the absorption of the long wavelength side of the PVA-I 5 - complexes will decrease, i.e., a transmittance of about 700nm to the long wavelength side will rise, while the red color will polarizing . Example

4.實施例及比較例 以下係一併說明實施例與比較例,而本發明理應不限於該等實施例所記載者。 實施例及比較例中,準備了「偏光膜之膜厚(μm)」、及/或「偏光膜之碘濃度(wt.%)」、及/或「偏光薄膜積層體之水分量(g/m2 )」相異的各種偏光薄膜積層體之試樣。4. Examples and Comparative Examples The following describes the examples and comparative examples together, and the present invention should not be limited to those described in these examples. In the examples and comparative examples, "the film thickness of the polarizing film (μm)", and/or "the iodine concentration of the polarizing film (wt.%)", and/or the "water content of the polarizing film laminate (g/ m 2 )" samples of different polarizing film laminates.

<偏光膜之膜厚> 使用分光膜厚計MCPD-1000(大塚電子(股)製)測定偏光膜之膜厚(μm)。偏光膜保護薄膜之厚度亦使用其來測定。試樣中所含之偏光膜可藉由將試樣浸漬於溶劑中使偏光膜保護薄膜溶解來取出。溶劑例如可分別在偏光膜保護薄膜為三醋酸纖維素樹脂時使用二氯甲烷,在偏光膜保護薄膜為環烯烴樹脂時使用環己烷,而在偏光膜保護薄膜為丙烯酸樹脂時使用甲基乙基酮。另外,在設置於偏光膜之一面的偏光膜保護薄膜之樹脂與設置於另一面的偏光膜保護薄膜之樹脂相異時,則使用上述溶劑依次分別溶解各樹脂。<Film thickness of polarizing film> The film thickness (μm) of the polarizing film was measured using a spectrophotometer MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The thickness of the polarizing film protective film is also measured using it. The polarizing film contained in the sample can be taken out by immersing the sample in a solvent to dissolve the polarizing film protective film. For the solvent, for example, dichloromethane is used when the polarizing film protective film is triacetyl cellulose resin, cyclohexane is used when the polarizing film protective film is cycloolefin resin, and methyl ethyl is used when the polarizing film protective film is acrylic resin.基ketone. In addition, when the resin of the protective film of the polarizing film provided on one side of the polarizing film is different from the resin of the protective film of the polarizing film provided on the other side, the above-mentioned solvents are used to sequentially dissolve the resins.

<偏光膜之碘濃度> 偏光膜的碘濃度(wt.%)可在製造偏光膜時,例如藉由調整用來浸漬PVA系薄膜或PVA層之碘水溶液的濃度或浸漬時間來變更。 偏光膜之碘濃度係以以下方法測定。另外,試樣中所含之偏光膜可依與測定偏光膜之膜厚時同樣方式,藉由將試樣浸漬於溶劑中使偏光膜保護薄膜溶解來取出。 (X射線螢光測定) 測定偏光膜之碘濃度時,首先係使用X射線螢光分析之檢量曲線法來定量碘濃度。裝置係使用X射線螢光分析裝置ZSX-PRIMUS IV((股)Rigaku製)。 利用X射線螢光分析裝置直接取得之值並非各元素之濃度,而是各元素固有之波長的X射線螢光強度(kcps)。因此,欲求得偏光膜所含碘濃度,須使用檢量曲線將X射線螢光強度轉換為濃度。本說明書等中之偏光膜的碘濃度係指以偏光膜之重量為基準之碘濃度(wt%)。<Iodine concentration of polarizing film> The iodine concentration (wt.%) of the polarizing film can be changed when the polarizing film is manufactured, for example, by adjusting the concentration or immersion time of the iodine aqueous solution used to immerse the PVA-based film or the PVA layer. The iodine concentration of the polarizing film was measured by the following method. In addition, the polarizing film contained in the sample can be taken out by immersing the sample in a solvent to dissolve the protective film of the polarizing film in the same manner as when measuring the film thickness of the polarizing film. (X-ray fluorescence measurement) When measuring the iodine concentration of the polarizing film, firstly, the iodine concentration is quantified by the calibration curve method of X-ray fluorescence analysis. An X-ray fluorescence analyzer ZSX-PRIMUS IV (manufactured by Rigaku) was used as the device. The value directly obtained by the X-ray fluorescence analysis device is not the concentration of each element, but the X-ray fluorescence intensity (kcps) of the inherent wavelength of each element. Therefore, in order to obtain the concentration of iodine contained in the polarizing film, a calibration curve must be used to convert the X-ray fluorescence intensity into a concentration. The iodine concentration of the polarizing film in this specification and the like refers to the iodine concentration (wt%) based on the weight of the polarizing film.

(作成檢量曲線) 依以下程序作成檢量曲線。 1.將已知量的碘化鉀溶解至PVA水溶液中,製作出7種包含已知濃度之碘的PVA水溶液。將該PVA水溶液塗佈於聚對苯二甲酸乙二酯並乾燥後剝離,製作出含有已知濃度之碘的PVA薄膜之試料1~7。 此外,PVA薄膜的碘濃度(wt%)係利用以下數學式1算出。 [數學式1] 碘濃度(wt%)={碘化鉀量(g)/(碘化鉀量(g)+PVA量(g))}×(127/166) (碘的分子量:127 鉀的分子量:39)(Create calibration curve) Make the calibration curve according to the following procedure. 1. Dissolve a known amount of potassium iodide into the PVA aqueous solution to make 7 kinds of PVA aqueous solutions containing iodine with a known concentration. The PVA aqueous solution was applied to polyethylene terephthalate, dried, and then peeled off to produce samples 1-7 of PVA film containing iodine of known concentration. In addition, the iodine concentration (wt%) of the PVA film is calculated using the following Mathematical Formula 1. [Math 1]  Iodine concentration (wt%) = {Amount of potassium iodide (g)/(Amount of potassium iodide (g) + Amount of PVA (g))}×(127/166) (Molecular weight of iodine: 127  Molecular weight of potassium: 39)

2.針對所製作出之PVA薄膜,使用X射線螢光分析裝置ZSX-PRIMUS IV((股)Rigaku製),測定出對應碘的X射線螢光強度(kcps)。此外,X射線螢光強度(kcps)係取X射線螢光光譜之峰值。且,使用分光膜厚計MCPD-1000(大塚電子(股)製)測定製出之PVA薄膜之膜厚。2. For the produced PVA film, the X-ray fluorescence analyzer ZSX-PRIMUS IV (manufactured by Rigaku) was used to measure the X-ray fluorescence intensity (kcps) corresponding to iodine. In addition, the X-ray fluorescence intensity (kcps) is the peak value of the X-ray fluorescence spectrum. In addition, the thickness of the produced PVA film was measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.).

3.將X射線螢光強度除以PVA薄膜之厚度(μm),算出薄膜每單位厚度之X射線螢光強度(kcps/μm)。於表1顯示各試料之碘濃度與每單位厚度之X射線螢光強度。3. Divide the X-ray fluorescence intensity by the thickness of the PVA film (μm) to calculate the X-ray fluorescence intensity per unit thickness of the film (kcps/μm). Table 1 shows the iodine concentration of each sample and the X-ray fluorescence intensity per unit thickness.

[表1]

Figure 02_image003
[Table 1]
Figure 02_image003

4.以表1所示結果為基礎,以PVA薄膜每單位厚度之X射線螢光強度(kcps/μm)為橫軸,並以PVA薄膜所含碘濃度(wt%)為縱軸,繪製出檢量曲線。於圖3顯示作成之檢量曲線。可由檢量曲線所得PVA薄膜每單位厚度之X射線螢光強度求出碘濃度的數學式定如數學式2所示。此外,圖3中之R2 係相關係數。 [數學式2] (碘濃度)(wt%)=14.474×(PVA薄膜每單位厚度的X射線螢光強度)(kcps/μm)4. Based on the results shown in Table 1, the X-ray fluorescence intensity per unit thickness of the PVA film (kcps/μm) is taken as the horizontal axis, and the iodine concentration in the PVA film (wt%) is taken as the vertical axis. Calibration curve. Figure 3 shows the completed calibration curve. The mathematical formula for obtaining the iodine concentration from the X-ray fluorescence intensity per unit thickness of the PVA film obtained from the calibration curve is shown in mathematical formula 2. In addition, R 2 in Figure 3 is the correlation coefficient. [Math 2] (Iodine concentration) (wt%) = 14.474 × (X-ray fluorescence intensity per unit thickness of PVA film) (kcps/μm)

(算出碘濃度) 將測定試樣而得之X射線螢光強度除以厚度,求出每單位厚度之X射線螢光強度(kcps/μm)。將各試樣的每單位厚度的X射線螢光強度代入數學式2來求出碘濃度。(Calculate the iodine concentration) The X-ray fluorescence intensity obtained by measuring the sample is divided by the thickness to obtain the X-ray fluorescence intensity per unit thickness (kcps/μm). The X-ray fluorescence intensity per unit thickness of each sample is substituted into Equation 2 to obtain the iodine concentration.

<偏光薄膜積層體之水分量> 偏光薄膜積層體之水分量(g/m2 )主要可藉由調整偏光膜之膜厚、與偏光膜接合之偏光膜保護薄膜的材質、厚度等來決定。又,亦可藉由製造偏光膜時之交聯處理(硼酸含量等)等來調整。 偏光薄膜積層體之水分量係依以下方法測定。 首先,將實施例及比較例所得偏光薄膜積層體裁切成0.1m×0.1m之正方形。 將裁切好之試樣投入恆溫恆濕機內,並於溫度23℃、相對濕度55%之環境下放置48小時。之後,於已設定成與恆溫恆濕機內相同環境即溫度23℃、相對溼度55%的無塵室中取出試樣,並於取出後5分鐘以內測定重量。將此時之試樣重量作為初始重量W1(g)。另外,在取出後,只要在約15分鐘以內,則即使無塵室內的溫度變動2℃~3℃左右、或無塵室內的相對濕度變動±10%左右,仍不會對初始重量造成實質影響。 接著,將取出之試樣投入乾燥器內,在120℃下乾燥2小時。之後,在上述已設定成溫度23℃、相對濕度約55%的無塵室中取出乾燥後之試樣,並於取出後10分鐘以內測定重量。將此時之試樣重量作為乾燥後重量W2(g)。不同於上述設為5分鐘以內而設為10分鐘以內係因考慮到冷卻時間之故。另外,與上述相同,在取出後只要在約15分鐘以內,則不會對乾燥後重量造成實質影響。 由依上述所得試樣之初始重量W1與乾燥後重量W2,利用下式算出偏光薄膜積層體之平衡水分量M(g/m2 )。 (式)  M=(W1―W2)/(0.1×0.1) 本發明所提「偏光薄膜積層體之水分量」意指以上述方法算出之平衡水分量。<Moisture content of the polarizing film laminate> The moisture content (g/m 2 ) of the polarizing film laminate can be determined mainly by adjusting the film thickness of the polarizing film, and the material and thickness of the polarizing film protective film bonded to the polarizing film. Moreover, it can also be adjusted by the crosslinking process (boric acid content etc.) etc. at the time of manufacturing a polarizing film. The moisture content of the polarizing film laminate is measured according to the following method. First, the polarizing film laminates obtained in the examples and comparative examples were cut into a square of 0.1 m×0.1 m. Put the cut sample into a constant temperature and humidity machine, and place it in an environment with a temperature of 23°C and a relative humidity of 55% for 48 hours. After that, the sample was taken out in a clean room set to the same environment as the constant temperature and humidity machine, that is, a temperature of 23°C and a relative humidity of 55%, and the weight was measured within 5 minutes after taking it out. The weight of the sample at this time is taken as the initial weight W1 (g). In addition, after taking it out, as long as within about 15 minutes, even if the temperature in the clean room fluctuates by about 2°C to 3°C, or the relative humidity in the clean room fluctuates by about ±10%, the initial weight will not be substantially affected. . Next, put the taken-out sample into a desiccator and dry it at 120°C for 2 hours. After that, the dried sample was taken out in the above-mentioned clean room set to a temperature of 23°C and a relative humidity of about 55%, and the weight was measured within 10 minutes after taking it out. The weight of the sample at this time was taken as the weight after drying W2 (g). Different from the above-mentioned setting within 5 minutes and within 10 minutes, it is because the cooling time is taken into consideration. In addition, similar to the above, as long as it is within about 15 minutes after taking it out, the weight after drying will not be substantially affected. From the initial weight W1 and the dried weight W2 of the sample obtained above, the equilibrium moisture content M (g/m 2 ) of the polarizing film laminate was calculated using the following formula. (Formula) M=(W1―W2)/(0.1×0.1) The "moisture content of the polarizing film laminate" mentioned in the present invention means the equilibrium moisture content calculated by the above method.

(製作黏著劑層A) 首先,於具備攪拌葉片、溫度計、氮氣導入管及冷卻器之四口燒瓶中饋入丙烯酸丁酯80.9份、丙烯酸苄酯18份、丙烯酸1份、丙烯酸4-羥丁酯0.1份,藉此獲得單體混合物。並相對於單體混合物(固體成分)100份,將作為聚合引發劑的2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100份一起饋入。一邊緩慢地攪拌混合物一邊將氮氣導入燒瓶內進行氮取代。藉由將燒瓶內之液溫維持在55℃附近進行8小時聚合反應,而調製出重量平均分子量(Mw)185萬、Mw/Mn=3.8之丙烯酸系聚合物之溶液。(Making adhesive layer A) First, a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler was charged with 80.9 parts of butyl acrylate, 18 parts of benzyl acrylate, 1 part of acrylic acid, and 0.1 part of 4-hydroxybutyl acrylate to obtain Monomer mixture. And with respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was fed together with 100 parts of ethyl acetate. While slowly stirring the mixture, nitrogen was introduced into the flask for nitrogen substitution. By maintaining the liquid temperature in the flask at around 55°C for 8 hours, the polymerization reaction was carried out to prepare an acrylic polymer solution with a weight average molecular weight (Mw) of 1.85 million and Mw/Mn=3.8.

接下來,相對於丙烯酸系聚合物之溶液的固體成分100份,進一步摻混異氰酸酯交聯劑(Tosoh公司製之Coronate L,三羥甲丙烷二異氰酸甲苯酯)0.45份、過氧化苯甲醯(日本油脂公司製之NYPER BMT)0.1份及γ-環氧丙氧基丙基甲氧基矽烷(信越化學工業公司製:KBM-403)0.2份,而調製出丙烯酸系黏著劑組成物之溶液。Next, with respect to 100 parts of the solid content of the acrylic polymer solution, 0.45 parts of isocyanate crosslinking agent (Coronate L manufactured by Tosoh, trimethylolpropane toluene diisocyanate) and benzyl peroxide were further blended. 0.1 part of 醯 (NYPER BMT manufactured by Nippon Oil & Fat Co., Ltd.) and 0.2 part of γ-glycidoxypropyl methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) to prepare an acrylic adhesive composition Solution.

接著,將所得溶液塗佈於分離件(三菱化學聚酯薄膜公司製之MRF38)之單面。分離件係業經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜。使所得塗佈膜在155℃下乾燥1分鐘,藉此於分離件表面形成黏著劑層A。黏著劑層之厚度為20μm。Next, the obtained solution was applied to one side of a separator (MRF38 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). The separation part is a polyethylene terephthalate film that has been treated with a silicone-based release agent. The obtained coating film was dried at 155° C. for 1 minute, thereby forming an adhesive layer A on the surface of the separator. The thickness of the adhesive layer is 20 μm.

(製作黏著劑層B) 首先,將丙烯酸丁酯99重量份(以下同)、丙烯酸4-羥丁酯1.0份及2,2'-偶氮雙異丁腈0.3份與乙酸乙酯100份一同饋入具備攪拌葉片、溫度計、氮氣導入管及冷卻器的4口燒瓶中。一邊緩慢地攪拌混合物一邊將氮氣導入燒瓶內進行氮取代。藉由將燒瓶內之液溫維持在55℃附近進行4小時聚合反應,而調製出重量平均分子量(Mw)165萬、Mw/Mn=3.7之丙烯酸系聚合物之溶液。(Making adhesive layer B) First, 99 parts by weight of butyl acrylate (the same hereinafter), 1.0 part of 4-hydroxybutyl acrylate, 0.3 part of 2,2'-azobisisobutyronitrile and 100 parts of ethyl acetate are fed into a stirring blade and a thermometer. , Nitrogen introduction pipe and 4-necked flask with cooler. While slowly stirring the mixture, nitrogen was introduced into the flask for nitrogen substitution. By maintaining the liquid temperature in the flask at around 55°C for 4 hours, the polymerization reaction was carried out to prepare an acrylic polymer solution with a weight average molecular weight (Mw) of 1.65 million and Mw/Mn=3.7.

接著,相對於該丙烯酸系聚合物溶液之固體成分每100份,摻混0.3份過氧化二苯甲醯(日本油脂製(股):NYPER BMT)、0.1份三羥甲丙烷二異氰酸二甲苯酯(MITSUI TAKEDA CHEMICALS,INC.:TAKENATE D110N)與0.2份矽烷耦合劑(綠研化學股份公司製:A-100,含乙醯乙醯基之矽烷耦合劑),藉此來調整黏著劑組成物。Next, for every 100 parts of the solid content of the acrylic polymer solution, 0.3 part of dibenzoyl peroxide (Nippon Oil & Fat Co., Ltd.: NYPER BMT) and 0.1 part of trimethylolpropane diisocyanate were blended. Toluene ester (MITSUI TAKEDA CHEMICALS, INC.: TAKENATE D110N) and 0.2 parts of silane coupling agent (manufactured by Luken Chemical Co., Ltd.: A-100, silane coupling agent containing acetyl acetyl group) to adjust the composition of the adhesive Things.

接著,將所得溶液塗佈於分離件(三菱化學聚酯薄膜公司製之MRF38)之單面。分離件係業經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜。使所得塗佈膜在155℃下乾燥1分鐘,藉此於分離件表面形成黏著劑層B。黏著劑層之厚度為20μm。Next, the obtained solution was applied to one side of a separator (MRF38 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). The separation part is a polyethylene terephthalate film that has been treated with a silicone-based release agent. The obtained coating film was dried at 155° C. for 1 minute, thereby forming an adhesive layer B on the surface of the separator. The thickness of the adhesive layer is 20 μm.

(製作黏著劑層C) 於製作黏著劑層A中將丙烯酸系聚合物之聚合時間設為2小時,除此之外以相同方式而製出黏著劑層C。丙烯酸系聚合物之重量平均分子量(Mw)為190萬,Mw/Mn=2.5。(Making adhesive layer C) In the preparation of the adhesive layer A, the polymerization time of the acrylic polymer was set to 2 hours, except that the adhesive layer C was produced in the same manner. The weight average molecular weight (Mw) of the acrylic polymer is 1.9 million, and Mw/Mn=2.5.

(製作黏著劑層D) 於製作黏著劑層A中,將丙烯酸系聚合物之組成設為丙烯酸丁酯80.9份、丙烯酸苄酯18份、丙烯酸4.8份、丙烯酸4-羥丁酯0.1份,除此之外以相同方式而製出黏著劑層D。丙烯酸系聚合物之重量平均分子量(Mw)為210萬,Mw/Mn=4.0。(Making adhesive layer D) In making the adhesive layer A, the composition of the acrylic polymer was 80.9 parts of butyl acrylate, 18 parts of benzyl acrylate, 4.8 parts of acrylic acid, and 0.1 part of 4-hydroxybutyl acrylate. The adhesive layer D is prepared. The weight average molecular weight (Mw) of the acrylic polymer is 2.1 million, and Mw/Mn=4.0.

(製作黏著劑層E) 首先,於具備攪拌葉片、溫度計、氮氣導入管及冷卻器之四口燒瓶中饋入丙烯酸丁酯71.9份、丙烯酸苄酯18份、丙烯酸10份、丙烯酸4-羥丁酯0.1份,藉此獲得單體混合物。並相對於單體混合物(固體成分)100份,將作為聚合引發劑的2,2’-偶氮雙異丁腈0.1份與乙酸乙酯70份及甲苯30份一起饋入。一邊緩慢地攪拌混合物一邊將氮氣導入燒瓶內進行氮取代。藉由將燒瓶內之液溫維持在55℃附近進行8小時聚合反應,而調製出重量平均分子量(Mw)80萬、Mw/Mn=3.6之丙烯酸系聚合物之溶液。(Making adhesive layer E) First, a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler was fed with 71.9 parts of butyl acrylate, 18 parts of benzyl acrylate, 10 parts of acrylic acid, and 0.1 part of 4-hydroxybutyl acrylate to obtain Monomer mixture. With respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was fed together with 70 parts of ethyl acetate and 30 parts of toluene. While slowly stirring the mixture, nitrogen was introduced into the flask for nitrogen substitution. By maintaining the liquid temperature in the flask at around 55°C for 8 hours, the polymerization reaction was carried out to prepare an acrylic polymer solution with a weight average molecular weight (Mw) of 800,000 and Mw/Mn=3.6.

接下來,相對於丙烯酸系聚合物之溶液的固體成分100份,進一步摻混異氰酸酯交聯劑(Tosoh公司製之Coronate L,三羥甲丙烷二異氰酸甲苯酯)1份、過氧化苯甲醯(日本油脂公司製之NYPER BMT)0.1份及γ-環氧丙氧基丙基甲氧基矽烷(信越化學工業公司製:KBM-403)0.2份,而調製出丙烯酸系黏著劑組成物之溶液。Next, with respect to 100 parts of the solid content of the acrylic polymer solution, 1 part of isocyanate crosslinking agent (Coronate L manufactured by Tosoh Co., Ltd., trimethylolpropane toluene diisocyanate), and benzyl peroxide were further blended. 0.1 part of 醯 (NYPER BMT manufactured by Nippon Oil & Fat Co., Ltd.) and 0.2 part of γ-glycidoxypropyl methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) to prepare an acrylic adhesive composition Solution.

接著,將所得溶液塗佈於分離件(三菱化學聚酯薄膜公司製之MRF38)之單面。分離件係業經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜。使所得塗佈膜在155℃下乾燥1分鐘,藉此於分離件表面形成黏著劑層E。黏著劑層之厚度為20μm。Next, the obtained solution was applied to one side of a separator (MRF38 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). The separation part is a polyethylene terephthalate film that has been treated with a silicone-based release agent. The obtained coating film was dried at 155° C. for 1 minute, thereby forming an adhesive layer E on the surface of the separator. The thickness of the adhesive layer is 20 μm.

[實施例1] (製作偏光膜) 樹脂基材是使用長條狀非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯薄膜(間苯二甲酸基改質度:5mol%,厚度:100μm)。(改質度=間苯二甲酸乙二酯單元/(對苯二甲酸乙二酯單元+間苯二甲酸乙二酯單元))對樹脂基材之一面施行電暈處理(處理條件:55W・min/m2 ),並在常溫下於該電暈處理面塗佈PVA與相對於PVA為13重量份之碘化鉀摻混而成的水溶液,其中前述PVA係以PVA(聚合度4200,皂化度99.2莫耳%)90重量份及乙醯乙醯基改質PVA(日本合成化學工業公司製,商品名「GOHSEFIMER Z410」)10重量份摻混而成者。之後,在60℃下乾燥而形成厚度13μm之PVA系樹脂層,製出積層體。 在130℃之烘箱內,將所得積層體在周速相異的輥間沿縱方向(長邊方向)進行自由端單軸延伸成2.4倍(空中輔助延伸)。 接著,使積層體浸漬於液溫40℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 接著,將液溫30℃的染色浴(相對於水100重量份,以1:7之重量比摻混碘與碘化鉀而獲得之碘水溶液)調整濃度並浸漬於其中60秒以使成為指定透射率(染色處理)。 接著,使其浸漬於液溫40℃的交聯浴(相對於水100重量份摻混3重量份的碘化鉀並摻混5重量份的硼酸而獲得之硼酸水溶液)中30秒(交聯處理)。 然後,一邊使積層體浸漬於液溫70℃的硼酸水溶液(硼酸濃度3.0重量%)中,一邊在周速相異的輥間沿縱方向(長邊方向)進行單軸延伸以使總延伸倍率成5.5倍(水中延伸)。 之後,使積層體浸漬於液溫20℃的洗淨浴(相對於水100重量份,摻混4重量份的碘化鉀而得之水溶液)中(洗淨處理)。 之後,在保持於90℃之烘箱中進行乾燥(乾燥處理)的同時,使其接觸表面溫度經保持於75℃之SUS製金屬輥2秒以上(熱輥乾燥處理)。 經由以上程序,於樹脂基材上獲得了厚度5.4μm之偏光膜。[Example 1] (Preparation of polarizing film) The resin substrate is a long strip of amorphous isophthalic acid copolymer polyethylene terephthalate film (isophthalic acid-based modification degree: 5 mol%, thickness: 100μm). (Degree of modification = ethylene isophthalate unit / (ethylene terephthalate unit + ethylene isophthalate unit)) corona treatment is applied to one side of the resin substrate (treatment conditions: 55W・min/m 2 ), and coat the corona treated surface at room temperature with an aqueous solution of PVA blended with 13 parts by weight of potassium iodide relative to PVA, wherein the aforementioned PVA is PVA (polymerization degree 4200, saponification degree 99.2 Mole%) 90 parts by weight and 10 parts by weight of acetyl modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z410"). After that, it was dried at 60° C. to form a PVA-based resin layer with a thickness of 13 μm to produce a laminate. In an oven at 130°C, the resulting laminate was uniaxially stretched 2.4 times at the free end in the longitudinal direction (long side direction) between rolls with different peripheral speeds (air-assisted stretch). Next, the layered body was immersed in an insoluble bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insoluble treatment). Next, adjust the concentration of a dyeing bath (an iodine aqueous solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30°C and immerse it in it for 60 seconds to achieve a specified transmittance (Dyeing treatment). Next, it was immersed in a cross-linking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water with a liquid temperature of 40°C) for 30 seconds (cross-linking treatment) . Then, while immersing the layered body in a boric acid aqueous solution (boric acid concentration of 3.0% by weight) at a liquid temperature of 70°C, uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds to increase the total stretch magnification 5.5 times (extended in water). After that, the layered body was immersed in a washing bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water with a liquid temperature of 20°C) (washing treatment). After that, while drying in an oven kept at 90°C (drying treatment), the temperature of the contact surface is passed through a metal roll made of SUS kept at 75°C for 2 seconds or longer (hot roll drying treatment). Through the above procedures, a polarizing film with a thickness of 5.4 μm was obtained on the resin substrate.

(製作偏光薄膜積層體) 透過紫外線硬化型接著劑,將環烯烴系薄膜(日本Zeon公司製,ZT12,18μm)作為偏光膜保護薄膜接合於所得偏光膜之與樹脂基材相反之側的面。具體而言,是塗敷成以下記載之硬化型接著劑之總厚度成為1.0μm,並使用輥軋機進行接合。其後,從環烯烴系薄膜側照射UV光線使接著劑硬化。接著,剝離樹脂基材,而獲得含環烯烴系偏光保護薄膜與偏光膜之偏光薄膜積層體。 硬化型接著劑之詳細內容如下。混合N-羥乙基丙烯醯胺(HEAA)40重量份、丙烯醯基嗎福林(ACMO)60重量份與光引發劑「IRGACURE 819」(BASF公司製)3重量份,而調製出接著劑。以使硬化後之接著劑層之厚度成為1.0μm的方式塗佈於偏光膜上,並照射紫外線作為活性能量線使接著劑硬化。紫外線照射是使用充有鎵之金屬鹵素燈、照射裝置:Fusion UV Systems,Inc公司製的Light HAMMER10、燈泡:V燈泡、峰值照度:1600mW/cm2 、累積照射量1000/mJ/cm2 (波長380~440nm),紫外線的照度是使用Solatell公司製的Sola-Check系統來測定。(Preparation of a polarizing film laminate) A cycloolefin-based film (made by Zeon, Japan, ZT12, 18 μm) as a polarizing film protective film was bonded to the surface of the obtained polarizing film on the opposite side to the resin substrate through an ultraviolet curable adhesive. Specifically, it is applied so that the total thickness of the curable adhesive described below becomes 1.0 μm, and is joined using a rolling mill. Thereafter, UV rays were irradiated from the side of the cycloolefin-based film to cure the adhesive. Next, the resin substrate is peeled off, and a polarizing film laminate containing a cycloolefin-based polarizing protective film and a polarizing film is obtained. The details of the hardening adhesive are as follows. 40 parts by weight of N-Hydroxyethyl acrylamide (HEAA), 60 parts by weight of acrylophrine (ACMO), and 3 parts by weight of photoinitiator "IRGACURE 819" (manufactured by BASF) were mixed to prepare an adhesive . It is coated on the polarizing film so that the thickness of the adhesive layer after curing becomes 1.0 μm, and ultraviolet rays are irradiated as active energy rays to cure the adhesive. Ultraviolet radiation uses a gallium-filled metal halide lamp, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illuminance: 1600mW/cm 2 , cumulative irradiation amount 1000/mJ/cm 2 (wavelength 380~440nm), the illuminance of ultraviolet rays is measured using the Sola-Check system manufactured by Solarell.

(取出偏光膜) 使用環己烷作為溶劑,從偏光薄膜積層體取出偏光膜來測定偏光膜之碘濃度。(Remove the polarizing film) Using cyclohexane as a solvent, the polarizing film was taken out from the polarizing film laminate to measure the iodine concentration of the polarizing film.

(製作附黏著劑層之偏光薄膜積層體) 藉由將黏著劑層A轉印至偏光薄膜積層體之偏光膜的面,而製出實施例1之附黏著劑層之偏光薄膜積層體。(Making a polarizing film laminate with an adhesive layer) By transferring the adhesive layer A to the surface of the polarizing film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Example 1 was produced.

[實施例2] 於製作實施例1之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。其他條件則與實施例1相同。[Example 2] When producing the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. The other conditions are the same as in Example 1.

[實施例3] 於製作實施例1之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。且於製作實施例1之偏光薄膜積層體時,作為偏光膜保護薄膜係使環烯烴系薄膜(日本Zeon公司製,ZF12,13μm)接合。其他條件則與實施例1相同。[Example 3] When producing the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. When the polarizing film laminate of Example 1 was produced, a cycloolefin-based film (manufactured by Zeon Corporation, ZF12, 13 μm) was joined as a polarizing film protective film. The other conditions are the same as in Example 1.

[實施例4] 於製作實施例1之偏光薄膜積層體時,作為偏光膜保護薄膜係使三醋酸纖維素薄膜系薄膜(富士軟片(Fujifilm)公司製 TJ40UL 厚度40μm)接合。且,於製作實施例1之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度。其他條件則與實施例1相同。[Example 4] When the polarizing film laminate of Example 1 was produced, a cellulose triacetate film-based film (TJ40UL manufactured by Fujifilm Corporation, thickness 40 μm) was bonded as a protective film for the polarizing film. In addition, when producing the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration. The other conditions are the same as in Example 1.

[實施例5] 在製作實施例1之偏光薄膜積層體時,作為偏光膜保護薄膜係使由具有內酯環結構之改質丙烯酸系聚合物所構成的厚度40μm之透明保護薄膜(日東電工公司製)接合。且,於製作實施例1之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度。其他條件則與實施例1相同。[Example 5] When producing the polarizing film laminate of Example 1, as the polarizing film protective film, a transparent protective film (manufactured by Nitto Denko Corporation) with a thickness of 40 μm composed of a modified acrylic polymer having a lactone ring structure was joined. In addition, when producing the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration. The other conditions are the same as in Example 1.

[實施例6] (製作偏光膜) 於周速比相異之輥間將平均聚合度2700、厚度30μm之PVA薄膜一邊染色一邊延伸輸送。首先,一邊浸漬於30℃之水浴中1分鐘以使PVA薄膜膨潤,一邊往輸送方向延伸成1.2倍後,浸漬於碘化鉀(0.03重量%)及碘(0.3重量%)之水溶液(液溫30℃)中1分鐘以一邊染色一邊往輸送方向延伸成3倍(以未延伸薄膜為基準)。接著,一邊將該延伸薄膜浸漬於硼酸(4重量%)、碘化鉀(5重量%)及硫酸鋅(3.5重量%)之水溶液(浴液)中30秒,一邊往輸送方向延伸成6倍(以未延伸薄膜為基準)。延伸後,以40℃烘箱進行3分鐘的乾燥,獲得12.0μm的偏光膜。[Example 6] (Making polarizing film) The PVA film with an average degree of polymerization of 2700 and a thickness of 30μm is stretched and transported between rollers with different peripheral speed ratios. First, while immersing in a water bath at 30°C for 1 minute to swell the PVA film, it stretched 1.2 times in the conveying direction, and then immersed in an aqueous solution of potassium iodide (0.03% by weight) and iodine (0.3% by weight) (liquid temperature of 30°C) ) In 1 minute, stretch 3 times in the conveying direction while dyeing (based on unstretched film). Next, while immersing the stretched film in an aqueous solution (bath) of boric acid (4% by weight), potassium iodide (5% by weight), and zinc sulfate (3.5% by weight) for 30 seconds, it was stretched 6 times in the conveying direction (with The unstretched film is the basis). After stretching, it was dried in an oven at 40° C. for 3 minutes to obtain a polarizing film of 12.0 μm.

(製作偏光薄膜積層體) 接著劑係使用以重量比3:1含有含乙醯乙醯基之聚乙烯醇樹脂(平均聚合度1200,皂化度98.5莫耳%,乙醯乙醯基化度5莫耳%)與羥甲基三聚氰胺之水溶液。使用該接著劑,於30℃之溫度條件下,利用輥貼合機於偏光膜之一面接合由具有內酯環結構之改質丙烯酸系聚合物所構成的厚度20μm之透明保護薄膜(日東電工公司製),並於另一面接合在厚度25μm之三醋酸纖維素薄膜(Konica Minolta公司製,商品名「KC2UA」)上形成有厚度2μm之硬塗層(HC)之厚度27μm的透明保護薄膜後,繼續於烘箱內在70℃下使其加熱乾燥5分鐘,而獲得於偏光膜兩面接合有透明保護薄膜之偏光薄膜積層體。 硬塗層係依以下方法形成。首先,準備硬塗層形成材料。其係於經將以胺甲酸酯丙烯酸酯為主成分之紫外線硬化型樹脂單體或寡聚物溶解至乙酸丁酯而成之樹脂溶液(DIC(股)製,商品名「UNIDIC 17-806」,固體成分濃度80重量%)中,相對於該溶液中之固體成分每100重量份,添加光聚合引發劑(BASF(股)製,製品名「IRGACURE 906」)5重量份、調平劑(DIC(股)製,製品名「GRANDIC  PC4100」)0.01重量份後,以使上述溶液中之固體成分濃度成為36重量%之方式,以45:55之比率於上述摻混液中加入環戊酮(以下記為「CPN」)與丙二醇單甲基醚(以下記為「PGM」),藉此而製作出。將依上述製作出之硬塗層形成材料,以使硬化後之硬塗層厚度成為2μm之方式塗敷至透明保護薄膜上而形成塗膜。接著,於90℃下使其乾燥1分鐘,之後,以高壓水銀燈照射累積光量300mJ/cm2 之紫外線,將上述塗膜進行硬化處理。 (取出偏光膜) 使用二氯甲烷及甲基乙基酮作為溶劑,從偏光薄膜積層體取出偏光膜來測定偏光膜之碘濃度。(Production of polarizing film laminate) Adhesives are used in a weight ratio of 3:1 containing polyvinyl alcohol resin containing acetyl acetyl groups (average degree of polymerization 1200, saponification degree 98.5 mol%, acetyl acetylation degree 5 Mole%) and methylol melamine in water. Using this adhesive, a transparent protective film with a thickness of 20μm composed of a modified acrylic polymer having a lactone ring structure was bonded to one side of the polarizing film using a roll laminator at a temperature of 30°C (Nitto Denko Corporation Made), and after bonding a 25μm-thick tri-cellulose acetate film (manufactured by Konica Minolta, trade name "KC2UA") on the other side to form a 2μm-thick hard coat layer (HC) with a 27μm-thick transparent protective film, Continue heating and drying in an oven at 70°C for 5 minutes to obtain a polarizing film laminate in which a transparent protective film is bonded to both sides of the polarizing film. The hard coat layer is formed by the following method. First, prepare the hard coat layer forming material. It is based on a resin solution (made by DIC (stock), trade name "UNIDIC 17-806") made by dissolving ultraviolet curable resin monomers or oligomers mainly composed of urethane acrylate into butyl acetate. ", the solid content concentration is 80% by weight), per 100 parts by weight of the solid content in the solution, 5 parts by weight of a photopolymerization initiator (made by BASF, product name "IRGACURE 906") and a leveling agent are added (DIC Co., Ltd., product name "GRANDIC PC4100") After 0.01 parts by weight, cyclopentanone is added to the above-mentioned mixed solution at a ratio of 45:55 so that the solid content in the above-mentioned solution becomes 36% by weight. (Hereinafter referred to as "CPN") and propylene glycol monomethyl ether (hereinafter referred to as "PGM") were produced by this. The hard coat layer forming material produced as described above is applied to the transparent protective film so that the thickness of the hard coat layer after hardening becomes 2 μm to form a coating film. Next, it was dried at 90°C for 1 minute, and then irradiated with a high-pressure mercury lamp with a cumulative light intensity of 300 mJ/cm 2 of ultraviolet rays to cure the coating film. (Removing the polarizing film) Using dichloromethane and methyl ethyl ketone as a solvent, the polarizing film was taken out from the polarizing film laminate to measure the iodine concentration of the polarizing film.

(製作附黏著劑層之偏光薄膜積層體) 藉由將黏著劑層A轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,而製出實施例6之附黏著劑層之偏光薄膜積層體。(Making a polarizing film laminate with an adhesive layer) By transferring the adhesive layer A to the surface of the acrylic transparent protective film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Example 6 was produced.

[實施例7] 於製作實施例6之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度。且,製作實施例6之偏光薄膜積層體時,於所得偏光膜的一面,作為偏光膜保護薄膜接合由具有內酯環結構之改質丙烯酸系聚合物所構成的厚度30μm之透明保護薄膜(日東電工公司製),並於另一面接合在厚度40μm之三醋酸纖維素薄膜(Konica Minolta製,商品名「KC4UY」)上形成有厚度9μm之HC的厚度49μm之透明保護薄膜。其他條件則與實施例6相同。[Example 7] When producing the polarizing film of Example 6, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration. In addition, when the polarizing film laminate of Example 6 was produced, on one side of the obtained polarizing film, a transparent protective film (Nitto) composed of a modified acrylic polymer having a lactone ring structure was joined as a polarizing film protective film. Denko Corporation), and a 40 μm thick tri-cellulose acetate film (manufactured by Konica Minolta, trade name "KC4UY") was bonded to the other side to form a transparent protective film with a thickness of 9 μm and a thickness of 49 μm with HC. The other conditions are the same as in Example 6.

[實施例8] 將實施例7中黏著劑層C轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,除此之外以相同方式製作出附黏著劑層之偏光薄膜積層體。[Example 8] The adhesive layer C in Example 7 was transferred to the surface of the acrylic transparent protective film of the polarizing film laminate, except that the adhesive layer-attached polarizing film laminate was produced in the same manner.

[實施例9] 於製作實施例6之偏光膜時,於延伸處理中延伸輸送厚度45μm之PVA薄膜而獲得18.0μm之偏光膜,且於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度。且,於製作實施例6之偏光薄膜積層體時,於所得偏光膜的一面,作為偏光膜保護薄膜接合由具有內酯環結構之改質丙烯酸系聚合物所構成的厚度30μm之透明保護薄膜(日東電工公司製),並於另一面接合三醋酸纖維素薄膜系薄膜(富士軟片(Fujifilm)公司製 TJ40UL 厚度40μm)。其他條件則與實施例6相同。[Example 9] When producing the polarizing film of Example 6, the PVA film with a thickness of 45 μm was stretched and transported in the stretching process to obtain a polarizing film of 18.0 μm, and the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration. In addition, when the polarizing film laminate of Example 6 was produced, on one side of the obtained polarizing film, a transparent protective film of 30 μm thick composed of a modified acrylic polymer having a lactone ring structure was joined as a polarizing film protective film ( Nitto Denko Corporation), and a cellulose triacetate film-based film (Fujifilm Corporation TJ40UL, thickness 40 μm) was bonded to the other side. The other conditions are the same as in Example 6.

[實施例10]~[實施例13] 於製作實施例9之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。其他條件則與實施例9相同。[Example 10] ~ [Example 13] When producing the polarizing film of Example 9, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. The other conditions are the same as in Example 9.

[實施例14] 將實施例9中黏著劑層C轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,除此之外以相同方式製作出附黏著劑層之偏光薄膜積層體。[Example 14] The adhesive layer C in Example 9 was transferred to the surface of the acrylic transparent protective film of the polarizing film laminate, except that the adhesive layer-attached polarizing film laminate was produced in the same manner.

[實施例15] 將實施例9中黏著劑層D轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,除此之外以相同方式製作出附黏著劑層之偏光薄膜積層體。[Example 15] The adhesive layer D in Example 9 was transferred to the surface of the acrylic transparent protective film of the polarizing film laminate, except that the adhesive layer-attached polarizing film laminate was produced in the same manner.

[比較例1]~[比較例2] 於製作實施例1之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。 並且,藉由將黏著劑層B轉印至偏光薄膜積層體之偏光膜的面,而製出比較例1及2之附黏著劑層之偏光薄膜積層體。其他條件則與實施例1相同。[Comparative example 1]~[Comparative example 2] When producing the polarizing film of Example 1, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. In addition, by transferring the adhesive layer B to the surface of the polarizing film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Comparative Examples 1 and 2 was produced. The other conditions are the same as in Example 1.

[比較例3]~[比較例4] 於製作實施例6之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。 並且,藉由將黏著劑層B轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,而製出比較例3及4之附黏著劑層之偏光薄膜積層體。其他條件則與實施例6相同。[Comparative example 3]~[Comparative example 4] When producing the polarizing film of Example 6, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. And, by transferring the adhesive layer B to the surface of the acrylic transparent protective film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Comparative Examples 3 and 4 was produced. The other conditions are the same as in Example 6.

[比較例5] 於製作實施例7之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。 並且,藉由將黏著劑層B轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,而製出比較例5之附黏著劑層之偏光薄膜積層體。其他條件則與實施例7相同。[Comparative Example 5] When producing the polarizing film of Example 7, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. Furthermore, by transferring the adhesive layer B to the surface of the acrylic transparent protective film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Comparative Example 5 was produced. The other conditions are the same as in Example 7.

[比較例6] 於製作實施例9之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。 並且,藉由將黏著劑層B轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,而製出比較例6之附黏著劑層之偏光薄膜積層體。其他條件則與實施例9相同。[Comparative Example 6] When producing the polarizing film of Example 9, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. Furthermore, by transferring the adhesive layer B to the surface of the acrylic transparent protective film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Comparative Example 6 was produced. The other conditions are the same as in Example 9.

[比較例7] (製作偏光膜) 於製作實施例9之偏光膜時,於延伸處理中延伸輸送厚度60μm之PVA薄膜而獲得22.0μm之偏光膜。且,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。其他條件則與實施例9相同。 (製作偏光薄膜積層體) 於所得偏光膜的一面,作為偏光膜保護薄膜接合由具有內酯環結構之改質丙烯酸系聚合物所構成的厚度30μm之透明保護薄膜(日東電工公司製),並於另一面接合在厚度40μm之三醋酸纖維素薄膜(Konica Minolta製,商品名「KC4UY」)上形成有厚度9μm之HC的厚度49μm之透明保護薄膜。其他處理則與實施例9相同。 (取出偏光膜) 取出條件與實施例9相同。 (製作附黏著劑層之偏光薄膜積層體) 藉由將黏著劑層B轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,而製出比較例7之附黏著劑層之偏光薄膜積層體。[Comparative Example 7] (Making polarizing film) When the polarizing film of Example 9 was produced, a PVA film with a thickness of 60 μm was stretched and transported in a stretching process to obtain a polarizing film of 22.0 μm. In the dyeing process, the concentration of the iodine aqueous solution and the immersion time are adjusted to change the iodine concentration, and the thickness of the polarizing film protective film is adjusted to change the moisture content of the polarizing film laminate. The other conditions are the same as in Example 9. (Making polarizing film laminate) On one side of the obtained polarizing film, a transparent protective film (manufactured by Nitto Denko Corporation) with a thickness of 30 μm composed of a modified acrylic polymer having a lactone ring structure was bonded as a protective film of the polarizing film, and bonded to the other side with a thickness of 40 μm Third, a cellulose acetate film (manufactured by Konica Minolta, trade name "KC4UY") is formed with a transparent protective film of HC with a thickness of 9 μm and a thickness of 49 μm. The other processing is the same as in Example 9. (Remove the polarizing film) The extraction conditions are the same as in Example 9. (Making a polarizing film laminate with an adhesive layer) By transferring the adhesive layer B to the surface of the acrylic transparent protective film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Comparative Example 7 was produced.

[比較例8] 於製作比較例7之偏光膜時,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。且,於偏光膜的一面,作為偏光膜保護薄膜接合由具有內酯環結構之改質丙烯酸系聚合物所構成的厚度20μm之透明保護薄膜(日東電工公司製)。其他條件則與比較例7相同。[Comparative Example 8] When producing the polarizing film of Comparative Example 7, the concentration of the iodine aqueous solution and the immersion time were adjusted during the dyeing process to change the iodine concentration, and the thickness of the polarizing film protective film was adjusted to change the moisture content of the polarizing film laminate. And, on one side of the polarizing film, a transparent protective film (manufactured by Nitto Denko Corporation) with a thickness of 20 μm composed of a modified acrylic polymer having a lactone ring structure was joined as a protective film of the polarizing film. The other conditions are the same as in Comparative Example 7.

[比較例9] 於製作實施例9之偏光膜時,於延伸處理中延伸輸送厚度75μm之PVA薄膜而獲得28μm之偏光膜。且,於染色處理中調整碘水溶液的濃度及浸漬時間來變更碘濃度,且調整偏光膜保護薄膜之厚度,來變更偏光薄膜積層體的水分量。 並且,藉由將黏著劑層B轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,而製出比較例9之附黏著劑層之偏光薄膜積層體。其他條件則與實施例9相同。[Comparative Example 9] When the polarizing film of Example 9 was produced, a PVA film with a thickness of 75 μm was stretched and transported in a stretching process to obtain a polarizing film of 28 μm. In the dyeing process, the concentration of the iodine aqueous solution and the immersion time are adjusted to change the iodine concentration, and the thickness of the polarizing film protective film is adjusted to change the moisture content of the polarizing film laminate. Furthermore, by transferring the adhesive layer B to the surface of the acrylic transparent protective film of the polarizing film laminate, the adhesive layer-attached polarizing film laminate of Comparative Example 9 was produced. The other conditions are the same as in Example 9.

[比較例10] 將比較例9中黏著劑層D轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,除此之外以相同方式製作出比較例10之附黏著劑層之偏光薄膜積層體。[Comparative Example 10] The adhesive layer D of Comparative Example 9 was transferred to the surface of the acrylic transparent protective film of the polarizing film laminate, and the adhesive layer-attached polarizing film laminate of Comparative Example 10 was produced in the same manner.

[比較例11] 將比較例6中黏著劑層E轉印至偏光薄膜積層體之丙烯酸系透明保護薄膜的面,除此之外以相同方式製作出比較例11之附黏著劑層之偏光薄膜積層體。[Comparative Example 11] The adhesive layer E of Comparative Example 6 was transferred to the surface of the acrylic transparent protective film of the polarizing film laminate, and the adhesive layer-attached polarizing film laminate of Comparative Example 11 was produced in the same manner.

4-1.可靠性試驗 使用實施例及比較例中所得偏光薄膜積層體12,依圖4所示於偏光薄膜積層體12之兩面分別透過黏著劑11、13積層玻璃板(松浪硝子製載玻片,型號:S2000423,規格:水緣磨 65×165mm,厚度1.3mm),並將所得者作為試樣。4-1. Reliability test Using the polarizing film laminate 12 obtained in the Examples and Comparative Examples, as shown in Fig. 4, the adhesive 11, 13 laminated glass plates (glass slides made by Songnang Glass, model: S2000423, specifications) were penetrated on both sides of the polarizing film laminate 12, respectively. : Water-edge mill 65×165mm, thickness 1.3mm), and use the obtained as a sample.

作為黏著劑,係於偏光薄膜積層體中未設置黏著劑層A~D之面使用厚度200μm之CS9868US(日東電工公司製)。As the adhesive, CS9868US (manufactured by Nitto Denko Corporation) with a thickness of 200 μm was used on the side where the adhesive layers A to D were not provided in the polarizing film laminate.

將該試樣95℃下放置250小時(95℃/250H)後評估其褪色及加熱紅變,並在95℃下放置500小時(95℃/500H)後評估多烯化。The sample was placed at 95°C for 250 hours (95°C/250H) to evaluate its fading and heating red change, and after standing at 95°C for 500 hours (95°C/500H), the polyethylenization was evaluated.

4-2.評估基準 將多烯化、加熱紅變及褪色之評估基準記於下述。4-2. Evaluation criteria The evaluation criteria for polyolefination, heating red change, and discoloration are described below.

<多烯化> 在95℃/500H之加熱試驗前後測定試料的單體透射率,並以下式求出單體透射率的變化量ΔTs。 (式)  ΔTs=Ts500 -Ts0 此處,Ts0 係試料加熱前之單體透射率,Ts500 係95℃/500H加熱後之單體透射率。 將變化量ΔTs為負值者評估為試料之「多烯化(單體透射率降低)」。換言之,在95℃/500小時之加熱後的單體透射率與加熱前的單體透射率相同或較其更大時,評估為無多烯化之問題。 單體透射率係針對上述試料使用分光光度計(村上色彩技術研究所(股)製 製品名「DOT-3」)進行測定。另,單體透射率可依循JlS Z 8701而求得。<Polyolefinization> The monomer transmittance of the sample was measured before and after the heating test at 95°C/500H, and the monomer transmittance change ΔTs was obtained by the following formula. (Formula) ΔTs =Ts 500- Ts 0 Here, Ts 0 is the transmittance of the monomer before heating the sample, and Ts 500 is the transmittance of the monomer after heating at 95°C/500H. If the change ΔTs is a negative value, the sample is evaluated as "polyolefination (decrease in monomer transmittance)". In other words, when the transmittance of the monomer after heating at 95° C./500 hours is the same as or greater than the transmittance of the monomer before heating, it is estimated that there is no problem of polyalkylene. The monomer transmittance was measured with a spectrophotometer (product name "DOT-3" manufactured by Murakami Color Institute of Technology Co., Ltd.) for the above-mentioned sample. In addition, the transmittance of the monomer can be obtained according to JlS Z 8701.

<褪色、加熱紅變> 在95℃/250H之加熱試驗前後,將試料配置成正交偏光並利用上述分光光度計分別測定波長410nm及波長700nm之正交透射率(%),而分別求得變化量ΔHs410 及ΔHs700 。 將滿足以下全部2個條件者評估為試料之「褪色」。 ・變化量ΔHs410 為1%以上 ・變化量ΔHs700 為5%以上 換言之,經95℃/500小時之加熱處理,在波長410nm下之正交透射率的變化量小於1%、且在波長700nm下之正交透射率的變化量小於5%時,評估為無褪色問題。 且,將滿足以下條件者評估為試料之「加熱紅變」。 ・變化量ΔHs410 小於1% ・變化量ΔHs700 為5%以上 換言之,經95℃/500小時之加熱處理,在波長410nm下之正交透射率的變化量在1%以上、且在波長700nm下之正交透射率的變化量小於5%時,評估為無加熱紅變問題。<Fading, heating red change> Before and after the heating test at 95℃/250H, arrange the sample into cross-polarized light and use the above-mentioned spectrophotometer to measure the cross-transmittance (%) of wavelength 410nm and wavelength 700nm respectively, and obtain them separately The amount of change ΔHs 410 and ΔHs 700 . Those who meet all of the following two conditions are evaluated as "fading" of the sample.・The amount of change ΔHs 410 is more than 1%. The amount of change ΔHs 700 is more than 5%. In other words, after heating at 95°C/500 hours, the change in orthogonal transmittance at a wavelength of 410nm is less than 1%, and at a wavelength of 700nm When the change of the cross-transmittance below is less than 5%, it is estimated that there is no fading problem. In addition, the one that satisfies the following conditions is evaluated as the "heating red change" of the sample.・The amount of change ΔHs 410 is less than 1%. The amount of change ΔHs 700 is more than 5%. In other words, after heating at 95°C/500 hours, the change in orthogonal transmittance at a wavelength of 410nm is above 1% and at a wavelength of 700nm When the change in cross-transmittance below is less than 5%, it is estimated that there is no problem of heating red change.

<黏著耐久性> 將附黏著劑層之偏光薄膜積層體裁切成長420mm×寬320mm後,使用貼合機貼附於厚度0.7mm之無鹼玻璃板的兩面。接著,在50℃、5atm下進行15分鐘高壓釜處理,使上述試樣完全密著於無鹼玻璃板。對施行過所述處理之試樣在95℃下施行500小時處理(加熱試驗)後,依下述基準以肉眼評估發泡、剝落及浮凸之狀態。 「◎」:無發泡、剝落、浮凸等完全無外觀上的變化 「〇」:雖然極少而於端部有些許剝落或發泡,但實際使用上無問題 「△」:端部有剝落或發泡,但只要不作特別用途,實際使用上無問題 「×」:端部有顯著剝落、或有發泡,實際使用上有問題<Adhesion durability> The polarizing film laminate with the adhesive layer was cut into a length of 420mm×320mm in width, and then attached to both sides of an alkali-free glass plate with a thickness of 0.7mm using a laminator. Next, autoclave treatment was performed at 50°C and 5 atm for 15 minutes to completely adhere the above-mentioned sample to the alkali-free glass plate. After the sample subjected to the above treatment was treated at 95°C for 500 hours (heating test), the state of foaming, peeling and embossing was evaluated visually according to the following criteria. "◎": No foaming, peeling, embossing, etc., no appearance changes "〇": Although there is very little peeling or foaming at the end, there is no problem in actual use "△": There is peeling or foaming at the end, but as long as it is not used for special purposes, there is no problem in actual use "×": There is significant peeling or foaming at the end, which is problematic in actual use

<重工性> 將實施例及比較例中所得附黏著劑層之偏光薄膜積層體裁切成長200mm×寬100mm做成試樣。將該試樣用貼合機貼附於厚度0.7mm之無鹼玻璃(商品名:EG-XG,康寧公司製)上。接著,於50℃、0.5MPa下進行15分鐘高壓釜處理,使上述試樣完全密著。針對該試樣,用人手從無鹼玻璃剝除試樣,按下述基準評估重工性。重工性之評估係按上述程序製作3片,並重複3次來實施。 ◎:3片皆未產生殘膠或發生薄膜斷裂而可良好地剝離。 ○:3片中有一部分的薄膜斷裂,但再度剝離即可剝除。 △:3片薄膜皆斷裂,但再度剝離即可剝除。 ×:3片皆有產生殘膠、或不管剝離幾次,薄膜仍斷裂。<Heavy workability> The polarizing film laminate with the adhesive layer obtained in the Examples and Comparative Examples was cut to a length of 200 mm × a width of 100 mm to prepare samples. This sample was attached to alkali-free glass (trade name: EG-XG, manufactured by Corning Incorporated) with a thickness of 0.7 mm using a laminating machine. Next, autoclave treatment was performed at 50°C and 0.5 MPa for 15 minutes to completely adhere the above-mentioned sample. For this sample, the sample was peeled from the alkali-free glass by hand, and the reworkability was evaluated according to the following criteria. The evaluation of heavy workability is implemented by making 3 pieces according to the above procedure and repeating it 3 times. ⊚: No glue residue or film breakage occurred in all 3 sheets, and they could be peeled off well. ○: A part of the film was broken in 3 sheets, but it can be peeled off by peeling it off again. △: All three films are broken, but they can be peeled off when they are peeled off again. ×: Glue residue was generated in all 3 sheets, or the film was broken regardless of how many times it was peeled off.

將各實施例及比較例之評估結果列於以下表2。 [表2]

Figure 02_image005
The evaluation results of each Example and Comparative Example are listed in Table 2 below. [Table 2]
Figure 02_image005

5.評估結果整合 圖5係將實施例及比較例(比較例11除外)之結果繪製成x-y正交座標系的圖。x-軸(橫軸)表示偏光膜的碘濃度(wt.%),y-軸(縱軸)表示偏光薄膜積層體的水分量(g/m2 )。5. Integration of evaluation results FIG. 5 is a graph in which the results of Examples and Comparative Examples (except Comparative Example 11) are plotted in an xy orthogonal coordinate system. The x-axis (horizontal axis) represents the iodine concentration (wt.%) of the polarizing film, and the y-axis (vertical axis) represents the moisture content (g/m 2 ) of the polarizing film laminate.

(1)由繪圖結果及技術常識來看,大致上可說在碘濃度小且水分量過小時,易產生在高溫狀態下會發生的加熱紅變之問題;另一方面,在碘濃度大且水分量過大時,則易產生多烯化及褪色之問題。且,可說在碘濃度小且水分量過大時,易產生在高溫高濕狀態下會產生的褪色之問題,而此時,隨著碘濃度增加,會更容易產生多烯化之問題。尤其是在褪色與多烯化之間亦可見該等之間的過渡區域(比較例13、15)。 另一方面,可見在碘濃度及水分量被控制在預定之區域內時,可將加熱紅變、多烯化及褪色全部總括性解決。舉例而言,實施例之結果全部皆位在分隔線「α」即y=(1043-125x)/240的上側且位在分隔線「β」即y=(379-33x)/70的下側,該分隔線「α」係通過顯示具有最小水分量之實施例3的結果之作圖周邊、即碘濃度7.0wt.%及水分量0.7g/m2 之座標點(以下稱第1座標點)、與顯示具有最小碘濃度之實施例9的結果之作圖周邊、即碘濃度2.2wt.%及水分量3.2g/m2 之座標點(以下稱第2座標點),而分隔線「β」係通過顯示具有最大水分量之實施例8的結果之作圖周邊、即碘濃度3.0wt.%及水分量4.0g/m2 之座標點(以下稱第4座標點)、與顯示具有最大碘濃度之實施例2的結果之作圖周邊、即碘濃度10.0wt.%及水分量0.7g/m2 之座標點(以下稱第5座標點)。因此,可將該等分隔線「α」、「β」分隔出之區域視為顯示用以將加熱紅變、多烯化及褪色全部總括性解決時所需之要件的線。另外,該等分隔線「α」、「β」與偏光膜之膜厚無關,更進一步而言對於具有4~20μm左右之膜厚的所有偏光膜皆適用。 並且,使用黏著劑B(構成黏著劑聚合物之總單體成分中之酸成分量:0重量%)之比較例6中,雖觀察到加熱紅變但未發生多烯化之問題,相對於此,將黏著劑變更成黏著劑E(構成黏著劑之總單體成分中的酸成分之量:10重量%)之比較例11則有確認到多烯化。由此,吾等推測若以超出預定量來使用黏著劑聚合物的單體成分中包含酸成分者,會促進多烯化。(1) Judging from the drawing results and technical common sense, it can generally be said that when the iodine concentration is small and the water content is too small, the problem of heating red change that occurs at high temperatures is likely to occur; on the other hand, when the iodine concentration is large and When the moisture content is too large, the problems of polyolefination and fading are likely to occur. Moreover, it can be said that when the iodine concentration is small and the moisture content is too large, the problem of fading under high temperature and high humidity conditions is likely to occur. At this time, as the iodine concentration increases, the problem of polyolefination is more likely to occur. Especially between fading and polyolefination, the transition region between these areas can also be seen (Comparative Examples 13, 15). On the other hand, it can be seen that when the iodine concentration and moisture content are controlled within a predetermined area, the heating red change, polyolefinization and color fading can all be solved in a comprehensive manner. For example, the results of the examples are all located on the upper side of the dividing line "α" that is y=(1043-125x)/240 and on the lower side of the dividing line "β" that is y=(379-33x)/70 , The dividing line "α" is the coordinate point (hereinafter referred to as the first coordinate point) around the plot showing the result of Example 3 with the smallest moisture content, that is, the iodine concentration of 7.0wt.% and the moisture content of 0.7g/m 2 ), and the coordinates around the plot showing the results of Example 9 with the minimum iodine concentration, that is, the iodine concentration 2.2wt.% and the water content 3.2g/m 2 coordinate point (hereinafter referred to as the second coordinate point), and the dividing line " β” is the coordinate point (hereinafter referred to as the 4th coordinate point) of the results of Example 8 showing the maximum moisture content, that is, the iodine concentration of 3.0 wt.% and the moisture content of 4.0 g/m 2 (hereinafter referred to as the fourth coordinate point), and The maximum iodine concentration of the result of Example 2 is plotted around the coordinate point (hereinafter referred to as the fifth coordinate point) of the iodine concentration of 10.0 wt.% and the moisture content of 0.7 g/m 2. Therefore, the area separated by the dividing lines "α" and "β" can be regarded as a line showing the necessary requirements for comprehensively solving the heating red change, polyolefinization, and color fading. In addition, the separation lines "α" and "β" have nothing to do with the film thickness of the polarizing film, and furthermore, they are applicable to all polarizing films having a film thickness of about 4-20 μm. In addition, in Comparative Example 6 using adhesive B (the amount of acid in the total monomer components constituting the adhesive polymer: 0% by weight), although the heating red change was observed, the problem of polyalkenization did not occur, compared to Therefore, in Comparative Example 11 in which the adhesive was changed to the adhesive E (the amount of acid components in the total monomer components constituting the adhesive: 10% by weight), polyethylenization was confirmed. Therefore, we speculate that if an acid component is used in the monomer component of the adhesive polymer in excess of a predetermined amount, polyolefinization will be promoted.

(2)又,由繪圖結果及技術常識可知,尤其是具有4~20μm左右之膜厚的所有偏光膜,在碘濃度與偏光薄膜積層體之水分量包含在a至e所包圍之區域內時,即可將「多烯化」、「褪色」及「加熱紅變」全部總括性解決,而該區域更詳細而言為以下線段包圍之區域:連結碘濃度7.0wt.%及水分量0.7g/m2 之第1座標點(圖中之「a」)與碘濃度2.2wt.%及水分量3.2g/m2 之第2座標點(圖中之「b」)的第1線段、連結第2座標點「b」與碘濃度2.2wt.%及水分量4.0g/m2 之第3座標點(圖中之「c」)的第2線段、連結第3座標點「c」與碘濃度3.0wt.%及水分量4.0g/m2 之第4座標點(圖中之「d」)的第3線段、連結第4座標點「d」與碘濃度10.0wt.%及水分量0.7g/m2 之第5座標點(圖中之「e」)的第4線段、及連結第1座標點「a」與第5座標點「e」的第5線段。(2) Also, it can be known from the drawing results and technical common sense that especially all polarizing films with a film thickness of about 4-20μm, when the iodine concentration and the moisture content of the polarizing film laminate are contained in the area enclosed by a to e , You can solve all of "polyalkenization", "fading" and "heating red change". In more detail, this area is the area surrounded by the following line segment: connecting the iodine concentration of 7.0wt.% and the moisture content of 0.7g /m 2 The first coordinate point ("a" in the figure) and the first line segment of the second coordinate point ("b" in the figure) with an iodine concentration of 2.2wt.% and a moisture content of 3.2g/m 2 the second coordinate point "b" with iodine concentration 2.2wt.% and the amount of water 4.0g / m 2 of a third coordinate point ( "c" in the FIG.) of the second line segment connecting the third point coordinate "c" with iodine concentration of 3.0wt.% and the amount of water 4.0g / m 2 of a fourth coordinate point ( "d" of the figure) the third line segment connecting the fourth point coordinate "d" with iodine concentration 10.0wt.% and water content 0.7 The fourth line segment of the fifth coordinate point ("e" in the figure) of g/m 2 and the fifth line segment connecting the first coordinate point "a" and the fifth coordinate point "e".

(3)同樣可知,尤其是具有11~20μm左右之膜厚的偏光膜,在碘濃度與偏光薄膜積層體之水分量包含在f、b、c、d、g所包圍之區域內時,即可將「多烯化」、「褪色」及「加熱紅變」全部總括性解決,而該區域更詳細而言係以下線段包圍之區域:連結碘濃度4.5wt.%及水分量2.0g/m2 之第6座標點(圖中之「f」)與第2座標點「b」的第6線段、連結第2座標點「b」與第3座標點「c」的第2線段、連結第3座標點「c」與第4座標點「d」的第3線段、連結第4座標點「d」與碘濃度4.5wt.%及水分量3.3g/m2 之第7座標點(圖中之「g」)的第7線段、及連結第6座標點「f」與第7座標點「g」的第8線段。 吾等推測尤其是在第6座標點「f」為碘濃度4.0wt.%及水分量2.3g/m2 之座標點「f-1」,而第7座標點「g」為碘濃度4.0wt.%及水分量3.5g/m2 之座標點「g-1」時,特別能得到理想結果。 又,推測具有11~20μm左右之膜厚的偏光膜,在碘濃度與偏光薄膜積層體之水分量包含在f、b、c、d、g所包圍且由連接h與i之線段分隔出之區域內時,即可在「多烯化」、「褪色」及「加熱紅變」全部方面獲得更良好之結果,而該區域更詳細而言係以下線段包圍之區域:連結碘濃度3.3wt.%及水分量2.6g/m2 之第8座標點(圖中之「h」)與第2座標點「b」的第9線段、連結第2座標點「b」與第3座標點「c」的第2線段、連結第3座標點「c」與第4座標點「d」的第3線段、連結第4座標點「d」與第7座標點「g」的第7線段、連結第6座標點「f」與第7座標點「g」的第8線段、及連結第8座標點「h」與碘濃度6.0wt.%及水分量2.6g/m2 之第9座標點(圖中之「i」)的第10線段。(3) It can also be seen that, especially for a polarizing film with a film thickness of about 11 to 20 μm, when the iodine concentration and the moisture content of the polarizing film laminate are contained in the area surrounded by f, b, c, d, and g, that is "Polyolefinization", "fading" and "heating red change" can be solved in a comprehensive way. In more detail, this area is the area surrounded by the following line segment: connecting the iodine concentration of 4.5wt.% and the water content of 2.0g/m 2nd coordinate point 6 ("f" in the figure) and the 6th line segment of the 2nd coordinate point "b", the 2nd line segment connecting the 2nd coordinate point "b" and the 3rd coordinate point "c", and the second line segment connecting the second coordinate point "b" and the third coordinate point "c". The 3rd line segment between the 3 coordinate point "c" and the 4th coordinate point "d", the 7th coordinate point connecting the 4th coordinate point "d" with the iodine concentration of 4.5wt.% and the moisture content of 3.3g/m 2 (in the figure The 7th line segment of "g") and the 8th line segment connecting the 6th coordinate point "f" and the 7th coordinate point "g". We speculate that especially at the sixth coordinate point "f" is the iodine concentration 4.0wt.% and the moisture content is 2.3g/m 2 the coordinate point "f-1", and the seventh coordinate point "g" is the iodine concentration 4.0wt. When the coordinate point "g-1" of .% and the moisture content of 3.5g/m 2 is used, ideal results can be obtained in particular. In addition, it is estimated that a polarizing film with a film thickness of about 11 to 20 μm is surrounded by f, b, c, d, and g in the iodine concentration and the moisture content of the polarizing film laminate and separated by a line segment connecting h and i When it is in the area, better results can be obtained in all aspects of "polyalkenization", "fading" and "heating red change". In more detail, this area is the area surrounded by the following line segment: the connected iodine concentration is 3.3wt. % And moisture content of 2.6g/m 2 of the 8th coordinate point ("h" in the figure) and the 9th line segment of the second coordinate point "b", connecting the second coordinate point "b" and the third coordinate point "c" The second line segment connecting the third coordinate point “c” and the fourth coordinate point “d”, the seventh line segment connecting the fourth coordinate point “d” and the seventh coordinate point “g”, and the seventh line segment connecting the fourth coordinate point “d” and the seventh coordinate point “g”. The 8th line segment between the 6th coordinate point "f" and the 7th coordinate point "g", and the 9th coordinate point connecting the 8th coordinate point "h" with the iodine concentration of 6.0wt.% and the moisture content of 2.6g/m 2 (Figure The 10th line segment of "i").

(4)並且可知尤其是具有4~11μm左右之膜厚、較佳為4~7μm之膜厚、更佳為4.5~6μm之膜厚的偏光膜,在碘濃度與偏光薄膜積層體之水分量包含在a、h、i、e所包圍之區域內時,即可將「多烯化」、「褪色」及「加熱紅變」全部總括性解決,該區域更詳細而言係以下線段包圍之區域:連結第1座標點「a」與第8座標點「h」的第11線段、連結第8座標點「h」與第9座標點「i」的第10線段、連結第9座標點「i」與第5座標點「e」的第12線段、及連結第1座標點「a」與第5座標點「e」的第5線段。 推測尤其是在第8座標點「h」為第6座標點「f」,而第9座標點「i」為碘濃度7.2wt.%及水分量2.0g/m2 之第10座標點(圖中之「j」)時,特別能得到理想結果。 又,推測具有4~11μm左右之膜厚、較佳為4~7μm之膜厚、更佳為4.5~6μm之膜厚的偏光膜,在碘濃度與偏光薄膜積層體之水分量包含在a、k、i、e所包圍之區域內時,即可在「多烯化」、「褪色」及「加熱紅變」全部方面獲得更良好之結果,該區域更詳細而言係以下線段包圍之區域:連結第1座標點「a」與碘濃度6.0wt.%及水分量1.2g/m2 之第11座標點(圖中之「k」)的第13線段、連結第11座標點「k」與第9座標點「i」的第14線段、連結第9座標點「i」與第5座標點「e」的第12線段、及連結第1座標點「a」與第5座標點「e」的第5線段。 推測尤其是在第11座標點「k」為碘濃度6.5wt.%及水分量1.0g/m2 之座標點(k-1),而第9座標點「i」為碘濃度6.5wt.%及水分量2.3g/m2 之座標點(i-1)時,特別能得到更理想結果。(4) It can be seen that, in particular, a polarizing film having a film thickness of about 4 to 11 μm, preferably a film thickness of 4 to 7 μm, and more preferably a film thickness of 4.5 to 6 μm, in terms of the iodine concentration and the moisture content of the polarizing film laminate When it is included in the area surrounded by a, h, i, and e, all "polyolefinization", "fading" and "heating red change" can be solved in a comprehensive manner. In more detail, this area is surrounded by the following line segment Area: The 11th line segment connecting the 1st coordinate point "a" and the 8th coordinate point "h", the 10th line segment connecting the 8th coordinate point "h" and the 9th coordinate point "i", and the 9th coordinate point " The 12th line segment between i" and the 5th coordinate point "e", and the 5th line segment connecting the first coordinate point "a" and the 5th coordinate point "e". In particular, it is speculated that the 8th coordinate point "h" is the 6th coordinate point "f", and the 9th coordinate point "i" is the 10th coordinate point with an iodine concentration of 7.2wt.% and a moisture content of 2.0g/m 2 (Figure In the case of "j"), ideal results can be obtained in particular. In addition, it is estimated that a polarizing film having a film thickness of about 4 to 11 μm, preferably a film thickness of 4 to 7 μm, and more preferably a film thickness of 4.5 to 6 μm, is contained in a, In the area enclosed by k, i, and e, better results can be obtained in all aspects of "polyolefinization", "fading" and "heating red change". In more detail, this area is the area surrounded by the following line segment : The 13th line segment connecting the first coordinate point "a" with the iodine concentration 6.0wt.% and the moisture content of 1.2g/m 2 ("k" in the figure), and the 11th coordinate point "k" The 14th line segment with the 9th coordinate point "i", the 12th line segment connecting the 9th coordinate point "i" and the 5th coordinate point "e", and the first coordinate point "a" and the 5th coordinate point "e""The 5th line segment. Especially at the 11 presumed coordinate point "k" is an iodine concentration of 6.5wt.% And the amount of water 1.0g / m 2 of the coordinate point (k-1), and the ninth coordinate point "i" is an iodine concentration of 6.5wt.% And when the water content is 2.3g/m 2 coordinate point (i-1), more ideal results can be obtained.

1:光學性顯示面板 2:PVA層 6:非晶性PET基材 7:包含PVA層之積層體 8:延伸積層體 8':延伸積層體之捲材 9:著色積層體 10:光學性顯示單元 10a:光學性顯示單元之一面 10b:光學性顯示單元之另一面 11:透明接著劑 12:偏光薄膜積層體 13:透明接著劑 14:透明覆蓋板 16:透明接著劑 17:另一偏光薄膜積層體 18:光源(背光件) 20:積層體製作裝置 21:塗敷機構 22:乾燥機構 23:表面改質處理裝置 30:空中輔助延伸處理裝置 31:延伸機構 32:捲取裝置 33:烘箱 40:染色裝置 41:染色液 42:染色浴 43:釋出裝置 50:硼酸水中處理裝置 51:硼酸水溶液 52:硼酸浴 53:延伸機構 60:光學薄膜積層體 80:洗淨裝置 81:洗淨液 90:乾燥裝置 91:捲取裝置 120:偏光膜 121:偏光膜保護薄膜 122:偏光膜保護薄膜 (A):積層體製作處理 (B):空中輔助延伸處理 (C):染色處理 (D):硼酸水中延伸處理 (G):洗淨處理 (H):乾燥處理1: Optical display panel 2: PVA layer 6: Amorphous PET substrate 7: Laminated body including PVA layer 8: Extended layered body 8': Coil of extended laminate 9: Colored layered body 10: Optical display unit 10a: One side of the optical display unit 10b: The other side of the optical display unit 11: Transparent adhesive 12: Polarized film laminate 13: Transparent adhesive 14: Transparent cover plate 16: Transparent adhesive 17: Another polarizing film laminate 18: Light source (backlight part) 20: Laminated body making device 21: Coating mechanism 22: Drying mechanism 23: Surface modification treatment device 30: Aerial auxiliary extension processing device 31: Extension mechanism 32: Coiling device 33: Oven 40: Dyeing device 41: staining solution 42: dye bath 43: release device 50: Boric acid water treatment device 51: Boric acid aqueous solution 52: Boric acid bath 53: extension mechanism 60: Optical film laminate 80: Washing device 81: washing liquid 90: Drying device 91: Coiling device 120: Polarizing film 121: Polarizing film protective film 122: Polarizing film protective film (A): Laminated body production processing (B): Aerial auxiliary extension processing (C): Dyeing treatment (D): Boric acid water extension treatment (G): Washing treatment (H): Dry treatment

圖1係顯示光學性顯示面板之層構成的示意圖。 圖2係說明偏光膜之製造方法一例的圖。 圖3係顯示用以求得偏光膜之碘濃度的檢量曲線的圖。 圖4係顯示用於可靠性試驗之結構的圖。 圖5係繪製實施例及比較例之結果的圖。FIG. 1 is a schematic diagram showing the layer structure of an optical display panel. Fig. 2 is a diagram illustrating an example of a method of manufacturing a polarizing film. Fig. 3 is a diagram showing a calibration curve used to obtain the iodine concentration of the polarizing film. Figure 4 is a diagram showing the structure used for reliability testing. Fig. 5 is a graph plotting the results of Examples and Comparative Examples.

Claims (16)

一種偏光薄膜積層體,係附黏著劑層之偏光薄膜積層體,其具備包含聚乙烯醇系樹脂之偏光膜、與黏著劑層,該黏著劑層係直接或隔著光學上呈透明之偏光膜保護薄膜設置在前述偏光膜之至少一面; 該偏光薄膜積層體之特徵在於: 前述黏著劑層包含黏著劑聚合物,該黏著劑聚合物中酸成分經共聚合,且構成該黏著劑聚合物之總單體成分中之酸成分的量在5重量%以下; 在分別令x-軸為前述偏光膜之碘濃度(wt.%)、y-軸為前述偏光薄膜積層體之水分量(g/m2 )的x-y正交座標系中,具有包含在以下線段所包圍之區域內的碘濃度及水分量: 連結碘濃度7.0wt.%及水分量0.7g/m2 之第1座標點與碘濃度2.2wt.%及水分量3.2g/m2 之第2座標點的第1線段、 連結前述第2座標點與碘濃度2.2wt.%及水分量4.0g/m2 之第3座標點的第2線段、 連結前述第3座標點與碘濃度3.0wt.%及水分量4.0g/m2 之第4座標點的第3線段、 連結前述第4座標點與碘濃度10.0wt.%及水分量0.7g/m2 之第5座標點的第4線段、及 連結前述第1座標點與前述第5座標點的第5線段。A polarizing film laminate, a polarizing film laminate with an adhesive layer, comprising a polarizing film containing a polyvinyl alcohol resin, and an adhesive layer, the adhesive layer being directly or via an optically transparent polarizing film The protective film is provided on at least one side of the polarizing film; the polarizing film laminate is characterized in that: the adhesive layer includes an adhesive polymer, the acid component of the adhesive polymer is copolymerized, and constitutes the adhesive polymer The amount of the acid component in the total monomer component is less than 5% by weight; when the x-axis is the iodine concentration (wt.%) of the aforementioned polarizing film, and the y-axis is the moisture content of the aforementioned polarizing film laminate (g/ The xy orthogonal coordinate system of m 2 ) has the iodine concentration and water content included in the area surrounded by the following line segment: The first coordinate point connecting the iodine concentration 7.0wt.% and the water content 0.7g/m 2 and iodine The first line segment of the second coordinate point with a concentration of 2.2wt.% and a moisture content of 3.2g/m 2 connecting the aforementioned second coordinate point with the third coordinate point with an iodine concentration of 2.2wt.% and a moisture content of 4.0g/m 2 second line segment, the third line segment connecting the third point and the coordinate iodine concentration 3.0wt.% and the amount of water 4.0g / m 2 of a fourth coordinate point connecting point and the fourth coordinate iodine concentration 10.0wt.% water and The fourth line segment of the fifth coordinate point with an amount of 0.7g/m 2 and the fifth line segment connecting the aforementioned first coordinate point and the aforementioned fifth coordinate point. 如請求項1之偏光薄膜積層體,其中前述黏著劑聚合物的多分散性指數(重量平均分子量(Mw)/數量平均分子量(Mn))為3.0以下。The polarizing film laminate of claim 1, wherein the polydispersity index (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the aforementioned adhesive polymer is 3.0 or less. 如請求項1或2之偏光薄膜積層體,其中前述偏光膜之膜厚為4~20μm。The polarizing film laminate of claim 1 or 2, wherein the film thickness of the aforementioned polarizing film is 4-20 μm. 一種偏光薄膜積層體,係附黏著劑層之偏光薄膜積層體,其具備包含聚乙烯醇系樹脂之偏光膜、與黏著劑層,該黏著劑層係直接或隔著光學上呈透明之偏光膜保護薄膜設置在前述偏光膜之至少一面; 該偏光薄膜積層體之特徵在於: 前述黏著劑層包含黏著劑聚合物,該黏著劑聚合物中酸成分經共聚合,且構成該黏著劑聚合物之總單體成分中之酸成分的量在5重量%以下; 在分別令x-軸為前述偏光膜之碘濃度(wt.%)、y-軸為前述偏光薄膜積層體之水分量(g/m2 )的x-y正交座標系中,具有包含在以下線段所包圍之區域內的碘濃度及水分量: 連結碘濃度4.5wt.%及水分量2.0g/m2 之第6座標點與碘濃度2.2wt.%及水分量3.2g/m2 之第2座標點的第6線段、 連結前述第2座標點與碘濃度2.2wt.%及水分量4.0g/m2 之第3座標點的第2線段、 連結前述第3座標點與碘濃度3.0wt.%及水分量4.0g/m2 之第4座標點的第3線段、 連結前述第4座標點與碘濃度4.5wt.%及水分量3.3g/m2 之第7座標點的第7線段、及 連結前述第6座標點與前述第7座標點的第8線段。A polarizing film laminate, a polarizing film laminate with an adhesive layer, comprising a polarizing film containing a polyvinyl alcohol resin, and an adhesive layer, the adhesive layer being directly or via an optically transparent polarizing film The protective film is provided on at least one side of the polarizing film; the polarizing film laminate is characterized in that: the adhesive layer includes an adhesive polymer, the acid component of the adhesive polymer is copolymerized, and constitutes the adhesive polymer The amount of the acid component in the total monomer component is less than 5% by weight; when the x-axis is the iodine concentration (wt.%) of the aforementioned polarizing film, and the y-axis is the moisture content of the aforementioned polarizing film laminate (g/ The xy orthogonal coordinate system of m 2 ) has the iodine concentration and water content contained in the area enclosed by the following line segment: The sixth coordinate point and iodine connecting the iodine concentration of 4.5wt.% and the water content of 2.0g/m 2 The 6th line segment of the second coordinate point with a concentration of 2.2wt.% and a moisture content of 3.2g/m 2 connecting the aforementioned second coordinate point with the third coordinate point with an iodine concentration of 2.2wt.% and a moisture content of 4.0g/m 2 second line segment, the third line segment connecting the third point and the coordinate iodine concentration 3.0wt.% and the amount of water 4.0g / m 2 of a fourth coordinate point connecting point and the fourth coordinate iodine concentration 4.5wt.% water and The seventh line segment of the seventh coordinate point with an amount of 3.3 g/m 2 and the eighth line segment connecting the aforementioned sixth coordinate point and the aforementioned seventh coordinate point. 如請求項4之偏光薄膜積層體,其中前述第6座標點為碘濃度4.0wt.%及水分量2.3g/m2 之座標點,而前述第7座標點為碘濃度4.0wt.%及水分量3.5g/m2 之座標點。The requested item polarizing film of the laminate 4, wherein the sixth coordinate point iodine concentration of 4.0wt.% And the amount of water 2.3g / m 2 of the coordinate point, and the coordinate point 7 iodine concentration of 4.0wt.% Water and Coordinate point of 3.5g/m 2. 如請求項4或5之偏光薄膜積層體,其中前述偏光膜之膜厚為11~20μm。The polarizing film laminate of claim 4 or 5, wherein the film thickness of the aforementioned polarizing film is 11-20 μm. 一種偏光薄膜積層體,係附黏著劑層之偏光薄膜積層體,其具備包含聚乙烯醇系樹脂之偏光膜、與黏著劑層,該黏著劑層係直接或隔著光學上透明之偏光膜保護薄膜設置在前述偏光膜之至少一面; 該偏光薄膜積層體之特徵在於: 前述黏著劑層包含黏著劑聚合物,該黏著劑聚合物中酸成分經共聚合,且構成該黏著劑聚合物之總單體成分中之酸成分的量在5重量%以下; 在分別令x-軸為前述偏光膜之碘濃度(wt.%)、y-軸為前述偏光薄膜積層體之水分量(g/m2 )的x-y正交座標系中,具有包含在以下線段所包圍之區域內的碘濃度及水分量: 連結碘濃度7.0wt.%及水分量0.7g/m2 之第1座標點與碘濃度3.3wt.%及水分量2.6g/m2 之第8座標點的第11線段、 連結前述第8座標點與碘濃度6.0wt.%及水分量2.6g/m2 之第9座標點的第10線段、 連結前述第9座標點與碘濃度10.0wt.%及水分量0.7g/m2 之第5座標點的第12線段、及 連結前述第1座標點與前述第5座標點的第5線段。A polarizing film laminate, a polarizing film laminate with an adhesive layer, comprising a polarizing film containing a polyvinyl alcohol resin, and an adhesive layer, the adhesive layer being protected directly or via an optically transparent polarizing film The film is arranged on at least one side of the polarizing film; the polarizing film laminate is characterized in that: the adhesive layer includes an adhesive polymer, and the acid component in the adhesive polymer is copolymerized and constitutes the total of the adhesive polymer The amount of the acid component in the monomer component is less than 5% by weight; Let the x-axis be the iodine concentration of the aforementioned polarizing film (wt.%) and the y-axis be the moisture content of the aforementioned polarizing film laminate (g/m 2 ) The xy orthogonal coordinate system has the iodine concentration and water content included in the area enclosed by the following line segment: The first coordinate point and the iodine concentration connecting the iodine concentration of 7.0wt.% and the water content of 0.7g/m 2 3.3wt.% and the amount of water 2.6g / m of the coordinate point 82 of segment 11, connecting said first coordinate point and the eighth iodine concentration 6.0wt.% and the amount of water 2.6g / m 2 of the ninth coordinate point the first line segment 510, connecting the coordinate point and the ninth iodine concentration 10.0wt.%, and water content 0.7g / m of the coordinate point 52 of segment 12, and connecting said first coordinate point and the coordinate point 5 Line segment. 如請求項7之偏光薄膜積層體,其中前述第8座標點為碘濃度4.5wt.%及水分量2.0g/m2 之第6座標點,而前述第9座標點為碘濃度7.2wt.%及水分量2.0g/m2 之第10座標點。For example, the polarizing film laminate of claim 7, wherein the aforementioned 8th coordinate point is the 6th coordinate point with an iodine concentration of 4.5wt.% and a moisture content of 2.0g/m 2 , and the aforementioned 9th coordinate point is an iodine concentration of 7.2wt.% And the 10th coordinate point with a water content of 2.0g/m 2. 如請求項7或8之偏光薄膜積層體,其中前述偏光膜之膜厚為4~11μm。The polarizing film laminate of claim 7 or 8, wherein the film thickness of the aforementioned polarizing film is 4-11 μm. 如請求項1至9中任一項之偏光薄膜積層體,其中前述偏光膜含有鋅。The polarizing film laminate according to any one of claims 1 to 9, wherein the aforementioned polarizing film contains zinc. 如請求項1至10中任一項之偏光薄膜積層體,由如請求項1至10中任一項之偏光薄膜積層體與透過黏著劑積層於該偏光薄膜積層體之兩面的玻璃板所構成之試料,在95℃/500小時之加熱後的單體透射率係與加熱前的單體透射率相同或較其更大。The polarizing film laminate of any one of claims 1 to 10 is composed of the polarizing film laminate of any of claims 1 to 10 and a glass plate laminated on both sides of the polarizing film laminate through an adhesive For the sample, the transmittance of the monomer after heating at 95°C/500 hours is the same as or greater than the transmittance of the monomer before heating. 如請求項1至11中任一項之偏光薄膜積層體,由如請求項1至11中任一項之偏光薄膜積層體與透過黏著劑積層於該偏光薄膜積層體之兩面的玻璃板所構成之試料,進行95℃/500小時之加熱處理後,在波長410nm下的正交透射率之變化量小於1%,且在波長700nm下的正交透射率之變化量小於5%。The polarizing film laminate of any one of claims 1 to 11 is composed of the polarizing film laminate of any of claims 1 to 11 and a glass plate laminated on both sides of the polarizing film laminate through an adhesive After the sample is heated at 95°C/500 hours, the change in orthogonal transmittance at a wavelength of 410nm is less than 1%, and the change in orthogonal transmittance at a wavelength of 700nm is less than 5%. 如請求項1至11中任一項之偏光薄膜積層體,由如請求項1至11中任一項之偏光薄膜積層體與透過黏著劑積層於該偏光薄膜積層體之兩面的玻璃板所構成之試料,進行95℃/500小時之加熱處理後,在波長410nm下的正交透射率之變化量為1%以上,且在波長700nm下的正交透射率之變化量小於5%。The polarizing film laminate of any one of claims 1 to 11 is composed of the polarizing film laminate of any of claims 1 to 11 and a glass plate laminated on both sides of the polarizing film laminate through an adhesive After the sample is heated at 95℃/500 hours, the change in orthogonal transmittance at a wavelength of 410nm is more than 1%, and the change in orthogonal transmittance at a wavelength of 700nm is less than 5%. 一種光學顯示面板,特徵在於: 其具備: 光學性顯示單元; 如請求項1至13中任一項之偏光薄膜積層體,係直接或隔著其他光學薄膜接合於前述光學性顯示單元之一面;及 覆蓋板,係在光學上呈透明且於前述偏光薄膜積層體之與前述光學性顯示單元相反之側沿著前述偏光薄膜積層體配置;並且 前述光學性顯示單元、前述偏光薄膜積層體與前述透明覆蓋板係藉由透明接著層接著,且該透明接著層係以不使該等之間產生空隙之狀態充填於其中。An optical display panel, characterized in that: It has: Optical display unit; For example, the polarizing film laminate of any one of claims 1 to 13 is bonded to one side of the aforementioned optical display unit directly or via other optical films; and The cover plate is optically transparent and is arranged along the polarizing film laminate on the opposite side of the polarizing film laminate from the optical display unit; and The optical display unit, the polarizing film laminate, and the transparent cover plate are bonded by a transparent adhesive layer, and the transparent adhesive layer is filled in a state in which no gaps are generated between them. 如請求項14之光學顯示面板,其中前述透明覆蓋板具有電容型觸控感測器之機能。Such as the optical display panel of claim 14, wherein the aforementioned transparent cover plate has the function of a capacitive touch sensor. 如請求項15之光學顯示面板,其中於前述透明覆蓋板與前述偏光薄膜積層體之間設有成為電容型觸控感測器之構成要素的ITO層。The optical display panel of claim 15, wherein an ITO layer that becomes a component of a capacitive touch sensor is provided between the transparent cover plate and the polarizing film laminate.
TW109129209A 2019-08-28 2020-08-26 Polarizing film laminate with adhesive layer, and optical display panel using the polarizing film laminate with adhesive layer TWI858119B (en)

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