TWI764018B - Polarizing plate, manufacturing method thereof, and image display device - Google Patents

Polarizing plate, manufacturing method thereof, and image display device

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Publication number
TWI764018B
TWI764018B TW108125842A TW108125842A TWI764018B TW I764018 B TWI764018 B TW I764018B TW 108125842 A TW108125842 A TW 108125842A TW 108125842 A TW108125842 A TW 108125842A TW I764018 B TWI764018 B TW I764018B
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adhesive
layer
film
easy
polarizing plate
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TW108125842A
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Chinese (zh)
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TW202012166A (en
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岡田康彰
徐菁璠
品川雅
道下空
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日商日東電工股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00788—Producing optical films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00865—Applying coatings; tinting; colouring
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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  • Physics & Mathematics (AREA)
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  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

偏光板係於聚乙烯醇系偏光件之一主面具備易接著薄膜，該易接著薄膜係透過接著劑層而貼合於前述一主面。易接著薄膜係於透明薄膜基材之表面具備易接著層，且易接著層係與偏光件貼合。接著劑層係活性能量線硬化型接著劑之硬化層。在易接著層與接著劑層之界面宜存在一接著界面層，該接著界面層係易接著層之樹脂成分與接著劑層之樹脂成分相溶而存在。 The polarizing plate is provided with an easily bonding film on one main surface of the polyvinyl alcohol-based polarizer, and the easily bonding film is bonded to the above-mentioned one main surface through the adhesive layer. The easy-adhesive film is provided with an easy-adhesive layer on the surface of the transparent film substrate, and the easy-adhesive layer is attached to the polarizer. The adhesive layer is a hardened layer of an active energy ray hardening adhesive. An adhesive interface layer is preferably present at the interface between the easily adhesive layer and the adhesive layer, and the adhesive interface layer exists because the resin component of the easily adhesive layer and the resin component of the adhesive layer are compatible.

Description

偏光板及其製造方法、以及影像顯示裝置 Polarizing plate, manufacturing method thereof, and image display device

本發明涉及一種於偏光件表面貼合有易接著薄膜之偏光板及其製造方法、以及具備該偏光板之影像顯示裝置。 The present invention relates to a polarizing plate with an easily adhesive film attached to the surface of a polarizer, a manufacturing method thereof, and an image display device provided with the polarizing plate.

發明背景 Background of the Invention

現已廣泛使用液晶顯示裝置或有機EL顯示裝置作為行動機器、汽車導航裝置、個人電腦用監視器、電視機等各種影像顯示裝置。液晶顯示裝置基於其顯示原理，在液晶單元之視辨側表面配置有偏光板。在透射型液晶顯示裝置，則是在液晶單元兩面配置有偏光板。在有機EL顯示裝置為了防止外光被金屬電極(陰極)反射而看似鏡面，有時會於視辨側表面配置圓偏光板(典型上為偏光板與1/4波長板之積層體)。 Liquid crystal display devices and organic EL display devices have been widely used as various video display devices such as mobile devices, car navigation devices, monitors for personal computers, and televisions. Based on the display principle of the liquid crystal display device, a polarizing plate is arranged on the viewing side surface of the liquid crystal cell. In a transmissive liquid crystal display device, polarizers are arranged on both sides of the liquid crystal cell. In order to prevent external light from being reflected by the metal electrode (cathode) and appearing as a mirror surface, a circular polarizer (typically a laminate of a polarizer and a quarter-wave plate) is sometimes arranged on the viewing side surface of an organic EL display device.

偏光板一般會在偏光件之單面或兩面具備透明薄膜(偏光件保護薄膜)，其目的在於保護偏光件等。如今多廣泛使用使聚乙烯醇(PVA)系薄膜吸附有碘並藉由延伸等使分子進行配向者作為偏光件。 The polarizer generally has a transparent film (polarizer protective film) on one side or both sides of the polarizer to protect the polarizer and the like. Nowadays, a polyvinyl alcohol (PVA)-based film that adsorbs iodine and aligns molecules by stretching or the like is widely used as a polarizer.

貼合在偏光件表面的偏光件保護薄膜，基於與PVA系偏光件之接著性優異的觀點，多廣泛使用乙酸纖維素等纖維素系薄膜。透明保護薄膜也會使用由丙烯酸、 聚酯、聚碳酸酯、環狀聚烯烴等樹脂材料所構成之薄膜。比起纖維素系薄膜，由該等樹脂材料所構成之薄膜透濕較低，於偏光件表面貼合有低透濕樹脂薄膜之偏光板即使長時間放置在高濕環境下，光學特性之變化依舊很小，有耐久性優異之傾向。 As the polarizer protective film to be bonded on the surface of the polarizer, cellulose-based films such as cellulose acetate are widely used from the viewpoint of excellent adhesion to the PVA-based polarizer. Transparent protective films are also used with acrylic, Films made of polyester, polycarbonate, cyclic polyolefin and other resin materials. Compared with cellulose-based films, the films made of these resin materials have lower moisture permeability, and the polarizing plate with the low-moisture-permeable resin film attached to the surface of the polarizer will change its optical properties even if it is placed in a high-humidity environment for a long time. It is still small and tends to be excellent in durability.

另一方面，比起纖維素系薄膜，由丙烯酸、聚酯、聚碳酸酯、環狀聚烯烴等樹脂材料所構成之薄膜與PVA系偏光件之接著性有較低之傾向。所以，有文獻提議在作為偏光件保護薄膜使用之透明薄膜表面設置易接著層來提升與偏光件之接著性的方法。 On the other hand, films made of resin materials such as acrylic, polyester, polycarbonate, and cyclic polyolefin tend to have lower adhesion to PVA-based polarizers than cellulose-based films. Therefore, some documents propose a method of providing an easy-adhesion layer on the surface of a transparent film used as a polarizer protective film to improve the adhesion to the polarizer.

譬如，在專利文獻1中有記載，於丙烯酸系薄膜表面設有含有微粒子及黏結劑樹脂之易接著層的易接著薄膜與偏光件之接著性優異，而且可抑制將薄膜捲取成捲狀時之黏結。在專利文獻1之實施例中列出了用水系接著劑貼合易接著薄膜與偏光件之例，該易接著薄膜於丙烯酸系薄膜之表面具備含有1~7重量%之二氧化矽微粒子且平均厚度400nm(厚度範圍300~500nm)的胺甲酸乙酯易接著層。 For example, it is described in Patent Document 1 that an easily-bondable film having an easily-bonded layer containing fine particles and a binder resin on the surface of an acrylic film is excellent in adhesion to a polarizer, and it is possible to prevent the film from being wound into a roll. of bonding. The example of Patent Document 1 lists an example of laminating an easily-bondable film and a polarizer with a water-based adhesive. The easily-bonded film is provided on the surface of the acrylic film with silica particles containing 1 to 7% by weight and the average The urethane easy-bonding layer with a thickness of 400nm (thickness range of 300~500nm).

先前技術文獻 prior art literature 專利文獻 Patent Literature

專利文獻1：日本專利第5354733號 Patent Document 1: Japanese Patent No. 5354733

發明概要 Summary of Invention

在影像顯示裝置朝大型化或高亮度化進展之過程中，針對構成影像顯示裝置之偏光板亦發要求即使在嚴峻環境(譬如較高溫、高濕之條件)下，依舊不易在界面產生層間剝離，且光學特性之變化依舊小。伴隨而來的，是偏光件與偏光件保護薄膜之貼合現已逐漸使用可利用光照射或電子射線照射而硬化的活性光線硬化型接著劑。 In the process of increasing the size or brightness of image display devices, the polarizing plate constituting the image display device is also required to be less prone to interlayer peeling at the interface even under severe environments (such as high temperature and high humidity conditions). , and the change in optical properties is still small. Accompanying this, the bonding of the polarizer and the polarizer protective film is gradually using an active ray-curable adhesive which can be cured by light irradiation or electron beam irradiation.

本發明目的在於提供一種偏光件與偏光件保護薄膜之接著性優異、即使長時間曝露在高溫高濕環境下也不易產生層間剝離且切割加工性優異的偏光板。 An object of the present invention is to provide a polarizing plate which is excellent in adhesion between a polarizer and a polarizer protective film, does not easily cause interlayer peeling even if exposed to a high temperature and high humidity environment for a long time, and is excellent in cutting processability.

本發明涉及一種透過接著劑層貼合易接著薄膜與偏光件之偏光板及其製造方法。易接著薄膜係於透明薄膜基材之表面具備易接著層。易接著層含有黏結劑樹脂及平均一次粒徑為10~100nm之無機微粒子。易接著層之鹼成分含量宜為5~75ppm。易接著層之厚度宜為40~280nm。 The present invention relates to a polarizing plate for laminating an easily adhesive film and a polarizer through an adhesive layer and a manufacturing method thereof. The easy-adhesive film is provided with an easy-adhesive layer on the surface of the transparent film substrate. The easily bonding layer contains a binder resin and inorganic fine particles with an average primary particle size of 10-100 nm. The content of the alkali component in the easy-bonding layer is preferably 5-75 ppm. The thickness of the easy bonding layer is preferably 40-280 nm.

透明薄膜基材可使用丙烯酸系薄膜等。易接著層之黏結劑樹脂則可使用胺甲酸乙酯系樹脂等。易接著層中之無機微粒子含量宜為8~50重量%左右。易接著層之無機微粒子可埋設在透明薄膜基材中。 An acrylic film etc. can be used as a transparent film base material. As the adhesive resin of the easy-bonding layer, urethane resin or the like can be used. The content of the inorganic fine particles in the easily bonding layer is preferably about 8 to 50% by weight. The inorganic fine particles of the easily bonding layer can be embedded in the transparent film substrate.

於透明薄膜基材表面塗佈易接著組成物並加熱而形成易接著層。易接著組成物含有黏結劑樹脂或其前驅物質、平均一次粒徑為10~100nm之無機微粒子、鹼成分及溶劑。藉由易接著組成物含有鹼成分，可提升無機微粒子之分散性，獲得滑移性優異的易接著薄膜。而且， 鹼成分亦可作為促進黏結劑樹脂(前驅物)反應之觸媒起作用。若從利用加熱來促進鹼成分揮發的觀點來看，鹼成分之沸點宜為150℃以下。鹼成分可舉胺或氨等。 The easy-adhesive composition is coated on the surface of the transparent film substrate and heated to form an easy-adhesive layer. The easy-bond composition contains a binder resin or its precursor, inorganic fine particles with an average primary particle size of 10 to 100 nm, an alkali component and a solvent. When the easy-bonding composition contains an alkali component, the dispersibility of the inorganic fine particles can be improved, and an easy-bonding film having excellent slip properties can be obtained. and, The alkali component can also act as a catalyst for promoting the reaction of the binder resin (precursor). From the viewpoint of promoting volatilization of the alkali component by heating, the boiling point of the alkali component is preferably 150°C or lower. An amine, ammonia, etc. are mentioned as an alkali component.

藉由提高塗佈易接著組成物後的加熱溫度，可促進鹼成分揮發而形成殘留鹼成分少的易接著層。舉例而言，可在比透明薄膜基材之玻璃轉移溫度高10℃以上的溫度下加熱易接著組成物。藉由提高加熱溫度，便可輕易形成易接著層之無機微粒子埋設在透明薄膜基材之區域，而透明薄膜基材與易接著層之密著性有提升的傾向。 By increasing the heating temperature after applying the easily bonding composition, volatilization of the alkali component is accelerated, and an easily bonding layer with less residual alkali component can be formed. For example, the easily bonding composition can be heated at a temperature 10°C or more higher than the glass transition temperature of the transparent film substrate. By increasing the heating temperature, the inorganic microparticles that can easily form the easily bonding layer can be embedded in the area of the transparent film substrate, and the adhesion between the transparent film substrate and the easily bonding layer tends to be improved.

於透明薄膜基材上塗佈易接著組成物後，亦可在加熱透明薄膜基材的同時進行延伸。尤其，藉由在比透明薄膜基材之玻璃轉移溫度高10℃以上之溫度下加熱易接著組成物的同時，將透明薄膜基材予以延伸，會有使透明薄膜基材與易接著層之密著性提升的傾向。 After coating the easy-adhesion composition on the transparent film substrate, the transparent film substrate can be heated and extended. In particular, by heating the easily bondable composition at a temperature 10°C or more higher than the glass transition temperature of the transparent film base material, while extending the transparent film base material, the transparent film base material and the easily bondable layer can be made denser. Tendency to improve sexuality.

上述易接著薄膜可作為偏光件保護薄膜使用。於聚乙烯醇系偏光件之表面透過接著劑層貼合易接著薄膜，可製得偏光板。接著劑宜為活性能量線硬化型接著劑。在將接著劑硬化後，於易接著層與接著劑層之界面宜存在一接著界面層，該接著界面層係易接著層之樹脂成分與接著劑層之樹脂成分相溶而存在。接著界面層之厚度宜為40nm以上，接著劑層之接著界面層以外之部分的厚度宜為120nm以上。 The above-mentioned easily bonding film can be used as a polarizer protective film. A polarizing plate can be prepared by laminating an easy-adhesive film on the surface of the polyvinyl alcohol-based polarizer through an adhesive layer. The adhesive is preferably an active energy ray hardening adhesive. After the adhesive is hardened, an adhesive interface layer is preferably present at the interface between the easily adhesive layer and the adhesive layer, and the adhesive interface layer exists because the resin component of the easily adhesive layer and the resin component of the adhesive layer are compatible. The thickness of the interface layer is preferably 40 nm or more, and the thickness of the part other than the interface layer of the adhesive layer is preferably 120 nm or more.

接著劑層之厚度(接著劑層與接著界面層之合計厚度)宜為0.3~3μm。接著界面層之厚度宜相對於接 著劑層與接著界面層之合計厚度為5~90%。 The thickness of the adhesive layer (the total thickness of the adhesive layer and the adhesive interface layer) is preferably 0.3-3 μm. Then the thickness of the interface layer should be relative to the The total thickness of the adhesive layer and the interface layer is 5-90%.

藉由於液晶顯示單元或有機EL單元等影像顯示單元之表面配置偏光板，可形成影像顯示裝置。 An image display device can be formed by arranging a polarizer on the surface of an image display unit such as a liquid crystal display unit or an organic EL unit.

本發明之偏光板之偏光件與易接著薄膜之接著性相當優異。而且切割加工時很少產生微裂，切割加工性佳。 The polarizer of the polarizing plate of the present invention has excellent adhesion to the easily adhesive film. In addition, micro-cracks are rarely generated during cutting, and the cutting workability is good.

1:易接著薄膜 1: Easy to bond film

2:透明保護薄膜 2: Transparent protective film

5:偏光件 5: Polarizer

7:接著劑層 7: Adhesive layer

11:薄膜基材 11: Film substrate

15:易接著層 15: Easy Adhesion Layer

18:基材界面層 18: Substrate interface layer

60:接著劑單獨層 60: Adhesive separate layer

61:接著界面層 61: Then the interface layer

100:偏光板 100: polarizer

圖1係顯示易接著薄膜之構成例的截面圖。 FIG. 1 is a cross-sectional view showing a configuration example of an easily adhesive film.

圖2係顯示偏光板之構成例的截面圖，放大圖係表示偏光件與易接著薄膜之接著界面的層構成一例。 2 is a cross-sectional view showing a configuration example of a polarizing plate, and an enlarged view showing an example of the layer configuration of the bonding interface between the polarizer and the easily bonding film.

圖3係在薄膜基材與易接著層之界面形成有基材界面層之易接著薄膜的截面TEM觀察影像。 FIG. 3 is a cross-sectional TEM observation image of the easily bondable film with the substrate interface layer formed at the interface between the film substrate and the easily bondable layer.

圖4係未在薄膜基材與易接著層之界面形成基材界面層之易接著薄膜的截面TEM觀察影像。 FIG. 4 is a cross-sectional TEM observation image of the easy-bond film with no substrate interface layer formed at the interface between the film substrate and the easily-bonded layer.

圖5係偏光板於耐久試驗前後的正交偏光鏡觀察照片。 Figure 5 is a photograph of the crossed polarizer before and after the durability test of the polarizing plate.

圖6係在易接著層與接著劑層之界面形成有接著界面層之偏光板的截面TEM觀察影像。 6 is a cross-sectional TEM observation image of a polarizing plate with an adhesive interface layer formed at the interface between the easily adhesive layer and the adhesive layer.

用以實施發明之形態 Form for carrying out the invention

圖1係顯示易接著薄膜之構成例的概略截面圖。易接著薄膜1係於薄膜基材11之至少一面具備易接著層15。亦可在薄膜基材兩面設有易接著層。易接著薄膜係與其他薄膜或玻璃基板等貼合來使用。 FIG. 1 is a schematic cross-sectional view showing a configuration example of an easily adhesive film. The easily bonding film 1 includes an easily bonding layer 15 on at least one side of the film substrate 11 . An easy-bonding layer can also be provided on both sides of the film substrate. The easy-bond film is used by lamination with other films, glass substrates, and the like.

就易接著薄膜之使用形態而言，可舉偏光件保護薄膜。圖2係顯示具備作為偏光件保護薄膜之易接著薄膜1的偏光板之構成例的截面圖。偏光板100係於偏光件5之一面(第一主面)具備易接著薄膜1，該易接著薄膜1係透過接著劑層而貼合。在圖2所示之偏光板100中，易接著薄膜1在薄膜基材11之與偏光件5的貼合面具有易接著層15。亦可於未貼合偏光件5之面設置易接著層。在圖2所示之偏光板100中，於偏光件5之另一面(第二主面)透過接著劑層7貼合有透明保護薄膜2。 As the usage form of the easily adhesive film, a polarizer protective film is mentioned. FIG. 2 is a cross-sectional view showing a configuration example of a polarizing plate provided with an easily bonding film 1 as a polarizer protective film. The polarizing plate 100 is provided with the easily bonding film 1 on one surface (the first main surface) of the polarizer 5, and the easily bonding film 1 is bonded through the adhesive layer. In the polarizing plate 100 shown in FIG. 2 , the easily bonding film 1 has an easily bonding layer 15 on the bonding surface of the film substrate 11 and the polarizer 5 . An easy-bonding layer may also be provided on the surface not attached to the polarizer 5 . In the polarizing plate 100 shown in FIG. 2 , the transparent protective film 2 is attached to the other surface (second main surface) of the polarizer 5 through the adhesive layer 7 .

[易接著薄膜] [Easy Bonding Film]

易接著薄膜1係於薄膜基材11之至少一面具備易接著層15。 The easily bonding film 1 includes an easily bonding layer 15 on at least one side of the film substrate 11 .

<薄膜基材> <Film substrate>

薄膜基材11宜為透明薄膜。透明薄膜基材之全光線透光率宜為80%以上，85%以上較佳，90%以上更佳。構成薄膜基材11之樹脂材料可舉丙烯酸系樹脂、聚酯系樹脂、聚碳酸酯系樹脂、聚烯烴系樹脂、環狀聚烯烴系樹脂、聚苯乙烯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂等。易接著薄膜作為光學各向同性之偏光件保護薄膜使用時，從雙折射小的方面而言，薄膜基材11之樹脂材料宜為丙烯酸系樹脂或環狀聚烯烴系樹脂，且以丙烯酸系樹脂尤佳。 The film substrate 11 is preferably a transparent film. The total light transmittance of the transparent film substrate is preferably above 80%, preferably above 85%, and more preferably above 90%. The resin material constituting the film base 11 includes acrylic resins, polyester resins, polycarbonate resins, polyolefin resins, cyclic polyolefin resins, polystyrene resins, polyamide resins, and polyamide resins. imide resin, etc. When the easy-to-bond film is used as an optically isotropic polarizer protective film, from the aspect of small birefringence, the resin material of the film substrate 11 is preferably acrylic resin or cyclic polyolefin resin, and acrylic resin is used. Excellent.

環狀聚烯烴系樹脂可舉如聚降莰烯。環狀聚烯烴系樹脂之市售物可舉日本ZEON製造之Zeonor及ZEONEX、JSR製造之ARTON、三井化學製造之APEL、 TOPAS ADVANCED POLYMERS製造之TOPAS等。環狀聚烯烴系薄膜宜為含有50重量%以上環狀烯烴系樹脂者。 As a cyclic polyolefin resin, polynorbornene is mentioned, for example. Commercially available cyclic polyolefin resins include Zeonor and ZEONEX manufactured by ZEON Japan, ARTON manufactured by JSR, APEL manufactured by Mitsui Chemicals, TOPAS, etc. manufactured by TOPAS ADVANCED POLYMERS. The cyclic polyolefin-based film preferably contains 50% by weight or more of the cyclic olefin-based resin.

丙烯酸系樹脂可舉：聚甲基丙烯酸甲酯等聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、具有脂環族烴基之聚合物(例如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降莰酯共聚物等)。 Examples of acrylic resins include poly(meth)acrylates such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymers, methyl methacrylate-(meth)acrylate copolymers, Methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-styrene copolymer (MS resin, etc.), polymers with alicyclic hydrocarbon groups (such as methyl methacrylate) - cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth)acrylate copolymer, etc.).

本說明書中，「(甲基)丙烯酸」意指丙烯酸及/或甲基丙烯酸。丙烯酸系樹脂包含以丙烯酸或其衍生物作為構成單體成分者及以甲基丙烯酸或其衍生物作為構成單體成分者。 In this specification, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. The acrylic resin includes those having acrylic acid or its derivatives as constituent monomer components and those having methacrylic acid or its derivatives as constituent monomer components.

丙烯酸系樹脂亦可使用日本特開2006-283013號公報、日本特開2006-335902號公報、日本特開2006-274118號公報等中記載之具有戊二酸酐結構的丙烯酸系樹脂；及/或日本特開2000-230016號公報、日本特開2001-151814號公報、日本特開2002-120326號公報、日本特開2002-254544號公報、日本特開2005-146084號公報等中記載之具有內酯環結構的丙烯酸系樹脂。具有戊二酸酐結構之丙烯酸系樹脂及具有內酯環結構之丙烯酸系樹脂具有高耐熱性、高透明性及高機械強度，所以適合用來製造偏光度高且耐久性優異的偏光板。 As the acrylic resin, acrylic resins having a glutaric anhydride structure described in Japanese Patent Laid-Open No. 2006-283013, Japanese Patent Laid-Open No. 2006-335902, Japanese Patent Laid-Open No. 2006-274118, etc.; Lactones described in Japanese Patent Laid-Open No. 2000-230016, Japanese Patent Laid-Open No. 2001-151814, Japanese Patent Laid-Open No. 2002-120326, Japanese Patent Laid-Open No. 2002-254544, Japanese Patent Laid-Open No. 2005-146084, etc. Ring-structured acrylic resin. Acrylic resins with a glutaric anhydride structure and acrylic resins with a lactone ring structure have high heat resistance, high transparency and high mechanical strength, so they are suitable for producing polarizing plates with high degree of polarization and excellent durability.

薄膜基材11為丙烯酸系薄膜時，薄膜基材中之丙烯酸系樹脂含量宜為50重量%以上，60~98重量%較佳，70~97重量%更佳。丙烯酸系薄膜亦可含有丙烯酸系樹脂以外之熱塑性樹脂。譬如，藉由摻混其他熱塑性樹脂，可消除丙烯酸系樹脂之雙折射而獲得光學各向同性優異的丙烯酸系薄膜。另，為了提升薄膜之機械強度等，亦可摻混丙烯酸系樹脂以外之熱塑性樹脂。 When the film substrate 11 is an acrylic film, the content of the acrylic resin in the film substrate is preferably more than 50% by weight, preferably 60-98% by weight, more preferably 70-97% by weight. The acrylic film may contain thermoplastic resins other than acrylic resins. For example, by blending other thermoplastic resins, the birefringence of the acrylic resin can be eliminated to obtain an acrylic film having excellent optical isotropy. Moreover, in order to improve the mechanical strength of a film, etc., you may mix|blend thermoplastic resin other than acrylic resin.

丙烯酸系樹脂以外之熱塑性樹脂可舉烯烴系聚合物、鹵化乙烯系聚合物、聚苯乙烯、苯乙烯與丙烯酸系單體之共聚物、聚酯、聚醯胺、聚縮醛、聚碳酸酯、聚伸苯醚、聚伸苯硫、聚醚醚酮、聚碸、聚醚碸、聚氧苯甲酯(polyoxybenzylene)、聚醯胺醯亞胺、橡膠系聚合物等。 Examples of thermoplastic resins other than acrylic resins include olefin polymers, halogenated vinyl polymers, polystyrene, copolymers of styrene and acrylic monomers, polyesters, polyamides, polyacetals, polycarbonates, Polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polystilbene, polyether slag, polyoxybenzylene, polyamide imide, rubber-based polymers, etc.

薄膜基材11亦可含有抗氧化劑、穩定劑、補強材、紫外線吸收劑、阻燃劑、抗靜電劑、著色劑、充填劑、塑化劑、滑劑、填料等添加劑。亦可將樹脂材料與添加劑等混合，預先做成丸粒等熱塑性樹脂組成物後再予以薄膜化。 The film substrate 11 may also contain additives such as antioxidants, stabilizers, reinforcing materials, ultraviolet absorbers, flame retardants, antistatic agents, colorants, fillers, plasticizers, lubricants, and fillers. The resin material may be mixed with additives and the like, and the thermoplastic resin composition such as pellets may be prepared in advance, and then the film may be formed.

薄膜基材11之厚度為5~200μm左右。從機械強度、透明性及處置性等觀點來看，薄膜基材11之厚度宜為10~100μm，15~60μm較佳。 The thickness of the film substrate 11 is about 5 to 200 μm. From the viewpoints of mechanical strength, transparency, and handling properties, the thickness of the film substrate 11 is preferably 10 to 100 μm, preferably 15 to 60 μm.

薄膜基材11之玻璃轉移溫度Tg宜為100℃以上，110℃以上較佳。薄膜基材11為丙烯酸系薄膜時，如前述，藉由使用具有戊二酸酐結構之丙烯酸系樹脂或具 有內酯環結構之丙烯酸系樹脂作為丙烯酸系樹脂，可提高丙烯酸系薄膜之Tg，並可提升耐熱性。薄膜基材11之Tg上限並無特別限定，但由成形性等觀點則宜為170℃以下。 The glass transition temperature Tg of the film substrate 11 is preferably 100°C or higher, preferably 110°C or higher. When the film substrate 11 is an acrylic film, as described above, by using an acrylic resin having a glutaric anhydride structure or a The acrylic resin having a lactone ring structure, as the acrylic resin, can increase the Tg of the acrylic film and improve the heat resistance. The upper limit of Tg of the film substrate 11 is not particularly limited, but is preferably 170° C. or lower from the viewpoint of formability and the like.

薄膜基材11之製造方法可舉溶液澆鑄法、熔融擠製法、砑光法、壓縮成形法等。薄膜基材11可為未延伸薄膜及延伸薄膜中任一者。薄膜基材11為丙烯酸系薄膜時，基於提升機械強度之觀點，丙烯酸系薄膜宜為至少朝1方向延伸之延伸薄膜，且以雙軸延伸薄膜尤佳。藉由摻混其他熱塑性樹脂以消除丙烯酸系樹脂之雙折射，可獲得即使將之予以延伸後延遲依舊小且光學各向同性優異的丙烯酸系薄膜。 A solution casting method, a melt extrusion method, a calendering method, a compression molding method, etc. are mentioned as the manufacturing method of the film base material 11. The film substrate 11 may be either an unstretched film or a stretched film. When the film substrate 11 is an acrylic film, from the viewpoint of improving mechanical strength, the acrylic film is preferably a stretched film extending in at least one direction, and a biaxially stretched film is particularly preferred. By blending other thermoplastic resins to eliminate the birefringence of the acrylic resin, an acrylic film having a small retardation and excellent optical isotropy can be obtained even after extending it.

<易接著層> <Easy bonding layer>

設置在薄膜基材11之表面的易接著層15含有黏結劑樹脂及微粒子。藉由設置易接著層15，可提升偏光件等對於薄膜或玻璃基板等的接著性。易接著層15含有微粒子，可於易接著層15之表面形成微細凹凸，提升薄膜之滑移性。所以，有助於減少易接著薄膜1於滾筒輸送時受損或是抑制捲取成卷狀時沾黏。 The easily bonding layer 15 provided on the surface of the film base 11 contains a binder resin and fine particles. By providing the easy-adhesion layer 15, the adhesiveness of the polarizer or the like to a film, a glass substrate, or the like can be improved. The easy-bonding layer 15 contains fine particles, and fine irregularities can be formed on the surface of the easily-bonding layer 15 to improve the slipperiness of the thin film. Therefore, it is helpful to reduce the damage of the easy-to-bond film 1 when being transported by the roller or to prevent sticking when it is wound into a roll.

(黏結劑樹脂) (binder resin)

從與丙烯酸系薄膜等薄膜基材之密著性優異的觀點來看，黏結劑樹脂可使用聚胺甲酸乙酯樹脂、環氧樹脂、異氰酸酯樹脂、聚酯樹脂、分子中含有胺基之聚合物類、具有

Figure 108125842-A0305-02-0011-19
唑啉基等交聯性官能基之丙烯酸樹脂等具有反應性基的樹脂(聚合物)。易接著層15之黏結劑樹脂以聚胺甲酸 乙酯樹脂尤佳。含有聚胺甲酸乙酯樹脂黏結劑的易接著層15與薄膜基材11之密著性很高。而且，易接著層15含有聚胺甲酸乙酯樹脂黏結劑的易接著薄膜1透過接著劑層積層偏光件等薄膜時，有展現高接著性之傾向。 From the viewpoint of excellent adhesion to film substrates such as acrylic films, polyurethane resins, epoxy resins, isocyanate resins, polyester resins, and polymers containing an amine group in the molecule can be used as the binder resin. class, has
Figure 108125842-A0305-02-0011-19
Resins (polymers) having reactive groups, such as acrylic resins with crosslinkable functional groups such as oxazoline groups. The adhesive resin of the easy-bonding layer 15 is preferably a polyurethane resin. The adhesion between the easily bonding layer 15 containing the polyurethane resin adhesive and the film substrate 11 is high. In addition, the easily adhesive film 1 in which the easily adhesive layer 15 contains a polyurethane resin adhesive tends to exhibit high adhesiveness when a film such as a polarizer is laminated through the adhesive.

胺甲酸乙酯樹脂代表上為多元醇與聚異氰酸酯之反應生成物。多元醇成分宜使用聚丙烯醯多元醇、聚酯多元醇、聚醚多元醇等高分子多元醇。 Urethane resins are representatively the reaction products of polyols and polyisocyanates. As the polyol component, polymer polyols such as polypropylene polyol, polyester polyol, and polyether polyol are preferably used.

聚丙烯醯多元醇代表上可藉由(甲基)丙烯酸酯與含羥基之單體聚合而得。(甲基)丙烯酸酯可舉如(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯等。含羥基之單體可舉(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸2-羥戊酯等(甲基)丙烯酸之羥烷酯；甘油、三羥甲丙烷等多元醇之(甲基)丙烯酸單酯；N-羥甲基(甲基)丙烯醯胺等。 Polypropylene polyols are typically obtained by polymerizing (meth)acrylates with hydroxyl-containing monomers. (Meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. are mentioned, for example. Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate , Hydroxyalkyl esters of (meth)acrylic acid such as 4-hydroxybutyl (meth)acrylate and 2-hydroxypentyl (meth)acrylate; (meth)acrylic acid monoesters of polyols such as glycerol and trimethylolpropane ; N-methylol (meth) acrylamide and so on.

聚丙烯醯多元醇亦可含有上述以外之單體成分。其他單體成分可舉(甲基)丙烯酸等不飽和單羧酸；馬來酸等不飽和二羧酸以及其酐及二酯類；(甲基)丙烯腈等不飽和腈類；(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺等不飽和醯胺類；乙酸乙烯酯、丙酸乙烯酯等乙烯酯類；甲基乙烯基醚等乙烯基醚類；乙烯、丙烯等α-烯烴類；氯乙烯、二氯亞乙烯等鹵化α,β-不飽和脂肪族單體；苯乙烯、α-甲基苯乙烯等α,β-不飽和芳香族單體等。 The polypropylene polyol may contain monomer components other than the above. Other monomer components include unsaturated monocarboxylic acids such as (meth)acrylic acid; unsaturated dicarboxylic acids such as maleic acid and their anhydrides and diesters; unsaturated nitriles such as (meth)acrylonitrile; ) unsaturated amides such as acrylamide and N-methylol(meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; ethylene, α-olefins such as propylene; halogenated α,β-unsaturated aliphatic monomers such as vinyl chloride and vinylidene chloride; α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene, etc.

聚酯多元醇代表上可藉由多元酸與多元醇之反應製得。多元酸可舉鄰苯二甲酸、異酞酸、對酞酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、聯苯二羧酸、四氫酞酸等芳香族二羧酸；草酸、琥珀酸、丙二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、十二烷二羧酸、十八烷二羧酸、酒石酸、烷基琥珀酸、次亞麻油酸、馬來酸、延胡索酸、中康酸、檸康酸、伊康酸等脂肪族二羧酸；六氫酞酸、四氫酞酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸等脂環式二羧酸；或是該等之酸酐、烷基酯、醯鹵等反應性衍生物等。 Polyester polyols are typically prepared by the reaction of polyacids and polyols. The polybasic acid includes phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, Aromatic dicarboxylic acids such as tetrahydrophthalic acid; oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, Dodecanedicarboxylic acid, octadecanedicarboxylic acid, tartaric acid, alkylsuccinic acid, hypolinoleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itonic acid and other aliphatic dicarboxylic acids; Alicyclic dicarboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; or their anhydrides, alkyl esters, Reactive derivatives such as halide, etc.

多元醇可舉乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、戊二醇、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、1-甲基-1,3-丁二醇、2-甲基-1,3-丁二醇、1-甲基-1,4-戊二醇、2-甲基-1,4-戊二醇、1,2-二甲基-新戊二醇、2,3-二甲基-新戊二醇、1-甲基-1,5-戊二醇、2-甲基-1,5-戊二醇、3-甲基-1,5-戊二醇、1,2-二甲基丁二醇、1,3-二甲基丁二醇、2,3-二甲基丁二醇、1,4-二甲基丁二醇、二乙二醇、三乙二醇、聚乙二醇、二丙二醇、聚丙二醇、1,4-環己烷二甲醇、1,4-環己二醇、雙酚A、雙酚F、加氫雙酚A、加氫雙酚F等。 Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, and 1,6-hexanediol. Diol, 1,8-octanediol, 1,10-decanediol, 1-methyl-1,3-butanediol, 2-methyl-1,3-butanediol, 1-methyl- 1,4-pentanediol, 2-methyl-1,4-pentanediol, 1,2-dimethyl-neopentyl glycol, 2,3-dimethyl-neopentyl glycol, 1-methyl base-1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-dimethylbutanediol, 1,3 -Dimethylbutanediol, 2,3-dimethylbutanediol, 1,4-dimethylbutanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol , 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, etc.

聚醚多元醇代表上可對多元醇進行開環聚合使其加成環氧烷而製得。多元醇可舉如乙二醇、二乙二醇、丙二醇、二丙二醇、甘油、三羥甲丙烷等。環氧烷可舉如環氧乙烷、環氧丙烷、環氧丁烷、苯環氧乙烷、四氫 呋喃等。 Polyether polyols can be prepared by ring-opening polymerization of polyols to add alkylene oxides. As a polyhydric alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, etc. are mentioned, for example. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydro Furan etc.

聚異氰酸酯可舉二異氰酸四亞甲酯、二異氰酸十二亞甲酯、1,4-丁烷二異氰酸酯、二異氰酸六亞甲酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、2-甲基戊烷-1,5-二異氰酸酯、3-甲基戊烷-1,5-二異氰酸酯等脂肪族二異氰酸酯；異佛酮二異氰酸酯、加氫伸茬基二異氰酸酯、4,4′-環己基甲烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基環伸己基二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷等脂環族二異氰酸酯；苯亞甲基二異氰酸酯、2,2′-二苯甲烷二異氰酸酯、2,4′-二苯甲烷二異氰酸酯、4,4′-二苯甲烷二異氰酸酯、4,4′-二苯基二甲基甲烷二異氰酸酯、4,4′-二苄基二異氰酸酯、1,5-伸萘基二異氰酸酯、伸茬基二異氰酸酯、1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯等芳香族二異氰酸酯；二烷基二苯甲烷二異氰酸酯、四烷基二苯甲烷二異氰酸酯、α,α,α,α-四甲基伸茬基二異氰酸酯等芳香脂肪族二異氰酸酯等。 Examples of polyisocyanates include tetramethylene diisocyanate, dodecylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethyl. Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane- Aliphatic diisocyanates such as 1,5-diisocyanate; isophorone diisocyanate, hydrogenated diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methyl ring Alicyclic diisocyanates such as hexylene diisocyanate and 1,3-bis(isocyanate methyl)cyclohexane; benzylidene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylene Methane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate , Aromatic diisocyanates such as stubble diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate; dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, Aromatic aliphatic diisocyanates such as α,α,α,α-tetramethyl diisocyanate, etc.

構成易接著層15之胺甲酸乙酯樹脂宜具有羧基。藉由胺甲酸乙酯樹脂具有羧基，可導入交聯結構，故而有提升易接著薄膜1與偏光件等之接著耐久性的傾向。具有羧基之胺甲酸乙酯樹脂譬如可藉由使多元醇、聚異氰酸酯與具有游離羧基之鏈增長劑反應而製得。具有游離羧基之鏈增長劑可舉二羥基羧酸、二羥基琥珀酸等。二羥基羧酸可舉二羥甲基烷酸(譬如二羥甲基乙酸、二羥甲基 丁烷酸、二羥甲基丙酸、二羥甲基丁酸、二羥甲基戊烷酸)等二烷醇基烷酸(dialkylol alkanoic acid)等。 The urethane resin constituting the easily bonding layer 15 preferably has a carboxyl group. Since the urethane resin has a carboxyl group, a cross-linked structure can be introduced, so that the adhesion durability of the easy-bond film 1 to a polarizer and the like tends to be improved. The urethane resin having a carboxyl group can be prepared, for example, by reacting a polyol, a polyisocyanate and a chain extender having a free carboxyl group. The chain extender having a free carboxyl group includes dihydroxycarboxylic acid, dihydroxysuccinic acid, and the like. Dihydroxycarboxylic acids include dimethylolalkanoic acids (such as dimethylolacetic acid, dimethylol butane acid, dimethylol propionic acid, dimethylol butyric acid, dimethylol pentanoic acid) and other dialkyl alkanoic acids (dialkylol alkanoic acid) and the like.

胺甲酸乙酯樹脂之製造方法並無特別限定，可為使單體成分一次反應之單發法及使單體成分階段性反應之多階段法中之任一者。使用具有游離羧基之鏈增長劑將羧基導入胺甲酸乙酯樹脂時，宜為多階段法。製造胺甲酸乙酯樹脂時，亦可視需求使用胺甲酸乙酯反應觸媒。 The production method of the urethane resin is not particularly limited, and may be any of a single-shot method in which the monomer components are reacted at one time and a multi-stage method in which the monomer components are reacted in stages. When a chain extender having a free carboxyl group is used to introduce the carboxyl group into the urethane resin, a multi-stage method is preferred. When manufacturing urethane resin, urethane reaction catalyst can also be used as required.

胺甲酸乙酯樹脂之數量平均分子量宜為5,000~600,000，10,000~400,000較佳。胺甲酸乙酯樹脂之酸價宜為10~50，20~45較佳。 The number average molecular weight of the urethane resin is preferably 5,000-600,000, more preferably 10,000-400,000. The acid value of the urethane resin is preferably 10-50, preferably 20-45.

胺甲酸乙酯樹脂亦可具有交聯結構。藉由將交聯結構導入至胺甲酸乙酯樹脂，有提升易接著薄膜1與偏光件5之接著耐久性的傾向。交聯劑可無特別限制使用可與胺甲酸乙酯樹脂之交聯性官能基進行反應者。胺甲酸乙酯樹脂具有羧基時，可使用含有胺基、

Figure 108125842-A0305-02-0015-13
唑啉基、環氧基、碳二醯亞胺基等的交聯劑。該等中又以具有
Figure 108125842-A0305-02-0015-14
唑啉基之交聯劑為宜。
Figure 108125842-A0305-02-0015-15
唑啉基常溫下與羧基的反應性較小，所以與胺甲酸乙酯樹脂混合後的使用期限較長，可彈性應對步驟的前置時間。 The urethane resin may also have a cross-linked structure. By introducing the cross-linked structure into the urethane resin, there is a tendency that the adhesion durability between the easily-bondable film 1 and the polarizer 5 is improved. As the crosslinking agent, one that can react with the crosslinkable functional group of the urethane resin can be used without particular limitation. When the urethane resin has a carboxyl group, an amine group containing,
Figure 108125842-A0305-02-0015-13
Crosslinking agent of oxazoline group, epoxy group, carbodiimide group, etc. Among these, there are also
Figure 108125842-A0305-02-0015-14
An oxazoline-based crosslinking agent is suitable.
Figure 108125842-A0305-02-0015-15
The oxazoline group has less reactivity with the carboxyl group at room temperature, so it has a longer service life after mixing with the urethane resin, and can flexibly cope with the lead time of the step.

交聯劑可為低分子化合物，亦可為聚合物。若從對水系組成物之溶解性高、且與胺甲酸乙酯樹脂之相溶性亦佳的觀點來看，交聯劑宜為丙烯酸系聚合物。尤其，使用具有

Figure 108125842-A0305-02-0015-21
唑啉基之丙烯酸系聚合物作為交聯劑時，有提升易接著薄膜1與偏光件等薄膜之接著性的傾向。 The crosslinking agent may be a low molecular compound or a polymer. The crosslinking agent is preferably an acrylic polymer from the viewpoint of high solubility in water-based compositions and good compatibility with urethane resins. In particular, using
Figure 108125842-A0305-02-0015-21
When the oxazoline-based acrylic polymer is used as a crosslinking agent, the adhesiveness of the easily adhesive film 1 to films such as polarizers tends to be improved.

交聯劑之使用量宜相對於胺甲酸乙酯樹脂100重量份為1~30重量份，且3~20重量份較佳。 The usage amount of the crosslinking agent is preferably 1-30 parts by weight, preferably 3-20 parts by weight, relative to 100 parts by weight of the urethane resin.

(微粒子) (fine particles)

藉由於易接著層15含有微粒子，而於易接著層表面形成微細的凹凸形狀，可提升易接著薄膜1之滑移性，從而可抑制沾黏。從形成有助於提升滑移性之凹凸的觀點來看，微粒子之粒徑(平均一次粒徑)宜為10nm以上，15nm以上較佳，20nm以上更佳。藉由使微粒子之平均一次粒徑小於可見光波長，可抑制可見光在黏結劑樹脂與微粒子之界面散射，獲得透明性高的易接著薄膜。所以，微粒子粒徑宜為100nm以下，80nm以下較佳，60nm以下更佳，50nm以下尤佳。 Since the easily-bondable layer 15 contains fine particles, the surface of the easily-bonded layer is formed with fine concavo-convex shapes, so that the slippage of the easily-bonded film 1 can be improved, and sticking can be suppressed. The particle size (average primary particle size) of the fine particles is preferably 10 nm or more, more preferably 15 nm or more, and more preferably 20 nm or more, from the viewpoint of forming irregularities that contribute to the improvement of slippage. By making the average primary particle size of the microparticles smaller than the wavelength of visible light, scattering of visible light at the interface between the binder resin and the microparticles can be suppressed, and an easy-to-bond film with high transparency can be obtained. Therefore, the particle size of the fine particles is preferably 100 nm or less, more preferably 80 nm or less, more preferably 60 nm or less, and still more preferably 50 nm or less.

若從分散性及粒徑之均勻性優異的觀點來看，易接著層15之微粒子宜為無機微粒子。無機微粒子可舉二氧化鈦、氧化鋁、二氧化鋯等無機氧化物；碳酸鈣、滑石、黏土、燒成高嶺土、燒成矽酸鈣、水合矽酸鈣、矽酸鋁、矽酸鎂、磷酸鈣等。該等中又以無機氧化物為佳。為了抑制因微粒子而產生光散射，黏結劑樹脂(一般折射率約1.5左右)與微粒子之折射率差宜小。若從與黏結劑樹脂之折射率差小、且分散性優異的觀點來看，易接著層15之微粒子宜為二氧化矽粒子。 From the viewpoint of excellent dispersibility and uniformity of particle size, the fine particles of the easily bonding layer 15 are preferably inorganic fine particles. Inorganic fine particles include inorganic oxides such as titanium dioxide, aluminum oxide, and zirconium dioxide; calcium carbonate, talc, clay, fired kaolin, fired calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, etc. . Of these, inorganic oxides are preferred. In order to suppress light scattering due to fine particles, the difference in refractive index between the binder resin (generally about 1.5 refractive index) and the fine particles should be small. From the viewpoint of having a small difference in refractive index with the binder resin and having excellent dispersibility, the fine particles of the easily bonding layer 15 are preferably silica particles.

從水系組成物形成易接著層15時，宜使用水分散性高的微粒子。亦可將微粒子之水分散液摻混至組成物中。為了提高無機微粒子之分散性，宜添加胺或氨等鹼 成分，使易接著組成物為弱鹼性。 When forming the easily bonding layer 15 from a water-based composition, fine particles with high water dispersibility are preferably used. Aqueous dispersions of microparticles can also be incorporated into the composition. In order to improve the dispersibility of the inorganic fine particles, it is advisable to add a base such as amine or ammonia. ingredient to make the easy-adhesive composition weakly alkaline.

水分散性之二氧化矽粒子宜使用膠質氧化矽。膠質氧化矽亦可使用扶桑化學工業(股)製Quartron PL系列、日產化學工業(股)製SNOWTEX系列、日本Aerosil(股)AERODISP系列及AEROSIL系列等市售物。 The water-dispersible silica particles are preferably colloidal silica. As the colloidal silica, commercially available products such as Quartron PL series manufactured by Fuso Chemical Industry Co., Ltd., SNOWTEX series manufactured by Nissan Chemical Industry Co., Ltd., AERODISP series and AEROSIL series manufactured by Japan Aerosil Co., Ltd. can also be used.

從藉由於易接著層15表面形成凹凸來提高易接著薄膜1之滑移性的觀點來看，易接著層15中之微粒子含量宜為8重量%以上，10重量%以上較佳，12重量%以上更佳。尤其，易接著層15之厚度為280nm以下時，宜增加微粒子含量，提高每單位面積之微粒子量(數量密度)，藉以在易接著層15之面內均勻形成凹凸。易接著層15之微粒子含量若太大，恐因在黏結劑樹脂與微粒子之界面的光散射增大而招致光學特性降低。又，隨著微粒子含量增大，黏結劑樹脂的相對含量則變少，而可能降低易接著層之接著性。所以，易接著層15中之微粒子含量宜為50重量%以下，40重量%以下較佳，30重量%以下更佳。 From the viewpoint of improving the slippage of the easily-bondable film 1 by forming the unevenness on the surface of the easily-bondable layer 15, the content of the fine particles in the easily-bonded layer 15 is preferably 8 wt% or more, more preferably 10 wt% or more, 12 wt% The above is better. In particular, when the thickness of the easily bonding layer 15 is 280 nm or less, the content of fine particles should be increased to increase the amount of fine particles per unit area (number density), so as to uniformly form unevenness on the surface of the easily bonding layer 15 . If the fine particle content of the easily bonding layer 15 is too large, the optical properties may be degraded due to increased light scattering at the interface between the binder resin and the fine particles. In addition, as the content of fine particles increases, the relative content of the binder resin decreases, which may reduce the adhesion of the easily bonded layer. Therefore, the content of fine particles in the easily bonding layer 15 is preferably 50 wt % or less, preferably 40 wt % or less, and more preferably 30 wt % or less.

(鹼殘量) (Alkali Residual)

若為了提高無機微粒子之分散性而使用胺或氨等鹼成分，將無可避免在易接著層殘留鹼成分。將易接著薄膜1作為偏光件保護薄膜使用時，易接著層15之殘留鹼成分一旦被水分等溶出，可能會使偏光件劣化，而降低偏光板之偏光度或產生筋條狀不均等光學缺陷。 If an alkali component such as amine or ammonia is used in order to improve the dispersibility of the inorganic fine particles, the alkali component will inevitably remain in the easily bonding layer. When the easy-bond film 1 is used as a polarizer protective film, once the residual alkali component of the easily-bonded layer 15 is eluted by moisture, etc., it may deteriorate the polarizer, reduce the polarization degree of the polarizer, or produce optical defects such as rib-like unevenness. .

所以從提高偏光板之加濕耐久性的觀點來看，易接著層15之鹼殘量宜為75ppm以下，70ppm以下較 佳，60ppm以下更佳，55ppm以下尤佳。從提升偏光板之加濕耐久性的觀點來看，易接著層15之鹼殘量愈少愈佳。 Therefore, from the viewpoint of improving the humidification durability of the polarizing plate, the alkali residue in the easy-bonding layer 15 is preferably 75 ppm or less, and 70 ppm or less is preferable. Excellent, more preferably below 60ppm, particularly preferably below 55ppm. From the viewpoint of improving the humidification durability of the polarizing plate, the less alkali residue in the easily bonding layer 15 is, the better.

另一方面，易接著層15之鹼殘量若太少，將有損微粒子之分散性，可能因微粒子凝集而產生白濁等外觀不良。又，可能因為分散性降低使微粒子凝集或從易接著層脫落，而不能在易接著層表面形成適當的凹凸，從而有易接著薄膜之滑移性降低之傾向。所以，易接著層15之鹼殘量宜為5ppm以上，10ppm以上較佳，20ppm以上更佳。 On the other hand, if the alkali residue in the easily bonding layer 15 is too small, the dispersibility of the fine particles will be impaired, and the fine particles may aggregate and cause poor appearance such as cloudiness. In addition, due to the decrease in dispersibility, the fine particles may aggregate or fall off from the easily bonding layer, so that proper unevenness cannot be formed on the surface of the easily bonding layer, and the slippage of the easily bonding film tends to decrease. Therefore, the alkali residue in the easily bonding layer 15 is preferably 5 ppm or more, preferably 10 ppm or more, and more preferably 20 ppm or more.

易接著層中之鹼量可因應鹼成分的種類以液體層析分析或離子層析分析等定量。亦可利用層析分析與質量分析(MS)組合而成的分析法(譬如LC/MS)進行鹼成分之定量。易接著層中含有多種鹼成分時，以各成分之合計為易接著層之鹼成分含量(殘量)。 The amount of alkali in the easily bondable layer can be quantified by liquid chromatography analysis or ion chromatography analysis according to the type of the alkali component. The quantification of the base component can also be performed by an analytical method (eg, LC/MS) that combines chromatographic analysis and mass analysis (MS). When a plurality of alkali components are contained in the easily bonding layer, the total of each component is used as the alkali component content (residual amount) of the easily bonding layer.

<形成易接著層> <Formation of an easily bonding layer>

於薄膜基材11之表面形成易接著層15的形成方法並無特別限定。理想係將含有黏結劑樹脂及微粒子之易接著組成物(塗液)塗佈於薄膜基材11上並進行加熱而形成易接著層15。 The formation method of forming the easily bonding layer 15 on the surface of the film substrate 11 is not particularly limited. Ideally, the easily bonding layer 15 is formed by applying an easily bonding composition (coating liquid) containing a binder resin and fine particles on the film substrate 11 and heating it.

(易接著組成物) (Easy Adhesion Composition)

易接著組成物宜為以水作為溶劑(及用於微粒子之分散介質)之水系組成物。易接著組成物中之固體成分(不揮發成分)之濃度宜為1~30重量%，2~20重量%較佳，3~15重量%更佳。 The easily bonded composition is preferably an aqueous composition using water as a solvent (and a dispersion medium for fine particles). The concentration of the solid content (non-volatile content) in the easy-to-bond composition is preferably 1 to 30% by weight, preferably 2 to 20% by weight, and more preferably 3 to 15% by weight.

水系易接著組成物含有作為溶劑(及分散介 質)之水、黏結劑樹脂脂或其前驅物質及無機微粒子。易接著組成物宜更含有鹼成分。如前述，鹼成分具有促進無機微粒子分散的作用。所以，藉由易接著組成物含有鹼成分，可提升無機微粒子之分散性，從而可獲得外觀及滑移性優異的易接著薄膜。 The water-based easily bonding composition contains as a solvent (and a dispersing medium) quality) water, binder resin grease or its precursors, and inorganic fine particles. The easy-bonding composition preferably further contains an alkali component. As described above, the alkali component has the effect of promoting the dispersion of the inorganic fine particles. Therefore, when the easy-bonding composition contains an alkali component, the dispersibility of the inorganic fine particles can be improved, and an easy-bonding film excellent in appearance and slipperiness can be obtained.

另一方面，易接著組成物中所含之鹼若殘留於易接著層，可能會成為偏光板之耐濕熱性降低的原因。尤其，苛性等強鹼僅少量便可能成為使偏光件劣化之原因。所以，易接著組成物中所含之鹼成分宜為氨或胺等弱鹼成分。若從兼顧提升無機微粒子之分散性及防止偏光件劣化的觀點來看，易接著組成物(塗液)之pH宜在7.5~9左右。 On the other hand, if the alkali contained in the easily-bondable composition remains in the easily-bonded layer, it may be a cause of lowering the heat-and-moisture resistance of the polarizing plate. In particular, even a small amount of strong alkali such as caustic may cause deterioration of the polarizer. Therefore, the alkali component contained in the easy-bonding composition is preferably a weak alkali component such as ammonia or amine. From the viewpoint of both improving the dispersibility of the inorganic fine particles and preventing the deterioration of the polarizer, the pH of the easily bonding composition (coating solution) is preferably about 7.5 to 9.

若從提升無機微粒子之分散性的觀點來看，易接著組成物中所含之鹼成分的量宜相對於易接著組成物之固體成分為300ppm以上，500ppm以上較佳。另一方面，鹼成分含量若太大，可能會變得很難降低鹼殘量，所以易接著組成物中所含之鹼成分的量宜相對於易接著組成物之固體成分為50000ppm以下，10000ppm以下較佳，5000ppm以下更佳。 From the viewpoint of improving the dispersibility of the inorganic fine particles, the amount of the alkali component contained in the easily bonding composition is preferably 300 ppm or more, preferably 500 ppm or more, relative to the solid content of the easily bonding composition. On the other hand, if the content of the alkali component is too large, it may become difficult to reduce the residual alkali content. Therefore, the amount of the alkali component contained in the easy-bonding composition is preferably 50,000 ppm or less and 10,000 ppm relative to the solid content of the easy-bonding composition. The following is preferable, and 5000 ppm or less is more preferable.

易接著組成物中所含之鹼成分除了可提升無機微粒子之分散性，亦可為具有觸媒作用等之物。譬如，黏結劑樹脂為胺甲酸乙酯系樹脂時，作為聚胺甲酸乙酯前驅物質(多元醇、異氰酸酯等)之胺甲酸乙酯化觸媒，亦可於易接著組成物中含有三乙胺等三級胺。 In addition to improving the dispersibility of the inorganic fine particles, the alkali component contained in the easy-bonding composition may also have a catalytic effect. For example, when the binder resin is a urethane resin, as a urethane catalyst for the polyurethane precursor (polyol, isocyanate, etc.), triethylamine can also be included in the easy-to-bond composition. and other tertiary amines.

於薄膜基材上塗佈易接著組成物後進行加熱，揮發去除鹼成分，可減少易接著層15之殘留鹼成分。若從利用加熱來促進鹼成分揮發的觀點來看，易接著組成物中所含之鹼成分沸點宜為150℃以下。鹼成分的沸點宜為130℃以下較佳，120℃以下更佳，110℃以下尤佳。鹼成分的沸點亦可為100℃以下或90℃以下。易接著組成物含有多種鹼成分時，宜至少1種鹼成分的沸點在上述範圍內，且更宜2種以上鹼成分的沸點在上述範圍內。相對於易接著層中所含之鹼的總量100重量份，宜有50重量%以上之鹼成分的沸點在上述範圍內。易接著組成物中所含之全部鹼成分的沸點在上述範圍內為理想。 After coating the easily bonding composition on the film substrate, heating is performed to volatilize and remove the alkali component, which can reduce the residual alkali component of the easily bonding layer 15 . From the viewpoint of promoting volatilization of the alkali component by heating, the boiling point of the alkali component contained in the easily bonding composition is preferably 150°C or lower. The boiling point of the alkali component is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The boiling point of the alkali component may be 100°C or lower or 90°C or lower. When the easily bonding composition contains a plurality of alkali components, the boiling point of at least one alkali component is preferably within the above range, and the boiling point of two or more alkali components is more preferably within the above range. With respect to 100 parts by weight of the total amount of the alkali contained in the easily bonding layer, 50% by weight or more of the alkali component preferably has a boiling point within the above range. It is preferable that the boiling points of all the alkali components contained in the easy-bonding composition are within the above-mentioned range.

易接著組成物除了含有黏結劑樹脂(或其前驅物質)、無機微粒子及鹼成分以外，亦可含有交聯劑。易接著組成物亦可含有交聯促進劑等之觸媒、抗氧化劑、紫外線吸收劑、調平劑、抗黏結劑、抗靜電劑、分散穩定劑、消泡劑、增黏劑、分散劑、界面活性劑、滑劑等添加劑。 The easily bonding composition may contain a crosslinking agent in addition to the binder resin (or its precursor), inorganic fine particles, and an alkali component. The easy-adhesive composition may also contain catalysts such as cross-linking accelerators, antioxidants, ultraviolet absorbers, leveling agents, anti-blocking agents, antistatic agents, dispersion stabilizers, defoaming agents, tackifiers, dispersants, Additives such as surfactants and lubricants.

(於薄膜基材上形成易接著層) (Forming an easy-adhesive layer on a film substrate)

於薄膜基材11上塗佈易接著組成物之前，可進行薄膜基材之表面處理。藉由進行表面處理，可調整薄膜基材的濡濕張力，提升其與易接著層15之密著性。表面處理可舉電暈處理、電漿處理、噴吹臭氧、紫外線照射、火焰處理、化學藥物處理等。該等中又以電暈處理或電漿處理為宜。 Before coating the easily adhesive composition on the film substrate 11, the surface treatment of the film substrate can be performed. By performing the surface treatment, the wetting tension of the film substrate can be adjusted, and the adhesion between the film substrate and the easily adhesive layer 15 can be improved. The surface treatment includes corona treatment, plasma treatment, ozone injection, ultraviolet irradiation, flame treatment, chemical treatment, and the like. Among these, corona treatment or plasma treatment is suitable.

易接著組成物之塗佈方法可舉棒塗法、輥塗法、凹版塗佈法、桿塗法、狹孔塗佈法、簾幕式塗佈法、 噴泉式塗佈法等。將塗佈後之易接著組成物加熱，去除溶劑，藉此可形成易接著層15。亦可藉由加熱使黏結劑樹脂之前驅物質反應而硬化。譬如，當易接著組成物含有交聯劑時，藉由加熱可促進交聯反應。 The coating method of the easily adhered composition includes bar coating, roll coating, gravure coating, rod coating, slit coating, curtain coating, Fountain coating method, etc. The easy-bond layer 15 can be formed by heating the coated easily-bond composition to remove the solvent. The binder resin can also be cured by reacting with the precursor material by heating. For example, when the easily bondable composition contains a crosslinking agent, the crosslinking reaction can be accelerated by heating.

形成易接著層時之加熱溫度譬如為50~200℃左右。從促進易接著組成物之樹脂成分的硬化反應，並有效揮發去除易接著組成物中所含之鹼成分的觀點來看，加熱溫度宜為100℃以上，且120℃以上較佳，130℃以上更佳，135℃以上尤佳。又，加熱溫度宜高於易接著組成物中所含之鹼成分的沸點。 The heating temperature at the time of forming the easily bonding layer is, for example, about 50 to 200°C. The heating temperature is preferably 100°C or higher, more preferably 120°C or higher, and 130°C or higher from the viewpoint of promoting the hardening reaction of the resin component of the easily bonding composition and effectively volatilizing and removing the alkali component contained in the easily bonding composition. More preferably, above 135°C is particularly preferred. Further, the heating temperature is preferably higher than the boiling point of the alkali component contained in the easy-bonding composition.

形成易接著層時之加熱溫度宜比薄膜基材之玻璃轉移溫度(Tg)高溫。藉由高溫加熱，可促進易接著組成物之樹脂成分的硬化反應，並可有效揮發去除易接著組成物中所含鹼成分。加熱溫度宜為比薄膜基材之Tg高10℃以上的溫度。 The heating temperature for forming the easily bonding layer is preferably higher than the glass transition temperature (Tg) of the film substrate. By heating at a high temperature, the hardening reaction of the resin component of the easily bonded composition can be accelerated, and the alkali components contained in the easily bonded composition can be effectively volatilized and removed. The heating temperature is preferably a temperature higher than the Tg of the film substrate by 10°C or more.

吾等認為，藉由以比薄膜基材之Tg更高的溫度進行加熱，可提高易接著組成物中之鹼揮發去除效率，同時易接著組成物容易滲透薄膜基材表面，提升薄膜基材11與易接著層15之密著性。從提升易接著層之密著性的觀點來看，加熱溫度宜為薄膜基材之Tg+10℃以上，且Tg+15℃以上較佳，Tg+20℃以上更佳。 We believe that by heating at a higher temperature than the Tg of the film substrate, the alkali volatilization removal efficiency in the easy-bonding composition can be improved, and the easy-bonding composition can easily penetrate the surface of the film substrate, thereby improving the film substrate 11. Adhesion to the easy bonding layer 15 . From the viewpoint of improving the adhesion of the easily bonding layer, the heating temperature is preferably Tg+10°C or higher of the film substrate, more preferably Tg+15°C or higher, more preferably Tg+20°C or higher.

若以薄膜基材之Tg+10℃以上的溫度進行加熱，薄膜基材會從玻璃狀態變成橡膠狀態，表面變得容易變形，所以在薄膜基材11與易接著層15之界面容易形成一 薄膜基材之樹脂成分與易接著層之構成成分混雜的基材界面層18(參照圖2之放大圖)。藉由形成基材界面層，薄膜基材11與易接著層15之密著性有提升之傾向。 If the film substrate is heated at a temperature above Tg+10°C, the film substrate will change from a glass state to a rubber state, and the surface will be easily deformed. The base material interface layer 18 (refer to the enlarged view of FIG. 2 ) in which the resin components of the film base material and the constituent components of the easily bonding layer are mixed. By forming the substrate interface layer, the adhesion between the film substrate 11 and the easily bonding layer 15 tends to be improved.

尤其，如圖3之截面觀察影像所示，當薄膜基材11之表面存在易接著層15之微粒子嵌入埋設的區域時，可獲得薄膜基材11與易接著層15之密著性高的易接著薄膜。吾等認為，若以將薄膜基材加熱至比Tg更高溫度之橡膠狀態將微粒子埋設至薄膜基材中，然後使薄膜基材恢復到玻璃狀態，則埋設在薄膜基材表面之微粒子及存在其周圍的黏結劑樹脂會固著於薄膜基材之表面上，故而可提升薄膜基材11與易接著層15之密著性。 In particular, as shown in the cross-sectional observation image of FIG. 3 , when the surface of the film substrate 11 has a region where the microparticles of the easily bonding layer 15 are embedded and embedded, a high adhesion between the film substrate 11 and the easily bonding layer 15 can be obtained. Then the film. We believe that if the microparticles are embedded in the film substrate in a rubber state in which the film substrate is heated to a temperature higher than Tg, and then the film substrate is returned to a glass state, the microparticles embedded on the surface of the film substrate and the presence of The adhesive resin around it will be fixed on the surface of the film base material, so the adhesion between the film base material 11 and the easily adhesive layer 15 can be improved.

亦可在薄膜基材之製造步驟中形成易接著層。另，亦可利用形成薄膜基材時的加熱來形成易接著層。譬如，當薄膜基材為延伸薄膜時，可於延伸前之薄膜或縱向延伸後之薄膜表面上塗佈易接著組成物，並利用以拉幅機進行橫向延伸或同時雙軸延伸時之加熱，使溶劑乾燥或使樹脂硬化。 The easy-bonding layer can also be formed in the manufacturing step of the film substrate. In addition, the easily bonding layer may be formed by heating at the time of forming the film base material. For example, when the film substrate is a stretched film, the easy-to-bond composition can be coated on the surface of the film before stretching or the surface of the film after longitudinal stretching, and the heating during lateral stretching or simultaneous biaxial stretching with a tenter can be used. Allow the solvent to dry or harden the resin.

塗佈易接著組成物後再將薄膜基材予以延伸時，從抑制對易接著層產生龜裂等不良狀況的觀點來看，延伸倍率宜為5倍以下，且4倍以下較佳，3倍以下更佳，2.5倍以下尤佳。延伸倍率之下限並無特別限定，基於提升薄膜強度之觀點，延伸倍率宜為1.3倍以上，1.5倍以上較佳。薄膜基材若為丙烯酸系薄膜，基於提升薄膜強度之觀點，宜分別於輸送方向(MD)及寬度方向(TD)上，以 上述延伸倍率實施延伸。 When the film substrate is stretched after applying the easily bondable composition, the stretching ratio is preferably 5 times or less, more preferably 4 times or less, and 3 times from the viewpoint of suppressing the occurrence of defects such as cracks in the easily bondable layer. The following is more preferable, and 2.5 times or less is especially preferable. The lower limit of the stretching ratio is not particularly limited, but from the viewpoint of improving the strength of the film, the stretching ratio is preferably 1.3 times or more, more preferably 1.5 times or more. If the film substrate is an acrylic film, from the viewpoint of improving the strength of the film, it is advisable to make the film in the conveying direction (MD) and the width direction (TD), respectively. The stretching is carried out at the above stretching ratio.

進行薄膜基材之雙軸延伸時，雙軸延伸可逐次雙軸延伸亦可同時雙軸延伸。另外亦可進行斜向延伸。進行逐次雙軸延伸時，亦可如前述利用輥延伸將薄膜往1方向(MD)延伸後，於薄膜上塗佈易接著組成物，並在以拉幅機進行延伸時將易接著組成物加熱。 When the film substrate is biaxially stretched, the biaxial stretching can be either successive biaxial stretching or simultaneous biaxial stretching. In addition, it can also be extended obliquely. In the case of successive biaxial stretching, the film can also be stretched in one direction (MD) by means of roll stretching as described above, and then the easily bonding composition can be coated on the film, and the easily bonding composition can be heated during stretching with a tenter. .

延伸溫度就易接著層之加熱溫度而言如同前述，宜為比薄膜基材之Tg高的溫度，且Tg+10℃以上為佳，Tg+15℃以上較佳，Tg+20℃以上更佳。尤其，宜在塗佈易接著組成物後，以上述溫度往至少1方向進行延伸。若在比薄膜基材之Tg更高溫的橡膠狀態下進行延伸，便容易在薄膜基材表面形成埋設有易接著組成物中之微粒子的區域，而薄膜基材11與易接著層15之密著性有提升之傾向。在高溫下進行延伸而變得容易在薄膜基材中埋設微粒子的原因，可舉：若在橡膠狀態下進行延伸，則於薄膜基材變形時易接著組成物容易濡濕擴散，於是容易變成微粒子嵌入變形時形成之表面凹凸的凹部中之狀態。而且，吾等認為若在延伸後釋放應力的同時進行冷卻，則在薄膜基材收縮之際，嵌入薄膜基材表面的粒子會就此固著，因此容易於薄膜基材形成埋設有微粒子之區域。 The extension temperature is the same as the above-mentioned heating temperature of the easy-bond layer, and it is preferably a temperature higher than the Tg of the film substrate, and preferably above Tg+10°C, preferably above Tg+15°C, more preferably above Tg+20°C . In particular, it is preferable to extend in at least one direction at the above-mentioned temperature after applying the easily adhesive composition. If the stretching is performed in a rubber state higher than the Tg of the film substrate, a region in which the fine particles of the easily bonding composition are embedded is easily formed on the surface of the film substrate, and the film substrate 11 and the easily bonding layer 15 adhere to each other. Sex has a tendency to improve. The reasons why it becomes easier to embed fine particles in the film substrate by stretching at a high temperature include: if the stretching is performed in a rubber state, when the film substrate is deformed, the adhesive composition tends to wet and diffuse, so that the fine particles tend to be embedded. The state in the concave portion of the surface unevenness formed during deformation. Furthermore, we believe that if cooling is performed while releasing the stress after stretching, when the film substrate shrinks, the particles embedded in the surface of the film substrate will be fixed thereon, so that it is easy to form a region in which the microparticles are embedded in the film substrate.

藉由調整易接著組成物之固體成分濃度及塗佈厚度，可調整易接著層15之厚度。在塗佈易接著組成物後進行薄膜基材之延伸時，亦可藉由延伸倍率來調整易接著層15之厚度。 The thickness of the easily bonding layer 15 can be adjusted by adjusting the solid content concentration and coating thickness of the easily bonding composition. When the film substrate is stretched after applying the easily bonding composition, the thickness of the easily bonding layer 15 can also be adjusted by the stretching ratio.

易接著層15之厚度並無特別限定，若從可促進以加熱去除鹼成分的觀點來看，宜為280nm以下，250nm以下較佳，230nm以下更佳。將易接著薄膜1作為偏光件保護薄膜使用時，易接著層15之厚度愈小，愈能提升偏光板之加濕耐久性，而有減少筋條狀不均等光學缺陷發生的傾向。而且易接著層15之厚度愈小，愈有可在偏光板曝露在加濕環境時抑制偏光度降低的傾向。 The thickness of the easily bonding layer 15 is not particularly limited, but is preferably 280 nm or less, more preferably 250 nm or less, and more preferably 230 nm or less, from the viewpoint of promoting the removal of the alkali component by heating. When the easy-bond film 1 is used as a polarizer protective film, the smaller the thickness of the easily-bonded layer 15 is, the better the humidification durability of the polarizer can be improved, and the occurrence of optical defects such as rib-like unevenness tends to be reduced. In addition, the smaller the thickness of the easy-bond layer 15 is, the more likely it is that the decrease in the degree of polarization can be suppressed when the polarizing plate is exposed to a humidified environment.

在易接著組成物加熱乾燥時，若鹼成分被過度去除，則微粒子在黏結劑樹脂中之分散性降低，而容易發生微粒子凝集、及隨之而來的微粒子從易接著層表面脫落等。一旦發生微粒子的凝集或脫落，易接著薄膜之滑移性就會降低，而容易在輸送時發生損傷或在捲取時產生黏結。所以，易接著層15之厚度宜為40nm以上，50nm以上較佳，80nm以上更佳，100nm以上尤佳。而且，從可適當展現易接著層15之接著性提升效果的觀點來看，易接著層15之厚度亦宜在上述範圍內。 When the easy-bond composition is heated and dried, if the alkali component is excessively removed, the dispersibility of the fine particles in the binder resin decreases, and the fine particles tend to agglomerate and the fine particles come off from the surface of the easy-bond layer. Once the agglomeration or detachment of the fine particles occurs, the slipperiness of the easy-to-adhere film is reduced, and it is easy to be damaged during transportation or to be stuck during winding. Therefore, the thickness of the easy-bonding layer 15 is preferably 40 nm or more, preferably 50 nm or more, more preferably 80 nm or more, and particularly preferably 100 nm or more. Also, the thickness of the easy-bond layer 15 is preferably within the above-mentioned range from the viewpoint that the adhesion-improving effect of the easily-bonded layer 15 can be appropriately exhibited.

[偏光板] [polarizing plate]

偏光板可僅於偏光件之一面具備透明保護薄膜，亦可如圖2所示於偏光件5之兩面具備透明保護薄膜。藉由於偏光件之一面貼合上述易接著薄膜作為偏光件保護薄膜，可形成僅於偏光件之一面具有透明保護薄膜的偏光板。於偏光件之兩面具有偏光件保護薄膜的偏光板只要在偏光件之至少一面貼合有上述易接著薄膜即可。偏光板亦可在偏光件兩面貼合有上述易接著薄膜。偏光件5與易接著薄膜1則 可透過接著劑層貼合。 The polarizer can be provided with a transparent protective film only on one side of the polarizer, or can also be provided with a transparent protective film on both sides of the polarizer 5 as shown in FIG. 2 . By attaching the above-mentioned easy-bond film as a polarizer protective film on one side of the polarizer, a polarizer with a transparent protective film only on one side of the polarizer can be formed. The polarizer having the polarizer protective film on both sides of the polarizer only needs to be bonded with the above-mentioned easy-bonding film on at least one side of the polarizer. The polarizing plate may also be laminated with the above-mentioned easy-bonding films on both sides of the polarizer. Polarizer 5 and Easy Bonding Film 1 It can be attached through the adhesive layer.

<偏光件> <Polarizer>

作為偏光件5，可使用使聚乙烯醇、部分甲醛化聚乙烯醇等聚乙烯醇系薄膜上吸附碘或二色性染料等二色性物質並以使其朝1方向配向的聚乙烯醇(PVA)系偏光件。譬如，可藉由對聚乙烯醇系薄膜施行碘染色及延伸而製得PVA系偏光件。 As the polarizer 5, polyvinyl alcohol (polyvinyl alcohol) in which a dichroic substance such as iodine or a dichroic dye is adsorbed on a polyvinyl alcohol-based film such as polyvinyl alcohol and partially formaldehyde polyvinyl alcohol so as to be aligned in one direction can be used ( PVA) is a polarizer. For example, a PVA-based polarizer can be produced by dyeing and stretching a polyvinyl alcohol-based film with iodine.

在偏光件5之製造步驟中，亦可視需求進行水洗、膨潤、交聯等處理。延伸可在碘染色之前後任擇進行，或可一邊染色一邊進行延伸。延伸可任擇為在空中進行延伸(乾式延伸)、或是在水中或含有硼酸、碘化鉀等之水溶液中進行延伸(濕式延伸)，亦可將該等併用。偏光件5之膜厚並無特別限制，一般為1~50μm左右。 In the manufacturing steps of the polarizer 5, treatments such as water washing, swelling, and cross-linking may also be performed as required. The extension may optionally be performed before and after iodine staining, or may be performed concurrently with the dyeing. The stretching may be carried out in the air (dry stretching), or stretching in water or an aqueous solution containing boric acid, potassium iodide, etc. (wet stretching), or these may be used in combination. The film thickness of the polarizer 5 is not particularly limited, and is generally about 1 to 50 μm.

偏光件5亦可使用厚度為10μm以下之薄型PVA系偏光件。薄型偏光件可舉如日本特開昭51-069644號公報、日本特開2000-338329號公報、WO2010/100917號手冊、日本專利第4691205號說明書、日本專利第4751481號說明書等中所記載之薄型偏光件。該等薄型偏光件可藉由包含有將PVA系樹脂層與延伸用樹脂基材在積層體之狀態下進行延伸的步驟及進行碘染色的步驟之製法製得。若為此種製法，則即使PVA系樹脂層很薄，因其被延伸用樹脂基材支持著，故可在不因延伸造成斷裂等不良狀況下延伸。 The polarizer 5 can also use a thin PVA-based polarizer with a thickness of 10 μm or less. As the thin polarizer, the thin polarizers described in Japanese Patent Laid-Open No. Sho 51-069644, Japanese Patent Laid-Open No. 2000-338329, Handbook WO2010/100917, Japanese Patent No. 4691205, and Japanese Patent No. 4751481 can be used. polarizer. These thin polarizers can be produced by a production method including a step of extending a PVA-based resin layer and a resin substrate for extending in a state of a laminate and a step of iodine dyeing. According to such a production method, even if the PVA-based resin layer is thin, it is supported by the resin base material for stretching, so that it can be stretched without problems such as breakage due to stretching.

<接著劑> <Adhesive>

用來貼合偏光件5與易接著薄膜1之接著劑層只要在光學上呈透明，其材料即無特別限制，可舉環氧系樹脂、聚矽氧系樹脂、丙烯酸系樹脂、聚胺甲酸乙酯、聚醯胺、聚醚、聚乙烯醇等。接著劑層之厚度譬如為0.01~20μm左右，可因應被黏體之種類或接著劑之材料等來適當設定。使用藉由塗佈後之交聯反應顯現接著性的硬化型接著劑時，接著劑層之厚度宜為0.01~5μm，0.03~3μm較佳。 The material of the adhesive layer used to bond the polarizer 5 and the easy-adhesive film 1 is not particularly limited as long as it is optically transparent, and examples include epoxy resin, polysiloxane resin, acrylic resin, and polyurethane. Ethyl ester, polyamide, polyether, polyvinyl alcohol, etc. The thickness of the adhesive layer is, for example, about 0.01 to 20 μm, which can be appropriately set according to the type of the adherend or the material of the adhesive. When using a hardening adhesive that exhibits adhesiveness by a cross-linking reaction after coating, the thickness of the adhesive layer is preferably 0.01 to 5 μm, preferably 0.03 to 3 μm.

接著劑可使用水系接著劑、溶劑系接著劑、熱熔膠接著劑系、活性能量線硬化型接著劑等各種形態的接著劑。該等中，若從可縮小接著劑層之厚度、且在高溫高濕度條件下之接著耐久性高的觀點來看，又以活性能量線硬化型接著劑為佳。 Various types of adhesives such as water-based adhesives, solvent-based adhesives, hot-melt adhesives, and active energy ray-curable adhesives can be used as the adhesive. Among these, an active energy ray-curable adhesive is preferable from the viewpoint of reducing the thickness of the adhesive layer and having high adhesion durability under high-temperature and high-humidity conditions.

活性能量線硬化型接著劑係可藉由照射電子射線或紫外線等活性能量線進行自由基聚合、陽離子聚合或陰離子聚合的接著劑。其中，若從可低能量硬化且可縮小接著劑層之厚度的觀點來看，以藉由照射活性光線引發自由基聚合的光自由基聚合性接著劑為宜。 Active energy ray-curable adhesives are adhesives that can undergo radical polymerization, cationic polymerization, or anionic polymerization by irradiation with active energy rays such as electron beams or ultraviolet rays. Among them, a photo-radical polymerizable adhesive in which radical polymerization is initiated by irradiation with an actinic light beam is preferable from the viewpoint of being capable of low-energy curing and reducing the thickness of the adhesive layer.

(聚合性成分) (polymerizable component)

自由基聚合性接著劑之單體可舉具有(甲基)丙烯醯基之化合物及具有乙烯基之化合物。其中又以具有(甲基)丙烯醯基之化合物為佳。具有(甲基)丙烯醯基之化合物可舉C1-20鏈狀烷基(甲基)丙烯酸酯、脂環式烷基(甲基)丙烯酸酯、多環式烷基(甲基)丙烯酸酯等烷基(甲基)丙烯酸酯；含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸環氧丙酯等含環 氧基之(甲基)丙烯酸酯等。若從提升與易接著層之接著性及提升硬化速度的觀點來看，自由基聚合性接著劑宜含有羥乙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-乙氧基甲基(甲基)丙烯醯胺、(甲基)丙烯醯胺、(甲基)丙烯醯基嗎福林等之(甲基)丙烯醯胺衍生物。 As a monomer of a radically polymerizable adhesive agent, the compound which has a (meth)acryloyl group, and the compound which has a vinyl group are mentioned. Among them, compounds having a (meth)acryloyl group are preferred. Examples of compounds having a (meth)acryloyl group include C 1-20 chain alkyl (meth)acrylates, alicyclic alkyl (meth)acrylates, and polycyclic alkyl (meth)acrylates Alkyl (meth)acrylates; hydroxyl-containing (meth)acrylates; epoxy-containing (meth)acrylates such as glycidyl (meth)acrylate and the like. From the viewpoint of improving the adhesion to the easily bonded layer and increasing the curing speed, the radically polymerizable adhesive preferably contains hydroxyethyl (meth)acrylamide and N-methylol (meth)acrylamide , N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, (meth) acrylamide, (meth) acrylamide, etc. The (meth) acrylamide derivatives.

自由基聚合性接著劑除了可含有單官能單體作為單體成分，亦可含有多官能單體。藉由接著劑組成物含有多官能單體，可於硬化後之接著劑層形成交聯結構，故有提升接著力之傾向。多官能單體可舉：三丙二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、環狀三羥甲丙烷甲縮醛(甲基)丙烯酸酯、二

Figure 108125842-A0305-02-0027-17
烷二醇二(甲基)丙烯酸酯、EO改質二甘油四(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯。 The radically polymerizable adhesive agent may contain a polyfunctional monomer in addition to a monofunctional monomer as a monomer component. Since the adhesive composition contains a polyfunctional monomer, a cross-linked structure can be formed in the adhesive layer after curing, so the adhesive force tends to be improved. Examples of polyfunctional monomers include tripropylene glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclic trihydroxyl Methylpropane methylal (meth)acrylate, dimethacrylate
Figure 108125842-A0305-02-0027-17
Esters of (meth)acrylic acid and polyhydric alcohol such as alkanediol di(meth)acrylate and EO modified diglycerol tetra(meth)acrylate.

併用單官能單體與多官能單體時，相對於聚合性單體之合計100重量份，多官能單體之量宜為3~75重量份左右，5~50重量份較佳，10~30重量份更佳。多官能單體量只要在上述範圍內，便容易形成兼具高接著強度及柔軟性的接著劑層。 When using a monofunctional monomer and a multifunctional monomer together, the amount of the multifunctional monomer is preferably about 3 to 75 parts by weight, preferably 5 to 50 parts by weight, and 10 to 30 parts by weight relative to the total 100 parts by weight of the polymerizable monomers. Parts by weight are better. As long as the amount of the polyfunctional monomer is within the above range, it is easy to form an adhesive layer having both high adhesive strength and flexibility.

就接著劑之構成成分，藉由增加與易接著層之相溶性高的單體之量，有容易於易接著層15與接著劑層之界面形成接著界面層的傾向，該接著界面層係易接著層15之黏結劑樹脂(譬如，胺甲酸乙酯)與接著劑相溶而存在。舉例來說，易接著層之黏結劑樹脂為胺甲酸乙酯系樹 脂時，藉由使用溶解度參數(SP)為20以上(宜為21~24)之單體作為構成接著劑之聚合性單體，接著劑層便會與具有胺甲酸乙酯等黏結劑樹脂成分之易接著層15相溶，而輕易地於易接著薄膜與接著劑層之界面形成接著界面層。與易接著層之相溶性高的聚合性單體可為單官能單體，亦可為多官能單體。 As for the constituent components of the adhesive, by increasing the amount of the monomer having high compatibility with the easily-bonded layer, there is a tendency that an adhesive interface layer is easily formed at the interface between the easily-bonded layer 15 and the adhesive layer, and the adhesive interface layer is easy to form. The adhesive resin (eg, urethane) of the adhesive layer 15 is compatible with the adhesive and exists. For example, the adhesive resin of the easy bonding layer is urethane resin In the case of grease, by using a monomer with a solubility parameter (SP) of 20 or more (preferably 21 to 24) as the polymerizable monomer constituting the adhesive, the adhesive layer will be combined with the urethane and other adhesive resin components The easy-bond layer 15 is compatible with each other, and an adhesive interface layer is easily formed at the interface between the easily-bonded film and the adhesive layer. The polymerizable monomer having high compatibility with the easily adhesive layer may be a monofunctional monomer or a polyfunctional monomer.

易接著層之黏結劑樹脂為胺甲酸乙酯系樹脂時，從促進接著界面層之形成的觀點來看，相對於聚合性單體之合計100重量份，SP為20以上之單體的量宜為30重量份以上，40重量份以上較佳，50重量份以上更佳，60重量份以上尤佳。SP為21~24之範圍內的單體之量宜為20重量份以上，30重量份以上較佳，40重量份以上更佳。SP為21~24之範圍內的聚合性單體可舉丙烯醯基嗎福林(SP：22.9)、N-甲氧基甲基丙烯醯胺(SP：22.9)、N-乙氧基甲基丙烯醯胺(SP：22.3)等。 When the adhesive resin of the easily bonding layer is urethane resin, from the viewpoint of promoting the formation of the bonding interface layer, the amount of the monomer having SP of 20 or more is suitable with respect to the total 100 parts by weight of the polymerizable monomers. It is 30 parts by weight or more, preferably 40 parts by weight or more, more preferably 50 parts by weight or more, and even more preferably 60 parts by weight or more. The amount of the monomer whose SP is in the range of 21 to 24 is preferably 20 parts by weight or more, preferably 30 parts by weight or more, and more preferably 40 parts by weight or more. Examples of polymerizable monomers whose SP is in the range of 21 to 24 include acryl molyfrine (SP: 22.9), N-methoxymethacrylamide (SP: 22.9), N-ethoxymethyl Acrylamide (SP: 22.3) and the like.

<光聚合引發劑> <Photopolymerization initiator>

光自由基聚合性接著劑等之光硬化型接著劑宜含有光聚合引發劑。光聚合引發劑亦可視反應種類適當選擇。舉例來說，針對自由基聚合性接著劑，就光聚合引發劑而言可舉藉由光照射行開裂而生成自由基的光自由基產生劑、或藉由光照射從其他分子奪氫而生成氫的奪氫型聚合引發劑。亦可併用光自由基產生劑與奪氫型聚合引發劑。相對於單體100重量份，光聚合引發劑之含量通常為0.1~10重量份左右，宜為0.5~3重量份。另，設定自由基 聚合性接著劑為電子射線硬化型來使用時，就不特別需要光聚合引發劑。 The photocurable adhesive such as a photoradical polymerizable adhesive preferably contains a photopolymerization initiator. The photopolymerization initiator may be appropriately selected depending on the type of reaction. For example, as for the radically polymerizable adhesive, the photopolymerization initiator includes a photoradical generator that generates radicals by cleaving by light irradiation, or a photoradical generator that generates hydrogen from other molecules by light irradiation. Hydrogen abstraction type polymerization initiator. A photo-radical generator and a hydrogen abstraction type polymerization initiator may be used in combination. The content of the photopolymerization initiator is usually about 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the monomer. Also, set free radicals When the polymerizable adhesive is used as an electron beam curable type, a photopolymerization initiator is not particularly required.

亦可視需求於自由基聚合性接著劑添加以羰基化合物等為代表的光敏化劑。光敏化劑係用來提升電子射線的硬化速度及敏感度。光敏化劑之使用量相對於單體100重量份通常為0.001~10重量份左右，宜為0.01~3重量份。 A photosensitizer represented by a carbonyl compound and the like can also be added to the radically polymerizable adhesive as required. The photosensitizer is used to improve the hardening speed and sensitivity of electron rays. The usage amount of the photosensitizer is usually about 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight, relative to 100 parts by weight of the monomer.

<其他成分> <Other ingredients>

接著劑組成物除含有單體及光聚合引發劑以外，亦可含有聚合物或寡聚物等樹脂成分。藉由接著劑組成物含有聚合物或寡聚物，可減輕使接著劑硬化時的硬化收縮。若從抑制硬化速度之降低並同時減輕硬化收縮的觀點來看，相對於單體100重量份，聚合物或寡聚物之含量宜為5~30重量份，10~25重量份較佳。 The adhesive composition may contain resin components such as polymers and oligomers in addition to monomers and photopolymerization initiators. When the adhesive composition contains a polymer or an oligomer, the curing shrinkage when the adhesive is cured can be reduced. From the viewpoint of suppressing the reduction of the hardening speed and simultaneously reducing the hardening shrinkage, the content of the polymer or oligomer is preferably 5-30 parts by weight, more preferably 10-25 parts by weight, relative to 100 parts by weight of the monomer.

若考慮到塗佈接著劑時的作業性及膜厚均勻性，添加至接著劑組成物的聚合物或寡聚物宜為低黏度。若從抑制接著劑組成物之黏度上升、且減輕硬化收縮的觀點來看，以重量平均分子量為500~15000左右的寡聚物為佳。寡聚物之分子量較宜為1000~10000，1500~5000更佳。若從上述單體及其與硬化物之相溶性優異的觀點來看，寡聚物以丙烯酸系寡聚物為佳。 The polymer or oligomer added to the adhesive composition preferably has a low viscosity in consideration of workability and film thickness uniformity when applying the adhesive. From the viewpoint of suppressing an increase in the viscosity of the adhesive composition and reducing curing shrinkage, an oligomer having a weight average molecular weight of about 500 to 15,000 is preferable. The molecular weight of the oligomer is preferably 1000-10000, more preferably 1500-5000. The oligomer is preferably an acrylic oligomer from the viewpoint of the above-mentioned monomers and their excellent compatibility with the cured product.

接著劑亦可視需求含有適宜的添加劑。添加劑之例可舉矽烷耦合劑、鈦矽烷耦合劑等矽烷耦合劑、環氧乙烷等接著促進劑、紫外線吸收劑、抗劣化劑、染料、 加工助劑、離子捕捉劑、抗氧化劑、賦黏劑、充填劑、塑化劑、調平劑、發泡抑制劑、抗靜電劑、耐熱穩定劑、耐水解穩定劑等。 The subsequent agent may also contain suitable additives as required. Examples of additives include silane coupling agents, silane coupling agents such as titanium silane coupling agents, adhesion accelerators such as ethylene oxide, ultraviolet absorbers, anti-deterioration agents, dyes, Processing aids, ion traps, antioxidants, tackifiers, fillers, plasticizers, leveling agents, foam inhibitors, antistatic agents, heat-resistant stabilizers, hydrolysis-resistant stabilizers, etc.

[製作偏光板] [Make a polarizer]

於偏光件5之一面(第一主面)透過接著劑層貼合易接著薄膜1，可製造偏光板。如圖2所示，藉由於易接著薄膜1之易接著層15的形成面透過接著劑層貼合偏光件5，則偏光件與偏光件保護薄膜(易接著薄膜1)之接著性高，可製得機械強度及耐久性優異的偏光板。 The easy-bond film 1 is attached to one surface (first main surface) of the polarizer 5 through an adhesive layer to manufacture a polarizing plate. As shown in FIG. 2 , by attaching the polarizer 5 through the adhesive layer on the formation surface of the easily bondable layer 15 of the easily bondable film 1, the polarizer and the polarizer protective film (the easily bondable film 1) have high adhesiveness, and can A polarizing plate excellent in mechanical strength and durability was obtained.

<利用接著劑貼合偏光件與易接著薄膜> <Lamination of polarizer and easy-bonding film by adhesive>

在貼合偏光件5與易接著薄膜1時，宜於偏光件5及易接著薄膜1之任一者或兩者塗佈接著劑組成物後，以輥壓貼合機等將偏光件5與易接著薄膜1貼合並使接著劑硬化。將接著劑組成物塗佈至偏光件5及/或易接著薄膜1上的塗佈方法可舉輥塗法、噴霧法、浸漬法等。於偏光件5及/或易接著薄膜1之表面上塗佈接著劑組成物之前，亦可先進行電暈處理、電漿處理、皂化處理等表面處理。 When laminating the polarizer 5 and the easy-bond film 1, it is suitable to apply the adhesive composition to either or both of the polarizer 5 and the easily-bonded film 1, and then use a roll laminating machine or the like to bond the polarizer 5 to the easy-bond film 1. The easy-adhesive film 1 is attached and the adhesive is hardened. The coating method of applying the adhesive composition to the polarizer 5 and/or the easily adhesive film 1 includes a roll coating method, a spray method, a dipping method, and the like. Before coating the adhesive composition on the surface of the polarizer 5 and/or the easily adhesive film 1 , surface treatments such as corona treatment, plasma treatment, and saponification treatment can also be performed.

貼合偏光件5與易接著薄膜1後，可因應接著劑之種類使接著劑硬化而形成接著劑層。使用活性能量線硬化型接著劑時，可藉由照射電子射線或紫外線等活性能量線來使接著劑硬化。 After the polarizer 5 and the easy-to-bond film 1 are bonded together, the adhesive layer can be formed by hardening the adhesive according to the type of the adhesive. When an active energy ray hardening type adhesive is used, the adhesive can be hardened by irradiating active energy rays such as electron beams or ultraviolet rays.

使接著劑硬化後，如圖2之放大圖所示，宜於易接著層15與接著劑層之界面形成有接著界面層61。接著界面層61係易接著層15之黏結劑樹脂成分與接著劑層 之樹脂成分(接著劑組成物之硬化物)相溶而存在的區域(相溶層)(參照圖6)，藉由於接著界面形成相溶層，有提升偏光件5與易接著薄膜1之接著性的傾向。 After the adhesive is hardened, as shown in the enlarged view of FIG. 2 , an adhesive interface layer 61 is preferably formed at the interface between the easily adhesive layer 15 and the adhesive layer. Then the interface layer 61 is the adhesive resin component of the easily adhesive layer 15 and the adhesive layer The region (compatibility layer) (refer to FIG. 6 ) where the resin component (hardened product of the adhesive composition) is compatible with each other, by forming a compatible layer at the adhesive interface, the bonding between the polarizer 5 and the easy-to-bond film 1 is improved. sexual orientation.

藉由形成接著界面層，除了可提升接著性外，還有提升偏光板之切割加工性的傾向。一般而言，偏光件業經高延伸倍率延伸，將偏光板切割加工成符合顯示裝置之畫面尺寸的大小時，容易在與延伸方向(吸收軸方向)垂直的切割端面產生微裂。而在易接著層與接著劑層之界面若形成有接著界面層，便有抑制切割加工時微裂產生的傾向，還有助於提升偏光板之生產性及提升成品率。 By forming the adhesive interface layer, in addition to improving the adhesiveness, there is a tendency to improve the cutting workability of the polarizing plate. Generally speaking, when the polarizer is stretched at a high extension ratio, when the polarizer is cut to fit the screen size of the display device, microcracks are likely to be generated on the cut end face perpendicular to the extension direction (absorption axis direction). If an adhesive interface layer is formed at the interface between the easy-bond layer and the adhesive layer, the tendency of micro-cracks to be suppressed during the cutting process will be suppressed, and the productivity and yield of the polarizing plate will also be improved.

吾等認為，接著劑組成物之單體成分是作為溶劑發揮作用，使易接著層之表層樹脂溶解或膨潤，讓易接著層之樹脂成分滲透接著劑組成物，而形成接著界面層。接著劑組成物只要含有許多使易接著層之黏結劑樹脂溶解或膨潤的單體成分，即可促進接著劑組成物滲透至易接著層之樹脂成分而形成接著界面層。 We believe that the monomer component of the adhesive composition acts as a solvent to dissolve or swell the surface layer resin of the easy-bond layer, allowing the resin component of the easy-bond layer to penetrate the adhesive composition to form an adhesive interface layer. As long as the adhesive composition contains many monomer components that dissolve or swell the binder resin of the easily adhesive layer, the adhesive composition can be promoted to penetrate into the resin component of the easily adhesive layer to form an adhesive interface layer.

塗佈接著劑時及/或貼合易接著薄膜與偏光件時的溫度也可能成為左右形成接著界面層的主因。溫度愈高，樹脂成分之滲透速度就愈大，因此可促進易接著層與接著劑層之樹脂成分的相溶，而有接著界面層之厚度變大的傾向。 The temperature at the time of applying the adhesive and/or laminating the easily-bondable film and the polarizer may also be the main factor for the formation of the adhesive interface layer. The higher the temperature, the greater the penetration rate of the resin component, thus promoting the compatibility of the resin component of the easy-bond layer and the adhesive layer, and the thickness of the bonding interface layer tends to increase.

用以於易接著層15與接著劑層之界面形成接著界面層61的貼合溫度依易接著層及接著劑之組成而異，宜為5℃以上，10℃以上較佳。貼合溫度愈高，愈有 接著界面層61之厚度變大的傾向。 The bonding temperature for forming the adhesive interface layer 61 at the interface between the easy-bond layer 15 and the adhesive layer varies depending on the composition of the easily-bonded layer and the adhesive, and is preferably 5°C or higher, preferably 10°C or higher. The higher the bonding temperature, the more Then, the thickness of the interface layer 61 tends to increase.

隨著接著界面層61之厚度增大，在接著劑層有未形成接著界面層61之區域(接著劑與易接著層不相溶、接著劑單獨存在之接著劑單獨層60)的厚度變小的傾向。接著劑單獨層60之厚度過小時(或不存在接著劑單獨層時)，可能會降低偏光板的切割加工性。若從在利用易接著層與接著劑相溶而形成接著界面層61的同時使接著劑單獨層60殘存的觀點來看，貼合溫度宜為50℃以下，且40℃以下較佳。 As the thickness of the adhesive interface layer 61 increases, the thickness of the adhesive layer in the region where the adhesive interface layer 61 is not formed (the adhesive agent and the easily adhesive layer are incompatible and the adhesive agent independent layer 60 exists alone) decreases. Propensity. If the thickness of the adhesive agent alone layer 60 is too small (or when there is no adhesive agent independent layer), the cutting workability of the polarizing plate may be reduced. The bonding temperature is preferably 50° C. or lower, and more preferably 40° C. or lower, from the viewpoint of leaving the adhesive agent-only layer 60 while forming the adhesive interface layer 61 by compatibility of the easily-bonded layer and the adhesive.

接著界面層之厚度若從提高其與易接著薄膜1(偏光件保護薄膜)之界面的接著性的觀點來看，宜為40nm以上，且50nm以上較佳。接著界面層61之厚度亦可為75nm以上、100nm以上、150nm以上或200nm以上。接著界面層之厚度愈大愈有提升接著性的傾向，但隨著接著界面層之厚度增大，可能會有接著劑單獨層之厚度變小、切割加工性降低的情況。接著劑單獨層60之厚度若從提高其與偏光件5之界面的接著性以及確保偏光板之切割加工性的觀點來看，宜為120nm以上，150nm以上較佳。 The thickness of the next interface layer is preferably 40 nm or more, and more preferably 50 nm or more, from the viewpoint of improving the adhesiveness of the interface with the easy-bond film 1 (polarizer protective film). Then, the thickness of the interface layer 61 may be 75 nm or more, 100 nm or more, 150 nm or more, or 200 nm or more. The greater the thickness of the interface layer, the better the adhesiveness tends to be. However, as the thickness of the interface layer increases, the thickness of the adhesive layer alone may decrease and the cutting processability may decrease. The thickness of the adhesive agent single layer 60 is preferably 120 nm or more, more preferably 150 nm or more, from the viewpoints of improving the adhesiveness of the interface with the polarizer 5 and ensuring the cutting workability of the polarizing plate.

若從使接著劑單獨層60及接著界面層61之厚度在上述範圍內的觀點來看，接著劑單獨層60與接著界面層61之厚度合計宜為300nm以上，400nm以上較佳，500nm以上更佳。從偏光板薄型化的觀點、及使接著界面層之厚度比落在適當範圍內的觀點來看，接著劑單獨層60與接著界面層61之厚度宜為3μm以下，2.5μm以下較 佳，2μm以下更佳。 From the viewpoint of keeping the thicknesses of the adhesive agent independent layer 60 and the adhesive interface layer 61 within the above-mentioned ranges, the total thickness of the adhesive agent independent layer 60 and the adhesive interface layer 61 is preferably 300 nm or more, preferably 400 nm or more, and more preferably 500 nm or more. good. From the viewpoint of reducing the thickness of the polarizing plate and from the viewpoint of keeping the thickness ratio of the adhesive interface layer within an appropriate range, the thickness of the adhesive agent individual layer 60 and the adhesive interface layer 61 is preferably 3 μm or less, and 2.5 μm or less is preferable. good, more preferably 2 μm or less.

相對於接著劑單獨層60與接著界面層61之厚度合計，接著界面層61之厚度宜為5~90%，10~85%較佳。相對於接著劑單獨層60與接著界面層61之合計厚度，接著界面層61之厚度亦可為15%以上或20%以上，或可為80%以下或75%以下。接著界面層之有無、以及接著界面層及接著劑單獨層之厚度可藉由穿透型電子顯微鏡(TEM)觀察偏光板截面來求得。 Relative to the total thickness of the adhesive separate layer 60 and the adhesive interface layer 61 , the thickness of the adhesive interface layer 61 is preferably 5-90%, preferably 10-85%. The thickness of the adhesive interface layer 61 may be 15% or more or 20% or more, or 80% or less or 75% or less, relative to the total thickness of the adhesive single layer 60 and the adhesive interface layer 61 . The presence or absence of the interface layer, and the thickness of the interface layer and the adhesive layer alone can be obtained by observing the cross section of the polarizing plate with a transmission electron microscope (TEM).

即使在易接著層15之接著劑層側之界面存在接著界面層61的情況，還是可於易接著層15之薄膜基材11側之界面形成有薄膜基材之樹脂成分與易接著層之構成成分混雜的基材界面層。藉由於易接著層15之接著劑層側及薄膜基材11側之兩面形成有界面層，可使基材薄膜牢固地接著於偏光件上，即使在高溫高濕環境等下也不易產生層間剝離。 Even if the adhesive interface layer 61 is present at the interface on the adhesive layer side of the easily adhesive layer 15, the composition of the resin component of the film substrate and the easily adhesive layer can be formed at the interface on the film substrate 11 side of the easily adhesive layer 15 Substrate interface layer with mixed composition. Since the interface layer is formed on both sides of the adhesive layer side of the easily adhesive layer 15 and the film substrate 11 side, the substrate film can be firmly bonded to the polarizer, and interlayer peeling is not easy to occur even in a high temperature and high humidity environment, etc. .

<透明保護薄膜> <Transparent protective film>

亦可於偏光件5之第二主面透過接著劑層7貼合透明保護薄膜2。透明保護薄膜2可採用任意適當的透明薄膜。透明保護薄膜2之厚度為5~200μm左右。從機械強度、透明性及處置性等觀點來看，透明保護薄膜2之厚度宜為10~100μm，15~60μm較佳。易接著薄膜1與透明保護薄膜2之厚度可相同亦可互異。 The transparent protective film 2 can also be attached to the second main surface of the polarizer 5 through the adhesive layer 7 . Any appropriate transparent film can be used as the transparent protective film 2 . The thickness of the transparent protective film 2 is about 5-200 μm. From the viewpoints of mechanical strength, transparency, and handling properties, the thickness of the transparent protective film 2 is preferably 10 to 100 μm, preferably 15 to 60 μm. The thickness of the easy-bonding film 1 and the transparent protective film 2 may be the same or different from each other.

形成透明保護薄膜2之材料可舉聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸 乙二酯(PEN)等聚酯類；二乙醯纖維素或三乙醯纖維素等纖維素系聚合物；聚苯乙烯或丙烯腈‧苯乙烯共聚物等苯乙烯系聚合物；聚降莰烯等環狀聚烯烴；聚碳酸酯等。 Materials for forming the transparent protective film 2 include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate Polyesters such as ethylene glycol (PEN); cellulose-based polymers such as diacetyl cellulose or triacetyl cellulose; styrene-based polymers such as polystyrene or acrylonitrile-styrene copolymer; polynorborn Cyclic polyolefins such as olefin; polycarbonate, etc.

透明保護薄膜2亦可在與偏光件5之貼合面具備易接著層(未圖示)。亦可於透明保護薄膜2設置與易接著薄膜1之易接著層15相同的易接著層。 The transparent protective film 2 may also have an easy-bonding layer (not shown) on the bonding surface with the polarizer 5 . The same easy-bonding layer as the easy-bonding layer 15 of the easy-bonding film 1 can also be provided on the transparent protective film 2 .

用於貼合偏光件5與透明保護薄膜2之接著劑層7可使用水系接著劑、溶劑系接著劑、熱熔膠接著劑系、自由基聚合硬化型接著劑等各種形態的接著劑。亦可於接著劑層與接著劑層7使用相同的接著劑組成物。 The adhesive layer 7 for bonding the polarizer 5 and the transparent protective film 2 can use various types of adhesives such as water-based adhesives, solvent-based adhesives, hot-melt adhesives, and radical polymerization-curable adhesives. The same adhesive composition can also be used for the adhesive layer and the adhesive layer 7 .

[偏光板之用途] [Use of polarizing plate]

偏光板上亦可設置用以貼合至液晶單元或有機EL單元等的黏著劑層。形成黏著劑層之黏著劑可適宜選擇使用以丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺甲酸乙酯、聚醯胺、聚醚、氟系或橡膠系等聚合物作為基底聚合物者。其中，從光學透明性優異、顯示出適度濡濕性與凝集性並且耐候性及耐熱性等優異的觀點來看，尤以丙烯酸系黏著劑為宜。 An adhesive layer for bonding to a liquid crystal cell, an organic EL cell, etc. may also be provided on the polarizing plate. The adhesive for forming the adhesive layer can be suitably selected from acrylic polymer, polysiloxane polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer as the base polymer. Among them, acrylic adhesives are particularly suitable from the viewpoints of being excellent in optical transparency, exhibiting moderate wettability and cohesiveness, and being excellent in weather resistance, heat resistance, and the like.

於偏光板附設黏著劑層可以適宜的方式進行。譬如，可舉使基底聚合物等溶解或分散至甲苯或乙酸乙酯等溶劑中調製出固體成分濃度10~40重量%左右之黏著劑溶液而附設於偏光板上的方式，或是將形成於適宜的基材上之黏著劑層轉印至偏光板上的方法等。 Attaching the adhesive layer to the polarizing plate can be performed in a suitable manner. For example, a method of dissolving or dispersing a base polymer or the like in a solvent such as toluene or ethyl acetate to prepare an adhesive solution with a solid content concentration of about 10 to 40% by weight, and attaching it to a polarizing plate, or forming it on a polarizing plate can be used. The method of transferring the adhesive layer on the suitable substrate to the polarizing plate, etc.

亦可在偏光板兩面設置黏著劑層。於偏光板 兩面設置黏著劑層時，表面與背面之黏著劑層之組成及厚度可相同亦可互異。黏著劑層之厚度一般為5~500μm左右。 Adhesive layers can also be provided on both sides of the polarizing plate. on polarizer When the adhesive layers are arranged on both sides, the composition and thickness of the adhesive layers on the front and back can be the same or different from each other. The thickness of the adhesive layer is generally about 5 to 500 μm.

在防止黏著劑層汙染等目的下，亦可於黏著劑層之表面暫設分離件。分離件宜使用塑膠薄膜表面業以聚矽氧系脫模劑、長鏈烷基系脫模劑、氟系脫模劑等剝離劑進行塗佈處理者。 For the purpose of preventing the contamination of the adhesive layer, a separator can also be temporarily provided on the surface of the adhesive layer. Separation parts should be treated with release agents such as polysiloxane-based mold release agents, long-chain alkyl-based mold release agents, and fluorine-based mold release agents on the surface of plastic films.

偏光板亦可為與其他光學層積層而成的積層偏光板。光學層可舉相位差板、視角補償薄膜、亮度提升薄膜等。 The polarizing plate may also be a laminated polarizing plate laminated with other optics. Examples of the optical layer include retardation plates, viewing angle compensation films, and brightness enhancement films.

藉由將偏光板貼合至液晶單元或有機EL單元等影像顯示單元之表面，可形成影像顯示裝置。液晶顯示裝置之形成可藉由將液晶單元與偏光板以及視需求之照明系統等構成零件適宜組裝並組入驅動電路等來形成。在有機EL顯示裝置中，藉由於有機EL單元表面貼合本發明之偏光板與相位差薄膜(典型上為1/4波長板)組合而成之圓偏光板，可降低外光之反射光因金屬電極等而再出射，提升視辨性。 An image display device can be formed by attaching a polarizing plate to the surface of an image display unit such as a liquid crystal cell or an organic EL cell. The liquid crystal display device can be formed by appropriately assembling components such as a liquid crystal cell, a polarizer, and an illumination system as required, and incorporating a driving circuit and the like. In the organic EL display device, the circular polarizing plate formed by attaching the polarizing plate of the present invention and the retardation film (typically a 1/4 wavelength plate) to the surface of the organic EL unit can reduce the reflected light factor of external light. The metal electrode waits and then emits to improve the visibility.

實施例 Example

以下列舉實施例更具體說明本發明，但本發明不受限於該等實施例。以下符號「%」之記載在未特別說明之前提下表示重量%。 The following examples are given to illustrate the present invention more specifically, but the present invention is not limited to these examples. The description of the symbol "%" below means % by weight unless otherwise specified.

[製作偏光件] [Make a polarizer]

<偏光件1> <Polarizer 1>

將厚度45μm之聚乙烯醇(PVA)系樹脂薄膜(Kuraray Co.,Ltd.製「PE4500」)的長條卷料以滾筒延伸機往長邊方向進行單軸延伸使長邊方向成5.9倍，同時按表1所示之膨潤浴、染色浴、交聯浴1、交聯浴2及洗淨浴依序輸送後，在70℃下乾燥5分鐘而製出厚度18μm之偏光件。染色浴中之碘濃度及碘化鉀濃度已調整成使偏光件之單體透射率為43.4%。 A long roll of polyvinyl alcohol (PVA)-based resin film ("PE4500" manufactured by Kuraray Co., Ltd.) with a thickness of 45 μm was uniaxially stretched in the longitudinal direction with a roll stretcher so that the longitudinal direction was 5.9 times. At the same time, the swelling bath, dyeing bath, cross-linking bath 1, cross-linking bath 2 and cleaning bath shown in Table 1 were transported in sequence, and then dried at 70°C for 5 minutes to produce a polarizer with a thickness of 18 μm. The iodine concentration and potassium iodide concentration in the dye bath were adjusted so that the monomer transmittance of the polarizer was 43.4%.

Figure 108125842-A0305-02-0036-1
Figure 108125842-A0305-02-0036-1

<偏光件2：薄型偏光件> <Polarizer 2: Thin Polarizer>

對厚度100μm之非晶質聚酯薄膜(聚對苯二甲酸乙二酯/聚間苯二甲酸乙二酯；玻璃轉移溫度75℃)的單面施行電暈處理後，在25℃下將以9：1之重量比含有聚乙烯醇(聚合度4200，皂化度99.2莫耳%)及乙醯乙醯基改質聚乙烯醇(日本合成化學工業「GOHSEFIMER Z200」；聚合度1200，乙醯乙醯基改質度4.6%，皂化度99.0莫耳%以上)的水溶液塗佈至電暈處理面上且使其乾燥，而製作出在非晶質聚酯薄膜基材上設有厚度11μm之PVA系樹脂層的積層體。 After corona treatment was performed on one side of an amorphous polyester film with a thickness of 100 μm (polyethylene terephthalate/polyethylene isophthalate; glass transition temperature of 75°C), the The weight ratio of 9:1 contains polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetyl acetyl group modified polyvinyl alcohol (Japan Synthetic Chemical Industry "GOHSEFIMER Z200"; degree of polymerization 1200, acetone B An aqueous solution with an acyl group modification degree of 4.6% and a saponification degree of 99.0 mol% or more) was applied to the corona treated surface and dried to produce a PVA with a thickness of 11 μm on the amorphous polyester film substrate. A laminate of resin layers.

使該積層體在120℃之烘箱內藉由空中補助延伸於長邊方向自由端單軸延伸2.0倍後，一邊將其進行輥輸送並一邊依序浸漬於30℃之4%硼酸水溶液中30秒鐘、30℃之染色液(0.2%碘、1.0%碘化鉀水溶液)60秒鐘。接著，將積層體一邊進行輥輸送並一邊使其浸漬於30℃之交聯液(使碘化鉀為3%、硼酸3%之水溶液)中30秒鐘進行交聯處理後，浸漬於70℃之硼酸4%、碘化鉀5%水溶液中，使其於長邊方向進行自由端單軸延伸且總延伸倍率為5.5倍。然後，將積層體浸漬於30℃之洗淨液(4%碘化鉀水溶液)中而獲得非晶質聚酯薄膜基材上設有厚度5μm之PVA系偏光件的積層體。 The layered body was uniaxially stretched 2.0 times at the free end in the longitudinal direction by air-assisted extension in an oven at 120°C, and then immersed in a 4% aqueous solution of boric acid at 30°C for 30 seconds while being transported by rollers. Clock, 30 ℃ staining solution (0.2% iodine, 1.0% potassium iodide aqueous solution) for 60 seconds. Next, the layered body was immersed in a cross-linking solution (aqueous solution of 3% potassium iodide and 3% boric acid) at 30° C. for 30 seconds while being transported by rollers to perform cross-linking treatment, and then immersed in boric acid at 70° C. 4%, potassium iodide 5% aqueous solution, the free end was uniaxially stretched in the longitudinal direction, and the total stretching ratio was 5.5 times. Then, the laminate was immersed in a cleaning solution (4% potassium iodide aqueous solution) at 30° C. to obtain a laminate having a PVA-based polarizer having a thickness of 5 μm on an amorphous polyester film substrate.

[製作易接著薄膜] [Production of Easy-Adhesive Film]

(調製易接著組成物) (Preparation of easily bonding composition)

將含有聚酯胺甲酸乙酯及異佛酮二異氰酸酯作為樹脂成分且更含有作為硬化觸媒之三乙胺及作為分散介質之甲基乙基酮的固體成分34%之水系聚胺甲酸乙酯(第一工業製藥製「SuperFlex 210R」)20.6重量份、固體成分25%之含

Figure 108125842-A0305-02-0037-16
唑啉之聚合物水溶液(日本觸媒製「Epocros WS-700」)5.2重量份、1重量%之氨水2.8重量份、平均一次粒徑35nm之膠質氧化矽的20%水分散液(扶桑化學工業製「Quartron PL-3」)7.5重量份及純水63.9重量份混合，而調製出易接著組成物。該易接著組成物係相對於固體成分100重量份含有15.3重量份二氧化矽粒子之濃度9.8%的水溶液。在以下各例中，係使用該易接著組成物來形成易 接著層。 Aqueous polyurethane with a solid content of 34% containing polyester urethane and isophorone diisocyanate as resin components and further containing triethylamine as a hardening catalyst and methyl ethyl ketone as a dispersion medium ("SuperFlex 210R" manufactured by Daiichi Kogyo Pharmaceutical) 20.6 parts by weight, 25% solid content
Figure 108125842-A0305-02-0037-16
Aqueous polymer solution of oxazoline ("Epocros WS-700" manufactured by Nippon Shokubai Co., Ltd.) 5.2 parts by weight, 2.8 parts by weight of 1% by weight ammonia water, 20% aqueous dispersion of colloidal silica with an average primary particle size of 35nm (Fuso Chemical Industry Co., Ltd. 7.5 parts by weight of "Quartron PL-3") and 63.9 parts by weight of pure water were mixed to prepare an easily bonding composition. The easily bonded composition was an aqueous solution containing 15.3 parts by weight of silica particles with a concentration of 9.8% with respect to 100 parts by weight of solid content. In the following examples, the easily bonding layer was formed using this easily bonding composition.

<易接著薄膜1> <Easy Bonding Film 1>

使用具備熔融擠製製膜裝置、凹版塗佈機、拉幅機式同時雙軸延伸裝置及捲取裝置之薄膜製造裝置來製作易接著薄膜。作為丙烯酸系樹脂，係使用與日本專利特開2017-26939號之實施例中記載用於製作「透明保護薄膜1A」者相同的醯亞胺化MS樹脂(玻璃轉移溫度：120℃)之丸粒。將丙烯酸系樹脂從T型模熔融擠製，以160μm之厚度進行製膜後，於薄膜之一面利用凹版塗佈機以約9μm之濕式厚度塗佈上述易接著組成物，在溫度140℃之加熱爐內以同時雙軸延伸拉幅機於長邊方向(MD)及寬度方向(TD)分別延伸成2倍，而獲得於厚度40μm之丙烯酸系薄膜之一面具備厚度30nm之易接著層的易接著薄膜。 The easily adhesive film was produced using a film production apparatus equipped with a melt extrusion film forming apparatus, a gravure coater, a tenter-type simultaneous biaxial stretching apparatus, and a winding apparatus. As the acrylic resin, pellets of the same imidized MS resin (glass transition temperature: 120°C) as described in the Example of Japanese Patent Laid-Open No. 2017-26939 for producing the "transparent protective film 1A" were used . The acrylic resin was melted and extruded from the T-die, and the film was formed with a thickness of 160 μm. Then, the above-mentioned easy-adhesive composition was applied on one side of the film with a wet thickness of about 9 μm by a gravure coater, and the temperature was 140 ° C. In the heating furnace, the simultaneous biaxial stretching tenter was stretched by 2 times in the longitudinal direction (MD) and the width direction (TD), respectively, to obtain an easy bonding layer with a thickness of 30 nm on one side of an acrylic film with a thickness of 40 μm. Then the film.

<易接著薄膜2~6> <Easy Bonding Film 2~6>

除了變更易接著組成物之塗佈厚度以外，以與製作易接著薄膜1同樣方式獲得易接著薄膜。易接著層之厚度(延伸後)如表2所示。 An easily-bondable film was obtained in the same manner as in the preparation of the easily-bonded film 1 except that the coating thickness of the easily-bonded composition was changed. The thickness of the easily bonding layer (after stretching) is shown in Table 2.

<易接著薄膜7~11> <Easy Bonding Film 7~11>

如表2所示改變拉幅機延伸時之爐內溫度(延伸溫度)。除了變更延伸溫度以外，以與製作易接著薄膜1同樣方式獲得易接著薄膜。 The furnace temperature (stretching temperature) during stretching of the tenter was changed as shown in Table 2. An easily-adhesive film was obtained in the same manner as in the preparation of the easily-adhesive film 1 except that the stretching temperature was changed.

<薄膜12> <Film 12>

未以凹版塗佈機塗佈易接著組成物而獲得不具備易接著層之厚度40μm的丙烯酸系薄膜。 An acrylic film having a thickness of 40 μm without an easily bonding layer was obtained without applying the easily bonding composition with a gravure coater.

[調製紫外線硬化型接著劑] [Preparation of UV-curable adhesive]

<接著劑1> <Adhesive 1>

調製紫外線硬化型接著劑，該紫外線硬化型接著劑含有N-羥乙基丙烯醯胺(SP：29.6)17重量份、丙烯醯基嗎福林(SP：22.9)50重量份、聚丙二醇(n≒3)二丙烯酸酯(東亞合成製「ARONIX M-220」，SP：19.0)17重量份及丙烯酸系塑化劑(東亞合成製「ARUFON UP-1190」)16重量份作為樹脂成分，更含有2-甲基-1-(4-甲基苯硫基)-2-嗎福林基丙-1-酮(BASF製「IRGACURE 907」)0.5重量份及2,4-二乙基9-氧硫

Figure 108125842-A0305-02-0039-11
(日本化藥製「KAYACURE DETX-S」)0.2重量份作為聚合引發劑。 A UV-curable adhesive containing 17 parts by weight of N-hydroxyethyl acrylamide (SP: 29.6), 50 parts by weight of acrylmophrine (SP: 22.9), polypropylene glycol (n ≒3) 17 parts by weight of diacrylate (“ARONIX M-220” manufactured by Toagosei, SP: 19.0) and 16 parts by weight of acrylic plasticizer (“ARUFON UP-1190” manufactured by Toagosei) as resin components, and further contained 2-Methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-one (“IRGACURE 907” manufactured by BASF) 0.5 parts by weight and 2,4-diethyl 9-oxo sulfur
Figure 108125842-A0305-02-0039-11
("KAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd.) 0.2 parts by weight was used as a polymerization initiator.

<接著劑2> <Adhesive 2>

調製紫外線硬化型接著劑，該紫外線硬化型接著劑含有N-羥乙基丙烯醯胺17重量份、丙烯醯基嗎福林17重量份、聚丙二醇(n≒3)二丙烯酸酯(東亞合成製「ARONIX M-220」)50重量份及丙烯酸系塑化劑(東亞合成製「ARUFON UP-1190」)16重量份作為樹脂成分，更含有2-甲基-1-(4-甲基苯硫基)-2-嗎福林基丙-1-酮(BASF製「IRGACURE 907」)0.5重量份及2,4-二乙基9-氧硫

Figure 108125842-A0305-02-0039-12
(日本化藥製「KAYACURE DETX-S」)0.2重量份作為聚合引發劑。 A UV-curable adhesive containing 17 parts by weight of N-hydroxyethyl acrylamide, 17 parts by weight of acryl molyfline, and polypropylene glycol (n≒3) diacrylate (manufactured by Toagosei) was prepared. 50 parts by weight of "ARONIX M-220") and 16 parts by weight of acrylic plasticizer ("ARUFON UP-1190", manufactured by Toagosei Corporation) as resin components, further containing 2-methyl-1-(4-methylphenylsulfide) base)-2-morpholinylpropan-1-one (“IRGACURE 907” manufactured by BASF) 0.5 parts by weight and 2,4-diethyl 9-oxothio
Figure 108125842-A0305-02-0039-12
("KAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd.) 0.2 parts by weight was used as a polymerization initiator.

<接著劑3> <Adhesive 3>

調製含有N-羥乙基丙烯醯胺40重量份及丙烯醯基嗎福林60重量份作為硬化性成分，更含有作為聚合引發劑之 2-甲基-1-(4-甲基苯硫基)-2-嗎福林基丙-1-酮(BASF製「IRGACURE 907」)3重量份的紫外線硬化型接著劑。 The preparation contains 40 parts by weight of N-hydroxyethyl acrylamide and 60 parts by weight of acryl molyfrin as curable components, and further contains as a polymerization initiator 2-methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-one (“IRGACURE 907” manufactured by BASF) is a UV-curable adhesive of 3 parts by weight.

[偏光板之製作1] [Production of polarizing plate 1]

一面之偏光件保護薄膜係使用上述易接著薄膜1~11及薄膜12，另一面之偏光件保護薄膜則使用雙軸延伸環狀聚烯烴(COP)薄膜(日本ZEON製「ZeonorFilm ZF-14」)。於易接著薄膜之易接著層形成面及ZeonorFilm表面以約1μm之厚度塗佈上述接著劑3並以輥壓貼合機貼合至偏光件1後，從兩面分別照射累積光量500/mJ/cm2之紫外線使接著劑硬化，而獲得於偏光件之一面貼合有丙烯酸系薄膜(易接著薄膜)且另一面貼合有ZeonorFilm的偏光板。 The polarizer protective film on one side uses the above-mentioned easy-to-bond films 1 to 11 and 12, and the polarizer protective film on the other side uses a biaxially stretched cyclic polyolefin (COP) film (ZeonorFilm ZF-14, manufactured by ZEON, Japan). . The above-mentioned adhesive agent 3 was applied to the easy-adhesive layer forming surface of the easy-adhesive film and the surface of ZeonorFilm with a thickness of about 1 μm, and the adhesive agent 3 was applied to the polarizer 1 by a roll laminating machine. The ultraviolet rays of 2 hardened the adhesive to obtain a polarizing plate in which an acrylic film (easy-bonding film) was attached to one side of the polarizer and ZeonorFilm was attached to the other side.

[評估] [Evaluate]

<易接著層之鹼殘量> <Alkali Residual Amount of Easy Bonding Layer>

定量出殘留在易接著層之三乙胺及氨之量。三乙胺之殘量係秤量出從易接著薄膜表面削出易接著層的粉末並將之溶解於甲醇中後，利用溶液之氣相層析質量分析(GC/MS)法來定量。氨之殘量則係將易接著薄膜浸漬於25℃之純水中後，以120℃之乾燥機進行60分鐘加熱萃取後，以離子層析分析定量出溶出在水中之氨。將三乙胺之量與氨之量的合計定為鹼殘量。 The amounts of triethylamine and ammonia remaining in the easily bondable layer were quantified. The residual amount of triethylamine was quantified by the gas chromatography mass spectrometry (GC/MS) method of the solution after weighing and dissolving the powder of the easily bonding layer from the surface of the easily bonding film by weighing and dissolving it in methanol. The residual amount of ammonia is obtained by immersing the easily bondable film in pure water at 25°C, heating and extracting it in a dryer at 120°C for 60 minutes, and then quantifying the ammonia dissolved in the water by ion chromatography. The total of the amount of triethylamine and the amount of ammonia was defined as the alkali residual amount.

<易接著層之密著性> <Adhesion of Easy Bonding Layer>

於易接著薄膜之易接著層形成面在線壓8kg/m、壓接速度0.3m/分鐘下壓接黏著膠帶(日東電工製「No.31B」)，並在50℃下保存48小時後，把持黏著膠帶的前端以拉伸速 度30m/分鐘進行180°剝離試驗，並按下述基準判定易接著層之密著性。 On the easy-adhesive layer forming surface of the easy-adhesive film, press-bond an adhesive tape (No. 31B, manufactured by Nitto Denko) at a line pressure of 8 kg/m and a pressure-bonding speed of 0.3 m/min, and store it at 50°C for 48 hours. The front end of the adhesive tape is stretched at the A 180° peel test was performed at a temperature of 30 m/min, and the adhesion of the easily bonding layer was judged according to the following criteria.

○：易接著層未從丙烯酸系薄膜剝離而在黏著膠帶與易接著層之界面剝離者 ○: The easy-adhesive layer was not peeled from the acrylic film but was peeled off at the interface between the adhesive tape and the easy-adhesive layer

×：在丙烯酸系薄膜與易接著層之界面發生剝離者 ×: peeling occurred at the interface between the acrylic film and the easily bonding layer

<肉眼評估> <Visual evaluation>

以肉眼觀察易接著薄膜的表面，評估有無因二氧化矽粒子凝集而產生局部的混濁(霧度上升)及在易接著層非形成面有無損傷。 The surface of the easy-bond film was observed with the naked eye, and the presence or absence of local turbidity (increase in haze) caused by the aggregation of silica particles and the presence or absence of damage on the non-formed surface of the easily-bonded layer were evaluated.

○：無二氧化矽粒子凝集、面內均勻性良好且未發現損傷者 ○: No aggregation of silica particles, good in-plane uniformity, and no damage found

△：雖未見因二氧化矽粒子凝集產生之混濁，但在易接著層非形成面確認有深度1μm以下的損傷者 △: Although no turbidity caused by the aggregation of silica particles was observed, damage with a depth of 1 μm or less was confirmed on the non-forming surface of the easily bonding layer

×：因二氧化矽粒子凝集產生混濁及確認易接著層非形成面有損傷者 ×: Cloudiness caused by aggregation of silica particles and damage to the non-formed surface of the easy-bond layer was confirmed

<基材界面層之有無> <Presence or absence of substrate interface layer>

以穿透型電子顯微鏡(TEM)觀察易接著薄膜之截面，確認在丙烯酸系薄膜與易接著層之界面有無易接著層中之粒子埋設在丙烯酸系薄膜的區域(基材界面層)。於圖3顯示使用易接著薄膜4之偏光板(有基材界面層)之TEM觀察影像，於圖4顯示使用易接著薄膜8之偏光板(無基材界面層)之TEM觀察影像。 The cross section of the easily bondable film was observed with a transmission electron microscope (TEM) to confirm whether there was a region (substrate interface layer) where particles in the easily bondable layer were embedded in the acrylic film at the interface between the acrylic film and the easily bondable layer. FIG. 3 shows the TEM observation image of the polarizer (with substrate interface layer) using the easily bondable film 4, and FIG. 4 shows the TEM observation image of the polarizer using the easily bondable film 8 (without the substrate interface layer).

<偏光板之加濕耐久性> <Humidification Durability of Polarizing Plates>

將偏光板裁切成320mm×240mm之尺寸後，將環狀聚 烯烴薄膜側之面透過厚度20μm之丙烯酸系黏著劑貼合至玻璃上。將該試料放入溫度60℃且相對濕度90%(條件1)之恆溫恆濕槽、或溫度85℃、相對濕度85%(條件2)之恆溫恆濕槽中，並保持500小時實施加熱、加濕耐久試驗。 After cutting the polarizing plate into a size of 320mm×240mm, The surface on the side of the olefin film was pasted to the glass through an acrylic adhesive with a thickness of 20 μm. The sample was placed in a constant temperature and humidity tank with a temperature of 60°C and a relative humidity of 90% (condition 1), or a constant temperature and humidity tank with a temperature of 85°C and a relative humidity of 85% (condition 2), and kept for 500 hours to carry out heating, Humidification durability test.

測定耐久試驗前的偏光度P0及耐久試驗後的偏光度P，算出偏光度的變化量△P=| P-P0 |。並且在正交偏光鏡下於耐久試驗後的偏光板上配置其他偏光板，以肉眼觀察確認有無筋條狀不均，並按以下基準做評估。 The degree of polarization P 0 before the durability test and the degree of polarization P after the durability test were measured, and the amount of change in the degree of polarization ΔP=|PP 0 | was calculated. In addition, another polarizing plate was placed on the polarizing plate after the durability test under a crossed polarizer, and the presence or absence of rib-like unevenness was confirmed by visual observation, and the evaluation was made according to the following criteria.

◎：在條件1及條件2之耐久試驗後的試料皆未觀察到條痕不均 ⊚: No uneven streak was observed in the samples after the durability test of Condition 1 and Condition 2

○：於條件1之耐久試驗後的試料未觀察到條痕不均，於條件2之耐久試驗後的試料可視辨出些許的條痕不均 ○: No uneven streaks were observed in the samples after the endurance test under Condition 1, and some uneven streaks were seen in the samples after the endurance test under Condition 2

△：在條件1及條件2之耐久試驗後的試料皆可視辨出些許的條痕不均 △: Slight uneven streaks can be seen in the samples after the durability test of Condition 1 and Condition 2

×：在條件1及條件2之耐久試驗後的試料皆可清楚視辨出條痕不均 ×: Uneven streaks can be clearly seen in the samples after the durability test of Condition 1 and Condition 2

於圖5顯示使用易接著薄膜2之偏光板及使用易接著薄膜6之偏光板於耐久試驗(60℃ 90%Rh 500小時)前後在正交偏光鏡下的觀察照片(以低亮度用不均計測系統，I System Co.製「EYESCALE-4W」拍攝)。 Figure 5 shows the observation photos under the crossed polarizer before and after the durability test (60°C, 90%Rh, 500 hours) of the polarizing plate using the easy-bonding film 2 and the polarizing plate using the easy-bonding film 6 (with unevenness at low brightness). Measurement system, photographed by "EYESCALE-4W" manufactured by I System Co.).

於表2顯示易接著薄膜1~11之製作條件(延伸溫度及延伸後之易接著層的厚度)、易接著薄膜之評估結果(肉眼、密著性、有無基材界面層)、以及偏光板的耐久 試驗結果(有無條痕不均及偏光度的變化量△P)。 Table 2 shows the fabrication conditions (stretching temperature and the thickness of the easily-bonded layer after stretching) of the easily-bonded films 1 to 11, the evaluation results of the easily-bonded films (the naked eye, the adhesion, the presence or absence of the substrate interface layer), and the polarizing plate durability Test results (presence or absence of uneven streaks and change in degree of polarization ΔP).

Figure 108125842-A0305-02-0043-2
Figure 108125842-A0305-02-0043-2

使用未形成易接著層之丙烯酸系薄膜(薄膜 12)的偏光板，於加濕耐久試驗後依舊未觀察到條痕不均，且偏光度降低的情況小，展現良好的光學特性。然而，丙烯酸系薄膜與偏光件之接著性低，於加濕耐久試驗後在偏光板之端部發現了丙烯酸系薄膜從偏光件剝離。 Use an acrylic film without an easily bonding layer (film The polarizing plate of 12) still has no uneven streaks after the humidification durability test, and the decrease in the degree of polarization is small, showing good optical properties. However, the adhesion between the acrylic film and the polarizer was low, and the acrylic film was found to be peeled from the polarizer at the end of the polarizing plate after the humidification durability test.

具備厚度350nm之易接著層的易接著薄膜6，丙烯酸系薄膜與易接著層之密著性良好，易接著薄膜之外觀亦佳。但，將易接著薄膜6作為偏光件保護薄膜使用的偏光板於加濕耐久試驗後的偏光度降低明顯，確認有顯著的筋條狀不均。在延伸溫度(易接著層形成時之加熱溫度)為120℃以下的易接著薄膜7~9中，亦與易接著薄膜6同樣於加濕耐久試驗後之偏光度降低明顯，確認有顯著的筋條狀不均。 The easy-bonding film 6 having the easy-bonding layer with a thickness of 350 nm has good adhesion between the acrylic film and the easy-bonding layer, and the appearance of the easy-bonding film is also good. However, the polarization degree after the humidification durability test of the polarizing plate using the easily adhesive film 6 as a polarizer protective film was significantly decreased, and it was confirmed that there was a significant streak-like unevenness. In the easily bondable films 7 to 9 whose stretching temperature (heating temperature during the formation of the easily bondable layer) was 120° C. or lower, the polarization degree after the humidification endurance test was markedly decreased similarly to the easily bondable film 6, and it was confirmed that there were marked streaks. Uneven stripes.

在延伸溫度140℃下形成50nm~250nm之易接著層的易接著薄膜2~5，未見因微粒子凝集而產生的白濁，展現良好的外觀。另，易接著薄膜2雖於易接著層非形成面發現微細的損傷，但該損傷程度在與其他構件貼合時會被黏著劑或接著劑等填埋，不構成光學缺陷。而且，使用易接著薄膜2~5的偏光板，比起使用易接著薄膜6的偏光板，加濕耐久性更為優異，且抑制了條痕不均的發生。 The easily-bondable films 2 to 5 in which an easily-bonded layer of 50 nm to 250 nm was formed at the stretching temperature of 140° C. showed good appearance without cloudiness due to aggregation of fine particles. In addition, the easily bonding film 2 has fine damages on the non-forming surface of the easily bonding layer, but the damages are buried by an adhesive or an adhesive when bonding with other members, and do not constitute optical defects. Furthermore, the polarizing plates using the easily adhesive films 2 to 5 were more excellent in humidification durability than the polarizing plates using the easily adhesive film 6, and the occurrence of uneven streaks was suppressed.

形成有厚度30nm之易接著層的易接著薄膜1，雖然偏光板之加濕耐久性良好，但可見因二氧化矽微粒子凝集而產生的白濁及易接著層非形成面的損傷，外觀不良。吾等認為，會發生損傷是因為分散性降低使得二氧化矽微粒子從易接著層表面脫落，造成易接著薄膜的滑移 性降低所致。 The easily-bondable film 1 having the easily-bonded layer with a thickness of 30 nm was formed, although the humidification durability of the polarizing plate was good, the appearance was poor due to cloudiness caused by the aggregation of silica fine particles and damage to the non-formed surface of the easily-bondable layer. We believe that the damage occurs because the reduced dispersibility causes the silica particles to fall off the surface of the easy-bond layer, resulting in slippage of the easy-to-bond film due to decreased sexuality.

從使用易接著薄膜2~5之偏光板與使用易接著薄膜1、6之偏光板的對比可知，易接著層之厚度小、且殘留鹼成分愈少，愈可抑制於加濕耐久試驗後產生條痕不均，而獲得加濕耐久性優異的偏光板。另外亦知，易接著層之厚度若過小、且殘留鹼成分過少，會因微粒子分散性降低而發生外觀不良或滑移性降低的情況。 From the comparison between the polarizers using the easy-bond films 2 to 5 and the polarizers using the easy-bond films 1 and 6, it can be seen that the thickness of the easy-bond layer is small and the residual alkali component is less, the more it can be suppressed from occurring after the humidification durability test. Streaks were uneven, and a polarizing plate excellent in humidification durability was obtained. In addition, it is also known that when the thickness of the easily bonding layer is too small and the residual alkali component is too small, the dispersibility of the fine particles is lowered, resulting in poor appearance or reduced slippage.

在延伸溫度160℃或180℃下形成厚度200nm之易接著層的易接著薄膜10、11與易接著薄膜4相同，易接著薄膜之外觀及偏光板的加濕耐久性優異。另一方面，在延伸溫度80~120℃下形成厚度200nm之易接著層的易接著薄膜7~9，易接著層的鹼殘量多，與易接著薄膜6同樣，偏光板於加濕耐久試驗後確認有明顯的條痕不均。 The easily-bondable films 10 and 11 having an easily-bonded layer with a thickness of 200 nm formed at a stretching temperature of 160° C. or 180° C. were the same as the easily-bonded film 4, and the easily-bonded films were excellent in appearance and humidification durability of the polarizing plate. On the other hand, the easily-bondable films 7 to 9 in which an easily-bonded layer with a thickness of 200 nm was formed at a stretching temperature of 80 to 120° C. had a large amount of alkali residue in the easily-bonded layer. Similar to the easily-bonded film 6, the polarizing plate was subjected to the humidification durability test. After confirming that there are obvious uneven streaks.

由該等結果可知，在不使無機微粒子之分散性降低的範圍內減少易接著層的鹼殘量，可獲得在作為偏光件保護薄膜使用時偏光板之加濕耐久性優異的易接著薄膜。 From these results, it was found that by reducing the alkali residue in the easily bonding layer within the range that does not reduce the dispersibility of the inorganic fine particles, an easily bonding film excellent in humidification durability of the polarizing plate when used as a polarizer protective film can be obtained.

在低溫下進行延伸的易接著薄膜7~9，相較於其他例，丙烯酸系薄膜與易接著層之密著性較差。在易接著薄膜43等中，在丙烯酸系薄膜與易接著層之界面形成有粒子埋在丙烯酸系薄膜中之狀態的基材界面層(參照圖3)；相對地，在易接著薄膜7~9中並未形成界面層(參照圖4)。由該等結果可知，藉由提高塗佈易接著組成物後的加熱溫度，可使易接著組成物中之鹼成分有效揮發而降低鹼 殘量，而且可提升薄膜基材與易接著層之界面的密著性。 The easy-bond films 7 to 9 stretched at a low temperature have poor adhesion between the acrylic film and the easy-bond layer compared to the other examples. In the easily bonding film 43 and the like, a substrate interface layer in a state where particles are embedded in the acrylic film is formed at the interface between the acrylic film and the easily bonding layer (refer to FIG. 3 ); on the other hand, the easily bonding films 7 to 9 The interface layer is not formed (see FIG. 4 ). From these results, it can be seen that by increasing the heating temperature after coating the easy-bond composition, the alkali component in the easily-bonded composition can be effectively volatilized and the alkali can be reduced. residual amount, and can improve the adhesiveness of the interface between the film substrate and the easily bonding layer.

[偏光板之製作2] [Production of polarizing plate 2]

<實施例1> <Example 1>

使用上述易接著薄膜3作為一面之偏光件保護薄膜，另一面之偏光件保護薄膜則使用雙軸延伸COP薄膜(日本ZEON製「ZeonorFilm ZF-14」)。在溫度5.2℃之氣體環境下，於易接著薄膜之易接著層形成面及ZeonorFilm表面以約1μm之厚度塗佈上述接著劑1，並以輥壓貼合機貼合至偏光件1。然後在室溫下分別從兩面照射累積光量500/mJ/cm2之紫外線使接著劑硬化，而獲得於偏光件之一面貼合有丙烯酸系薄膜(易接著薄膜)且另一面貼合有ZeonorFilm的偏光板。 The above-mentioned easy-bonding film 3 was used as the polarizer protective film on one side, and a biaxially stretched COP film (“ZeonorFilm ZF-14” manufactured by ZEON, Japan) was used as the polarizer protective film on the other side. In a gas atmosphere at a temperature of 5.2° C., the above-mentioned adhesive agent 1 was coated with a thickness of about 1 μm on the easy-bond layer-forming surface of the easy-bond film and the surface of ZeonorFilm, and was bonded to the polarizer 1 by a roll laminating machine. Then, at room temperature, ultraviolet rays with a cumulative light intensity of 500/mJ/ cm2 were irradiated from both sides to harden the adhesive to obtain a polarizer with an acrylic film (easy-to-bond film) attached to one side and ZeonorFilm attached to the other side. polarizer.

<實施例2~5及比較例1、2> <Examples 2 to 5 and Comparative Examples 1 and 2>

除了將貼合時之溫度如表3所示加以變更以外，以與實施例1同樣方式獲得偏光板。 Except having changed the temperature at the time of bonding as shown in Table 3, it carried out similarly to Example 1, and obtained the polarizing plate.

<比較例3> <Comparative Example 3>

使用接著劑2替代接著劑1，並將貼合溫度設為23.0℃，除此以外以與實施例1同樣方式獲得偏光板。 A polarizing plate was obtained in the same manner as in Example 1, except that the adhesive 2 was used instead of the adhesive 1, and the bonding temperature was set to 23.0°C.

<實施例6> <Example 6>

在溫度23.5℃之氣體環境下，於易接著薄膜3之易接著層形成面以約1μm之厚度塗佈上述接著劑1，並以輥壓貼合機將其貼合至偏光件2之積層體的偏光件側之面後，從易接著薄膜側照射累積光量500/mJ/cm2之紫外線使接著劑硬化。然後，將非晶質聚酯薄膜基材自積層體剝離， 而獲得於偏光件之單面貼合有丙烯酸系薄膜(易接著薄膜)、且另一面未設有偏光件保護薄膜的偏光板。 In a gas atmosphere at a temperature of 23.5° C., the above-mentioned adhesive agent 1 was applied to the easily-bonded layer-forming surface of the easily-bonded film 3 with a thickness of about 1 μm, and was bonded to the laminate of the polarizer 2 by a roll-bonding machine. After the polarizer side, the adhesive was cured by irradiating ultraviolet rays with a cumulative light intensity of 500/mJ/cm 2 from the easily bonded film side. Then, the amorphous polyester film substrate was peeled off from the laminate to obtain a polarizer having an acrylic film (easy-bonding film) bonded to one side of the polarizer and no polarizer protective film provided on the other side.

[評估] [Evaluate]

<觀察接著劑層截面> <Observation of the cross section of the adhesive layer>

以穿透型電子顯微鏡(TEM)觀察易接著薄膜之截面，確認在接著劑層與易接著層之界面有無兩者相溶的區域(接著界面層)。並且從截面影像求出接著界面層之厚度、及接著劑層未與易接著層相溶而單獨存在之區域(單獨層)的厚度。 The cross section of the easily-bondable film was observed with a transmission electron microscope (TEM), and it was confirmed whether there was a compatible region (adhesion interface layer) at the interface between the adhesive layer and the easily-bonded layer. Furthermore, the thickness of the adhesive interface layer and the thickness of the region (single layer) where the adhesive layer is not compatible with the easily-bonded layer and exist alone are obtained from the cross-sectional image.

<接著性> <adhesion>

將偏光板裁切成在與偏光件延伸方向成平行方向(吸收軸方向)上為200mm、成正交方向(透射軸方向)上為20mm的大小，並在丙烯酸系透明保護薄膜與偏光件之間用美工刀劃下切痕後，將偏光板貼合至玻璃板上。以拉伸壓縮試驗機(Minebea Inc.製「TG-1kN」)在剝離角度90°、剝離速度1000mm/分鐘下進行剝離試驗，測定接著力。接著強度為1.0N/20mm以上者評估為○，小於1.0N/20mm者評估為×。 The polarizer is cut to a size of 200mm in the direction parallel to the extension direction of the polarizer (absorption axis direction) and 20mm in the orthogonal direction (transmission axis direction), and is placed between the acrylic transparent protective film and the polarizer. After making cuts with a utility knife, attach the polarizer to the glass plate. The peeling test was performed at a peeling angle of 90° and a peeling speed of 1000 mm/min with a tensile compression tester ("TG-1kN" manufactured by Minebea Inc.), and the adhesive force was measured. Next, those with a strength of 1.0 N/20 mm or more were evaluated as ○, and those less than 1.0 N/20 mm were evaluated as ×.

<加工性> <Workability>

使用安裝有150mm×50mm之湯姆森刃型的油壓式裁切機(曙機械製「OP-23H」)，將衝程設定為26.4mm進行打孔做出以偏光板之吸收軸方向為長邊的矩形。以光學顯微鏡(Olympus製「MX61L-F」)觀察經打孔之偏光板所有4邊的端面，最長微裂的長度小於1mm者評估為○，為1mm 以上者評估為×。 Using a hydraulic cutting machine ("OP-23H" manufactured by Akebono Machinery) with a Thomson blade of 150mm x 50mm, set the stroke to 26.4mm, and punch holes with the direction of the absorption axis of the polarizing plate as the long side. rectangle. The end faces of all four sides of the perforated polarizing plate were observed with an optical microscope ("MX61L-F" manufactured by Olympus), and the longest microcrack length was less than 1mm, and it was evaluated as ○ and 1mm The above are evaluated as ×.

於表3顯示實施例及比較例之偏光板的構成(易接著薄膜之種類、偏光件之厚度、積層在與易接著薄膜為相反側之面的偏光件保護薄膜之種類及接著劑之種類)、接著時的貼合溫度、接著劑層的截面觀察結果(接著界面層及接著劑單獨層之厚度)、以及偏光板的評估結果(接著性及加工性)。 Table 3 shows the configurations of the polarizers of Examples and Comparative Examples (type of easy-to-bond film, thickness of polarizer, type of polarizer protective film laminated on the surface opposite to the easily-bonded film, and type of adhesive) , the bonding temperature during bonding, the cross-sectional observation results of the adhesive layer (the thickness of the bonding interface layer and the adhesive layer alone), and the evaluation results (adhesion and processability) of the polarizing plate.

Figure 108125842-A0305-02-0048-3
Figure 108125842-A0305-02-0048-3

比較例3中使用接著劑2，未形成接著界面層，易接著薄膜與偏光件之接著性及切割加工性不足。實施例1~6及比較例1、2使用接著劑1，於接著劑層與易接著層之界面形成有如圖6所示之接著界面層61。在接著劑1中，丙烯醯基嗎福林(SP：22.9)之含量多，因此易接著層之胺甲酸乙酯系樹脂黏結劑與接著劑的相溶性高，推斷確實有藉由相溶形成界面層。 In Comparative Example 3, the adhesive agent 2 was used, the adhesive interface layer was not formed, and the adhesiveness and cutting processability between the easily adhesive film and the polarizer were insufficient. In Examples 1 to 6 and Comparative Examples 1 and 2, the adhesive 1 was used, and an adhesive interface layer 61 as shown in FIG. 6 was formed at the interface between the adhesive layer and the easily adhesive layer. In Adhesive 1, the content of acryl molyfrin (SP: 22.9) is high, so the urethane resin adhesive of the easy-bond layer has high compatibility with the adhesive, and it is presumed that it is formed by compatibility. interface layer.

在實施例1~6及比較例1中可觀察到易接著薄膜與偏光件之貼合溫度愈高，接著界面層之厚度愈大，隨之而來地接著劑單獨層之厚度愈小的傾向。吾等推斷此與溫度愈高、愈能促進接著劑組成物與易接著層之相溶的機制有關。 In Examples 1 to 6 and Comparative Example 1, it can be observed that the higher the bonding temperature between the easy-to-bond film and the polarizer, the greater the thickness of the interface layer and the smaller the thickness of the adhesive layer. . We deduce that this is related to the mechanism by which the higher the temperature, the better the compatibility of the adhesive composition with the easily bonded layer.

實施例1~5之偏光板的接著性及切割加工性皆良好。實施例6之偏光板使用厚度小的偏光件，且僅於偏光件之單面貼合有易接著薄膜，同樣是接著性及切割加工性皆良好。在比較例1及比較例2中，接著性雖佳，但接著劑單獨層之厚度小(或沒有單獨層)，切割加工性降低。由該等結果可知，當易接著層與接著劑相溶成殘存接著劑單獨層之情況而存在接著界面層與接著劑單獨層兩者時，可獲得接著性與切割加工性優異的偏光板。 The polarizing plates of Examples 1 to 5 had good adhesion and cutting workability. The polarizing plate of Example 6 used a polarizer with a small thickness, and an easy-bonding film was only attached to one side of the polarizer, and the adhesiveness and cutting processability were also good. In Comparative Example 1 and Comparative Example 2, although the adhesiveness was good, the thickness of the individual adhesive layer was small (or there was no individual layer), and the cutting workability was lowered. From these results, it can be seen that when both the adhesive interface layer and the adhesive independent layer are present in the case where the easily adhesive layer and the adhesive are compatible to form a residual adhesive independent layer, a polarizing plate excellent in adhesiveness and dicing processability can be obtained.

1:易接著薄膜 1: Easy to bond film

2:透明保護薄膜 2: Transparent protective film

5:偏光件 5: Polarizer

7:接著劑層 7: Adhesive layer

11:薄膜基材 11: Film substrate

15:易接著層 15: Easy Adhesion Layer

18:基材界面層 18: Substrate interface layer

60:接著劑單獨層 60: Adhesive separate layer

61:接著界面層 61: Then the interface layer

100:偏光板 100: polarizer

Claims (11)

一種偏光板，具備：聚乙烯醇系偏光件，其具有第一主面及第二主面；以及易接著薄膜，其係透過接著劑層而貼合於前述偏光件之第一主面上；前述易接著薄膜係於透明薄膜基材之表面具備易接著層，且前述易接著層透過前述接著劑層與前述偏光件貼合；前述易接著層含有黏結劑樹脂及平均一次粒徑為10~100nm之無機微粒子；前述接著劑層係活性能量線硬化型接著劑之硬化層，並且在前述易接著層與前述接著劑層之界面存在一接著界面層，該接著界面層係前述易接著層之樹脂成分與前述接著劑層之樹脂成分相溶而存在；前述接著界面層之厚度為40nm以上，前述接著劑層之前述接著界面層以外之部分，即接著劑單獨層，的厚度為120nm以上。 A polarizing plate comprising: a polyvinyl alcohol-based polarizer having a first main surface and a second main surface; and an easy-adhesive film, which is attached to the first main surface of the polarizer through an adhesive layer; The easy-adhesive film is provided with an easy-adhesive layer on the surface of the transparent film substrate, and the easy-adhesive layer is pasted with the polarizer through the adhesive layer; the easy-adhesive layer contains a binder resin and has an average primary particle size of 10~ 100nm inorganic fine particles; the adhesive layer is a hardened layer of an active energy ray hardening adhesive, and there is an adhesive interface layer at the interface between the easily adhesive layer and the adhesive layer, and the adhesive interface layer is between the easily adhesive layers. The resin component and the resin component of the adhesive layer are compatible and exist; the thickness of the adhesive interface layer is 40 nm or more, and the part of the adhesive layer other than the adhesive interface layer, that is, the adhesive layer alone, the thickness is 120 nm or more. 如請求項1之偏光板，其中相對於前述接著劑單獨層與前述接著界面層之合計厚度，前述接著界面層之厚度為5~90%。 The polarizing plate of claim 1, wherein the thickness of the adhesive interface layer is 5-90% relative to the total thickness of the adhesive layer alone and the adhesive interface layer. 如請求項1或2之偏光板，其中前述接著劑單獨層與前述接著界面層之合計厚度為0.3~3μm。 The polarizing plate according to claim 1 or 2, wherein the total thickness of the aforementioned adhesive single layer and the aforementioned adhesive interface layer is 0.3-3 μm. 如請求項1或2之偏光板，其中前述透明薄膜基材為丙烯酸系薄膜。 The polarizing plate according to claim 1 or 2, wherein the transparent film substrate is an acrylic film. 如請求項1或2之偏光板，其中前述易接著層中之前述無機微粒子的含量為8~50重量%。 The polarizing plate according to claim 1 or 2, wherein the content of the inorganic fine particles in the easily bonded layer is 8 to 50% by weight. 如請求項1或2之偏光板，其中前述易接著層之前述黏結劑樹脂為胺甲酸乙酯系樹脂。 The polarizing plate according to claim 1 or 2, wherein the binder resin of the easily bonding layer is a urethane resin. 如請求項1或2之偏光板，其中在前述透明薄膜基材與前述易接著層之界面存在一前述透明薄膜基材中埋設有前述無機微粒子之區域。 The polarizing plate according to claim 1 or 2, wherein there is a region in which the inorganic fine particles are embedded in the transparent film substrate at the interface between the transparent film substrate and the easily bonding layer. 如請求項1或2之偏光板，其中前述易接著層之胺及氨的含量合計為5~75ppm。 The polarizing plate according to claim 1 or 2, wherein the total content of amine and ammonia in the easily bonded layer is 5 to 75 ppm. 如請求項1或2之偏光板，其中前述易接著層之厚度為40~280nm。 The polarizing plate according to claim 1 or 2, wherein the thickness of the aforementioned easily bonding layer is 40-280 nm. 一種偏光板之製造方法，係製造如請求項1至9中任一項之偏光板的方法，該製造方法係透過活性能量線硬化型之接著劑組成物，貼合聚乙烯醇系偏光件之第一主面與易接著薄膜之易接著層形成面，並且照射活性光線，使前述接著劑組成物硬化而形成接著劑層。 A method for manufacturing a polarizing plate, which is a method for manufacturing a polarizing plate as claimed in any one of claims 1 to 9, wherein the manufacturing method is to attach a polyvinyl alcohol-based polarizer to an adhesive composition of an active energy ray hardening type. The first principal surface and the easily bonding layer forming surface of the easily bonding film are irradiated with actinic light to harden the aforementioned adhesive composition to form an adhesive layer. 一種影像顯示裝置，具有影像顯示單元與如請求項1至9中任一項之偏光板。 An image display device has an image display unit and the polarizing plate according to any one of claims 1 to 9.
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