TWI763976B - Easy-adhesive film and method for producing the same, polarizing plate, and image display device - Google Patents

Easy-adhesive film and method for producing the same, polarizing plate, and image display device

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TWI763976B
TWI763976B TW108105314A TW108105314A TWI763976B TW I763976 B TWI763976 B TW I763976B TW 108105314 A TW108105314 A TW 108105314A TW 108105314 A TW108105314 A TW 108105314A TW I763976 B TWI763976 B TW I763976B
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film
easy
adhesive
layer
polarizer
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Chinese (zh)
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TW202007743A (en
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品川雅
道下空
岡田康彰
徐菁璠
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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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—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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    • 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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    • B32B27/306—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
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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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • 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
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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
    • 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
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    • 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
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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
    • B32B2307/00—Properties of the layers or laminate
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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
    • 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
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
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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
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
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Abstract

本發明課題在於提供一種易接著薄膜，其對偏光件等薄膜展現高度的接著性、不易產生黏結且均勻性及耐久性優異。 解決手段即為一種易接著薄膜，其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為5~75ppm。藉由將含有黏結劑樹脂或其前驅物質、無機微粒子、鹼成分及溶劑之易接著組成物塗佈於透明薄膜基材上並予以加熱，可形成易接著層。An object of the present invention is to provide an easy-adhesive film which exhibits a high degree of adhesion to films such as polarizers, does not easily cause sticking, and is excellent in uniformity and durability. The solution is an easy-bonding film, which is provided with an easy-bonding 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 alkali content of the easy-bond layer is 5-75 ppm. An easily bonding layer can be formed by applying an easily bonding composition containing a binder resin or its precursor, inorganic fine particles, an alkali component and a solvent on a transparent film substrate and heating it.

Description

易接著薄膜及其製造方法、偏光板、以及影像顯示裝置Easy-adhesive film and method for producing the same, polarizing plate, and image display device

本發明涉及一種於透明薄膜基材表面具備易接著層之易接著薄膜及其製造方法。並且，本發明還涉及一種於偏光件表面貼合有易接著薄膜之偏光板、及具備該偏光板之影像顯示裝置。The present invention relates to an easy-adhesive film having an easy-adhesive layer on the surface of a transparent film substrate and a method for producing the same. In addition, the present invention also relates to a polarizing plate with an easily adhesive film attached to the surface of the polarizer, and an image display device provided with the polarizing plate.

發明背景 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)。Background of the Invention 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。透明保護薄膜也變得會使用由丙烯酸、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. As transparent protective films, films made of resin materials such as acrylic, polyester, polycarbonate, and cyclic polyolefin are also used. 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射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之實施例中係顯示使用易接著薄膜作為偏光件保護薄膜之例，該易接著薄膜於丙烯酸系薄膜表面具備含有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 in which an easily-bonded layer containing fine particles and a binder resin is sprayed 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 shows an example of using an easily-bonded film as the polarizer protective film. The easily-bonded film contains 1-7 wt% of silica fine particles on the surface of the acrylic film and has an average thickness of 400 nm (thickness range 300~500nm) urethane easy bonding layer.

先前技術文獻 專利文獻 專利文獻1：日本專利第5354733號prior art literature Patent Literature Patent Document 1: Japanese Patent No. 5354733

發明概要 發明欲解決之課題 在影像顯示裝置朝大型化或高亮度化進展之中，針對構成影像顯示裝置之偏光板亦變得要求即使在嚴峻環境(譬如較高溫、高濕之條件)下，光學特性之變化依舊很小。使用專利文獻1中記載之易接著薄膜作為偏光件保護薄膜的偏光板，其中偏光件與偏光件保護薄膜之接著性相當優異，接著可靠性亦高。但如今已確定有一個新問題：使用專利文獻1中揭示之易接著薄膜作為偏光件保護薄膜的偏光板若長時間曝露在高濕度環境下，會產生筋條狀不均，招致顯示特性降低的情況。Summary of Invention The problem to be solved by the invention As image display devices progress toward larger size or higher brightness, the polarizing plate constituting the image display device is also required to have little change in optical properties even under severe environments (such as high temperature and high humidity conditions). . The polarizing plate using the easy-bonding film described in Patent Document 1 as the polarizer protective film has excellent adhesion between the polarizer and the polarizer protective film, and the adhesion reliability is also high. However, a new problem has now been identified: if a polarizing plate using the easy-adhesive film disclosed in Patent Document 1 as a polarizer protective film is exposed to a high humidity environment for a long time, rib-like unevenness occurs, resulting in a decrease in display characteristics. Happening.

有鑑於上述課題，本發明目的在於提供一種易接著薄膜，其與偏光件等之接著性優異，不易產生黏結，且即使長時間曝露在高溫高濕環境下也不易產生筋條狀不均等光學缺陷。In view of the above problems, an object of the present invention is to provide an easy-to-bond film, which is excellent in adhesion to polarizers and the like, is less likely to cause adhesion, and is less likely to generate optical defects such as rib-like unevenness even if it is exposed to a high temperature and high humidity environment for a long time. .

用以解決課題之手段 有鑑於上述課題，本發明人等研討的結果發現，在提升無機微粒子之分散性等目的下添加至易接著組成物中之氨或胺等鹼成分殘留在易接著層中的情況係加濕環境下耐久性降低之原因之一，並且發現藉由將易接著層中之鹼殘量制定在預定範圍內，可解決上述課題。means of solving problems In view of the above problems, the inventors of the present invention, as a result of studies, found that the case where alkali components such as ammonia or amines added to the easily bonding composition for the purpose of improving the dispersibility of the inorganic fine particles and the like remain in the easily bonding layer is a humidified environment. It is one of the reasons why the lower durability is lowered, and it has been found that the above-mentioned problems can be solved by setting the alkali residual amount in the easily bonding layer within a predetermined range.

本發明涉及一種於透明薄膜基材表面具備易接著層之易接著薄膜及其製造方法。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 an easy-adhesive film having an easy-adhesive layer on the surface of a transparent film substrate and a method for producing the same. 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。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可形成易接著層。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。藉由使易接著組成物含有鹼成分，可提升無機微粒子之分散性，獲得平滑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 layer can be formed by coating the easy-adhesive composition on the surface of the transparent film substrate and heating. 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. By containing an alkali component in the easily bonding composition, the dispersibility of the inorganic fine particles can be improved, and an easily bonding film excellent in smoothness can be obtained. Moreover, 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，透明薄膜基材與易接著層之密著性有提升的傾向。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, the transparent film base material is stretched, and the adhesion between the transparent film base material and the easily bondable layer is improved. tendency to increase.

上述易接著薄膜與其他薄膜或玻璃基板等之接著性優異。易接著薄膜可作為譬如偏光件保護薄膜使用。舉例而言，於聚乙烯醇系偏光件表面透過接著劑層貼合易接著薄膜，可製得偏光板。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。The above-mentioned easily adhesive film is excellent in adhesion to other films, glass substrates, and the like. The easily adhesive film can be used, for example, as a polarizer protective film. For example, a polarizing plate can be produced by laminating an easily adhesive film on the surface of a polyvinyl alcohol-based polarizer through an adhesive layer. An image display device can be formed by disposing a polarizing plate on the surface of an image display unit such as a liquid crystal display unit or an organic EL unit.

發明效果 本發明之易接著薄膜接著性佳，不易產生黏結，且即使長時間曝露在高溫高濕環境下也不易產生光學缺陷，可適宜作為偏光件保護薄膜等顯示裝置用薄膜使用。Invention effect The easy-adhesive film of the present invention has good adhesion, is not easy to produce adhesion, and is not easy to produce optical defects even if it is exposed to a high temperature and high humidity environment for a long time, and can be suitably used as a film for display devices such as a polarizer protective film.

用以實施發明之形態 圖1係顯示本發明一實施形態之易接著薄膜之構成例的概略截面圖。易接著薄膜1於薄膜基材11之至少一面設有易接著層15。亦可在薄膜基材兩面設有易接著層。易接著薄膜係用來與其他薄膜或玻璃基板等貼合。Form for carrying out the invention FIG. 1 is a schematic cross-sectional view showing a configuration example of an easily bonding film according to an embodiment of the present invention. The easily bonding film 1 is provided with 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 for bonding with other films or glass substrates.

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6而貼合。在圖2所示之偏光板100中，易接著薄膜1在與薄膜基材11之偏光件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-bondable film 1 on one surface (the first main surface) of the polarizer 5 , and the easily-bonded film 1 is bonded through the adhesive layer 6 . In the polarizing plate 100 shown in FIG. 2 , the easily bonding film 1 has the easily bonding layer 15 on the bonding surface with the polarizer 5 of the film substrate 11 . 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] 易接著薄膜1於薄膜基材11之至少一面備有易接著層15。[Easy Bonding Film] The easily adhesive film 1 is provided with an easily adhesive layer 15 on at least one side of the film substrate 11 .

＜薄膜基材＞ 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，因雙折射小，所以薄膜基材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。<Film base material> 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, the birefringence is small, so the resin material of the film base 11 is preferably acrylic resin or cyclic polyolefin resin, and acrylic resin is particularly preferred.

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-based resins include Zeonor and ZEONEX manufactured by ZEON Japan, ARTON manufactured by JSR, APEL manufactured by Mitsui Chemicals, and TOPAS 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 an acrylic resin having a lactone ring structure as the acrylic resin, the Tg of the acrylic film can be increased, and the Tg of the acrylic film can be increased. Improve 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＞ 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，可提升偏光件等之相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，提升薄膜之平滑性。所以，有助於減少易接著薄膜1以滾筒輸送時受損或是抑制捲取成卷狀時沾黏。＜Easy bonding layer＞ 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 and the like to a film, a glass substrate, or the like can be improved. The easily bonding layer 15 contains fine particles, and fine irregularities can be formed on the surface of the easily bonding layer 15 to improve the smoothness of the film. Therefore, it is helpful to reduce the damage of the easy-bond film 1 when it is transported by a roll or to suppress sticking when it is wound into a roll.

(黏結劑樹脂) 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 108105314-A0304-12-01
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。(Binder resin) From the viewpoint of excellent adhesion to film substrates such as acrylic films, as the binder resin, polyurethane resins, epoxy resins, isocyanate resins, polyester resins, and those containing Amine-based polymers, with
Figure 108105314-A0304-12-01
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. As an alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, etc. are mentioned, for example.

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 (eg, dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid) Dialkylol alkanoic acid, etc.

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與偏光件等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 108105314-A0304-12-01
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 108105314-A0304-12-01
唑啉基之交聯劑為宜。
Figure 108105314-A0304-12-01
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 a crosslinked structure to the urethane resin, the adhesion durability of the easily bonding film 1 to a polarizer and the like tends to be 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 108105314-A0304-12-01
Crosslinking agent of oxazoline group, epoxy group, carbodiimide group, etc. Among these, there are also
Figure 108105314-A0304-12-01
An oxazoline-based crosslinking agent is suitable.
Figure 108105314-A0304-12-01
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 108105314-A0304-12-01
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 108105314-A0304-12-01
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) 藉由於易接著層15含有微粒子，可於易接著層表面形成微細的凹凸形狀，提升易接著薄膜1之平滑性，從而可抑制沾黏。從形成有助於提升平滑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。(fine particles) Since the easily bonding layer 15 contains fine particles, fine concavo-convex shapes can be formed on the surface of the easily bonding layer, the smoothness of the easily bonding film 1 is 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 improving smoothness. 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 preferable to add an alkali component such as amine or ammonia to make the easy-bonding 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.

藉由於易接著層15之表面形成凹凸，可提高易接著薄膜1之平滑性，由此觀點來看，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，恐招致黏結劑樹脂與微粒子之界面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會隨之縮小，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。The smoothness of the easy-bond film 1 can be improved by forming concavities and convexities on the surface of the easily-bondable layer 15. From this point of view, the content of fine particles in the easily-bonded layer 15 is preferably 8 wt% or more, preferably 10 wt% or more, 12 More preferably, it is more than % by weight. 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 content of the microparticles in the easy-bond layer 15 is too large, it may lead to increased light scattering at the interface between the binder resin and the microparticles, resulting in a decrease in optical properties. In addition, as the content of fine particles increases, the relative content of the binder resin decreases, which may reduce the adhesion of the easy-bond 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) 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。(Alkali Residual) 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 easily bonding layer 15 is preferably 75 ppm or less, preferably 70 ppm or less, more preferably 60 ppm or less, and particularly preferably 55 ppm or less. 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平滑性降低之傾向。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 smoothness 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＞ 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。<Forming an easily bonding layer> 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) 易接著組成物宜為以水作為溶劑(及用於微粒子之分散媒)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。(Easy Adhesion Composition) 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(及分散媒)之水、黏結劑樹脂脂或其前驅物質及無機微粒子。易接著組成物更宜含有鹼成分。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，從而可獲得外觀及平滑性優異的易接著薄膜。The water-based easy-adhesive composition contains water as a solvent (and dispersion medium), a binder resin grease or its precursor, and inorganic fine particles. The easy-bonding composition preferably 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 smoothness 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全量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) 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。(Forming an easy-adhesive layer on a film substrate) 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。Examples of the coating method of the easily adhesive composition include bar coating, roll coating, gravure coating, rod coating, slit coating, curtain coating, fountain coating, and the like. 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之構成成分混雜的界面層。藉由形成界面層，薄膜基材11與易接著層15之密著性有提升之傾向。If the film base material is heated at a temperature above Tg+10°C, the film base material will change from a glass state to a rubber state, and the surface will be easily deformed, so a thin film is easily formed at the interface between the film base material 11 and the easily bonding layer 15 . An interface layer in which the resin component of the base material and the easily bonded component are mixed. By forming the 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 preferable to carry out stretching at the above stretching ratios in the conveying direction (MD) and the width direction (TD), respectively.

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 are easily 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，若過度去除鹼成分，有黏結劑樹脂中之微粒子的分散性降低，而容易發生微粒子凝集、或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，易接著薄膜之平滑性就會降低，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 easily bonding 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 or the resulting fine particles fall off the surface of the easily bonding layer. Once the agglomeration or detachment of the fine particles occurs, the smoothness of the easy-to-bond film is reduced, and it is likely to be damaged during transportation or sticking 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 easily-bondable 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] 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6貼合。[polarizing plate] 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. The polarizer 5 and the easily adhesive film 1 can be pasted through the adhesive layer 6 .

＜偏光件＞ 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。＜Polarizer＞ 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＞ 用來貼合偏光件5與易接著薄膜1之接著劑層6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6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6之厚度宜為0.01~5μm，0.03~3μm較佳。＜Adhesive＞ The material of the adhesive layer 6 used to bond the polarizer 5 and the easy-adhesive film 1 is not particularly limited as long as it is optically transparent, such as epoxy resin, polysiloxane resin, acrylic resin, polyamine Ethyl formate, polyamide, polyether, polyvinyl alcohol, etc. The thickness of the adhesive layer 6 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 type adhesive that exhibits adhesiveness by a cross-linking reaction after coating, the thickness of the adhesive layer 6 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厚度的觀點來看，以水系接著劑或活性能量線硬化型接著劑為宜。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, from the viewpoint of reducing the thickness of the adhesive layer, a water-based adhesive or an active energy ray-curable adhesive is preferable.

水系接著劑之聚合物成分可舉乙烯基聚合物、明膠、乙烯基系乳膠、聚胺甲酸乙酯、聚酯系、環氧等。該等中，若從易接著薄膜與偏光件之接著性優異來看，又以乙烯基聚合物為佳，聚乙烯醇系樹脂尤佳。聚乙烯醇系樹脂中又以含乙醯乙醯基之聚乙烯醇為宜。The polymer component of the water-based adhesive includes vinyl polymers, gelatin, vinyl-based latex, polyurethane, polyester-based, epoxy, and the like. Among these, vinyl polymers are preferable, and polyvinyl alcohol-based resins are especially preferable in view of excellent adhesion between the easily adhesive film and the polarizer. Among the polyvinyl alcohol-based resins, polyvinyl alcohol containing an acetyl acetyl group is suitable.

從接著性的觀點來看，聚乙烯醇系樹脂之平均聚合度宜為100~5000左右，1000~4000較佳。聚乙烯醇系樹脂之平均皂化度宜為85莫耳%以上，90莫耳%以上較佳。From the viewpoint of adhesiveness, the average degree of polymerization of the polyvinyl alcohol-based resin is preferably about 100 to 5000, more preferably 1000 to 4000. The average degree of saponification of the polyvinyl alcohol-based resin is preferably 85 mol% or more, preferably 90 mol% or more.

水系接著劑組成物(溶液)可含有聚乙烯醇系樹脂等聚合物以及交聯劑。交聯劑可使用於1分子中至少具有2個具有構成接著劑之聚合物與反應性之官能基的化合物。聚乙烯醇系樹脂之交聯劑可舉伸烷基二胺類；異氰酸酯類；環氧類；醛類；羥甲基尿素、羥甲基三聚氰胺等胺基-甲醛。該等中又以胺基-甲醛為宜。胺基-甲醛樹脂以具有羥甲基之化合物為宜，羥甲基三聚氰胺尤佳。接著劑組成物中之交聯劑的摻混量宜相對於聚乙烯醇系樹脂100重量份為10~60重量份左右，且20~50重量份較佳。The water-based adhesive composition (solution) may contain a polymer such as a polyvinyl alcohol-based resin and a crosslinking agent. The crosslinking agent can be used for a compound having at least two functional groups having a polymer constituting an adhesive and a reactive functional group in one molecule. Examples of crosslinking agents for polyvinyl alcohol-based resins include alkyl diamines; isocyanates; epoxy; aldehydes; amine-formaldehyde such as methylol urea and methylol melamine. Among these, amino-formaldehyde is again suitable. The amino-formaldehyde resin is preferably a compound having a methylol group, and methylol melamine is particularly preferred. The blending amount of the crosslinking agent in the adhesive composition is preferably about 10-60 parts by weight relative to 100 parts by weight of the polyvinyl alcohol-based resin, and preferably 20-50 parts by weight.

活性能量線硬化型接著劑係可藉由照射電子束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，若從低能量且可硬化的觀點來看，以利用紫外線照射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 irradiating active energy rays such as electron beams or ultraviolet rays. Among them, from the viewpoint of low energy and curability, a photo-radical polymerizable adhesive that initiates radical polymerization by ultraviolet irradiation is preferable.

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。自由基聚合性接著劑亦可含有羥乙基(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

Figure 108105314-A0304-12-02
啉等含氮單體。自由基聚合性接著劑中作為交聯成分可含有三丙二醇二丙烯酸酯、1,9‐壬二醇二丙烯酸酯、三環癸烷二甲醇二丙烯酸酯、環狀三羥甲丙烷甲縮醛丙烯酸酯、二
Figure 108105314-A0304-12-01
烷二醇二丙烯酸酯、EO改質二甘油四丙烯酸酯等多官能單體。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. The radically polymerizable adhesive may contain hydroxyethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N- Ethoxymethyl (meth)acrylamide, (meth)acrylamide, (meth)acrylamide
Figure 108105314-A0304-12-02
Nitrogen-containing monomers such as phenoline. The radical polymerizable adhesive may contain tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and cyclic trimethylolpropane methyl acrylate as a crosslinking component Ester, Di
Figure 108105314-A0304-12-01
Multifunctional monomers such as alkanediol diacrylate and EO modified diglycerol tetraacrylate.

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宜選擇。譬如，宜於自由基聚合性接著劑摻混可利用光照射生成自由基的光自由基發生劑作為光聚合引發劑。光自由基發生劑之具體例容於後述。光自由基發生劑之含量相對於單體100重量份通常為0.1~10重量份左右，宜為0.5~3重量份。另，將自由基聚合性接著劑作為電子束硬化型使用時，無光聚合引發劑的特別需求。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束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。The photocurable adhesive such as a photoradical polymerizable adhesive preferably contains a photopolymerization initiator. The photopolymerization initiator may also be appropriately selected depending on the type of reaction. For example, a photo-radical generator that can generate radicals by light irradiation is suitable for blending a radical-polymerizable adhesive as a photopolymerization initiator. Specific examples of the photoradical generator will be described later. The content of the photoradical generator 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. In addition, when the radically polymerizable adhesive is used as an electron beam curing type, there is no particular need for a photopolymerization initiator. 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 increase the hardening speed and sensitivity of electron beam. 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.

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 promoters such as ethylene oxide, ultraviolet absorbers, anti-deterioration agents, dyes, processing aids, ion scavengers, antioxidants, tackifiers Agents, fillers, plasticizers, leveling agents, foam inhibitors, antistatic agents, heat-resistant stabilizers, hydrolysis-resistant stabilizers, etc.

[製作偏光板] 於偏光件5之一面(第一主面)透過接著劑層6貼合易接著薄膜1，可製造偏光板。易接著薄膜1可以易接著層形成面透過接著劑層與偏光件5貼合，亦可以易接著層非形成面透過接著劑層與偏光件5貼合。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6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。易接著層非形成面透過接著劑層與偏光件5貼合時，可提升其與設置在易接著薄膜上之其他薄膜、黏著劑層、玻璃基板等的接著性。[Make a polarizer] The easy-bond film 1 is attached to one surface (first main surface) of the polarizer 5 through the adhesive layer 6 to manufacture a polarizing plate. The easily bonding film 1 may be bonded to the polarizer 5 through the adhesive layer on the easily bonding layer-forming surface, or may be bonded to the polarizer 5 through the adhesive layer on the non-forming surface of the easily bonding layer. As shown in FIG. 2 , by attaching the polarizer 5 through the adhesive layer 6 on the formation surface of the easily bondable layer 15 of the easily bondable film 1 , the adhesion between the polarizer and the polarizer protective film (the easily bondable film 1 ) is high, Polarizing plates with excellent mechanical strength and durability can be obtained. When the non-formed surface of the easily bonding layer is bonded to the polarizer 5 through the adhesive layer, the adhesiveness to other films, adhesive layers, glass substrates, etc. provided on the easily bonding film can be improved.

在貼合偏光件5與易接著薄膜時，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, it is suitable to apply an adhesive composition to either or both of the polarizer 5 and the easy-to-bond film 1, and then use a roll press or the like to separate the polarizer 5 and the easy-to-bond film. 1Attach and harden the adhesive. 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.

使偏光件5與易接著薄膜1貼合後，可因應接著劑之種類使接著劑硬化而形成接著劑層6。使用水系接著劑時，可利用加熱乾燥使接著劑硬化。使用活性能量線硬化型接著劑時，可藉由照射電子束或紫外線等活性能量線來使接著劑硬化。After the polarizer 5 and the easily adhesive film 1 are bonded together, the adhesive layer 6 can be formed by curing the adhesive according to the type of the adhesive. When a water-based adhesive is used, the adhesive can be hardened by heating and drying. 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.

＜透明保護薄膜＞ 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可採用任意且適當的透明薄膜。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。＜Transparent protective film＞ The transparent protective film 2 can also be attached to the second main surface of the polarizer 5 through the adhesive layer 7 . As the transparent protective film 2, an arbitrary and appropriate transparent film can be used. 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。The materials for forming the transparent protective film 2 include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); Cellulose-based polymers such as acyl cellulose or triacetyl cellulose; styrene-based polymers such as polystyrene or acrylonitrile-styrene copolymer; cyclic polyolefins such as polynorbornene; polycarbonate, etc.

透明保護薄膜2亦可在與偏光件5之貼合面備有易接著層(不圖示)。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 be provided with 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6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 6 and the adhesive layer 7 .

[偏光板之用途] 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。[Use of polarizing plate] 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. When the adhesive layers are arranged on both sides of the polarizing plate, 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。 實施例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. 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.

[調製易接著組成物] 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媒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 108105314-A0304-12-01
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。在以下的實施例及比較例中，係使用該易接著組成物來形成易接著層。[Preparation of easy-adhesive composition] Solid content 34% containing polyester urethane and isophorone diisocyanate as resin components, and further containing triethylamine as a hardening catalyst and methyl ethyl ketone as a dispersing medium 20.6 parts by weight of water-based polyurethane (“SuperFlex 210R” manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), containing 25% of solid content
Figure 108105314-A0304-12-01
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 bonding 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 and Comparative Examples, the easily bonding layer was formed using this easily bonding composition.

[實施例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2倍，而獲得於厚度40μm之丙烯酸系薄膜之一面具備厚度200nm之易接著層的易接著薄膜。[Example 1] 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, a simultaneous biaxial stretching tenter was used to extend 2 times in the longitudinal direction (MD) and the width direction (TD), respectively, to obtain an easy-bonding layer with a thickness of 200 nm on one side of an acrylic film with a thickness of 40 μm. film.

[實施例2~4及比較例1、2] 除了變更易接著組成物之塗佈厚度以外，以與實施例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。[Examples 2 to 4 and Comparative Examples 1 and 2] An easily adhesive film was obtained in the same manner as in Example 1 except that the coating thickness of the easily adhesive composition was changed. The thickness of the easily bonding layer (after stretching) is shown in Table 2.

[實施例5、6及比較例3~5] 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，以與實施例1同樣方式獲得易接著薄膜。[Examples 5, 6 and Comparative Examples 3 to 5] 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 Example 1 except that the stretching temperature was changed.

[比較例6] 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。[Comparative Example 6] 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.

[製作偏光板] (偏光件之製作) 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%。[Make a polarizer] (Production of polarizer) 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%.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

(調製紫外線硬化型接著劑) 調製含有N-羥乙基丙烯酸醯胺40重量份及丙烯醯基

Figure 108105314-A0304-12-02
啉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-
Figure 108105314-A0304-12-02
啉基丙-1-酮(BASF製「IRGACURE 819」)3重量份的紫外線硬化型接著劑。(Preparation of UV-curable adhesive) Preparation containing 40 parts by weight of N-hydroxyethyl acrylate and acrylamide
Figure 108105314-A0304-12-02
60 parts by weight of phenoline as a sclerosing component, further containing 2-methyl-1-(4-methylphenylthio)-2- as a polymerization initiator
Figure 108105314-A0304-12-02
Linopropan-1-one ("IRGACURE 819" manufactured by BASF) is a UV-curable adhesive of 3 parts by weight.

(貼合偏光件與偏光件保護薄膜) 作為單面的偏光件保護薄膜係使用各實施例及比較例之易接著薄膜，另一面的偏光件保護薄膜則使用雙軸延伸環狀聚烯烴薄膜(日本ZEON製「ZeonorFilm ZF-14」)。於易接著薄膜之易接著層形成面及ZeonorFilm之表面以約1μm之厚度塗佈上述紫外線硬化型接著劑並以輥壓機貼合至偏光件後，照射累積光量1000/mJ/cm2 之紫外線使接著劑硬化，而獲得於偏光件之一面具備丙烯酸系薄膜(易接著薄膜)且於另一面具備ZeonorFilm之偏光板。(Lamination of polarizer and polarizer protective film) As the polarizer protective film on one side, the easy-bonding films of the examples and comparative examples were used, and the polarizer protective film on the other side was a biaxially stretched cyclic polyolefin film ( "ZeonorFilm ZF-14" made by ZEON, Japan). The above-mentioned UV-curable adhesive was coated with a thickness of about 1 μm on the easy-adhesive layer forming surface of the easy-bond film and the surface of ZeonorFilm, and then attached to the polarizer by a roller press, and then irradiated with ultraviolet rays with a cumulative light intensity of 1000/mJ/cm 2 The adhesive was cured to obtain a polarizing plate having an acrylic film (easy-bonding film) on one side of the polarizer and ZeonorFilm on the other side.

[評估] ＜易接著層之鹼殘量＞ 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。[Evaluate] <Residual amount of alkali in easily bonding layer> 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＞ 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。 〇：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 ×：在丙烯酸系薄膜與易接著層之界面發生剝離者<Adhesion of the easy-bonding layer> 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 was subjected to a 180° peel test at a tensile speed of 30 m/min, and the adhesion of the easily bonding layer was judged according to the following criteria. 〇: The easy-bond layer was not peeled from the acrylic film but peeled off at the interface between the adhesive tape and the easy-bond layer ×: peeling occurred at the interface between the acrylic film and the easily bonding layer

＜肉眼評估＞ 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。 〇：無二氧化矽粒子凝集、面內均勻性良好且未發現傷傷者 △：雖未因二氧化矽粒子凝集產生混濁，但在易接著層非形成面確認有深度1μm以下的損傷者 ×：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＜Visual evaluation＞ 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. 〇: No aggregation of silica particles, good in-plane uniformity, and no injuries were found △: No turbidity caused by aggregation of silica particles, but damage with a depth of 1 μm or less was confirmed on the non-forming surface of the easy-bonding layer ×: Cloudiness caused by aggregation of silica particles and damage to the non-formed surface of the easy-bond layer was confirmed

＜有無界面層＞ 以穿透型電子顯微鏡(TEM)觀察易接著薄膜之截面，在丙烯酸系薄膜與易接著層之界面確認有無易接著層中之粒子埋設在丙烯酸系薄膜的區域(界面層)。於圖3顯示實施例3(有界面層)之TEM觀察影像，於圖4顯示比較例4(無界面層)之TEM觀察影像。<With or without interface layer> The cross section of the easily bondable film was observed with a transmission electron microscope (TEM), and at the interface between the acrylic film and the easily bondable layer, it was confirmed whether or not particles in the easily bondable layer were embedded in the region (interface layer) of the acrylic film. FIG. 3 shows the TEM observation image of Example 3 (with the interface layer), and FIG. 4 shows the TEM observation image of the Comparative Example 4 (without the interface layer).

＜偏光板之加濕耐久性＞ 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。＜Wetting durability of polarizers＞ After cutting the polarizing plate into a size of 320 mm×240 mm, the surface on the side of the cyclic polyolefin 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ΔP＝｜P-P0 ｜。並且於耐久試驗後的偏光板上將其他偏光板配置成正交偏光後，以肉眼觀察確認有無筋條狀不均，並按以下基準做評估。 ◎：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 〇：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些許的條痕不均 △：在條件1及條件2之耐久試驗後的試料皆可視辨些許的條痕不均 ×：在條件1及條件2之耐久試驗後的試料皆可清楚視辨條痕不均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, after arranging other polarizing plates in cross-polarized light on the polarizing plate after the durability test, the presence or absence of rib-like unevenness was confirmed by visual observation, and the evaluation was made according to the following criteria. ⊚: No uneven streak was observed in the samples after the durability test of Condition 1 and Condition 2. ○: No uneven streak was observed in the sample after the durability test of Condition 1, and the sample after the durability test of Condition 2 Slightly uneven streaks can be seen △: Slightly uneven streaks can be seen in the samples after the endurance test of Condition 1 and Condition 2 ×: The samples after the endurance test of Condition 1 and Condition 2 can be clearly seen uneven streaking

於圖5顯示實施例1及比較例2之偏光板在耐久試驗(60℃90%Rh 500小時)前後在正交偏光下的觀察照片(以低亮度用不均計測系統，I System Co.製「EYESCALE-4W」拍攝)。Figure 5 shows the observation photographs of the polarizing plates of Example 1 and Comparative Example 2 before and after the durability test (60° C. 90%Rh for 500 hours) under crossed polarized light (using an uneven measurement system for low brightness, manufactured by I System Co. "EYESCALE-4W" shooting).

於表2顯示實施例及比較例之易接著薄膜的製作條件(延伸溫度及延伸後的易接著層之厚度)、易接著薄膜的評估結果(肉眼、密著性、有無界面層)、以及偏光板的耐久試驗結果(有無條痕不均及偏光度之變化量ΔP)。Table 2 shows the fabrication conditions (stretching temperature and the thickness of the easily-bonded layer after stretching), the evaluation results of the easily-bonded films (the naked eye, the adhesion, the presence or absence of an interface layer), and the polarized light of the easily-bonded films of the Examples and Comparative Examples. The results of the durability test of the board (with or without uneven streaks and the amount of change in the degree of polarization ΔP).

[表2]

Figure 02_image003
[Table 2]
Figure 02_image003

在使用比較例6之未形成易接著層之丙烯酸系薄膜的偏光板，於加濕耐久試驗後亦未觀察到條痕不均，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。In the polarizing plate using the acrylic film of Comparative Example 6 without forming an easy-bond layer, no uneven streak was observed after the humidification durability test, and the degree of polarization was less decreased, 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.

比較例2之具備厚度350nm之易接著層的易接著薄膜，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，將該易接著薄膜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。在比較例3~5中延伸溫度(易接著層形成時之加熱溫度)為120℃以下，亦與比較例2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 having the easy-bonding layer with a thickness of 350 nm of Comparative Example 2 had good adhesion between the acrylic film and the easy-bonding layer, and the appearance of the easy-bonding film was also good. However, the polarization degree after the humidification durability test of the polarizing plate using this easily-bonded film as a polarizer protective film was remarkably lowered, and it was confirmed that there was a remarkable streak-like unevenness. In Comparative Examples 3 to 5, the elongation temperature (heating temperature during formation of the easily bonded layer) was 120° C. or lower, and the polarization degree decreased significantly after the humidification endurance test as in Comparative Example 2, and it was confirmed that there was a significant rib-like defect. all.

實施例1~4係在延伸溫度140℃下形成50nm~250nm之易接著層，於易接著薄膜未見因微粒子凝集而產生的白濁，顯示了良好的外觀。另，實施例1之易接著薄膜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，即被黏著劑或接著劑等填埋，不構成光學缺陷。而且，使用實施例1~4之易接著薄膜的偏光板，比起使用比較例2之易接著薄膜的偏光板，加濕耐久性更為優異，且抑制了條痕不均的發生。In Examples 1 to 4, an easily bonding layer of 50 nm to 250 nm was formed at a stretching temperature of 140° C., and no cloudiness caused by aggregation of fine particles was observed in the easily bonding film, and they showed good appearance. In addition, in the easily bonding film of Example 1, fine damage was found on the non-forming surface of the easily bonding layer, but the damage level was buried by an adhesive or an adhesive when it was bonded to other members, and did not constitute an optical defect. Furthermore, the polarizing plates using the easily adhesive films of Examples 1 to 4 were more excellent in humidification durability than the polarizing plates using the easily adhesive films of Comparative Example 2, and the occurrence of uneven streaks was suppressed.

比較例1形成了厚度30nm之易接著層，其易接著薄膜的偏光板之加濕耐久性良好，但可確認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，造成易接著薄膜的平滑性降低所致。In Comparative Example 1, an easily bonding layer with a thickness of 30 nm was formed, and the polarizing plate of the easily bonding film had good humidification durability, but cloudiness caused by the aggregation of silica fine particles and damage to the non-forming surface of the easily bonding layer were confirmed. bad. We believe that the damage occurred because the decrease in dispersibility caused the silica particles to fall off the surface of the easily bonded layer, resulting in a decrease in the smoothness of the easily bonded film.

從實施例1~4與比較例1、2的對比可知，易接著層之厚度小、且殘留鹼成分愈少，便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、且殘留鹼成分過小，會因微粒子分散性降低而發生外觀不良或平滑性降低的情況。From the comparison between Examples 1 to 4 and Comparative Examples 1 and 2, it can be seen that the thickness of the easy-bond layer is small and the residual alkali component is less, the uneven streak after the humidification endurance test can be suppressed, and the humidification endurance can be obtained. Excellent polarizer. 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 and low smoothness.

實施例5及實施例6係在延伸溫度160℃或180℃下形成厚度200nm之易接著層，與實施例3同樣地，易接著薄膜之外觀及偏光板的加濕耐久性優異。另一方面，比較例3~5係在延伸溫度80~120℃下形成厚度200nm之易接著層，易接著層的鹼殘量多，且與比較例2相同偏光板於加濕耐久試驗後確認有明顯的條痕不均。In Examples 5 and 6, an easily bonding layer having a thickness of 200 nm was formed at a stretching temperature of 160°C or 180°C. Similar to Example 3, the easily bonded film was excellent in appearance and humidification durability of the polarizing plate. On the other hand, in Comparative Examples 3 to 5, an easily bonding layer with a thickness of 200 nm was formed at a stretching temperature of 80 to 120° C., and the alkali residue in the easily bonding layer was large, and the same polarizing plate as in Comparative Example 2 was confirmed after the humidification durability test. 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.

比較例3~5係在低溫下進行延伸，相較於其他例子，丙烯酸系薄膜與易接著層之密著性較差。在實施例3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界面層(參照圖3)；相對地，在比較例3~5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。In Comparative Examples 3 to 5, the stretching was performed at a low temperature, and the adhesion between the acrylic film and the easily bonding layer was poor compared to the other examples. In Example 3 and the like, an interface layer in which particles are embedded in the acrylic thin film is formed at the interface between the acrylic thin film and the easily bonding layer (see FIG. 3 ); on the other hand, in Comparative Examples 3 to 5, the interface layer was not formed. interface layer (see Figure 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 easy-bond composition can be effectively volatilized to reduce the residual amount of alkali, and the interface between the film substrate and the easily-bonded layer can be improved. the tightness.

1‧‧‧易接著薄膜 2‧‧‧透明保護薄膜 5‧‧‧偏光件 6、7‧‧‧接著劑層 11‧‧‧薄膜基材 15‧‧‧易接著層 100‧‧‧偏光板1‧‧‧Easy Bonding Film 2‧‧‧Transparent protective film 5‧‧‧Polarizer 6.7‧‧‧Adhesive layer 11‧‧‧Film substrate 15‧‧‧Easy bonding layer 100‧‧‧Polarizer

圖1係顯示易接著薄膜之構成例的截面圖。 圖2係顯示偏光板之構成例的截面圖。 圖3係在薄膜基材與易接著層之界面形成有界面層之易接著薄膜的截面TEM觀察影像。 圖4係未在薄膜基材與易接著層之界面形成界面層之易接著薄膜的截面TEM觀察影像。 圖5係偏光板於耐久試驗前後的正交偏光觀察照片。FIG. 1 is a cross-sectional view showing a configuration example of an easily adhesive film. FIG. 2 is a cross-sectional view showing a configuration example of a polarizing plate. FIG. 3 is a cross-sectional TEM observation image of the easy-bond film with an interface layer formed at the interface between the film substrate and the easily-bonded layer. FIG. 4 is a cross-sectional TEM observation image of the easy-bond film with no interface layer formed at the interface between the film substrate and the easily-bonded layer. FIG. 5 is a photograph of the cross-polarized light observation of the polarizing plate before and after the durability test.

1‧‧‧易接著薄膜 1‧‧‧Easy Bonding Film

11‧‧‧薄膜基材 11‧‧‧Film substrate

15‧‧‧易接著層 15‧‧‧Easy bonding layer

Claims (12)

一種易接著薄膜，係於透明薄膜基材之表面具備易接著層者；前述易接著層含有黏結劑樹脂及平均一次粒徑為10~100nm之膠質氧化矽，前述易接著層中之前述膠質氧化矽含量為10~50重量%，前述易接著層之厚度為150~280nm，且前述易接著層之胺及氨的含量合計為20~75ppm。 An easy-adhesive film is provided with an easy-adhesive layer on the surface of a transparent film substrate; the easy-adhesive layer contains a binder resin and a colloidal silicon oxide with an average primary particle size of 10-100 nm, and the above-mentioned colloidal oxide in the easy-adhesive layer is oxidized The silicon content is 10 to 50 wt %, the thickness of the easily bonded layer is 150 to 280 nm, and the total content of amine and ammonia in the easily bonded layer is 20 to 75 ppm. 如請求項1之易接著薄膜，其中前述易接著層中之前述膠質氧化矽的含量為12~30重量%。 The easily bonding film according to claim 1, wherein the content of the aforementioned colloidal silicon oxide in the aforementioned easily bonding layer is 12-30 wt %. 如請求項1或2之易接著薄膜，其中前述透明薄膜基材為丙烯酸系薄膜。 The easily adhesive film according to claim 1 or 2, wherein the transparent film substrate is an acrylic film. 如請求項1或2之易接著薄膜，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 easily bonding film according to claim 1 or 2, wherein the aforementioned binder resin of the aforementioned easily bonding layer is a urethane resin. 如請求項1或2之易接著薄膜，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膠質氧化矽之區域。 The easily bonding film according to claim 1 or 2, wherein there is a region in which the colloidal silicon oxide is embedded in the transparent film substrate at the interface between the transparent film substrate and the easily bonding layer. 一種易接著薄膜之製造方法，係用以製造如請求項1至5中任一項之易接著薄膜，該方法係將含有黏結劑樹脂或其前驅物質、平均一次粒徑為10~100nm之膠質氧化矽、選自胺及氨所構成群組之1種以上的鹼成分及溶劑的易接著組成物塗佈於透明薄膜基材之表面，並在比前述透明薄膜基材之玻璃轉移溫度 高10℃以上的溫度下將前述易接著組成物加熱，使前述溶劑及前述鹼成分揮發。 A method for producing an easy-bond film, which is used to produce the easy-bond film as claimed in any one of claims 1 to 5. The method comprises a colloid containing a binder resin or its precursor and an average primary particle size of 10 to 100 nm. An easily bonding composition comprising silicon oxide, one or more alkali components selected from the group consisting of amines and ammonia, and a solvent is coated on the surface of the transparent film substrate at a temperature higher than the glass transition temperature of the transparent film substrate. The easily bonding composition is heated at a temperature higher than 10° C. to volatilize the solvent and the alkali component. 如請求項6之易接著薄膜之製造方法，其中前述鹼成分具有促進前述膠質氧化矽分散之作用。 The method for producing an easily bonded thin film according to claim 6, wherein the alkali component has the effect of promoting the dispersion of the colloidal silica. 如請求項6或7之易接著薄膜之製造方法，其中前述易接著組成物含有聚胺甲酸乙酯前驅物質作為前述黏結劑樹脂之前驅物質，且含有三級胺作為前述鹼成分。 The method for producing an easily bondable film according to claim 6 or 7, wherein the easily bondable composition contains a polyurethane precursor as the binder resin precursor and a tertiary amine as the alkali component. 如請求項6或7之易接著薄膜之製造方法，其中前述易接著組成物含有沸點為150℃以下之胺作為前述鹼成分。 The method for producing an easily bondable film according to claim 6 or 7, wherein the easily bondable composition contains an amine having a boiling point of 150° C. or less as the base component. 如請求項6或7之易接著薄膜之製造方法，其係在比前述透明薄膜基材之玻璃轉移溫度高10℃以上的溫度下將前述易接著組成物加熱，同時將塗佈了前述易接著組成物之前述透明薄膜基材朝至少1方向延伸。 The method for producing an easily-bondable film according to claim 6 or 7, wherein the easily-bonded composition is heated at a temperature 10° C. or more higher than the glass transition temperature of the transparent film substrate, and the easily-bonded film is coated at the same time. The aforementioned transparent film substrate of the composition extends in at least one direction. 一種偏光板，具備具有第一主面及第二主面之聚乙烯醇系偏光件、及透明薄膜，且該透明薄膜係透過接著劑層貼合在前述偏光件之第一主面；並且前述透明薄膜係如請求項1至5中任一項之易接著薄膜。 A polarizing plate, comprising a polyvinyl alcohol-based polarizer having a first main surface and a second main surface, and a transparent film, and the transparent film is attached to the first main surface of the polarizer through an adhesive layer; and the above-mentioned The transparent film is an easily adhesive film as claimed in any one of claims 1 to 5. 一種影像顯示裝置，具有影像顯示單元與如請求項11之偏光板。 An image display device has an image display unit and a polarizing plate as claimed in item 11.
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