TW201546233A - Protective film, and protective-film-attached film on which transparent conductive film is to be laminated - Google Patents
Protective film, and protective-film-attached film on which transparent conductive film is to be laminated Download PDFInfo
- Publication number
- TW201546233A TW201546233A TW104110394A TW104110394A TW201546233A TW 201546233 A TW201546233 A TW 201546233A TW 104110394 A TW104110394 A TW 104110394A TW 104110394 A TW104110394 A TW 104110394A TW 201546233 A TW201546233 A TW 201546233A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- transparent conductive
- protective film
- conductive film
- adhesive
- Prior art date
Links
Classifications
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
-
- 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
- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Human Computer Interaction (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明係有關一種用於保護透明導電膜積層用薄膜等之保護薄膜及其製造方法、以及帶保護薄膜之透明導電膜積層用薄膜者。 The present invention relates to a protective film for protecting a film for a transparent conductive film laminate or the like, a method for producing the same, and a film for a transparent conductive film laminate with a protective film.
近年來,智慧型手機和平板電腦等各種移動電子設備中,作為顯示器,使用觸摸面板之情況逐漸增加。作為觸摸面板的方式,有電阻膜方式、靜電電容方式等,但上述移動電子設備中,主要採用靜電電容方式。 In recent years, in various mobile electronic devices such as smart phones and tablet computers, the use of touch panels as displays has gradually increased. Examples of the touch panel include a resistive film method and a capacitive method. However, in the above mobile electronic device, a capacitive method is mainly used.
該等觸摸面板中,有時在以透明塑膠基材為主體之透明導電膜積層用薄膜上使用積層有已圖案化之由錫摻雜氧化銦(ITO)等構成之透明導電膜之透明導電性薄膜。另外,作為一例,在透明塑膠基材中之未積層透明導電膜之一側設有硬塗層。 In the touch panel, a transparent conductive film made of a patterned tin-doped indium oxide (ITO) or the like is laminated on a film for a transparent conductive film layer mainly composed of a transparent plastic substrate. film. Further, as an example, a hard coat layer is provided on one side of the uncoated transparent conductive film in the transparent plastic substrate.
為了保護如上述透明導電膜積層用薄膜(或透明導電性薄膜)中之未積層透明導電膜之一側的表面,並且為了提高操作性,提出在該表面上貼附保護薄膜(專利文獻1、2)。該種保護薄膜包括基材薄膜和黏著劑層,經由該黏著劑層貼附於透明導電膜積層用薄膜。 In order to protect the surface on one side of the uncoated transparent conductive film in the above-mentioned film for transparent electroconductive film lamination (or transparent conductive film), and in order to improve operability, it is proposed to attach a protective film on the surface (Patent Document 1) 2). Such a protective film includes a base film and an adhesive layer, and is attached to the film for a transparent conductive film laminate via the adhesive layer.
【專利文獻1】日本特開2003-154593號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-154593
【專利文獻2】日本特開2003-170535號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-170535
在此,在貼附有上述保護薄膜之透明導電膜積層用薄膜(帶保護薄膜之透明導電膜積層用薄膜)中之未貼附上述保護薄膜之一側的表面上,藉由真空蒸鍍法、濺射法、CVD法、離子鍍法等進行透明導電膜的製膜。並且,其後,該透明導電膜藉由經蝕刻處理等而被圖案化。 Here, on the surface of the film for transparent conductive film lamination (film for transparent conductive film lamination with protective film) to which the protective film is attached, the surface on one side of the protective film is not attached, by vacuum evaporation The transparent conductive film is formed by a sputtering method, a CVD method, an ion plating method, or the like. Then, the transparent conductive film is patterned by etching treatment or the like.
然而,近年來,從提高導電性能之觀點考慮,上述透明導電膜經常在圖案化製程之前或之後進行加熱處理來提高形成透明導電膜之材料(例如,ITO)的結晶度。 However, in recent years, from the viewpoint of improving electrical conductivity, the above transparent conductive film is often subjected to heat treatment before or after the patterning process to increase the crystallinity of a material (for example, ITO) which forms a transparent conductive film.
專利文獻1及2所公開之保護薄膜的黏著劑層中使用之黏著劑為熱硬化型的丙烯酸系黏著劑,若如上所述進行加熱,則黏著力(剝離力)顯著上升。因此,想要在使用保護薄膜之後剝離保護薄膜,亦難以從透明導電性薄膜剝離,作業性下降。 The adhesive used in the adhesive layer of the protective film disclosed in Patent Documents 1 and 2 is a thermosetting acrylic adhesive, and when heated as described above, the adhesive force (peeling force) is remarkably increased. Therefore, when the protective film is peeled off after using the protective film, it is difficult to peel off from the transparent conductive film, and workability is lowered.
本發明係鑑於上述實際情況而完成者,其目的為提供一種加熱後剝離性仍優異之保護薄膜及其製造方法、以及加熱後保護薄膜的剝離性仍優異之帶保護薄膜之透明導電膜積層用薄膜。 The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a protective film which is excellent in peelability after heating, a method for producing the same, and a transparent conductive film layer with a protective film which is excellent in peelability of the protective film after heating. film.
為了實現上述目的,第一、本發明提供一種保護薄膜,其包括基材和積層於前述基材的一面之黏著劑層,其中,前述黏著劑層由使黏著性組成物硬化而成之黏著劑構成,前述黏著性組成物中含有60質量%以上的分子量為500~10000的能量射線硬化性化合物的一種或兩種以上,前述保護薄膜相對於無鹼性玻璃之黏著力為20~300mN/25mm(發明1)。 In order to achieve the above object, a first aspect of the present invention provides a protective film comprising a substrate and an adhesive layer laminated on one side of the substrate, wherein the adhesive layer is an adhesive formed by hardening an adhesive composition. In the above-mentioned adhesive composition, one or two or more kinds of energy ray curable compounds having a molecular weight of 500 to 10,000 are contained in an amount of 60% by mass or more, and the adhesion of the protective film to the alkali-free glass is 20 to 300 mN/25 mm. (Invention 1).
依上述發明(發明1),藉由黏著劑層由使上述黏著性組成物硬化而成之黏著劑構成,且黏著力設定在上述範圍內,即使經使透明導電膜結晶化時的加熱條件,黏著力的上升亦得到抑制,發揮優異之剝離性。如此,由於本發明之保護薄膜的加熱後的剝離性亦即耐熱性優異,因此還可以稱為“耐熱保護薄膜”。 According to the invention (Invention 1), the adhesive layer is formed of an adhesive obtained by curing the adhesive composition, and the adhesive force is set within the above range, even when the transparent conductive film is crystallized, The increase in adhesion is also suppressed, and excellent peeling properties are exerted. As described above, since the protective film of the present invention is excellent in heat resistance after heating, it can also be referred to as a "heat-resistant protective film".
上述發明(發明1)中,前述能量射線硬化性化合物的至少一種具有氧化烯鏈,前述氧化烯在前述能量射線硬化性化合物的合計量中之量為35~90質量%為較佳(發明2)。 In the above invention (Invention 1), at least one of the energy ray-curable compounds has an oxyalkylene chain, and the amount of the alkylene oxide in the total amount of the energy ray-curable compound is preferably from 35 to 90% by mass. ).
上述發明(發明2)中,具有前述氧化烯鏈之能量射線硬化性化合物在前述能量射線硬化性化合物的合計量中之量為40質量%以上為較佳(發明3)。 In the above invention (Invention 2), the amount of the energy ray-curable compound having the oxyalkylene chain in the total amount of the energy ray-curable compound is preferably 40% by mass or more (Invention 3).
上述發明(發明1~3)中,前述能量射線硬化性化合物為多官能(甲基)丙烯酸酯為較佳(發明4)。 In the above invention (Inventions 1 to 3), it is preferred that the energy ray curable compound is a polyfunctional (meth) acrylate (Invention 4).
上述發明(發明4)中,前述多官能(甲基)丙烯酸酯為3官能以上的(甲基)丙烯酸酯為較佳(發明5)。 In the above invention (Invention 4), it is preferred that the polyfunctional (meth) acrylate is a trifunctional or higher (meth) acrylate (Invention 5).
上述發明(發明1~5)中,前述黏著性組成物中 不含有重量平均分子量超過10000的黏著成份為較佳(發明6)。 In the above invention (Inventions 1 to 5), the above-mentioned adhesive composition It is preferred that the adhesive component having a weight average molecular weight of more than 10,000 is not contained (Invention 6).
上述發明(發明1~6)中,前述保護薄膜係貼附於透明導電膜積層用薄膜中之未積層透明導電膜之一側的表面,在前述透明導電膜積層用薄膜上積層透明導電膜之後,在任意階段被剝離為較佳(發明7)。 In the above invention (Inventions 1 to 6), the protective film is attached to the surface of one side of the uncoated transparent conductive film in the film for a transparent conductive film layer, and the transparent conductive film is laminated on the film for the transparent conductive film layer. It is preferred to be stripped at any stage (Invention 7).
上述發明(發明7)中,當在前述透明導電膜積層用薄膜中之未積層透明導電膜之一側形成有硬塗層時,前述保護薄膜貼附於前述硬塗層為較佳(發明8)。 In the above invention (Invention 7), when a hard coat layer is formed on one side of the uncoated transparent conductive film in the film for a transparent conductive film layer, the protective film is preferably attached to the hard coat layer (Invention 8) ).
第二、本發明提供一種保護薄膜的製造方法,其係前述保護薄膜(發明1~8)的製造方法,其中,在前述基材的一面塗佈含有前述黏著性組成物之塗佈液並進行乾燥,從而形成前述黏著性組成物的塗佈層,並對前述塗佈層照射能量射線,使前述塗佈層硬化,從而形成黏著劑層(發明9)。 The present invention provides a method for producing a protective film, which is a method for producing the protective film (Inventions 1 to 8), wherein a coating liquid containing the adhesive composition is applied to one surface of the substrate. The coating layer of the adhesive composition is formed by drying, and the coating layer is irradiated with an energy ray to cure the coating layer to form an adhesive layer (Invention 9).
上述發明(發明9)中,在氧的存在下進行對前述塗佈層之能量射線的照射為較佳(發明10)。 In the above invention (Invention 9), it is preferred to irradiate the energy ray of the coating layer in the presence of oxygen (Invention 10).
第三、本發明提供一種帶保護薄膜之透明導電膜積層用薄膜,其包括:透明導電膜積層用薄膜;及前述保護薄膜(發明1~8),貼附於前述透明導電膜積層用薄膜中之未積層透明導電膜之一側的表面(發明11)。 The present invention provides a film for a transparent conductive film layered with a protective film, comprising: a film for a transparent conductive film layer; and the protective film (Inventions 1 to 8) attached to the film for a transparent conductive film layer The surface of one side of the transparent conductive film is not laminated (Invention 11).
本發明之保護薄膜的剝離性在加熱後仍優異。依本發明之保護薄膜的製造方法,能夠輕鬆地製造該種保護薄膜。並且,本發明之帶保護薄膜之透明導電膜積層用薄膜的保 護薄膜的剝離性在加熱後仍優異,發揮良好的作業性。 The peeling property of the protective film of the present invention is still excellent after heating. According to the method for producing a protective film of the present invention, such a protective film can be easily produced. Further, the film for a transparent conductive film laminate with a protective film of the present invention is protected. The peeling property of the protective film is excellent after heating, and exhibits excellent workability.
1‧‧‧保護薄膜 1‧‧‧Protective film
11‧‧‧基材 11‧‧‧Substrate
12‧‧‧黏著劑層 12‧‧‧Adhesive layer
2‧‧‧透明導電膜積層用薄膜 2‧‧‧Transparent film for transparent conductive film
21‧‧‧透明塑膠基材 21‧‧‧Transparent plastic substrate
22‧‧‧硬塗層 22‧‧‧hard coating
23‧‧‧光學調整層 23‧‧‧Optical adjustment layer
3‧‧‧帶保護薄膜之透明導電膜積層用薄膜 3‧‧‧Thin film for transparent conductive film lamination with protective film
4‧‧‧透明導電膜 4‧‧‧Transparent conductive film
第1圖係本發明的一實施形態之保護薄膜的剖面圖。 Fig. 1 is a cross-sectional view showing a protective film according to an embodiment of the present invention.
第2圖係本發明的一實施形態之帶保護薄膜之透明導電膜積層用薄膜剖面圖。 Fig. 2 is a cross-sectional view showing a film for a transparent conductive film laminate with a protective film according to an embodiment of the present invention.
以下,對本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.
〔保護薄膜〕 [protective film]
本發明的一實施形態之保護薄膜1由基材11和積層於基材11的一面(第1圖中為上側)之黏著劑層12構成。 The protective film 1 according to an embodiment of the present invention comprises a substrate 11 and an adhesive layer 12 laminated on one surface (upper side in the first drawing) of the substrate 11.
(1)基材 (1) Substrate
作為基材11,可以使用具有能夠承受使透明導電膜結晶化時的加熱條件之耐熱性者。作為該加熱條件,通常係100~180℃,130~150℃左右為較佳。具體而言,使用在150℃下加熱1小時保護薄膜1之後的熱收縮率進入後述之範圍內者為較佳。 As the substrate 11, a heat resistance which can withstand the heating conditions when the transparent conductive film is crystallized can be used. The heating condition is usually 100 to 180 ° C, preferably about 130 to 150 ° C. Specifically, it is preferred to use a heat shrinkage ratio after heating the film 1 at 150 ° C for 1 hour into the range described later.
作為該種基材11,例如由聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醯亞胺、聚醚醯亞胺、聚碳酸酯、聚甲基戊烯、聚苯硫醚、液晶聚合物等樹脂構成之塑膠薄膜為較佳,可以係由單層構成之薄膜,亦可以係積層相同種類或不同種類的複數層而成之薄膜。在上述之中,聚對苯二甲酸乙二酯薄膜尤為佳。 As such a substrate 11, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polycarbonate, A plastic film composed of a resin such as polymethylpentene, polyphenylene sulfide or a liquid crystal polymer is preferable, and may be a film composed of a single layer or a film of a plurality of layers of the same type or different types. Among the above, polyethylene terephthalate film is particularly preferred.
另外,上述塑膠薄膜中,除填充劑以外,還可以 含有耐熱性提高劑、紫外線吸收劑等添加劑。 In addition, in the above plastic film, in addition to the filler, it is also possible It contains additives such as heat resistance improver and ultraviolet absorber.
上述基材11中,以提高與黏著劑層12之黏附性為目的,根據需要可以實施基於氧化法或凹凸化法等之表面處理、或底漆處理。作為上述氧化法,例如可以舉出電暈放電處理、電漿放電處理、鉻氧化處理(濕式)、火焰處理、熱風處理、臭氧/紫外線照射處理等,並且,作為凹凸化法,例如可以舉出噴砂法、噴鍍處理法等。該等表面處理法可以根據基材薄膜的種類適當地選擇。 In order to improve the adhesion to the adhesive layer 12, the substrate 11 may be subjected to a surface treatment such as an oxidation method or a roughening method or a primer treatment as needed. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone/ultraviolet irradiation treatment, and the like, and examples of the unevenness method include Sandblasting method, spray coating method, etc. These surface treatment methods can be appropriately selected depending on the type of the base film.
若考慮耐熱性、作業性及成本,則基材11的厚度為50~200μm為較佳,75~150μm尤為佳,100~125μm為進一步較佳。 In consideration of heat resistance, workability, and cost, the thickness of the substrate 11 is preferably 50 to 200 μm, particularly preferably 75 to 150 μm, and more preferably 100 to 125 μm.
(2)黏著劑層 (2) Adhesive layer
黏著劑層12由使含有60質量%以上的分子量為500~10000的能量射線硬化性化合物的一種或兩種以上之黏著性組成物(以下,有時稱為“黏著性組成物P”)硬化而成之黏著劑構成。由使該種黏著性組成物P硬化而成之黏著劑構成之黏著劑層12即使經使透明導電膜結晶化時的加熱條件,黏著力的上升亦得到抑制,發揮優異之剝離性。並且,由於包括該種黏著劑層12之保護薄膜1無需風乾(不需要養生期間),因此成本上的優點亦較大。 The adhesive layer 12 is cured by one or two or more adhesive compositions (hereinafter sometimes referred to as "adhesive composition P") containing 60% by mass or more of the energy ray curable compound having a molecular weight of 500 to 10,000. Made of adhesive. The adhesive layer 12 composed of the adhesive which cures the adhesive composition P is suppressed from the heating condition when the transparent conductive film is crystallized, and the adhesive strength is suppressed, and the peeling property is excellent. Further, since the protective film 1 including the adhesive layer 12 does not need to be air-dried (during the need for maintenance), the cost advantage is also large.
上述能量射線硬化性化合物的分子量為500~10000,1000~7500為較佳,1500~5000尤為佳。藉由能量射線硬化性化合物的分子量為500以上,能夠形成穩定的黏著劑層12。並且,藉由能量射線硬化性化合物的分子量為10000 以下,所得到之黏著劑的加熱後的黏著力的上升得到抑制。 The energy ray-curable compound has a molecular weight of 500 to 10,000, preferably 1,000 to 7,500, more preferably 1,500 to 5,000. When the molecular weight of the energy ray curable compound is 500 or more, a stable adhesive layer 12 can be formed. And, the molecular weight of the energy ray curable compound is 10,000 Hereinafter, the increase in the adhesive strength after heating of the obtained adhesive is suppressed.
黏著性組成物P中之上述能量射線硬化性化合物的含量為60質量%以上,75質量%以上為較佳,90質量%以上尤為佳。藉由上述能量射線硬化性化合物的含量為60質量%以上,所得到之黏著劑的加熱後的黏著力的上升得到抑制。 The content of the energy ray-curable compound in the adhesive composition P is 60% by mass or more, preferably 75% by mass or more, and particularly preferably 90% by mass or more. When the content of the energy ray curable compound is 60% by mass or more, the increase in the adhesive strength after heating of the obtained adhesive is suppressed.
若考慮黏著劑的加熱後的剝離性,則黏著性組成物P中不含有重量平均分子量超過10000的黏著成份,例如不含有一般用作黏著主劑之丙烯酸系聚合物為較佳。假如含有時,其含量在黏著性組成物P中為40質量%以下為較佳,25質量%以下尤為佳,10質量%以下為進一步較佳。另外,本說明書中之重量平均分子量係藉由凝膠滲透色譜(GPC)法測定之標準聚苯乙烯換算的值。 In consideration of the peeling property after the heating of the adhesive, the adhesive composition P does not contain an adhesive component having a weight average molecular weight of more than 10,000, and for example, an acrylic polymer which is generally used as an adhesive main component is preferably contained. When it is contained, the content is preferably 40% by mass or less in the adhesive composition P, more preferably 25% by mass or less, and still more preferably 10% by mass or less. Further, the weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.
上述能量射線硬化性化合物的至少一種具有氧化烯鏈為較佳,具有碳數2~4的任意一種烯基之氧化烯鏈更為佳,具有氧化乙烯鏈尤為佳。該氧化烯鏈對所得到之黏著劑賦予黏著力。 It is preferable that at least one of the energy ray-curable compounds has an oxyalkylene chain, and an oxyalkylene chain having any alkenyl group having 2 to 4 carbon atoms is more preferable, and an oxyethylene chain is particularly preferable. The oxyalkylene chain imparts adhesion to the resulting adhesive.
氧化烯在能量射線硬化性化合物的合計量中之量為35~95質量%為較佳,45~90質量%尤為佳,55~85質量%為進一步較佳。藉由氧化烯在能量射線硬化性化合物的合計量中之量為35質量%以上,所得到之黏著劑發揮良好的黏著力,藉由氧化烯的量為95質量%以下,能夠輕鬆地使黏著劑硬化,並且,能夠確保與基材11之充份的黏附性。 The amount of the alkylene oxide in the total amount of the energy ray-curable compound is preferably from 35 to 95% by mass, particularly preferably from 45 to 90% by mass, and more preferably from 55 to 85% by mass. When the amount of the alkylene oxide in the total amount of the energy ray-curable compound is 35% by mass or more, the obtained adhesive exhibits a good adhesive force, and the amount of the alkylene oxide is 95% by mass or less, whereby the adhesive can be easily adhered. The agent is hardened, and sufficient adhesion to the substrate 11 can be ensured.
並且,具有氧化烯鏈之能量射線硬化性化合物在能量射線硬化性化合物的合計量中之量為40質量%以上為較 佳,60質量%以上尤為佳,90質量%以上為進一步較佳。藉由具有氧化烯鏈之能量射線硬化性化合物的量為40質量%以上,所得到之黏著劑發揮良好的黏著力。 Further, the amount of the energy ray-curable compound having an oxyalkylene chain in the total amount of the energy ray-curable compound is 40% by mass or more. Preferably, 60% by mass or more is particularly preferable, and 90% by mass or more is further more preferable. When the amount of the energy ray-curable compound having an oxyalkylene chain is 40% by mass or more, the obtained adhesive exerts a good adhesive force.
作為上述能量射線硬化性化合物,使用保護薄膜1的黏著力在後述之範圍內者,丙烯酸系單體或寡聚物為較佳。具體可以舉出多官能(甲基)丙烯酸酯、氨酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯等,其中,多官能(甲基)丙烯酸酯為較佳。因而,具有氧化烯鏈之能量射線硬化性化合物為氧化烯改性多官能(甲基)丙烯酸酯為較佳。另外,本說明書中,(甲基)丙烯酸酯係指丙烯酸酯及甲基丙烯酸酯這兩者。其他類似術語亦相同。 As the energy ray-curable compound, an acrylic monomer or an oligomer is preferably used in the range in which the adhesion of the protective film 1 is within the range described later. Specific examples thereof include polyfunctional (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate. Among them, polyfunctional (meth) acrylate is preferred. Therefore, the energy ray-curable compound having an oxyalkylene chain is preferably an alkylene oxide-modified polyfunctional (meth) acrylate. In the present specification, (meth) acrylate means both acrylate and methacrylate. Other similar terms are also the same.
從硬化性的觀點考慮,多官能(甲基)丙烯酸酯為3官能以上為較佳,4官能~6官能尤為佳,4官能~5官能為進一步較佳。 From the viewpoint of curability, the polyfunctional (meth) acrylate is preferably a trifunctional or higher functional group, the tetrafunctional hexa-6 functional group is particularly preferred, and the tetrafunctional quinone-5 functional group is further preferred.
作為多官能(甲基)丙烯酸酯,例如可以舉出乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、三烯丙基(甲基)丙烯酸酯等。在上述之中,季戊四醇四(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯為較佳,季戊四醇四丙烯酸酯及二季戊四醇六丙烯酸酯尤為佳。 因而,作為具有氧化烯鏈之多官能(甲基)丙烯酸酯,氧化烯改性季戊四醇四丙烯酸酯及氧化烯改性二季戊四醇六丙烯酸酯尤為佳。依該等,所得到之黏著劑成為加熱後的剝離性尤其優異者。 Examples of the polyfunctional (meth) acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and neopentyl glycol. (Meth) acrylate, hexanediol di(meth) acrylate, trimethylolethane tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tris (methyl) ) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acrylate, triallyl (methyl) Acrylate and the like. Among the above, pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred, and pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate are particularly preferred. Therefore, as the polyfunctional (meth) acrylate having an oxyalkylene chain, an oxyalkylene-modified pentaerythritol tetraacrylate and an alkylene oxide-modified dipentaerythritol hexaacrylate are particularly preferable. According to these, the obtained adhesive is particularly excellent in peelability after heating.
上述多官能(甲基)丙烯酸酯可以單獨使用一種,或者組合使用兩種以上。作為多官能(甲基)丙烯酸酯,僅使用氧化烯(尤其係乙烯)改性季戊四醇四丙烯酸酯和/或氧化烯(尤其係乙烯)改性二季戊四醇六丙烯酸酯,或者組合使用氧化烯(尤其係乙烯)改性季戊四醇四丙烯酸酯和/或氧化烯(尤其係乙烯)改性二季戊四醇六丙烯酸酯和未經氧化烯改性之季戊四醇四丙烯酸酯和/或二季戊四醇六丙烯酸酯更為佳。 The above polyfunctional (meth) acrylate may be used alone or in combination of two or more. As the polyfunctional (meth) acrylate, only the alkylene oxide (especially ethylene)-modified pentaerythritol tetraacrylate and/or alkylene oxide (especially ethylene)-modified dipentaerythritol hexaacrylate, or a combination of alkylene oxides (especially It is more preferred to modify the pentaerythritol tetraacrylate and/or alkylene oxide (especially ethylene)-modified dipentaerythritol hexaacrylate and the non-oxyalkylene-modified pentaerythritol tetraacrylate and/or dipentaerythritol hexaacrylate.
當使用紫外線作為使黏著性組成物P硬化之活性能量射線時,黏著性組成物P中含有光聚合引發劑為較佳。藉由含有光聚合引發劑,能夠有效地使能量射線硬化性化合物硬化,並且能夠減少硬化時間及活性能量射線的照射量。 When ultraviolet rays are used as the active energy ray for curing the adhesive composition P, it is preferred that the adhesive composition P contains a photopolymerization initiator. By containing a photopolymerization initiator, the energy ray curable compound can be effectively cured, and the hardening time and the amount of irradiation of the active energy ray can be reduced.
作為光聚合引發劑,例如可以舉出安息香、安息香甲醚、安息香***、安息香異丙醚、安息香正丁醚、安息香異丁醚、苯乙酮、二甲基氨基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯丙基-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代-丙-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯甲酮、對苯基二苯甲酮、4,4’-二乙基氨基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、2-氨基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2,4-二甲 基噻噸酮、2,4-二乙基噻噸酮、苯偶醯二甲基縮酮、苯乙酮二甲基縮酮、對二甲基氨基安息香酸酯、寡聚[2-羥基-2-甲基-1[4-(1-甲基乙烯基)苯基]丙酮]、2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。該等可以單獨使用,亦可以組合使用兩種以上。 Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropyl-1-one, 1 -hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)benzene 2-(hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2- Methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 2-amino hydrazine, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2 , 4-dimethyl Thiophenone, 2,4-diethylthioxanthone, benzoin dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo[2-hydroxy- 2-methyl-1[4-(1-methylvinyl)phenyl]acetone], 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, and the like. These may be used alone or in combination of two or more.
關於光聚合引發劑,相對於能量射線硬化性化合物的合計量100質量份以0.1~20質量份範圍的量使用,以1~10質量份範圍的量使用尤為佳。 The photopolymerization initiator is used in an amount ranging from 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the energy ray-curable compound, and is preferably used in an amount of from 1 to 10 parts by mass.
黏著性組成物P中,根據需要可以含有各種添加劑例如抗靜電劑、增黏劑、抗氧化劑、紫外線吸收劑、光穩定劑、軟化劑、填充劑等。 The adhesive composition P may contain various additives such as an antistatic agent, a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a filler, and the like as needed.
黏著劑層12的厚度為5~100μm為較佳,10~75μm尤為佳,15~50μm為進一步較佳。藉由黏著劑層12的厚度在上述範圍內,能夠發揮良好的黏著力及剝離力。 The thickness of the adhesive layer 12 is preferably 5 to 100 μm, particularly preferably 10 to 75 μm, and further preferably 15 to 50 μm. When the thickness of the adhesive layer 12 is within the above range, good adhesion and peeling force can be exhibited.
(3)用途 (3) Use
本實施形態之保護薄膜1將透明導電膜積層用薄膜中之未積層透明導電膜之一側的表面用作被黏物為較佳。藉此,能夠保護透明導電膜積層用薄膜(或在該透明導電膜積層用薄膜上積層有透明導電膜之透明導電性薄膜),並且能夠提高操作性。 In the protective film 1 of the present embodiment, it is preferable that the surface of one side of the uncoated transparent conductive film in the film for a transparent conductive film laminate is used as an adherend. Thereby, the film for a transparent conductive film laminate (or a transparent conductive film in which a transparent conductive film is laminated on the film for a transparent conductive film laminate) can be protected, and workability can be improved.
亦即,保護薄膜1係貼附於透明導電膜積層用薄膜中之未積層透明導電膜之一側的表面,在透明導電膜積層用薄膜上積層透明導電膜之後,在任意階段被剝離為較佳。另外,有時在透明導電膜積層用薄膜中之未積層透明導電膜之一側形成硬塗層等,此時,保護薄膜1貼附於該硬塗層等(參閱第2圖)。 In other words, the protective film 1 is attached to the surface of one side of the uncoated transparent conductive film in the film for a transparent conductive film layer, and after the transparent conductive film is laminated on the film for a transparent conductive film layer, it is peeled off at any stage. good. In addition, a hard coat layer or the like may be formed on one side of the unconfined transparent conductive film in the film for a transparent conductive film laminate. In this case, the protective film 1 is attached to the hard coat layer or the like (see FIG. 2).
但是,保護薄膜1的用途並非限定於此者,可以將置於加熱條件下之各種物品用作被黏物。 However, the use of the protective film 1 is not limited thereto, and various articles placed under heating conditions can be used as the adherend.
(4)物性 (4) Physical properties
(4-1)黏著力 (4-1) Adhesion
本實施形態之保護薄膜1相對於無鹼性玻璃之黏著力為20~300mN/25mm,30~250mN/25mm為較佳,40~150mN/25mm尤為佳。藉由黏著力在上述範圍內,當貼附於透明導電膜積層用薄膜時,在製程中能夠防止翹起和剝落等,並且容易使加熱後的剝離力進入後述之範圍內。 The adhesion of the protective film 1 of the present embodiment to the alkali-free glass is 20 to 300 mN/25 mm, preferably 30 to 250 mN/25 mm, and particularly preferably 40 to 150 mN/25 mm. When the adhesive film is adhered to the film for a transparent conductive film layer by the adhesive force, it is possible to prevent lifting and peeling during the process, and it is easy to bring the peeling force after heating into the range described later.
另外,本說明書中之黏著力基本上係指藉由按照JIS Z0237:2009之180°剝離法測定之黏著力,係將測定樣品設為25mm寬度、100mm長度,在0.5MPa、50℃下將該測定樣品經20分鐘加壓貼附於被黏物之後,在常壓、23℃、50%RH的條件下放置24小時之後,以剝離速度300mm/分鐘測定者。 Further, the adhesive force in the present specification basically means an adhesive force measured by a 180° peeling method according to JIS Z0237:2009, and the measurement sample is set to have a width of 25 mm and a length of 100 mm, and this is measured at 0.5 MPa and 50 ° C. The measurement sample was attached to the adherend after pressurization for 20 minutes, and then allowed to stand under normal pressure, 23 ° C, and 50% RH for 24 hours, and then measured at a peeling speed of 300 mm/min.
(4-2)加熱前的剝離力 (4-2) Peel force before heating
關於本實施形態之保護薄膜1,將保護薄膜1貼附於透明導電膜積層用薄膜中之未積層透明導電膜之一側的表面之後,從透明導電膜積層用薄膜剝離保護薄膜1時的剝離力(加熱前的剝離力)為150mN/25mm以下為較佳,20~125mN/25mm尤為佳,40~100mN/25mm為進一步較佳。另外,當在透明導電膜積層用薄膜中之未積層透明導電膜之一側形成有硬塗層等時,上述保護薄膜1貼附於該硬塗層等(以下相同)。 In the protective film 1 of the present embodiment, the protective film 1 is adhered to the surface of one side of the uncoated transparent conductive film in the film for a transparent conductive film layer, and then peeled off when the protective film 1 is peeled off from the film for transparent conductive film laminate. The force (peeling force before heating) is preferably 150 mN/25 mm or less, particularly preferably 20 to 125 mN/25 mm, and further preferably 40 to 100 mN/25 mm. In addition, when a hard coat layer or the like is formed on one side of the uncoated transparent conductive film in the film for a transparent conductive film layer, the protective film 1 is attached to the hard coat layer or the like (the same applies hereinafter).
若上述剝離力(加熱前的剝離力)為150mN/25mm以下,則能夠有效地防止加熱後的剝離力變得過大。並且,若 上述剝離力為20mN/25mm以上,則在各種製程中途能夠防止保護薄膜1從透明導電膜積層用薄膜剝落。 When the peeling force (peeling force before heating) is 150 mN/25 mm or less, it is possible to effectively prevent the peeling force after heating from becoming excessive. And if When the peeling force is 20 mN/25 mm or more, the protective film 1 can be prevented from peeling off from the film for transparent conductive film lamination in various processes.
(4-3)加熱後的剝離力 (4-3) Peeling force after heating
關於本實施形態之保護薄膜1,將保護薄膜1貼附於透明導電膜積層用薄膜中之未積層透明導電膜之一側的表面,並在150℃下加熱1小時之後,從透明導電膜積層用薄膜剝離保護薄膜1時的剝離力(加熱後的剝離力)為150mN/25mm以下為較佳,50~125mN/25mm尤為佳,75~100mN/25mm為進一步較佳。 In the protective film 1 of the present embodiment, the protective film 1 is attached to the surface of one side of the uncoated transparent conductive film in the film for a transparent conductive film layer, and is heated at 150 ° C for 1 hour, and then laminated from the transparent conductive film. The peeling force (peeling force after heating) when the protective film 1 is peeled off by the film is preferably 150 mN/25 mm or less, more preferably 50 to 125 mN/25 mm, and further preferably 75 to 100 mN/25 mm.
若上述剝離力(加熱後的剝離力)為150mN/25mm以下,則能夠毫無問題地從透明導電膜積層用薄膜剝離保護薄膜1。依本實施形態之保護薄膜1,由於加熱後的黏著力的上升得到抑制,因此發揮如上述那樣優異之剝離性。 When the peeling force (peeling force after heating) is 150 mN/25 mm or less, the protective film 1 can be peeled off from the film for transparent conductive film lamination without any problem. According to the protective film 1 of the present embodiment, since the increase in the adhesive force after heating is suppressed, the peeling property excellent as described above is exhibited.
另外,本說明書中之剝離力基本上係指藉由按照JIS Z0237:2009之180°剝離法測定之黏著力,係將測定樣品設為25mm寬度、100mm長度,在0.5MPa、50℃下將該測定樣品經20分鐘加壓貼附於被黏物之後,在常壓、150℃下加熱1小時,接著,在常壓、23℃、50%RH的條件下放置24小時之後,以剝離速度300mm/分鐘測定者。 Further, the peeling force in the present specification basically means an adhesive force measured by a 180° peeling method according to JIS Z0237:2009, and the measurement sample is set to have a width of 25 mm and a length of 100 mm, and this is measured at 0.5 MPa and 50 ° C. The measurement sample was attached to the adherend after pressurization for 20 minutes, and heated at normal pressure at 150 ° C for 1 hour, and then placed under normal pressure, 23 ° C, and 50% RH for 24 hours, at a peeling speed of 300 mm. /minator.
(4-4)加熱後的熱收縮率 (4-4) Thermal shrinkage after heating
本實施形態之保護薄膜1在150℃下加熱1小時之後的熱收縮率在基材11的MD(Machine Direction)方向(製造生產線方向)上為0.0~1.0%為較佳,0.0~0.7%尤為佳,0.0~0.5%為進一步較佳。並且,在基材11的TD(Transverse Direction) 方向(與製造生產線正交之方向;寬度方向)上為-0.2~0.5%為較佳,-0.1~0.4%尤為佳,0.0~0.3%為進一步較佳。並且,保護薄膜1與後述之透明導電膜積層用薄膜的熱收縮率之差的絕對值在MD方向及TD方向上均小於0.1百分比為較佳。 The heat shrinkage rate of the protective film 1 of the present embodiment after heating at 150 ° C for 1 hour is preferably 0.0 to 1.0% in the MD direction (manufacturing line direction) of the substrate 11 , and particularly preferably 0.0 to 0.7%. Preferably, 0.0 to 0.5% is further preferred. And, in the TD (Transverse Direction) of the substrate 11 The direction (the direction orthogonal to the manufacturing line; the width direction) is preferably -0.2 to 0.5%, particularly preferably -0.1 to 0.4%, and further preferably 0.0 to 0.3%. Further, the absolute value of the difference in thermal shrinkage ratio between the protective film 1 and the film for transparent conductive film lamination described later is preferably less than 0.1% in both the MD direction and the TD direction.
藉由保護薄膜1的加熱後的熱收縮率在上述範圍內,進而藉由保護薄膜1與透明導電膜積層薄膜的熱收縮率之差的絕對值在上述範圍內,能夠抑制貼附有保護薄膜1之透明導電膜積層用薄膜(帶保護薄膜之透明導電膜積層用薄膜)的彎曲,能夠良好地維持操作性。 When the heat shrinkage rate after the heating of the protective film 1 is within the above range, and the absolute value of the difference in heat shrinkage ratio between the protective film 1 and the transparent conductive film laminated film is within the above range, the protective film can be suppressed from being attached. The bending of the film for transparent conductive film lamination (the film for transparent conductive film lamination with a protective film) can maintain operability satisfactorily.
(5)保護薄膜的製造方法 (5) Method for producing protective film
為了製造本實施形態之保護薄膜1,作為一例,最初,在基材11的一面(第1圖中為上側的表面)塗佈包含黏著性組成物P且根據需要包含稀釋溶劑之塗佈液並進行乾燥,從而形成黏著劑組成物P的塗佈層。 In order to manufacture the protective film 1 of the present embodiment, as an example, first, a coating liquid containing an adhesive composition P and optionally a diluent solvent is applied to one surface (the upper surface in the first drawing) of the substrate 11 and Drying is performed to form a coating layer of the adhesive composition P.
作為稀釋溶劑,例如可以使用己烷、庚烷、環己烷等脂肪族烴、甲苯、二甲苯等芳香族烴、二氯甲烷、二氯化乙烯等鹵化烴、甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等醇、丙酮、甲乙酮、2-戊酮、異佛爾酮、環己酮等酮、醋酸乙酯、醋酸丁酯等酯、乙基溶纖劑等溶纖劑系溶劑等。 As the diluent solvent, for example, an aliphatic hydrocarbon such as hexane, heptane or cyclohexane, an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as dichloromethane or ethylene dichloride, methanol, ethanol, propanol or butyl can be used. Alcohol, 1-methoxy-2-propanol and other alcohols, acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl acetate and other esters, ethyl cellosolve The cellosolve is a solvent or the like.
作為如此製備之塗佈液的濃度/黏度,只要在能夠塗佈之範圍內即可,並沒有特別限制,可以根據狀況適當地選定。例如,稀釋成黏著性組成物P的固體成份濃度成為10~80質量%。另外,當得到塗佈溶液時,稀釋溶劑等的添加並非必要條件,只要係能夠塗佈黏著性組成物P之黏度等,則亦可 以不添加稀釋溶劑。 The concentration/viscosity of the coating liquid prepared in this manner is not particularly limited as long as it is within the range that can be applied, and may be appropriately selected depending on the situation. For example, the solid content concentration diluted to the adhesive composition P is 10 to 80% by mass. In addition, when a coating solution is obtained, the addition of a diluent solvent or the like is not a requirement, and as long as the viscosity of the adhesive composition P can be applied, So as not to add a dilution solvent.
塗佈液的乾燥可以藉由風乾來進行,但通常藉由加熱處理(熱風乾燥為較佳)來進行。當進行加熱處理時,加熱溫度為50~120℃為較佳,50~100℃尤為佳。並且,加熱時間為10秒~10分鐘為較佳,50秒~2分鐘尤為佳。 The drying of the coating liquid can be carried out by air drying, but it is usually carried out by heat treatment (hot air drying is preferred). When the heat treatment is performed, the heating temperature is preferably from 50 to 120 ° C, and particularly preferably from 50 to 100 ° C. Further, the heating time is preferably from 10 seconds to 10 minutes, and particularly preferably from 50 seconds to 2 minutes.
接著,對黏著劑組成物P的塗佈層照射活性能量射線,並使塗佈層硬化而形成黏著劑層,從而得到保護薄膜1。 Next, the coating layer of the adhesive composition P is irradiated with an active energy ray, and the coating layer is cured to form an adhesive layer, whereby the protective film 1 is obtained.
作為活性能量射線,通常使用紫外線、電子射線等。活性能量射線的照射量根據能量射線的種類而不同,例如為紫外線時,50~1000mJ/cm2的光量為較佳,100~500mJ/cm2尤為佳。並且,當為電子射線時,10~1000krad左右為較佳。 As the active energy ray, ultraviolet rays, electron rays, and the like are usually used. The amount of irradiation of the active energy ray varies depending on the type of the energy ray. For example, when it is ultraviolet ray, the amount of light of 50 to 1000 mJ/cm 2 is preferably 100 to 500 mJ/cm 2 . Further, when it is an electron beam, it is preferably about 10 to 1000 krad.
可以在氧的存在下進行上述活性能量射線的照射。亦即,無需進行氮氣吹掃或者在黏著劑組成物P的塗佈層上積層覆蓋材等而能夠在通常的氣氛下照射活性能量射線。藉此,黏著劑組成物P充份硬化。亦即,本實施形態之保護薄膜1能夠藉由如上述簡便的方法來製造。 The irradiation of the above active energy ray can be carried out in the presence of oxygen. In other words, it is possible to irradiate the active energy ray in a normal atmosphere without performing a nitrogen purge or by laminating a coating material on the coating layer of the adhesive composition P. Thereby, the adhesive composition P is sufficiently hardened. That is, the protective film 1 of the present embodiment can be produced by the above-described simple method.
〔透明導電膜積層用薄膜〕 [Thin film for transparent conductive film laminate]
本發明的一實施形態之帶保護薄膜之透明導電膜積層用薄膜3構成為包括透明導電膜積層用薄膜2、以及在透明導電膜積層用薄膜2中之未積層透明導電膜4之一側的表面(第2圖中為下側的表面)經由黏著劑層12貼附之保護薄膜1。 The film 3 for a transparent conductive film laminate with a protective film according to the embodiment of the present invention comprises a film 2 for a transparent conductive film layer 2 and one side of the uncoated transparent film 4 in the film 2 for a transparent conductive film layer. The surface (the surface on the lower side in FIG. 2) is attached to the protective film 1 via the adhesive layer 12.
作為一例,本實施形態中之透明導電膜積層用薄膜2構成為包括透明塑膠基材21、在透明塑膠基材21中之未積層透明導電膜4之一側的表面(第2圖中為下側的表面)上 形成之硬塗層22、以及在透明塑膠基材21中之未積層透明導電膜4之一側的表面(第2圖中為上側的表面)上形成之折射率匹配層23。但是,可以省略硬塗層22和/或折射率匹配層23,或者替代為具有其他功能之層。 As an example, the transparent conductive film laminate film 2 of the present embodiment is configured to include a transparent plastic substrate 21 and a surface on one side of the uncoated transparent conductive film 4 in the transparent plastic substrate 21 (in FIG. 2, the lower side) Side surface) The formed hard coat layer 22 and the refractive index matching layer 23 formed on the surface (the upper surface in FIG. 2) on one side of the uncoated transparent conductive film 4 in the transparent plastic substrate 21 are formed. However, the hard coat layer 22 and/or the index matching layer 23 may be omitted or replaced with layers having other functions.
作為透明塑膠基材21,可以從作為習知的光學用基材而公知的塑膠薄膜中適當地選擇具有透明性及耐熱性者來進行使用。作為該種塑膠薄膜,例如可以舉出聚對苯二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚萘二甲酸乙二酯薄膜等聚酯薄膜、聚乙烯薄膜、聚丙烯薄膜、二乙醯纖維素薄膜、三乙醯纖維素薄膜、乙醯纖維素丁酸酯薄膜、聚氯乙烯薄膜、聚偏二氯乙烯薄膜、聚乙烯醇薄膜、乙烯-乙酸乙烯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚甲基戊烯薄膜、聚砜薄膜、聚醚醚酮薄膜、聚醚砜薄膜、聚醚醯亞胺薄膜、聚醯亞胺薄膜、氟樹脂薄膜、聚醯胺薄膜、丙烯酸樹脂薄膜、降冰片烯系樹脂薄膜、環烯烴樹脂薄膜等塑膠薄膜、或該等的積層薄膜。 As the transparent plastic substrate 21, those having a transparency and heat resistance can be appropriately selected from plastic films known as conventional optical substrates. Examples of such a plastic film include a polyester film such as a polyethylene terephthalate film, a polybutylene terephthalate film, or a polyethylene naphthalate film, a polyethylene film, and a polypropylene film. , diethyl phthalocyanine film, triethylene fluorene cellulose film, acetonitrile cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate film, poly Styrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyether quinone film, polyimine film, fluororesin film, polyfluorene A plastic film such as an amine film, an acrylic resin film, a norbornene resin film or a cycloolefin resin film, or a laminated film thereof.
在上述之中,為了使觸摸面板等具有適當的強度,聚酯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、降冰片烯系樹脂薄膜、環烯烴樹脂薄膜等為較佳。在該等之中,從透明性和厚度精度等的觀點考慮,聚酯薄膜尤為佳,其中,聚對苯二甲酸乙二酯薄膜為進一步較佳。 In the above, in order to provide appropriate strength to a touch panel or the like, a polyester film, a polycarbonate film, a polyimide film, a norbornene resin film, a cycloolefin resin film, or the like is preferable. Among these, a polyester film is particularly preferable from the viewpoints of transparency and thickness precision, and a polyethylene terephthalate film is further preferable.
透明塑膠基材21的厚度並沒有特別限制,但通常係15~300μm,30~250μm的範圍為較佳。並且,該透明塑膠基材21以提高與設置於其表面之層之黏附性之目的,可以實施與前述之保護薄膜1的基材11相同的表面處理。 The thickness of the transparent plastic substrate 21 is not particularly limited, but is usually 15 to 300 μm, and preferably 30 to 250 μm. Further, the transparent plastic substrate 21 can be subjected to the same surface treatment as the substrate 11 of the protective film 1 described above for the purpose of improving the adhesion to the layer provided on the surface thereof.
作為硬塗層22並沒有特別限定,可以由以往公知的材料、例如含有能量射線硬化型化合物之材料形成。作為能量射線硬化型化合物,例如可以舉出丙烯酸系單體或寡聚物,具體可以舉出多官能(甲基)丙烯酸酯、氨酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯等。 The hard coat layer 22 is not particularly limited, and may be formed of a conventionally known material, for example, a material containing an energy ray-curable compound. Examples of the energy ray-curable compound include an acrylic monomer or an oligomer, and specific examples thereof include polyfunctional (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate. Wait.
硬塗層22的厚度並沒有特別限制,但通常係1~20μm,2~10μm的範圍為較佳。 The thickness of the hard coat layer 22 is not particularly limited, but is usually 1 to 20 μm, and preferably 2 to 10 μm.
折射率匹配層23係用於難以觀察到形成於透明導電膜積層用薄膜2之透明導電膜4的圖案且提高觸摸面板的視認性之層。該折射率匹配層23例如藉由組合高折射率層和低折射率層來構成,材料並沒有特別限定。 The refractive index matching layer 23 is used for a layer in which it is difficult to observe the pattern of the transparent conductive film 4 formed on the transparent conductive film laminate film 2 and to improve the visibility of the touch panel. The index matching layer 23 is composed of, for example, a combination of a high refractive index layer and a low refractive index layer, and the material is not particularly limited.
折射率匹配層23的厚度並沒有特別限制,但通常係0.03~1μm,0.05~0.5μm的範圍為較佳。 The thickness of the index matching layer 23 is not particularly limited, but is usually 0.03 to 1 μm, and preferably 0.05 to 0.5 μm.
本實施形態中之帶保護薄膜之透明導電膜積層用薄膜3中,在透明導電膜積層用薄膜2中之折射率匹配層23的露出面積層已圖案化之透明導電膜4,從而得到透明導電性薄膜。作為一例,該透明導電膜4係藉由真空蒸鍍法、濺射法、CVD法、離子鍍法等形成膜之後,藉由光刻及蝕刻等進行圖案化來形成。另外,在上述圖案化之前或之後,為了提高透明導電膜的結晶度而進行加熱處理。 In the transparent conductive film laminate film 3 with a protective film according to the present embodiment, the transparent conductive film 4 patterned in the exposed area layer of the index matching layer 23 in the transparent conductive film laminate film 2 is obtained to obtain transparent conductive Film. As an example, the transparent conductive film 4 is formed by forming a film by a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, or the like, and then patterning by photolithography, etching, or the like. Further, heat treatment is performed in order to increase the crystallinity of the transparent conductive film before or after the above patterning.
作為透明導電膜4的材料,只要係兼備透明性和導電性之材料,則可以沒有特別限制地進行使用,例如可以舉出錫摻雜氧化銦(ITO)、氧化銥(IrO2)、氧化銦(In2O3)、氧化錫(SnO2)、氟摻雜氧化錫(FTO)、氧化銦-氧化鋅(IZO)、 氧化鋅(ZnO)、鎵摻雜氧化鋅(GZO)、鋁摻雜氧化鋅(AZO)、氧化鉬(MoO3)、氧化鈦(TiO2)等透明導電性金屬氧化物。 The material of the transparent conductive film 4 can be used without any particular limitation as long as it has both transparency and conductivity. Examples thereof include tin-doped indium oxide (ITO), iridium oxide (IrO 2 ), and indium oxide. (In 2 O 3 ), tin oxide (SnO 2 ), fluorine-doped tin oxide (FTO), indium oxide-zinc oxide (IZO), zinc oxide (ZnO), gallium-doped zinc oxide (GZO), aluminum doping A transparent conductive metal oxide such as zinc oxide (AZO), molybdenum oxide (MoO 3 ), or titanium oxide (TiO 2 ).
在透明導電膜4的結晶化製程中,帶保護薄膜之透明導電膜積層用薄膜3通常加熱至100~180℃,加熱至130~150℃左右為較佳。保護薄膜1在加熱後仍發揮優異之剝離性,因此在透明導電膜4的積層後,能夠輕鬆地從透明導電膜積層用薄膜2(透明導電性薄膜)剝離保護薄膜1。 In the crystallization process of the transparent conductive film 4, the film 3 for a transparent conductive film layered with a protective film is usually heated to 100 to 180 ° C and heated to about 130 to 150 ° C. Since the protective film 1 exhibits excellent releasability after heating, the protective film 1 can be easily peeled off from the film 2 for transparent conductive film (transparent conductive film) after lamination of the transparent conductive film 4.
以上說明之實施形態係為了便於理解本發明而記載者,並非為了限定本發明而記載者。因而,上述實施形態所公開之各要件係還包含屬於本發明的技術範圍之所有設計變更和均等物之趣旨。 The embodiments described above are described in order to facilitate the understanding of the present invention, and are not intended to limit the present invention. Therefore, each of the embodiments disclosed in the above embodiments includes all the design changes and equivalents belonging to the technical scope of the present invention.
例如,在保護薄膜1中之基材11與黏著劑層12之間可以夾有其他層,在基材11中之與黏著劑層12側相反一側的表面可以積層其他層(例如硬塗層等)。 For example, another layer may be interposed between the substrate 11 and the adhesive layer 12 in the protective film 1, and other layers (for example, a hard coat layer) may be laminated on the surface of the substrate 11 on the side opposite to the side of the adhesive layer 12. Wait).
以下,藉由實施例對本發明進行進一步具體的說明,但本發明的範圍並非限定於該等實施例等者。 Hereinafter, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the examples and the like.
〔製備例1〕 [Preparation Example 1]
均勻地混合作為能量射線硬化性化合物之氧化乙烯改性季戊四醇四丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名”NK Ester ATM-35E”,分子量:1892,氧化乙烯含量:81質量%)100質量份(固體成份換算;以下相同)、作為光引發劑之2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代-丙-1-酮(BASF Corporation製,商品名“IRGACURE907”)3質量份、 以及作為稀釋溶劑之甲苯67質量份,製備固體成份濃度為約60質量%的黏著性組成物的塗佈液1。該黏著性組成物中,氧化乙烯在能量射線硬化性化合物的合計量中之量為81質量%。 Ethylene oxide-modified pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester ATM-35E"), molecular weight: 1892, ethylene oxide content: 81 mass, uniformly mixed as an energy ray-curable compound %) 100 parts by mass (converted in solid content; the same below), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one as photoinitiator ( 3 parts by mass, manufactured by BASF Corporation, trade name "IRGACURE 907" And 67 parts by mass of toluene as a diluent solvent, the coating liquid 1 of the adhesive composition having a solid content concentration of about 60% by mass was prepared. In the adhesive composition, the amount of ethylene oxide in the total amount of the energy ray-curable compound was 81% by mass.
〔製備例2〕 [Preparation Example 2]
均勻地混合作為能量射線硬化性化合物之氧化乙烯改性季戊四醇四丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester ATM-35E”,分子量:1892,氧化乙烯含量:81質量%)60質量份、作為能量射線硬化性化合物之二季戊四醇六丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester A-DPH”,分子量:578)40質量份、作為光引發劑之2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代-丙-1-酮(BASF Corporation製,商品名“IRGACURE907”)3質量份、以及作為稀釋溶劑之甲苯67質量份,製備固體成份濃度為約60質量%的黏著性組成物的塗佈液2。該黏著性組成物中,氧化乙烯在能量射線硬化性化合物的合計量中之量為49質量%。 Ethylene oxide-modified pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester ATM-35E", molecular weight: 1892, ethylene oxide content: 81 mass, uniformly mixed as an energy ray-curable compound %) as a light ray-curable compound, dipentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester A-DPH", molecular weight: 578), 40 parts by mass, as light 2 parts by mass of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (manufactured by BASF Corporation, trade name "IRGACURE 907"), and as an initiator The coating liquid 2 of the adhesive composition having a solid content concentration of about 60% by mass was prepared by diluting 67 parts by mass of toluene in the solvent. In the adhesive composition, the amount of ethylene oxide in the total amount of the energy ray-curable compound was 49% by mass.
〔製備例3〕 [Preparation Example 3]
均勻地混合作為能量射線硬化性化合物之氧化乙烯改性二季戊四醇六丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester A-DPH-12E”,分子量:1106,氧化乙烯含量:48質量%)100質量份、作為光引發劑之2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代-丙-1-酮(BASF Corporation製,商品名“IRGACURE907”)3質量份、以及作為稀釋溶劑之甲苯67質量份,製備固體成份濃度為約60質量%的黏著性組成物的塗佈液3。該黏著性組成物中,氧化乙烯在能量射線硬 化性化合物的合計量中之量為48質量%。 Ethylene oxide-modified dipentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester A-DPH-12E", molecular weight: 1106, ethylene oxide content, which is an energy ray-curable compound : 48 mass %) 100 parts by mass of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one as a photoinitiator (manufactured by BASF Corporation) 3 parts by mass of "IRGACURE 907") and 67 parts by mass of toluene as a diluent solvent, a coating liquid 3 of an adhesive composition having a solid content concentration of about 60% by mass was prepared. In the adhesive composition, ethylene oxide is hard in energy rays The amount in the total amount of the compound was 48% by mass.
〔製備例4〕 [Preparation Example 4]
均勻地混合作為能量射線硬化性化合物之氧化乙烯改性二季戊四醇六丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester A-DPH-12E”,分子量:1106,氧化乙烯含量:48質量%)80質量份、作為能量射線硬化性化合物之二季戊四醇六丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester A-DPH”,分子量:578)20質量份、作為光引發劑之2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代-丙-1-酮(BASF Corporation製,商品名“IRGACURE907”)3質量份、以及作為稀釋溶劑之甲苯67質量份,製備固體成份濃度為約60質量%的黏著性組成物的塗佈液4。該黏著性組成物中,氧化乙烯在能量射線硬化性化合物的合計量中之量為38質量%。 Ethylene oxide-modified dipentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester A-DPH-12E", molecular weight: 1106, ethylene oxide content, which is an energy ray-curable compound 80 parts by mass of 80 parts by mass of dipentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester A-DPH", molecular weight: 578) 20 parts by mass as an energy ray curable compound 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (manufactured by BASF Corporation, trade name "IRGACURE 907") as a photoinitiator, 3 parts by mass And 67 parts by mass of toluene as a diluent solvent, a coating liquid 4 of an adhesive composition having a solid content concentration of about 60% by mass was prepared. In the adhesive composition, the amount of ethylene oxide in the total amount of the energy ray-curable compound was 38% by mass.
〔製備例5〕 [Preparation Example 5]
均勻地混合作為能量射線硬化性化合物之氧化乙烯改性季戊四醇四丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester ATM-35E”,分子量:1892,氧化乙烯含量:81質量%)30質量份、作為能量射線硬化性化合物之二季戊四醇六丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO.,LTD.製,商品名“NK Ester A-DPH”,分子量:578)70質量份、作為光引發劑之2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代-丙-1-酮(BASF Corporation製,商品名“IRGACURE907”)3質量份、以及作為稀釋溶劑之甲苯67質量份,製備固體成份濃度為約 60質量%的黏著性組成物的塗佈液5。該黏著性組成物中,氧化乙烯在能量射線硬化性化合物的合計量中之量為24質量%。 Ethylene oxide-modified pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester ATM-35E", molecular weight: 1892, ethylene oxide content: 81 mass, uniformly mixed as an energy ray-curable compound %) 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., trade name "NK Ester A-DPH", molecular weight: 578), 70 parts by mass as light ray-curable compound, as light 2 parts by mass of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (manufactured by BASF Corporation, trade name "IRGACURE 907"), and as an initiator Diluting the solvent to 67 parts by mass of toluene to prepare a solid concentration of about 60% by mass of the coating liquid 5 of the adhesive composition. In the adhesive composition, the amount of ethylene oxide in the total amount of the energy ray-curable compound was 24% by mass.
〔製備例6〕 [Preparation Example 6]
使丙烯酸2-乙基己酯20質量份、丙烯酸丁酯75質量份及丙烯酸4-羥基丁酯5質量份共聚合而製備丙烯酸酯共聚物。利用後述之方法測定該丙烯酸酯共聚物的分子量之結果,重量平均分子量(Mw)為20萬。 An acrylate copolymer was prepared by copolymerizing 20 parts by mass of 2-ethylhexyl acrylate, 75 parts by mass of butyl acrylate, and 5 parts by mass of 4-hydroxybutyl acrylate. The molecular weight of the acrylate copolymer was measured by the method described later, and the weight average molecular weight (Mw) was 200,000.
均勻地混合上述丙烯酸酯共聚物100質量份、作為交聯劑之六亞甲基二異氰酸酯系異氰脲酸酯(Nippon Polyurethane Industry Co.,Ltd.製,商品名“CORONATE HX”)6質量份、以及作為稀釋溶劑之甲乙酮,製備固體成份濃度為約28質量%的黏著性組成物的塗佈液6。 6 parts by mass of hexamethylene diisocyanate-based isocyanurate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE HX") as a crosslinking agent in an amount of 100 parts by mass of the above acrylate copolymer Further, as the methyl ethyl ketone as a diluent solvent, a coating liquid 6 of an adhesive composition having a solid concentration of about 28% by mass was prepared.
在此,前述重量平均分子量(Mw)係利用凝膠滲透色譜(GPC)法在以下的條件下測定(GPC測定)之聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method under the following conditions (GPC measurement).
<測定條件> <Measurement conditions>
.GPC測定裝置:TOSOH CORPORATION製,HLC-8020 . GPC measuring device: manufactured by TOSOH CORPORATION, HLC-8020
.GPC色譜柱(按以下順序通過):TOSOH CORPORATION製 . GPC column (passed in the following order): manufactured by TOSOH CORPORATION
TSK guard column HXL-H TSK guard column HXL-H
TSK gel GMHXL(×2) TSK gel GMHXL (×2)
TSK gel G2000HXL TSK gel G2000HXL
.測定溶劑:四氫呋喃 . Determination of solvent: tetrahydrofuran
.測定溫度:40℃ . Measuring temperature: 40 ° C
〔實施例1〕 [Example 1]
作為基材,在具有易接著層之聚對苯二甲酸乙二酯薄膜(厚度:125μm,熱收縮率:MD方向0.5%/TD方向0.3%)的易接著層上,藉由Meyer Bar以乾燥後的膜厚成為15μm之方式塗佈製備例1中製備之塗佈液1。在70℃的烘箱中將該塗佈層乾燥1分鐘之後,藉由高壓水銀燈對該塗佈層照射光量200mJ/cm2的紫外線而形成黏著劑層,從而得到保護薄膜。 As a substrate, it was dried by Meyer Bar on an easy-adhesion layer of a polyethylene terephthalate film (thickness: 125 μm, heat shrinkage ratio: MD direction 0.5% / TD direction 0.3%) having an easy-adhesion layer. The coating liquid 1 prepared in Preparation Example 1 was applied in such a manner that the film thickness after the film thickness became 15 μm. After the coating layer was dried in an oven at 70 ° C for 1 minute, the coating layer was irradiated with ultraviolet rays having a light amount of 200 mJ/cm 2 by a high pressure mercury lamp to form an adhesive layer, thereby obtaining a protective film.
將所得到之保護薄膜貼附於在一面具有折射率匹配層且在另一面具有硬塗層之透明導電膜積層用薄膜(LINTEC Corporation製,商品名“OPTERIA HM540-50”,厚度:50μm,熱收縮率:MD方向0.5%/TD方向0.3%)的硬塗層側,從而得到帶保護薄膜之透明導電膜積層用薄膜。另外,基材及透明導電膜積層用薄膜的熱收縮率係藉由與後述之試驗例3相同的方法測定之值(以下相同)。 The obtained protective film was attached to a film for a transparent conductive film laminate having a refractive index matching layer on one side and a hard coat layer on the other surface (manufactured by LINTEC Corporation, trade name "OPTERIA HM540-50", thickness: 50 μm, heat The shrinkage ratio: 0.5% in the MD direction / 0.3% in the TD direction) on the hard coat side, thereby obtaining a film for a transparent conductive film laminate with a protective film. In addition, the heat shrinkage rate of the film for the base material and the transparent conductive film laminate was measured by the same method as the test example 3 described later (the same applies hereinafter).
〔實施例2〕 [Example 2]
使用製備例2中製備之塗佈液2作為黏著性組成物的塗佈液,除此以外,與實施例1同樣地製作帶保護薄膜之透明導電膜積層用薄膜。 A film for a transparent conductive film laminate with a protective film was produced in the same manner as in Example 1 except that the coating liquid 2 prepared in Preparation Example 2 was used as the coating liquid of the adhesive composition.
〔實施例3〕 [Example 3]
使用製備例3中製備之塗佈液3作為黏著性組成物的塗佈液,除此以外,與實施例1同樣地製作帶保護薄膜之透明導電膜積層用薄膜。 A film for a transparent conductive film laminate with a protective film was produced in the same manner as in Example 1 except that the coating liquid 3 prepared in Preparation Example 3 was used as the coating liquid of the adhesive composition.
〔實施例4〕 [Example 4]
使用製備例4中製備之塗佈液4作為黏著性組成物的塗佈 液,除此以外,與實施例1同樣地製作帶保護薄膜之透明導電膜積層用薄膜。 Coating liquid 4 prepared in Preparation Example 4 was used as a coating for an adhesive composition A film for a transparent conductive film laminate with a protective film was produced in the same manner as in Example 1 except for the above.
〔實施例5〕 [Example 5]
使用具有易接著層之聚對苯二甲酸乙二酯薄膜(厚度:125μm,熱收縮率:MD方向0.4%/TD方向0.2%)作為基材,除此以外,與實施例1同樣地製作帶保護薄膜之透明導電膜積層用薄膜。 A tape was produced in the same manner as in Example 1 except that a polyethylene terephthalate film having an easy-adhesion layer (thickness: 125 μm, heat shrinkage ratio: 0.4% in the MD direction/0.2% in the TD direction) was used as the substrate. A film for laminating a transparent conductive film of a protective film.
〔比較例1〕 [Comparative Example 1]
使用製備例5中製備之塗佈液5作為黏著性組成物的塗佈液,除此以外,與實施例1同樣地製作帶保護薄膜之透明導電膜積層用薄膜。 A film for a transparent conductive film laminate with a protective film was produced in the same manner as in Example 1 except that the coating liquid 5 prepared in Preparation Example 5 was used as the coating liquid of the adhesive composition.
〔比較例2〕 [Comparative Example 2]
作為基材,在具有易接著層之聚對苯二甲酸乙二酯薄膜(厚度:125μm,熱收縮率:MD方向0.5%/TD方向0.3%)的易接著層上,藉由塗敷器(applicator)以乾燥後的膜厚成為20μm之方式塗佈製備例6中製備之塗佈液6,並在90℃的烘箱中將塗佈層乾燥1分鐘。將一面用矽酮系剝離劑進行剝離處理之剝離膜(LINTEC Corporation製,商品名“SP-PET381031”)以剝離處理面與塗佈層接蝕之方式積層於該塗佈層。其後,在23℃、50%RH的環境下風乾7日而形成黏著劑層,從而得到保護薄膜。 As a substrate, on an easy-adhesion layer of a polyethylene terephthalate film having an easy-adhesion layer (thickness: 125 μm, heat shrinkage ratio: 0.5% in the MD direction/0.3% in the TD direction), by an applicator ( The coating liquid 6 prepared in Preparation Example 6 was applied in such a manner that the film thickness after drying became 20 μm, and the coating layer was dried in an oven at 90 ° C for 1 minute. A release film (manufactured by LINTEC Corporation, trade name "SP-PET381031") which was subjected to a release treatment with an oxime-based release agent was laminated on the coating layer so that the release-treated surface and the coating layer were etched. Thereafter, the adhesive layer was formed by air drying in an environment of 23 ° C and 50% RH for 7 days to obtain a protective film.
使用上述保護薄膜,與實施例1同樣地製作帶保護薄膜之透明導電膜積層用薄膜。 A film for a transparent conductive film laminate with a protective film was produced in the same manner as in Example 1 using the above protective film.
〔試驗例1〕(黏著力的測定) [Test Example 1] (Measurement of adhesion)
將實施例及比較例中製作之保護薄膜裁剪為長度100mm、寬度25mm者作為試驗片,在0.5MPa、50℃下經20分鐘加壓貼附於無鹼性玻璃之後,在標準環境下(23℃,50%RH)下放置24小時。其後,在標準環境下(23℃,50%RH),使用拉伸試驗機,以180°的剝離角度、300mm/分鐘的剝離速度將保護薄膜側剝離,並測定黏著力(mN/25mm)。 The protective film prepared in the examples and the comparative examples was cut into a test piece of a length of 100 mm and a width of 25 mm, and was attached to the alkali-free glass at a pressure of 0.5 MPa and 50 ° C for 20 minutes, in a standard environment (23). Leave at °C, 50% RH) for 24 hours. Thereafter, in a standard environment (23 ° C, 50% RH), the protective film side was peeled off at a peeling angle of 180° and a peeling speed of 300 mm/min using a tensile tester, and the adhesion (mN/25 mm) was measured. .
〔試驗例2〕(剝離力的測定) [Test Example 2] (Measurement of peeling force)
將實施例及比較例中製作之帶保護薄膜之透明導電膜積層用薄膜裁剪為長度100mm、寬度25mm者作為試驗片,在標準環境下(23℃,50%RH),使用拉伸試驗機以180°的剝離角度、300mm/分鐘的剝離速度將保護薄膜側剝離,並測定剝離所需之力(剝離力;mN/25mm)(加熱前剝離力)。 The film for a transparent conductive film laminate with a protective film prepared in the examples and the comparative examples was cut into a test piece of a length of 100 mm and a width of 25 mm, and a tensile tester was used under a standard environment (23 ° C, 50% RH). The peeling angle of 180° and the peeling speed of 300 mm/min peeled off the protective film side, and the force required for peeling (peeling force; mN/25 mm) (peeling force before heating) was measured.
並且,藉由烘箱在150℃下加熱1小時上述試驗片之後,在標準環境下(23℃,50%RH)放置24小時,與上述同樣地測定剝離力(加熱後剝離力)。將結果示於表1。 Then, the test piece was heated at 150 ° C for 1 hour in an oven, and then left in a standard environment (23 ° C, 50% RH) for 24 hours, and the peeling force (peeling force after heating) was measured in the same manner as above. The results are shown in Table 1.
〔試驗例3〕(熱收縮率的測定) [Test Example 3] (Measurement of heat shrinkage rate)
從實施例及比較例中製作之保護薄膜切取100mm×100mm的試驗片,從一面上之MD方向及TD方向的端部向10mm內側標記標準線,測定初期的標準線間隔。接著,藉由烘箱,在150℃下加熱1小時試驗片之後,在標準環境下(23℃,50%RH)下放置24小時。在與試驗前相同的位置測定試驗後的尺寸,並藉由下述公式求出MD方向及TD方向的熱收縮率(%)。將結果示於表1。 From the protective film produced in the examples and the comparative examples, a test piece of 100 mm × 100 mm was cut out, and a standard line was marked from the end in the MD direction and the TD direction on one side to the inner side of 10 mm, and the initial standard line interval was measured. Next, the test piece was heated at 150 ° C for 1 hour in an oven, and then placed under a standard environment (23 ° C, 50% RH) for 24 hours. The dimensions after the test were measured at the same positions as before the test, and the heat shrinkage ratio (%) in the MD direction and the TD direction was determined by the following formula. The results are shown in Table 1.
熱收縮率(%)={(l0-l1)/l0}×100 Heat shrinkage rate (%) = {(l 0 - l 1 ) / l 0 } × 100
l1:試驗後的尺寸(mm) l 1 : size after test (mm)
l0:初期的標準線間隔(mm) l 0 : initial standard line spacing (mm)
〔試驗例4〕(彎曲量的測定) [Test Example 4] (Measurement of the amount of bending)
從實施例及比較例中製作之保護薄膜切取100mm×100mm的試驗片,藉由烘箱在150℃下加熱1小時之後,在標準環境下(23℃,50%RH)放置24小時。接著,將試驗片置於水平台上,測定距離台面之垂直距離(mm)的最大值,將此作為彎曲量(mm)。將結果示於表1。 Test pieces of 100 mm × 100 mm were cut out from the protective film prepared in the examples and the comparative examples, and heated at 150 ° C for 1 hour in an oven, and then left in a standard environment (23 ° C, 50% RH) for 24 hours. Next, the test piece was placed on a water platform, and the maximum value of the vertical distance (mm) from the table top was measured, and this was made into the bending amount (mm). The results are shown in Table 1.
由表1明確可知,實施例1~5中製作之保護薄膜的加熱後的剝離力的上升得到抑制。並且,實施例1~4中製作之保護薄膜的加熱後的彎曲亦得到抑制。 As is clear from Table 1, the increase in the peeling force after heating of the protective film produced in Examples 1 to 5 was suppressed. Further, the bending of the protective film produced in Examples 1 to 4 after heating was also suppressed.
本發明之保護薄膜對透明導電膜積層用薄膜或透明導電性薄膜的保護及操作性的提高有用。 The protective film of the present invention is useful for improving the protection and handleability of a film for a transparent conductive film laminate or a transparent conductive film.
1‧‧‧保護薄膜 1‧‧‧Protective film
11‧‧‧基材 11‧‧‧Substrate
12‧‧‧黏著劑層 12‧‧‧Adhesive layer
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2014/059567 WO2015151203A1 (en) | 2014-03-31 | 2014-03-31 | Protective film, and protective-film-attached film on which transparent conductive film is to be laminated |
??PCT/JP2014/059567 | 2014-03-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201546233A true TW201546233A (en) | 2015-12-16 |
TWI668288B TWI668288B (en) | 2019-08-11 |
Family
ID=54239572
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW104110394A TWI668288B (en) | 2014-03-31 | 2015-03-31 | Protective film and film for transparent conductive film lamination with protective film |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6190520B2 (en) |
KR (1) | KR102215677B1 (en) |
CN (1) | CN106133087B (en) |
TW (1) | TWI668288B (en) |
WO (1) | WO2015151203A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI706859B (en) * | 2016-02-18 | 2020-10-11 | 日商琳得科股份有限公司 | Transparent conductive film lamination film with protective film and manufacturing method of transparent conductive film |
TWI742031B (en) * | 2016-03-29 | 2021-10-11 | 日商琳得科股份有限公司 | Laminated body and protective film |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5957133B2 (en) * | 2014-11-20 | 2016-07-27 | 日東電工株式会社 | Transparent conductive film with protective film |
JP6851721B2 (en) * | 2016-02-18 | 2021-03-31 | リンテック株式会社 | A film for laminating a transparent conductive film with a protective film, and a method for manufacturing a transparent conductive film. |
CN106597579B (en) * | 2016-12-26 | 2019-05-21 | 宁波大榭开发区综研化学有限公司 | A kind of high shadow film and the preparation method of disappearing thoroughly of optics |
JP6284068B1 (en) * | 2017-05-16 | 2018-02-28 | 東洋インキScホールディングス株式会社 | Active energy ray-curable composition and index matching layer and laminate using the same |
KR102334954B1 (en) * | 2018-10-11 | 2021-12-02 | 주식회사 엘지화학 | Protection film for foldable display and foldable display device comprising same |
JP7150628B2 (en) * | 2019-01-31 | 2022-10-11 | 日東電工株式会社 | Transparent conductive film laminate |
JP6816237B1 (en) * | 2019-10-07 | 2021-01-20 | 日東電工株式会社 | Manufacturing method of film laminate with print layer |
CN112760053A (en) * | 2020-12-16 | 2021-05-07 | 苏州绍荣光学科技有限公司 | Preparation process of CPP (chlorinated Polypropylene) protective film for conductive film |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60233172A (en) * | 1984-05-07 | 1985-11-19 | Hitachi Chem Co Ltd | Radiation-curing pressure-sensitive adhesive for surface-protection film |
JPH0236611B2 (en) * | 1984-05-31 | 1990-08-20 | Hitachi Chemical Co Ltd | HYOMENHOGOFUIRUMUYOHOSHASENKOKAGATANENCHAKUZAI |
JPH0798924B2 (en) * | 1987-02-12 | 1995-10-25 | 日立化成工業株式会社 | Radiation curable pressure sensitive adhesive composition |
JPS63260977A (en) * | 1987-04-20 | 1988-10-27 | Hitachi Chem Co Ltd | Radiation-curable pressure sensitive adhesive composition |
JP2621457B2 (en) * | 1989-01-30 | 1997-06-18 | 日立化成工業株式会社 | Radiation-curable pressure-sensitive adhesive composition |
JPH0539465A (en) * | 1991-08-06 | 1993-02-19 | Dainippon Printing Co Ltd | Releasable tacky adhesive sheet |
JPH0820748A (en) * | 1994-07-11 | 1996-01-23 | Nichiban Co Ltd | Pressure-sensitive adhesive composition for ionizing-radiation-curing surface-protective material and surface-protective film |
JP2001214135A (en) * | 2000-01-31 | 2001-08-07 | Toppan Forms Co Ltd | Ultraviolet-curable pressure-sensitive adhesive and pressure-sensitive adhesive printing sheet prepared by using same |
JP4069997B2 (en) | 2001-11-22 | 2008-04-02 | 日東電工株式会社 | Surface protection method for transparent conductive film |
JP2003170535A (en) | 2001-12-05 | 2003-06-17 | Nitto Denko Corp | Surface protecting film for transparent conducting film |
JP2007231102A (en) * | 2006-02-28 | 2007-09-13 | Fujifilm Corp | Ultraviolet-curable removable pressure-bonding composition and removable adhesive-coated paper |
JP2007231103A (en) * | 2006-02-28 | 2007-09-13 | Fujifilm Corp | Ultraviolet-curable removable pressure-bonding composition and removable adhesive-coated paper |
JP5057697B2 (en) * | 2006-05-12 | 2012-10-24 | 日東電工株式会社 | Adhesive sheet for processing semiconductor wafers or semiconductor substrates |
KR20110021085A (en) * | 2009-08-25 | 2011-03-04 | 김기성 | Heat seal adhesion high hardness film for metal |
JP5820762B2 (en) * | 2012-04-24 | 2015-11-24 | 藤森工業株式会社 | Surface protective film for transparent conductive film and transparent conductive film using the same |
-
2014
- 2014-03-31 JP JP2016511223A patent/JP6190520B2/en active Active
- 2014-03-31 KR KR1020167029143A patent/KR102215677B1/en active IP Right Grant
- 2014-03-31 CN CN201480077747.5A patent/CN106133087B/en active Active
- 2014-03-31 WO PCT/JP2014/059567 patent/WO2015151203A1/en active Application Filing
-
2015
- 2015-03-31 TW TW104110394A patent/TWI668288B/en active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI706859B (en) * | 2016-02-18 | 2020-10-11 | 日商琳得科股份有限公司 | Transparent conductive film lamination film with protective film and manufacturing method of transparent conductive film |
TWI742031B (en) * | 2016-03-29 | 2021-10-11 | 日商琳得科股份有限公司 | Laminated body and protective film |
Also Published As
Publication number | Publication date |
---|---|
CN106133087B (en) | 2019-03-08 |
JPWO2015151203A1 (en) | 2017-04-13 |
CN106133087A (en) | 2016-11-16 |
KR102215677B1 (en) | 2021-02-16 |
JP6190520B2 (en) | 2017-08-30 |
KR20160140754A (en) | 2016-12-07 |
WO2015151203A1 (en) | 2015-10-08 |
TWI668288B (en) | 2019-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI668288B (en) | Protective film and film for transparent conductive film lamination with protective film | |
KR101686644B1 (en) | Plastic film laminate | |
KR101470463B1 (en) | Hard coating film | |
KR101470466B1 (en) | Laminated hard coating film | |
KR20150016893A (en) | Transparent conductive film having protection film | |
TWI706859B (en) | Transparent conductive film lamination film with protective film and manufacturing method of transparent conductive film | |
TW201643480A (en) | Optical film attached with adhesive layers | |
CN110392942B (en) | OLED panel lower protective film and organic light emitting display device including the same | |
TWI691569B (en) | Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer | |
KR20140085291A (en) | Transparent conductive film | |
KR20160071174A (en) | Flexible conductive substrate and touch screen panel comprising the same | |
KR102346393B1 (en) | Method for Manufacturing Flexible Display Device Comprising Touch Sensor | |
TW201736540A (en) | Adhesive sheet for conductive member, conductive member laminate, and image display device | |
KR102193536B1 (en) | The film for stacking of transparent conductive layer and transparent conductive film | |
KR101993273B1 (en) | Adhesive protective film having outstanding optical properties and method of manufacturing the same | |
CN107240441B (en) | Laminate and protective film | |
KR102071023B1 (en) | Touch sensor and manufacturing method thereof | |
KR102338420B1 (en) | Adhesive film, optical member comprising the same and optical display apparatus comprising the same | |
JP2011218586A (en) | Transparent gas-barrier film | |
KR102004026B1 (en) | Transparent conductor and display apparatus comprising the same | |
CN107093492B (en) | Film for laminating transparent conductive film having protective film and method for producing transparent conductive film | |
CN111117510B (en) | Bonding sheet for display and display including the same | |
TW201636655A (en) | Polarizing plate with adhesive layer | |
CN111100575A (en) | Bonding sheet for display and display including the same | |
JP6772564B2 (en) | Water contact angle control method of optical laminate, and optical laminate with protective film |