TW201841773A - Functional film and device - Google Patents

Functional film and device Download PDF

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TW201841773A
TW201841773A TW107110489A TW107110489A TW201841773A TW 201841773 A TW201841773 A TW 201841773A TW 107110489 A TW107110489 A TW 107110489A TW 107110489 A TW107110489 A TW 107110489A TW 201841773 A TW201841773 A TW 201841773A
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film
layer
functional film
functional
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TWI791502B (en
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古屋拓己
泉達矢
永縄智史
岩屋涉
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日商琳得科股份有限公司
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • C08J7/12—Chemical modification
    • 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
    • C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

This functional film comprises a process film, a resin coat layer provided directly on the process film, and a gas barrier layer provided directly on the resin coat layer or with another layer interposed therebetween, wherein the resin coat layer is formed from the cured product of a curable composition containing an energy curable resin and an inorganic filler; this device is obtained using the said functional film. In this way, a functional film having optical isotropy, bending resistance, and excellent workability during use, and a device obtained using said functional film, are provided.

Description

功能性薄膜及裝置Functional films and devices

本發明係關於一種具有良好之光學等方性、耐彎曲性和使用時之作業性之功能性薄膜、以及使用該功能性薄膜而得到之裝置。The present invention relates to a functional film having good optical isotropy, bending resistance, and workability during use, and a device obtained by using the functional film.

向來，在液晶顯示器和電激發光（EL）顯示器等之顯示器，為了實現薄型化、輕量化等，因此，使用透明塑膠薄膜，來作為具有電極之基板，進行玻璃板之取代。此種透明塑膠薄膜係要求具有良好之光學等方性和氣體障蔽性。Conventionally, in the displays such as liquid crystal displays and electroluminescence (EL) displays, in order to reduce thickness and weight, a transparent plastic film is used as a substrate having electrodes instead of a glass plate. Such transparent plastic films are required to have good optical isotropy and gas barrier properties.

又，在近年來，也進行可撓性顯示器之開發，使用於此時之塑膠薄膜係要求具有良好之耐彎曲性。In recent years, development of flexible displays has also been carried out, and plastic films used at this time are required to have good bending resistance.

在專利文獻1，記載：一種透明氣體障蔽性層積薄膜，其特徵為：作為具有良好之光學等方性和氣體障蔽性之薄膜，係在透明高分子薄膜之至少單面上，具有藉由聚矽氨烷而形成之陶瓷層（A層）和特定之硬化樹脂層（B層）呈相互地接合來構成之層。 [先前技術文獻] [專利文獻]Patent Document 1 describes a transparent gas-barrier laminated film, which is characterized in that as a film having good optical isotropy and gas-barrier properties, it is on at least one side of a transparent polymer film, A ceramic layer (layer A) and a specific hardened resin layer (layer B) formed by polysilazane are bonded to each other to form a layer. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開平10－016142號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 10-016142

[發明所欲解決的課題][Problems to be Solved by the Invention]

在專利文獻1，記載：藉由使用聚碳酸酯薄膜或聚芳基化物薄膜，來作為透明高分子薄膜，而得到具有良好之光學等方性之透明氣體障蔽性層積薄膜。Patent Document 1 describes that by using a polycarbonate film or a polyarylate film as a transparent polymer film, a transparent gas-barrier laminated film having good optical isotropic properties is obtained.

但是，在近年來，還要求具有更加良好之光學等方性和耐彎曲性之薄膜。 [用以解決課題的手段]However, in recent years, thin films having better optical isotropy and bending resistance have been required. [Means to solve the problem]

本發明人係為了解決前述課題，因此，關於具有良好之光學等方性、耐彎曲性和氣體障蔽性之功能性薄膜而全心地進行檢討。In order to solve the aforementioned problems, the present inventors have conducted a thorough review on a functional film having good optical isotropy, bending resistance, and gas barrier properties.

結果，得知雖然無使用基材層（所謂成為非載體薄膜），得到具有良好之光學等方性和耐彎曲性之功能性薄膜，並且，無具有基材層之功能性薄膜係其製造時或搬運時之處理，變得困難，但是，一直到使用為止之間，藉由設置可以發揮作為支持體之功能之製程薄膜，來作為至少一邊之最外層，而提高處理性。As a result, it was found that although a base film was not used (so-called a non-carrier film), a functional film having good optical isotropy and bending resistance was obtained, and a functional film without a base layer was produced at the time of manufacture. Handling during transportation or transportation becomes difficult. However, until it is used, a process film that can function as a support is provided as the outermost layer on at least one side to improve handling.

但是，在使用此種功能性薄膜之際，由於製程薄膜之剝離條件而粗糙露出面，或者是破壞具有規定之功能之層，結果，大幅度地降低功能性薄膜之性能。因此，在剝離及除去製程薄膜之際，必須特別慎重地進行處理。However, when such a functional film is used, the exposed surface is roughened due to the peeling conditions of the process film, or a layer having a predetermined function is destroyed. As a result, the performance of the functional film is greatly reduced. Therefore, when peeling and removing the process film, special care must be taken.

像這樣，具有製程薄膜之功能性薄膜係有所謂使用時之作業性變差之問題發生。As described above, the functional film having a process film has a problem that the workability during use is deteriorated.

本發明人係為了解決該問題而更加地進行檢討，結果發現：藉由在製程薄膜上，使用特定之硬化性組合物，形成樹脂塗佈層，而得到具有良好之使用時之作業性之功能性薄膜，以至於完成本發明。The present inventors conducted a review in order to solve this problem. As a result, they found that by using a specific hardening composition on a process film to form a resin coating layer, a function with good workability during use was obtained. Film, so that the present invention is completed.

像這樣，如果是藉由本發明的話，則提供下列之[1]～[13]之功能性薄膜以及[14]之裝置。As described above, according to the present invention, the following functional films [1] to [13] and the device [14] are provided.

[1]：一種功能性薄膜，係具有：製程薄膜、直接地設置於前述製程薄膜上之樹脂塗佈層、以及在前述樹脂塗佈層上呈直接或透過其他層而設置之氣體障蔽層的功能性薄膜，前述樹脂塗佈層係由含有能量硬化性樹脂和無機填充物之硬化性組合物之硬化物而組成的。[1]: A functional film having a process film, a resin coating layer directly provided on the process film, and a gas barrier layer provided directly or through another layer on the resin coating layer. In the functional film, the resin coating layer is composed of a cured product of a curable composition containing an energy curable resin and an inorganic filler.

[2]：如[1]所述之功能性薄膜，前述無機填充物係藉由有機化合物而修飾其表面。[2]: The functional film according to [1], in which the inorganic filler is modified on the surface with an organic compound.

[3]：如[2]所述之功能性薄膜，使用於前述無機填充物之表面修飾之有機化合物係包含：含有反應性不飽和鍵之基。[3]: The functional film according to [2], wherein the organic compound used for surface modification of the inorganic filler includes a group containing a reactive unsaturated bond.

[4]：如[1]所述之功能性薄膜，前述製程薄膜之樹脂成分係聚酯系樹脂。[4]: The functional film according to [1], wherein the resin component of the aforementioned process film is a polyester resin.

[5]：如[1]所述之功能性薄膜，前述製程薄膜之厚度係10～300μm。[5]: The functional film according to [1], wherein the thickness of the aforementioned process film is 10 to 300 μm.

[6]：如[1]所述之功能性薄膜，前述樹脂塗佈層之厚度係0.1～10μm。[6]: The functional film according to [1], wherein the thickness of the resin coating layer is 0.1 to 10 μm.

[7]：如[1]所述之功能性薄膜，前述樹脂塗佈層之相反於接合在製程薄膜之側之相反側之面粗糙曲線之剖面最大高度（Rt）係1～200nm。[7]: The functional film according to [1], wherein the maximum cross-section height (Rt) of the surface roughness curve of the resin coating layer opposite to the side bonded to the side of the process film is 1 to 200 nm.

[8]：如[1]所述之功能性薄膜，前述氣體障蔽層係含有由矽氧化物、矽氮化物、矽氟化物、矽碳化物、金屬氧化物、金屬氮化物、金屬氟化物、金屬碳化物、以及包含構成這些化合物之元素之複合化合物而組成之群組來選出之至少一種。[8]: The functional film according to [1], wherein the gas barrier layer contains silicon oxide, silicon nitride, silicon fluoride, silicon carbide, metal oxide, metal nitride, metal fluoride, At least one selected from the group consisting of a metal carbide and a composite compound containing elements constituting these compounds.

[9]：如[1]所述之功能性薄膜，前述氣體障蔽層係藉由接受重整處理，而對於可以變化成為含有無機化合物之層之層表面，來進行重整而得到的。[9]: The functional film according to [1], wherein the gas barrier layer is obtained by reforming the surface of a layer that can be changed to a layer containing an inorganic compound by undergoing a reforming treatment.

[10]：如[1]所述之功能性薄膜，前述氣體障蔽層之厚度係20～3000nm。[10]: The functional film according to [1], wherein the thickness of the gas barrier layer is 20 to 3000 nm.

[11]：如[1]所述之功能性薄膜，還成為具有接著劑層之功能性薄膜，前述接著劑層係直接或透過其他層而設置在前述氣體障蔽層上。[11]: The functional film described in [1] also becomes a functional film having an adhesive layer, and the adhesive layer is provided on the gas barrier layer directly or through another layer.

[12]：如[1]所述之功能性薄膜，在依據JIS K5600－5而以直徑6mm來進行心軸彎曲試驗後，在溫度40℃、相對濕度90％條件下之水蒸氣透過率係未滿0.2g‧m-2 ‧day-1 。[12]: The functional film according to [1], after a mandrel bending test with a diameter of 6 mm in accordance with JIS K5600-5, the water vapor transmission rate at a temperature of 40 ° C and a relative humidity of 90% is Less than 0.2g‧m -2 ‧day -1 .

[13]：如[1]所述之功能性薄膜，使用於光學裝置。[13]: The functional film according to [1], used in optical devices.

[14]：一種裝置，在如前述[1]～[13]中任一項所述之功能性薄膜來貼附於對象物之後，剝離及除去製程薄膜而組成。 [發明效果][14]: A device comprising the functional film according to any one of the above [1] to [13], after being attached to an object, the device is formed by peeling and removing a process film. [Inventive effect]

如果是藉由本發明的話，則提供一種具有良好之光學等方性、耐彎曲性和使用時之作業性之功能性薄膜、以及使用該功能性薄膜而得到之裝置。According to the present invention, there is provided a functional film having good optical isotropy, bending resistance, and workability during use, and a device obtained by using the functional film.

本發明之功能性薄膜，係具有：製程薄膜、直接地設置於前述製程薄膜上之樹脂塗佈層、以及在前述樹脂塗佈層上呈直接或透過其他層而設置之氣體障蔽層的功能性薄膜，其特徵為：前述樹脂塗佈層係由含有能量硬化性樹脂和無機填充物之硬化性組合物之硬化物而組成的。 [製程薄膜]The functional film of the present invention has the functions of a process film, a resin coating layer directly provided on the process film, and a gas barrier layer provided on the resin coating layer directly or through other layers. The film is characterized in that the resin coating layer is composed of a cured product of a curable composition containing an energy curable resin and an inorganic filler. [Process film]

構成本發明之功能性薄膜之製程薄膜係在功能性薄膜之製造時和使用時，發揮作為支持體之功能，提高這些作業時之處理性。又，該製程薄膜係在功能性薄膜之保管時和搬運時，擔任作為保護層之任務，保護樹脂塗佈層和氣體障蔽層。正如後面之敘述，通常係最終剝離及除去製程薄膜。The process film constituting the functional film of the present invention functions as a support during the production and use of the functional film, and improves the rationality of these operations. In addition, this process film functions as a protective layer during storage and transportation of the functional film, and protects the resin coating layer and the gas barrier layer. As will be described later, the process film is usually finally stripped and removed.

作為製程薄膜係最好是樹脂薄膜。又，該樹脂薄膜係最好是在表面，無具有容易接著層或剝離層等。在使用表面具有這些層之樹脂薄膜來作為製程薄膜之時，恐怕會使得包含於這些層之成分來污染樹脂塗佈層，或者是在剝離及除去製程薄膜之際，破壞樹脂塗佈層，或者是不容易進行功能性薄膜之捲繞作業。The process film system is preferably a resin film. Moreover, it is preferable that this resin film is on the surface, and does not have an easy adhesion layer, a peeling layer, etc. When a resin film having these layers on the surface is used as a process film, the components included in these layers may cause the resin coating layer to be contaminated, or the resin coating layer may be damaged when the process film is peeled and removed, or It is not easy to wind the functional film.

作為樹脂薄膜之樹脂成分係列舉聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚伸苯基醚、聚醚酮、聚醚醚酮、聚烯烴、聚酯系樹脂、聚碳酸酯、聚碸、聚醚碸、聚伸苯基硫醚、丙烯基系樹脂、環烯烴系聚合物、芳香族系聚合物等。As the resin component of the resin film, polyimide, polyimide, polyimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester resin, polycarbonate , Polyfluorene, polyetherfluorene, polyphenylene sulfide, propylene-based resin, cycloolefin-based polymer, aromatic polymer, etc.

即使是在這些當中，也由於透明性更加良好並且具有通用性，因此，最好是聚酯系樹脂、聚碳酸酯、環烯烴系聚合物或芳香族系聚合物，更加理想是聚酯系樹脂。Even among these, polyester resins, polycarbonates, cycloolefin polymers, or aromatic polymers are preferred because they are more transparent and versatile, and polyester resins are more preferred. .

作為聚酯系樹脂係列舉聚伸乙基對苯二甲酸酯、聚伸丁基對苯二甲酸酯、聚伸乙基萘二甲酸酯、聚芳基化物等，最好是聚伸乙基對苯二甲酸酯。As the polyester resin series, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc. are preferred. Polyethylene terephthalate Ethyl terephthalate.

作為聚碳酸酯係列舉2,2－雙（4－羥苯基）丙烷（別稱：雙酚A）、2,2－雙（4－羥苯基）丁烷、1,1－雙（4－羥苯基）環己烷、1,1－雙（4－羥苯基）異丁烷、1,1－雙（4－羥苯基）乙烷等之雙酚類和二氯化羰或二苯基碳酸酯來進行反應而得到之聚合物。As the polycarbonate series, 2,2-bis (4-hydroxyphenyl) propane (other name: bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, and 1,1-bis (4- Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutane, 1,1-bis (4-hydroxyphenyl) ethane and other bisphenols and carbonyl dichloride or dichloride A polymer obtained by reacting phenyl carbonate.

作為環烯烴系聚合物係列舉原菠烷系聚合物、單環之環狀烯烴系聚合物、環狀共軛二烯烴系聚合物、乙烯基脂環式烴聚合物以及這些之氫化物。作為其具體例係列舉APEL（三井化學公司製之乙烯－環烯烴共聚物）、ARTON（JSR公司製之原菠烷系聚合物）、ZEONOR（日本ZEON公司製之原菠烷系聚合物）等。Examples of the cyclic olefin-based polymer series include original spinane-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these. Specific examples include APEL (ethylene-cycloolefin copolymer made by Mitsui Chemicals), ARTON (original spinane polymer made by JSR), ZEONOR (original spinane polymer made by ZEON, Japan), etc. .

作為芳香族系聚合物係列舉聚苯乙烯等。Examples of the aromatic polymer series include polystyrene.

前述樹脂薄膜係可以在無妨礙本發明效果之範圍內，含有各種之添加劑。作為添加劑係列舉紫外線吸收劑、帶電防止劑、安定劑、氧化防止劑、可塑劑、滑劑、著色顏料等。這些添加劑之含有量係可以配合目地而適度地決定。The said resin film may contain various additives within the range which does not prevent the effect of this invention. Examples of the additive series include ultraviolet absorbers, antistatic agents, stabilizers, oxidation inhibitors, plasticizers, lubricants, and pigments. The content of these additives can be appropriately determined depending on the purpose.

樹脂薄膜係可以藉由調製包含樹脂成分和由於要求之各種添加劑之樹脂組合物，將這個成形為薄膜狀，而得到樹脂薄膜。成形方法係並無特別限定，可以利用熔鑄法或熔融擠壓法等之習知方法。A resin film can be obtained by preparing a resin composition containing a resin component and various additives required, and shaping this into a film shape. The molding method is not particularly limited, and a known method such as a melt casting method or a melt extrusion method can be used.

製程薄膜之厚度係由處理性之觀點來看的話，則最好是10～300μm，更加理想是20～125μm。 [樹脂塗佈層]From the viewpoint of handleability, the thickness of the process film is preferably 10 to 300 μm, and more preferably 20 to 125 μm. [Resin coating layer]

因為構成本發明之功能性薄膜之樹脂塗佈層係直接地設置於前述製程薄膜上之層，該樹脂塗佈層係由含有能量硬化性樹脂和無機填充物之硬化性組合物之硬化物而組成的。The resin coating layer constituting the functional film of the present invention is a layer directly provided on the aforementioned process film, and the resin coating layer is a hardened product of a hardening composition containing an energy hardening resin and an inorganic filler. consist of.

可以藉由設置樹脂塗佈層，而無傷害氣體障蔽層等，效率良好地剝離及除去製程薄膜。It is possible to peel off and remove the process film efficiently by providing a resin coating layer without harming the gas barrier layer and the like.

所謂能量硬化性樹脂係指藉由照射電子線、紫外線等之能量射線，或者是進行加熱，而開始進行硬化反應，變化成為硬化物之樹脂。能量硬化性樹脂係通常是以聚合性化合物來作為主成分之混合物。The energy curable resin refers to a resin that undergoes a curing reaction by being irradiated with energy rays such as electron rays and ultraviolet rays, or is heated to change into a cured product. The energy curable resin is usually a mixture containing a polymerizable compound as a main component.

聚合性化合物係具有能量聚合性官能基之化合物。作為能量聚合性官能基係例舉（甲基）丙烯醯基、乙烯基、烯丙基、苯乙烯基等之乙烯性不飽和基。即使是在這些當中，也由反應性之高度來看的話，則能量聚合性官能基係最好是（甲基）丙烯醯基。又，在本說明書，所謂「（甲基）丙烯醯基」係表示丙烯醯基或甲基丙烯醯基。The polymerizable compound is a compound having an energy polymerizable functional group. Examples of the energy polymerizable functional group include ethylenically unsaturated groups such as (meth) acrylfluorenyl, vinyl, allyl, and styryl. Even among these, in view of the high degree of reactivity, the energy polymerizable functional group is preferably a (meth) acrylfluorenyl group. In the present specification, the "(meth) acrylfluorenyl group" means an acrylfluorenyl group or a methacrylfluorenyl group.

作為具有（甲基）丙烯醯基之聚合性化合物係列舉多官能丙烯酸酯系化合物。所謂多官能丙烯酸酯系化合物係指具有2個以上之參予聚合反應之不飽和鍵之丙烯酸酯化合物或甲基丙烯酸酯化合物。Examples of the polymerizable compound having a (meth) acrylfluorenyl group include polyfunctional acrylate compounds. The polyfunctional acrylate compound refers to an acrylate compound or a methacrylate compound having two or more unsaturated bonds participating in the polymerization reaction.

作為多官能丙烯酸酯系化合物係列舉三環癸烷二甲醇二（甲基）丙烯酸酯、1,4－丁烷二醇二（甲基）丙烯酸酯、1,6－己烷二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、新戊二醇己二酸酯二（甲基）丙烯酸酯、羥基三甲基乙酸新戊二醇二（甲基）丙烯酸酯、二環芬太尼二（甲基）丙烯酸酯、己內酯變體二環戊烯基二（甲基）丙烯酸酯、伸乙基氧化物變體磷酸二（甲基）丙烯酸酯、二（丙烯醯基氧乙基）異氰酸酯、烯丙基化環己基二（甲基）丙烯酸酯等之2官能丙烯酸酯系化合物、三羥甲基丙烷三（甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、丙酸變體二季戊四醇三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、伸丙基氧化物變體三羥甲基丙烷三（甲基）丙烯酸酯、三（2－丙烯醯基氧乙基）異氰酸酯等之3官能丙烯酸酯系化合物、二丙三醇四（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯等之4官能丙烯酸酯系化合物、丙酸變體二季戊四醇五（甲基）丙烯酸酯等之5官能丙烯酸酯系化合物、二季戊四醇六（甲基）丙烯酸酯、己內酯變體二季戊四醇六（甲基）丙烯酸酯等之6官能丙烯酸酯系化合物等。Examples of multifunctional acrylate compounds include tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (methyl) Base) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxytrimethylacetate Neopentyl glycol di (meth) acrylate, dicyclofentanyl di (meth) acrylate, caprolactone variants, dicyclopentenyl di (meth) acrylate, and ethylene oxide variants Bifunctional acrylate compounds such as phosphate di (meth) acrylate, bis (propenyloxyethyl) isocyanate, allyl cyclohexyl di (meth) acrylate, trimethylolpropane tris (methyl) Base) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid variant dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane modified propylene oxide Tris (meth) acrylate, tris (2-propenyloxyethyl) isocyanate 4-functional acrylate compounds such as esters, 4-functional acrylate compounds such as diglycerol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and propionic acid variants dipentaerythritol penta (methyl) 5-functional acrylate compounds such as acrylates, 6-functional acrylate compounds such as dipentaerythritol hexa (meth) acrylate, caprolactone modification dipentaerythritol hexa (meth) acrylate, and the like.

這些多官能丙烯酸酯系化合物係可以單獨一種或者是組合二種以上而使用。These polyfunctional acrylate-based compounds may be used alone or in combination of two or more.

能量硬化性樹脂係可以包含低聚合物。作為此種低聚合物係列舉聚酯丙烯酸酯系低聚合物、環氧丙烯酸酯系低聚合物、胺基甲酸乙酯丙烯酸酯系低聚合物、聚醇丙烯酸酯系低聚合物等。The energy curable resin system may contain a low polymer. Examples of such low-polymer series include polyester acrylate-based oligomers, epoxy acrylate-based oligomers, urethane acrylate-based oligomers, and polyol acrylate-based oligomers.

能量硬化性樹脂係可以包含光聚合起始劑或熱聚合起始劑等之聚合起始劑。The energy curable resin may include a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator.

作為光聚合起始劑係列舉2,2－二甲氧基－1,2－二苯基乙烷－1－酮、1－羥基－環己基－苯基酮等之酮系光聚合起始劑、2,4,6－三甲基苯甲醯基－二苯基膦氧化物、雙（2,4,6－三甲基苯甲醯基）－苯基膦氧化物、乙基（2,4,6－三甲基苯甲醯基）－苯基亞膦酸酯、雙（2,6－二甲氧基苯甲醯基）－2,4,4－三甲基－戊基膦氧化物等之磷系光聚合起始劑、雙（η5－2,4－環戊二烯－1－醯）－雙[2,6－二氟－3－（1H－吡咯－1－醯）－苯基]鈦等之環戊二烯鈦系光聚合起始劑、肟酯系光聚合起始劑、二苯基酮、p－氯二苯基酮、4,4'－二乙胺基二苯基酮等之二苯基酮系光聚合起始劑、噻噸酮等之噻噸酮系光聚合起始劑、三異丙醇胺等之胺系光聚合起始劑等。這些光聚合起始劑係可以單獨一種或者是組合二種以上而使用。Examples of photopolymerization initiators include ketone photopolymerization initiators such as 2,2-dimethoxy-1,2-diphenylethane-1-one, and 1-hydroxy-cyclohexyl-phenylketone. , 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, ethyl (2, 4,6-trimethylbenzylidene) -phenyl phosphinate, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine oxidation Phosphorus-based photopolymerization initiators such as bis (η5-2,4-cyclopentadiene-1-fluorene) -bis [2,6-difluoro-3- (1H-pyrrole-1- 醯)- Phenyl] titanium and other cyclopentadiene titanium photopolymerization initiators, oxime ester photopolymerization initiators, diphenyl ketones, p-chlorodiphenyl ketones, 4,4'-diethylamino di Diphenylketone-based photopolymerization initiators such as phenylketone, thioxanthone-based photopolymerization initiators such as thioxanthone, and amine-based photopolymerization initiators such as triisopropanolamine. These photopolymerization initiators may be used alone or in combination of two or more.

作為熱聚合起始劑係列舉過氧化氫、過氧二硫酸銨、過氧二硫酸鈉、過氧二硫酸鉀等之過氧二硫酸鹽、2,2'－偶氮基雙（2－脒基）二塩酸鹽、4,4'－偶氮基雙（4－氰基三戊醯甘油酸）、2,2'－偶氮基雙異丁腈、2,2'－偶氮基雙（4－甲氧基－2,4－二甲基戊腈）等之偶氮基系化合物、過氧化苯甲醯基、過氧化月桂醯、過乙酸、過琥珀酸、二－t－丁基過氧化物、t－丁基氫化過氧化物、枯烯氫化過氧化物等之有機過氧化物等。這些熱聚合起始劑係可以單獨一種或者是組合二種以上而使用。As the thermal polymerization initiator series, hydrogen peroxide, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate and other peroxodisulfates, 2,2'-azobis (2- 脒Group) diphosphonate, 4,4'-azobis (4-cyanotrivalerol glyceric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds, benzoyl peroxide, lauryl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxy Organic peroxides such as oxides, t-butyl hydroperoxides, and cumene hydroperoxides. These thermal polymerization initiators may be used alone or in combination of two or more.

在能量硬化性樹脂來含有聚合起始劑之狀態下，其含有量係相對於聚合性化合物100質量份而通常成為0.01～20質量份之範圍。When the energy-curable resin contains a polymerization initiator, its content is usually in the range of 0.01 to 20 parts by mass based on 100 parts by mass of the polymerizable compound.

能量硬化性樹脂係可以含有聚異氰酸酯系交聯劑。作為聚異氰酸酯系交聯劑係並無特別限定，使用在分子中具有2個以上之異氰酸酯基之化合物。作為此種聚異氰酸酯系交聯劑係甲伸苯基二異氰酸酯、二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等之芳香族聚異氰酸酯、六亞甲基二異氰酸酯等之脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯等之脂環式聚異氰酸酯、這些化合物之縮二脲體、異氰酸酯體、以及成為這些化合物和乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等之低分子活性含氫化合物之間之反應物之加成物體等。這些聚異氰酸酯系交聯劑係可以單獨一種或者是組合二種以上而使用。The energy curable resin system may contain a polyisocyanate-based crosslinking agent. The polyisocyanate-based crosslinking agent is not particularly limited, and a compound having two or more isocyanate groups in the molecule is used. Examples of such polyisocyanate-based cross-linking agents include aromatic polyisocyanates such as methylenephenyl diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate. Aliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, biuret form, isocyanate form of these compounds, and these compounds and ethylene glycol, propylene glycol, neopentyl glycol, three Additives such as reactants between low molecular active hydrogen-containing compounds such as methylolpropane and castor oil. These polyisocyanate-based crosslinking agents may be used alone or in combination of two or more.

在能量硬化性樹脂來含有聚異氰酸酯系交聯劑之狀態下，其含有量係相對於聚合性化合物100質量份而通常成為1～10質量份、最好是2～8質量份。When the energy curable resin contains a polyisocyanate-based crosslinking agent, its content is usually 1 to 10 parts by mass, and preferably 2 to 8 parts by mass, based on 100 parts by mass of the polymerizable compound.

作為能量硬化性樹脂係最好是藉由紫外線（UV）之照射而硬化之樹脂（紫外線硬化性樹脂）。可以藉由使用紫外線硬化性樹脂而效率良好地形成由能量硬化性樹脂之硬化物來組成之層。The energy curable resin is preferably a resin (ultraviolet curable resin) which is cured by irradiation with ultraviolet (UV) light. By using an ultraviolet curable resin, a layer composed of a cured product of an energy curable resin can be efficiently formed.

包含於硬化性組合物之無機填充物係用以在功能性薄膜，來提高製程薄膜之剝離性。The inorganic filler contained in the curable composition is used in a functional film to improve the peelability of a process film.

作為構成無機填充物之無機物係列舉二氧化矽、氧化鋁、氧化鋯、二氧化鈦、氧化鋅、氧化鍺、氧化銦、氧化錫、銦錫氧化物（ITO）、氧化銻、氧化鈰等之金屬氧化物、氟化鎂、氟化鈉等之金屬氟化物等。As a series of inorganic substances constituting inorganic fillers, metal oxides such as silicon dioxide, aluminum oxide, zirconia, titanium dioxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide are oxidized. Metals, magnesium fluoride, sodium fluoride, etc.

無機填充物之形狀係可以是球狀，也可以是非球狀。在成為非球狀之狀態下，可以是不定形，也可以是所謂針狀、鱗片狀之深寬度比變高之形狀。The shape of the inorganic filler may be spherical or non-spherical. In the state of being aspherical, the shape may be an indefinite shape, or a shape in which the depth-to-width ratio of a so-called needle-like or scaly shape becomes higher.

由於容易得到更加良好之光學等方性之功能性薄膜，因此，最好是深寬度比變低，更加良好是球狀。Since it is easy to obtain a functional film having better optical properties such as optical properties, it is preferable that the aspect ratio is lower and the spherical shape is more favorable.

無機填充物之平均粒徑係並無特別限定，通常是5～100nm。在無機填充物之平均粒徑呈過度小之時，恐怕會不容易充分地提高製程薄膜之剝離性。另一方面，在無機填充物之平均粒徑呈過度大之時，恐怕會降低形成於樹脂塗佈層上之氣體障蔽層之氣體障蔽性。The average particle size of the inorganic filler is not particularly limited, but is usually 5 to 100 nm. When the average particle diameter of the inorganic filler is excessively small, it may be difficult to sufficiently improve the peelability of the process film. On the other hand, when the average particle diameter of the inorganic filler is excessively large, the gas barrier property of the gas barrier layer formed on the resin coating layer may be reduced.

無機填充物之平均粒徑係可以使用粒度分布測定裝置，藉由動態光散亂法而進行測定。The average particle diameter of the inorganic filler can be measured by a dynamic light scattering method using a particle size distribution measuring device.

無機填充物係可以藉由有機化合物而修飾其表面。作為此種有機化合物係列舉將含有反應性不飽和鍵之基予以含有之有機化合物。藉由將含有反應性不飽和鍵之基予以含有之有機化合物而進行修飾之無機填充物係在表面，具備含有反應性不飽和鍵之基。藉由使用此種無機填充物，而以在剝離‧除去製程薄膜時之作業性，來容易得到良好之功能性薄膜。The surface of inorganic fillers can be modified by organic compounds. Examples of such organic compounds include organic compounds containing a group containing a reactive unsaturated bond. An inorganic filler modified with an organic compound containing a group containing a reactive unsaturated bond is provided on the surface with a group containing a reactive unsaturated bond. By using such an inorganic filler, it is easy to obtain a good functional film by the workability when peeling and removing the process film.

作為含有反應性不飽和鍵之基係列舉乙烯基、烯丙基、（甲基）丙烯醯基、（甲基）丙烯醯基氧化基、環氧丙基等。Examples of the group containing a reactive unsaturated bond include vinyl, allyl, (meth) acrylfluorenyl, (meth) acrylfluorenyl oxide, and epoxypropyl.

作為將含有反應性不飽和鍵之基予以含有之有機化合物係可以使用矽烷偶合劑。作為矽烷偶合劑係列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、p－苯乙烯基三甲氧基矽烷、3－（甲基）丙烯醯氧基丙基三甲氧基矽烷、3－（甲基）丙烯醯氧基丙基三乙氧基矽烷、3－環氧丙基氧化丙基三甲氧基矽烷等。As the organic compound system containing a reactive unsaturated bond-containing group, a silane coupling agent can be used. Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (Meth) acryloxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like.

在表面具備含有反應性不飽和鍵之基之無機填充物係可以使用矽烷偶合劑，藉由習知之方法而進行無機填充物之表面處理。The inorganic filler system having a group containing a reactive unsaturated bond on the surface can be treated with a silane coupling agent by a conventional method.

硬化性組合物係可以含有溶劑。The curable composition may contain a solvent.

作為溶劑係列舉n－己烷、n－庚烷等之脂肪族烴系溶媒、甲苯、二甲苯等之芳香族烴系溶媒、二氯甲烷、氯化乙烯、三氯甲烷、四氯化碳、2－二氯乙烷、單氯苯等之鹵化烴系溶媒、甲醇、乙醇、丙醇、丁醇、丙二醇單甲基醚等之醇系溶媒、丙酮、甲基乙基甲酮、2－戊酮、異佛爾酮、環己酮等之酮系溶媒、乙酸乙酯、乙酸丁酯等之酯系溶媒、乙基－2－乙氧乙醇等之2－乙氧乙醇系溶劑、1,3－二氧雜環戊烷等之醚系溶媒等。Examples of the solvent series include aliphatic hydrocarbon solvents such as n-hexane and n-heptane, aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, Halogenated hydrocarbon solvents such as dichloroethane, monochlorobenzene, alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, 2-pentyl Ketone solvents such as ketones, isophorone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; 2-ethoxyethanol solvents such as ethyl-2-ethoxyethanol; 1,3 -Ether solvents such as dioxolane.

構成本發明之功能性薄膜之樹脂塗佈層係可以藉由習知之塗佈方法而將前述硬化性組合物，塗佈於前述製程薄膜上，在配合需要而乾燥得到之塗膜後，藉由硬化塗膜而形成樹脂塗佈層。The resin coating layer constituting the functional film of the present invention can be obtained by applying the aforementioned hardening composition to the aforementioned process film by a conventional coating method, and drying the obtained coating film according to the need, and then The coating film is cured to form a resin coating layer.

作為塗佈硬化性組合物之方法係可以使用通常之濕式塗佈方法。列舉例如浸漬法、壓輥塗佈、照相凹版印刷塗佈、刮刀塗佈、空氣刀塗佈、壓輥刀塗佈、模塗佈、網版印刷法、噴射塗佈、照相凹版印刷偏心錯位法等。As a method for applying the curable composition, a general wet coating method can be used. Examples include dipping, roll coating, gravure coating, doctor blade coating, air knife coating, roll coating, die coating, screen printing, spray coating, and gravure offset printing. Wait.

作為乾燥塗膜之方法係列舉熱風乾燥、熱壓輥乾燥、紫外線照射等之向來習知之乾燥方法。As a method of drying the coating film, conventionally known drying methods include hot air drying, hot roller drying, and ultraviolet irradiation.

作為硬化塗膜之方法係並無特別限定，可以配合能量硬化性樹脂之特性而適度地選擇習知之方法。The method for curing the coating film is not particularly limited, and a conventional method can be appropriately selected in accordance with the characteristics of the energy-curable resin.

例如在能量硬化性樹脂承受活性能量射線而進行硬化之狀態下，可以藉由使用高壓水銀燈、無電極燈、氙燈等，在塗膜照射活性能量射線，而硬化塗膜。For example, in a state where the energy-curable resin is hardened by receiving active energy rays, the coating film can be hardened by applying active energy rays to the coating film by using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like.

活性能量射線之波長係最好是200～400nm，更加理想是350～400nm。照射量係通常為照度50～1000mW／cm2 、光量50～5000mJ／cm2 、最好是1000～5000mJ／cm2 之範圍。照射時間係通常為0.1～1000秒，最好是1～500秒，更加理想是10～100秒。為了考慮光照射製程之熱負荷而滿足前述光量，因此，可以照射複數次。The wavelength of the active energy ray is preferably 200 to 400 nm, and more preferably 350 to 400 nm. The irradiation amount is usually in the range of 50 to 1,000 mW / cm 2 and 50 to 5000 mJ / cm 2 , and preferably 1000 to 5000 mJ / cm 2 . The irradiation time is usually 0.1 to 1000 seconds, preferably 1 to 500 seconds, and more preferably 10 to 100 seconds. In order to satisfy the aforementioned light quantity in consideration of the heat load of the light irradiation process, the light can be irradiated multiple times.

又，在能量硬化性樹脂藉由加熱而進行硬化之狀態下，可以藉由在進行硬化反應之溫度，加熱塗膜，而硬化塗膜。In addition, in a state where the energy curable resin is cured by heating, the coating film can be cured by heating the coating film at a temperature at which the curing reaction proceeds.

包含於樹脂塗佈層之樹脂成分（來自於能量硬化性樹脂之成分）之含有量係並無特別限定，但是，以樹脂塗佈層之整體來作為基準而通常成為30～90質量％，最好是50～70質量％。The content of the resin component (the component derived from the energy curable resin) contained in the resin coating layer is not particularly limited, but it is usually 30 to 90% by mass based on the entire resin coating layer. It is preferably 50 to 70% by mass.

包含於樹脂塗佈層之無機填充物之含有量係並無特別限定，但是，以樹脂塗佈層之整體來作為基準而通常成為10～70質量％，最好是50～70質量％。The content of the inorganic filler contained in the resin coating layer is not particularly limited, but it is usually 10 to 70% by mass, preferably 50 to 70% by mass based on the entire resin coating layer.

在包含於樹脂塗佈層之無機填充物之含有量呈過度少之時，恐怕會不容易效率良好地剝離‧除去製程薄膜。另一方面，在包含於樹脂塗佈層之無機填充物之含有量呈過度多之時，恐怕會降低功能性薄膜之透明性及耐彎曲性。When the content of the inorganic filler contained in the resin coating layer is excessively small, it may be difficult to efficiently peel and remove the process film. On the other hand, when the content of the inorganic filler contained in the resin coating layer is excessively large, the transparency and bending resistance of the functional film may be reduced.

樹脂塗佈層之厚度係並無特別限定，但是，通常為0.1～10μm，最好是0.5～5μm。The thickness of the resin coating layer is not particularly limited, but is usually 0.1 to 10 μm, and preferably 0.5 to 5 μm.

在樹脂塗佈層呈過度薄之時，在剝離‧除去製程薄膜之際，恐怕會破壞氣體障蔽層等。另一方面，在樹脂塗佈層呈過度厚之時，恐怕會降低耐彎曲性。When the resin coating layer is excessively thin, the gas barrier layer may be damaged when the process film is peeled and removed. On the other hand, when the resin coating layer is excessively thick, bending resistance may be reduced.

樹脂塗佈層之相反於接合在製程薄膜之側之相反側之面粗糙曲線之剖面最大高度（Rt）係並無特別限定，但是，通常為1～200nm，最好是2～150nm。The maximum cross-section height (Rt) of the surface roughness curve of the resin coating layer opposite to the side opposite to the side where the process film is bonded is not particularly limited, but it is usually 1 to 200 nm, preferably 2 to 150 nm.

所謂樹脂塗佈層之相反於接合在製程薄膜之側之相反側之面係在製程薄膜上來形成樹脂塗佈層之時，成為露出之面。正如後面之敘述，在該面上，直接或透過其他層而形成氣體障蔽層。When the surface of the resin coating layer opposite to the side bonded to the process film is formed on the process film to form the resin coating layer, it becomes the exposed surface. As described later, a gas barrier layer is formed on this surface directly or through other layers.

該粗糙曲線之剖面最大高度（Rt）係如果是功能性薄膜之製造途中之狀態的話，則可以藉由以光干涉顯微鏡，來觀察露出之樹脂塗佈層之表面，而進行測定。The maximum height (Rt) of the cross section of the rough curve is a state in the middle of the production of the functional thin film, and it can be measured by observing the surface of the exposed resin coating layer with a light interference microscope.

在粗糙曲線之剖面最大高度（Rt）呈過度小之時，恐怕會不容易充分地提高製程薄膜之剝離性。另一方面，在粗糙曲線之剖面最大高度（Rt）呈過度大之時，恐怕會降低形成於樹脂塗佈層上之氣體障蔽層之氣體障蔽性。When the maximum height (Rt) of the cross section of the rough curve is excessively small, it may be difficult to sufficiently improve the peelability of the process film. On the other hand, when the maximum cross-section height (Rt) of the rough curve is excessively large, the gas barrier property of the gas barrier layer formed on the resin coating layer may be reduced.

粗糙曲線之剖面最大高度（Rt）係可以藉由調節使用之無機填充物之平均粒徑或量而進行最適當化。 [氣體障蔽層]The maximum profile height (Rt) of the rough curve can be optimized by adjusting the average particle size or amount of the inorganic filler used. [Gas barrier layer]

構成本發明之功能性薄膜之氣體障蔽層係具有抑制氧或水蒸氣等之氣體透過之特性（氣體障蔽性）。該氣體障蔽層係在前述樹脂塗佈層上，直接或透過啟發劑底層等之其他層而進行層積所組成。The gas-barrier layer constituting the functional film of the present invention has a property (gas-barrier property) that suppresses the permeation of gas such as oxygen or water vapor. The gas barrier layer is formed by laminating the resin coating layer directly or through other layers such as a primer layer.

作為氣體障蔽層係最好是含有：包含矽氧化物、矽氮化物、矽氟化物、矽碳化物、金屬氧化物、金屬氮化物、金屬氟化物、金屬碳化物、以及構成這些化合物之元素之複合化合物。The gas barrier layer system preferably contains: silicon oxide, silicon nitride, silicon fluoride, silicon carbide, metal oxide, metal nitride, metal fluoride, metal carbide, and elements constituting these compounds. Compound compounds.

作為此種氣體障蔽層係列舉例如無機蒸鍍膜或者是藉由承受重組處理而重組可以變化成為含有無機化合物之層之層表面來得到者[在該狀態下，所謂氣體障蔽層係並非僅表示重組之區域，表示「包含重組之區域之層」。]等。Examples of such gas barrier layer series include inorganic vapor-deposited films or those obtained by undergoing a reorganization process, which can be changed to a layer surface containing an inorganic compound layer. [In this state, the so-called gas barrier layer system does not merely mean reorganization The area means "the layer containing the reorganized area". ]Wait.

作為無機蒸鍍膜係列舉無機化合物和金屬之蒸鍍膜。Examples of the inorganic vapor-deposited film include vapor-deposited films of inorganic compounds and metals.

作為無機化合物之蒸鍍膜之原料係列舉氧化矽、氧化鋁、氧化鎂、氧化鋅、氧化銦、氧化錫等之無機氧化物、氮化矽、氮化鋁、氮化鈦等之無機氮化物、無機碳化物、無機硫化物、氧化氮化矽等之無機氧化氮化物、無機氧化碳化物、無機氮化碳化物、無機氧化氮化碳化物等。The raw materials for the vapor-deposited film of inorganic compounds include inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; Inorganic carbides, inorganic sulfides, inorganic oxide nitrides such as silicon oxide nitride, inorganic oxide carbides, inorganic nitride carbides, inorganic oxide nitride carbides, etc.

作為金屬之蒸鍍膜之原料係列舉鋁、鎂、鋅和錫等。As the raw material series of metal vapor-deposited film, aluminum, magnesium, zinc, and tin are mentioned.

這些係可以單獨一種或者是組合二種以上而使用。These systems can be used alone or in combination of two or more.

在這些當中，由氣體障蔽性之觀點來看的話，則最好是以無機氧化物、無機氮化物或金屬來作為原料之無機蒸鍍膜，並且，由透明性之觀點來看的話，則最好是以無機氧化物或無機氮化物來作為原料之無機蒸鍍膜。Among these, an inorganic vapor-deposited film using an inorganic oxide, an inorganic nitride, or a metal as a raw material is preferable from the viewpoint of gas barrier properties, and it is preferable from the viewpoint of transparency. It is an inorganic vapor-deposited film using inorganic oxide or inorganic nitride as a raw material.

作為形成無機蒸鍍膜之方法係列舉真空蒸鍍法、濺鍍法、離子植入法等之PVD（物理蒸鍍）法和熱CVD（化學蒸鍍）法、電漿CVD法、光CVD法等之CVD法。As a method for forming an inorganic vapor deposition film, there are a series of methods such as a PVD (physical vapor deposition) method, a thermal CVD (chemical vapor deposition) method, a plasma CVD method, and a photo CVD method, such as a vacuum deposition method, a sputtering method, and an ion implantation method. The CVD method.

無機蒸鍍膜之厚度係由於使用之無機化合物和金屬而不同，但是，由氣體障蔽性和處理性之觀點來看的話，則最好是20～3000nm、更加理想是20～1000nm、甚至最好是20～500nm之範圍。The thickness of the inorganic vapor-deposited film varies depending on the inorganic compound and metal used. However, from the standpoint of gas barrier properties and handling properties, it is preferably 20 to 3000 nm, more preferably 20 to 1000 nm, and even more preferably The range is 20 to 500 nm.

作為藉由承受重組處理而可以變化成為含有無機化合物之層之變化層係列舉含有含矽高分子化合物之層（在以下，稱為「高分子層」。）。又，在「藉由承受重組處理而可以變化成為含有無機化合物之層之變化層」，正如後面敘述之無機之聚矽氨烷，也包含成為含有無機高分子化合物之層之狀態。在該狀態下，藉由承受重組處理，而使得包含前述無機高分子化合物之層之至少一部分，變化成為含有不同組成之無機化合物之層。As a series of changing layers that can be changed to a layer containing an inorganic compound by undergoing recombination processing, a layer containing a silicon-containing polymer compound (hereinafter, referred to as a "polymer layer"). In addition, "a changeable layer that can be changed into a layer containing an inorganic compound by undergoing recombination treatment" includes an inorganic polysilazane as described later, and also includes a state of being a layer containing an inorganic polymer compound. In this state, at least a part of the layer containing the inorganic polymer compound is changed to a layer containing inorganic compounds having different compositions by undergoing recombination processing.

高分子層係可以除了含矽高分子化合物以外，在無妨礙本發明目地之範圍，含有其他之成分。作為其他之成分係列舉硬化劑、老化防止劑、光安定劑、難燃劑等。The polymer layer system may contain other components in addition to the silicon-containing polymer compound so long as the object of the present invention is not hindered. Examples of other components include hardeners, anti-aging agents, light stabilizers, and flame retardants.

高分子層中之含矽高分子化合物之含有量係由於可以形成氣體障蔽性更加良好之氣體障蔽層，因此，最好是50質量％以上，更加理想是70質量％以上。Since the content of the silicon-containing polymer compound in the polymer layer can form a gas barrier layer having better gas barrier properties, it is preferably 50% by mass or more, and more preferably 70% by mass or more.

高分子層之厚度係並無特別限制，通常為20～3000nm，最好是20～1000nm，更加理想是20～500nm之範圍。The thickness of the polymer layer is not particularly limited, but is usually 20 to 3000 nm, preferably 20 to 1000 nm, and more preferably 20 to 500 nm.

高分子層係可以例如藉由以習知之塗佈方法，直接或透過其他層，將含矽高分子化合物溶解或分散於有機溶劑之液體，塗佈在基材層上，乾燥得到之塗膜，而形成高分子層。The polymer layer can be, for example, a conventional coating method, directly or through other layers, dissolving or dispersing a silicon-containing polymer compound in an organic solvent liquid, coating it on a substrate layer, and drying the obtained coating film. A polymer layer is formed.

作為有機溶劑係列舉苯、甲苯等之芳香族烴系溶媒、乙酸乙酯、乙酸丁酯等之酯系溶媒、丙酮、甲基乙基甲酮、甲基異丁基酮等之酮系溶媒、n－戊烷、n－己烷、n－庚烷等之脂肪族烴系溶媒、環戊烷、環己烷等之脂環式烴系溶媒等。Examples of organic solvents include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and the like.

這些溶媒係可以單獨一種或者是組合二種以上而使用。These solvents may be used alone or in combination of two or more.

作為塗佈方法係列舉桿條塗佈法、旋轉塗佈法、浸漬法、壓輥塗佈法、照相凹版印刷塗佈法、刮刀塗佈法、空氣刀塗佈法、壓輥刀塗佈法、模塗佈法、網版印刷法、噴射塗佈法、照相凹版印刷偏心錯位法等。As the coating method series, a bar coating method, a spin coating method, a dipping method, a roll coating method, a gravure printing coating method, a doctor blade coating method, an air blade coating method, and a roller blade coating method , Die coating method, screen printing method, spray coating method, gravure offset printing method, etc.

作為塗膜之乾燥方法係列舉熱風乾燥、熱壓輥乾燥、紫外線照射等之向來習知之乾燥方法。加熱溫度係通常為80～150℃，加熱時間係通常為數十秒至數十分鐘。As a method for drying a coating film, conventionally known drying methods include hot air drying, hot-roller drying, and ultraviolet irradiation. The heating temperature is usually 80 to 150 ° C, and the heating time is usually tens of seconds to tens of minutes.

作為重組高分子層表面之方法係列舉離子注入處理、電漿處理、紫外線照射處理、熱處理等。As a method of reorganizing the surface of the polymer layer, a series of methods include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.

離子注入處理係正如後面之敘述，將加速之離子，注入至高分子層，重組高分子層之方法。The ion implantation process is a method of implanting accelerated ions into a polymer layer and reconstituting the polymer layer as described later.

電漿處理係高分子層曝露於電漿中而重組高分子層之方法。例如可以按照記載於日本特開2012－106421號公報之方法而進行電漿處理。Plasma treatment is a method of reorganizing a polymer layer by exposing the polymer layer to a plasma. For example, plasma processing can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.

紫外線照射處理係在高分子層，照射紫外線而重組高分子層之方法。例如可以按照記載於日本特開2013－226757號公報之方法而進行紫外線重組處理。Ultraviolet irradiation treatment is a method of restructuring a polymer layer by irradiating ultraviolet rays on a polymer layer. For example, the ultraviolet recombination process can be performed according to the method described in Japanese Patent Application Laid-Open No. 2013-226757.

作為含矽高分子化合物係列舉聚矽氨烷系化合物、聚矽碳烷系化合物、聚矽烷系化合物、有機聚矽氧烷系化合物、聚（二矽烷基伸苯基）系化合物以及聚（二矽烷基伸乙炔基）系化合物等，更加理想是聚矽氨烷系化合物。Examples of silicon-containing polymer compounds include polysilazane-based compounds, polysilazane-based compounds, polysilane-based compounds, organic polysiloxane compounds, poly (disylphenylene) -based compounds, and poly (disilanes). Polyethynyl) -based compounds and the like are more preferably polysilazane-based compounds.

聚矽氨烷系化合物係具有在分子內包含－Si－N－鍵（矽氨烷鍵）之重複單位之化合物。具體地說，最好是具有藉由化學式（1） 【化學1】所表示之重複單位之化合物。又，使用之聚矽氨烷系化合物之數平均分子量係並無特別限定，但是，最好是100～50,000。The polysilazane compound is a compound having a repeating unit including a -Si-N-bond (silazane bond) in the molecule. Specifically, it is preferable to have the formula (1) [Chemical 1] Compounds in the indicated repeating units. The number average molecular weight of the polysilazane-based compound used is not particularly limited, but it is preferably 100 to 50,000.

在前述化學式（1）中，n係表示任意之自然數。Rx、Ry、Rz係分別獨立地表示氫原子、無取代基或具有取代基之烷基、無取代基或具有取代基之環烷基、無取代基或具有取代基之鏈烯基、無取代基或具有取代基之芳基、或者是烷基甲矽烷基等之非水解性基。In the aforementioned chemical formula (1), n represents an arbitrary natural number. Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, and an unsubstituted group. Group, a aryl group having a substituent, or a non-hydrolyzable group such as an alkylsilyl group.

作為前述無取代基或具有取代基之烷基之烷基係列舉例如甲基、乙基、n－丙基、異丙基、n－丁基、異丁基、sec－丁基、t－丁基、n－戊基、異戊基、新戊基、n－己基、n－庚基、n－辛基等之碳數1～10之烷基。Examples of the above-mentioned unsubstituted or substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl. Alkyl groups having 1 to 10 carbon atoms, such as N-pentyl, iso-pentyl, neopentyl, n-hexyl, n-heptyl, and n-octyl.

作為無取代基或具有取代基之環烷基之環烷基係列舉例如環丁基、環戊基、環己基、環庚基等之碳數3～10之環烷基。Examples of the cycloalkyl group as a cycloalkyl group having no substituent or a substituent include a cycloalkyl group having 3 to 10 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

作為無取代基或具有取代基之鏈烯基之鏈烯基係列舉例如乙烯基、1－丙烯基、2－丙烯基、1－丁烯基、2－丁烯基、3－丁烯基等之碳數2～10之鏈烯基。Examples of the alkenyl group as an unsubstituted or substituted alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, etc. Alkenyl having 2 to 10 carbon atoms.

作為前述烷基、環烷基和鏈烯基之取代基係列舉氟原子、氯原子、溴原子、碘原子等之鹵素原子、羥基、硫代基、環氧基、環氧丙氧基、（甲基）丙烯醯氧基、苯基、4－甲苯基、4－氯苯基等之無取代基或具有取代基之芳基等。Examples of the substituents of the aforementioned alkyl, cycloalkyl, and alkenyl groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, hydroxyl group, thio group, epoxy group, propylene oxide group, ( (Meth) acrylic fluorenyloxy, phenyl, 4-tolyl, 4-chlorophenyl, and the like have no substituents or substituted aryl groups and the like.

作為無取代基或具有取代基之芳基之芳基係列舉例如苯基、1－萘基、2－萘基等之碳數6～15之芳基。Examples of the aryl group which is an unsubstituted group or an aryl group having a substituent include an aryl group having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

作為前述芳基之取代基係列舉氟原子、氯原子、溴原子、碘原子等之鹵素原子、甲基、乙基等之碳數1～6之烷基、甲氧基、乙氧基等之碳數1～6之烷氧基、硝基、氰基、羥基、硫代基、環氧基、環氧丙氧基、（甲基）丙烯醯氧基、苯基、4－甲苯基、4－氯苯基等之無取代基或具有取代基之芳基等。Examples of the substituent of the aforementioned aryl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group. Alkoxy, nitro, cyano, hydroxy, thio, epoxide, propylene oxide, (meth) acryloxy, phenyl, 4-tolyl, 4 carbon -An unsubstituted or aryl group having a substituent, such as a chlorophenyl group.

作為烷基甲矽烷基係列舉三甲基甲矽烷基、三乙基甲矽烷基、三異丙基甲矽烷基、三t－丁基甲矽烷基、甲基二乙基甲矽烷基、二甲基甲矽烷基、二乙基甲矽烷基、甲基甲矽烷基、乙基甲矽烷基等。Examples of the alkylsilyl series include trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, methyldiethylsilyl, and dimethylformyl. Silyl, diethylsilyl, methylsilyl, ethylsilyl and the like.

即使是在這些當中，作為Rx、Ry、Rz係也最好是氫原子、碳數1～6之烷基、或者是苯基，特別最好是氫原子。Even among these, the Rx, Ry, and Rz systems are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and particularly preferably a hydrogen atom.

作為具有藉由前述化學式（1）所表示之重複單位之聚矽氨烷系化合物係可以是Rx、Ry、Rz全部為氫原子之無機聚矽氨烷和Rx、Ry、Rz之至少一個並非為氫原子之有機聚矽氨烷之任何一種。The polysilazane-based compound having a repeating unit represented by the aforementioned chemical formula (1) may be an inorganic polysilazane in which Rx, Ry, and Rz are all hydrogen atoms, and at least one of Rx, Ry, and Rz is not Any of the organic polysilazane of hydrogen atom.

又，在本發明，作為聚矽氨烷系化合物係也可以使用聚矽氨烷變體物。作為聚矽氨烷變體物係列舉例如記載於日本特開昭62－195024號公報、日本特開平2－84437號公報、日本特開昭63－81122號公報、日本特開平1－138108號公報等、日本特開平2－175726號公報、日本特開平5－238827號公報、日本特開平5－238827號公報、日本特開平6－122852號公報、日本特開平6－306329號公報、日本特開平6－299118號公報、日本特開平9－31333號公報、日本特開平5－345826號公報、日本特開平4－63833號公報等。In the present invention, a polysilazane-based compound may be used as a polysilazane-based compound. Examples of polysilazane variants are described in Japanese Patent Laid-Open No. 62-195024, Japanese Patent Laid-Open No. 2-84437, Japanese Patent Laid-Open No. 63-81122, and Japanese Patent Laid-Open No. 1-138108. Etc., Japanese Patent Laid-Open No. 2-175726, Japanese Patent Laid-Open No. 5-238827, Japanese Patent Laid-Open No. 5-238827, Japanese Patent Laid-Open No. 6-122852, Japanese Patent Laid-Open No. 6-306329, Japanese Patent Laid-Open No. 6-306329 Japanese Patent Application Publication No. 6-299118, Japanese Patent Application Publication No. 9-31333, Japanese Patent Application Publication No. 5-345826, Japanese Patent Application Publication No. 4-63833, and the like.

即使是在這些當中，作為聚矽氨烷系化合物係也由入手容易性和可以形成具有良好之氣體障蔽性之離子注入層之觀點來看的話，則最好是是Rx、Ry、Rz全部為氫原子之全氫化聚矽氨烷。Even among these, as a polysilazane-based compound, from the standpoint of ease of starting and the ability to form an ion-implanted layer with good gas barrier properties, it is preferable that all of Rx, Ry, and Rz are Fully hydrogenated polysilazane of hydrogen atom.

又，作為聚矽氨烷系化合物係也可以仍然直接地使用市面販賣之市面販賣品，來作為玻璃塗佈材料等。In addition, as the polysilazane-based compound, a commercially available product may be used as it is as a glass coating material.

聚矽氨烷系化合物係可以單獨一種或者是組合二種以上而使用。The polysilazane-based compounds may be used singly or in combination of two or more kinds.

作為注入至高分子層之離子係列舉氬、氦、氖、氪、氙等之稀有氣體之離子、氟碳、氫、氮、氧、二氧化碳、氯、氟、硫等之離子、甲烷、乙烷等之鏈烷系氣體類之離子、乙烯、丙烯等之鏈烯系氣體類之離子、戊二烯、丁二烯等之二烯烴系氣體類之離子、乙炔等之炔系氣體類之離子、苯、甲苯等之芳香族烴系氣體類之離子、環丙烷等之環鏈烷系氣體類之離子、環戊烯等之環鏈烯系氣體類之離子、金屬離子、有機矽化合物之離子等。As the ion series implanted into the polymer layer, ions of rare gases such as argon, helium, neon, krypton, xenon, fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur and other ions, methane, ethane, etc. Ions of alkane-based gases, Ions of olefins such as ethylene and propylene, Ions of diene-based gases such as pentadiene and butadiene, Ions of acetylene-based gases, benzene , Ion of aromatic hydrocarbon gas such as toluene, ion of cycloalkane gas such as cyclopropane, ion of cycloalkene gas such as cyclopentene, metal ion, ion of organic silicon compound, etc.

這些離子係可以單獨一種或者是組合二種以上而使用。These ion systems can be used alone or in combination of two or more.

即使是在這些當中，也可以更加簡便地注入離子，可以形成具有更加良好之氣體障蔽性之氣體障蔽層，因此，最好是氬、氦、氖、氪、氙等之稀有氣體之離子。Even among these, ions can be implanted more easily and a gas barrier layer having better gas barrier properties can be formed. Therefore, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred.

離子之注入量係可以配合功能性薄膜之使用目的（必要之氣體障蔽性、透明性等）等而適度地決定。The amount of ion implantation can be appropriately determined in accordance with the purpose of use of the functional film (necessary gas barrier properties, transparency, etc.) and the like.

作為注入離子之方法係列舉照射藉由電場而加速之離子（離子束）之方法、注入電漿中之離子之方法等。即使是在其中，也由於可以簡便地形成氣體障蔽層，因此，最好是後者之注入電漿中之離子之方法（電漿離子注入法）。As a method of implanting ions, there are a method of irradiating ions (ion beams) accelerated by an electric field, a method of implanting ions in a plasma, and the like. Even in this case, since a gas barrier layer can be easily formed, the latter method of implanting ions in the plasma (plasma ion implantation method) is preferable.

電漿離子注入法係例如可以藉由在包含稀有氣體等之電漿生成氣體之氛圍下，產生電漿，在高分子層，施加負的高電壓脈衝，而使得該電漿中之離子（陽離子），注入至高分子層之表面部，進行電漿離子注入。更加具體地說，電漿離子注入法係可以藉由記載於WO2010／107018號之宣傳手冊等之方法而實施電漿離子注入法。Plasma ion implantation method can generate plasma in an atmosphere containing plasma-generating gas containing a rare gas, etc., and apply a negative high-voltage pulse to the polymer layer to make the ions (cations) in the plasma ), Implanted into the surface portion of the polymer layer, and plasma ion implantation. More specifically, the plasma ion implantation method can be performed by a method such as the brochure disclosed in WO2010 / 107018.

可以藉由離子之注入，而以離子之種類和施加電壓、處理時間等之注入條件，來控制注入離子之區域之厚度，可以配合高分子層之厚度和功能性薄膜之使用目的等而決定厚度，但是，通常為10～400nm。The thickness of the area where the ions are implanted can be controlled by the ion implantation and the implantation conditions such as the type of ions and the applied voltage and processing time. The thickness can be determined according to the thickness of the polymer layer and the purpose of the functional film. However, it is usually 10 to 400 nm.

注入離子係可以藉由使用X射線光電子分光分析（XPS），進行由高分子層之表面開始10nm附近之元素分析測定，而確認離子之注入。The implanted ions can be confirmed by X-ray photoelectron spectroscopy (XPS), and elemental analysis and measurement around 10 nm from the surface of the polymer layer can be performed.

氣體障蔽層之厚度係並無特別限定，但是，通常為20～3000nm，最好是20～1000nm，更加理想是20～500nm。 [功能性薄膜]The thickness of the gas barrier layer is not particularly limited, but is usually 20 to 3000 nm, preferably 20 to 1000 nm, and more preferably 20 to 500 nm. [Functional film]

本發明之功能性薄膜係除了製程薄膜、樹脂塗佈層和氣體障蔽層以外，還可以具有其他層[在以下，稱為「其他層（Ⅰ）」。]。The functional film of the present invention may have other layers in addition to the process film, the resin coating layer, and the gas barrier layer [hereinafter, referred to as "other layer (I)". ].

作為其他層（Ⅰ）係列舉接著劑層。接著劑層係通常在前述氣體障蔽層上，直接或透過其他層[在以下，稱為「其他層（Ⅱ）」。]而進行層積。作為其他層（Ⅱ）係列舉啟發劑底層等。As the other layer (I), a series of adhesive layers is mentioned. The adhesive layer is usually on the aforementioned gas barrier layer, directly or through other layers [hereinafter, referred to as "other layer (II)". ] While performing lamination. As the other layer (II) series, the bottom layer of enlightenment and so on.

接著劑層係使用在本發明之功能性薄膜接合於被接著物時之層。The adhesive layer is a layer used when the functional film of the present invention is bonded to an adherend.

接著劑層係例如可以藉由在氣體障蔽層上，直接或透過其他層，來塗佈接著劑，乾燥得到之塗膜，而形成接著劑層。又，在本發明，所謂「接著劑」係以包含「壓感接著劑（黏著劑）」之廣義之意思而進行使用。The adhesive agent layer can be formed on the gas barrier layer by applying the adhesive agent directly or through another layer, and drying the obtained coating film. In the present invention, the "adhesive" is used in a broad sense including "pressure-sensitive adhesive (adhesive)".

作為包含於接著劑之接著性樹脂係列舉橡膠系接著性樹脂、聚烯烴系接著性樹脂、環氧系接著性樹脂、丙烯系接著性樹脂等。Examples of the adhesive resin series included in the adhesive include rubber-based adhesive resins, polyolefin-based adhesive resins, epoxy-based adhesive resins, and acrylic-based adhesive resins.

作為橡膠系接著性樹脂係列舉天然橡膠、在天然橡膠來接枝‧聚合由（甲基）丙烯酸烷基酯、苯乙烯和（甲基）丙烯腈而選出之1種或2種以上之單體之變體天然橡膠來作為主成分之接著性樹脂；以異戊二烯橡膠、苯乙烯－丁二烯橡膠、丙烯腈－丁二烯橡膠、甲基丙烯酸甲基－丁二烯橡膠、胺基甲酸乙酯橡膠、聚異丁烯系樹脂、聚丁烯樹脂等來作為主成分之接著性樹脂等。As a series of rubber-based adhesive resins, natural rubber is used to graft and polymerize one or more monomers selected from alkyl (meth) acrylate, styrene, and (meth) acrylonitrile. A modified natural rubber as the main component of the adhesive resin; isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methacrylic acid methyl-butadiene rubber, amine-based Ethyl formate rubber, polyisobutylene-based resin, polybutene resin, and the like are adhesive resins as the main component.

即使是在這些當中，也最好是以聚異丁烯系樹脂來作為主成分之接著性樹脂。Even among these, a polyisobutylene-based resin is preferably an adhesive resin having a main component as a main component.

在本說明書，所謂「主成分」係指在固態成分中，占有50質量％以上之成分。In the present specification, the "main component" means a component which occupies 50% by mass or more of a solid component.

作為聚烯烴系接著性樹脂係列舉以變體聚烯烴樹脂來作為主成分之接著性樹脂。As the polyolefin-based adhesive resin series, a modified polyolefin resin is used as a main component of the adhesive resin.

變體聚烯烴系樹脂係在作為先驅體之聚烯烴樹脂，使用變體劑，施行變體處理而得到變體聚烯烴系樹脂，導入官能基之聚烯烴樹脂。The modified polyolefin-based resin is a polyolefin resin that is a precursor, and a modified agent is used to perform a modification treatment to obtain a modified polyolefin-based resin and a functional-functional polyolefin resin.

作為聚烯烴樹脂係列舉超低密度聚乙烯（VLDPE）、低密度聚乙烯（LDPE）、中密度聚乙烯（MDPE）、高密度聚乙烯（HDPE）、直鏈狀低密度聚乙烯、聚丙烯（PP）、乙烯－丙烯共聚物、烯烴系彈性體（TPO）、乙烯－乙酸乙烯共聚物（EVA）、乙烯－（甲基）丙烯酸共聚物、乙烯－（甲基）丙烯酸酯共聚物等。Examples of polyolefin resins include ultra-low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, and polypropylene ( PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic copolymer, ethylene- (meth) acrylate copolymer, etc.

使用於聚烯烴樹脂之變體處理之變體劑係在分子內，具有官能基、也就是可以貢獻於後面敘述之交聯反應之基之化合物。The modification agent used for the modification treatment of the polyolefin resin is a compound having a functional group, that is, a group that can contribute to the crosslinking reaction described later, in the molecule.

作為官能基係列舉羧基、羧酸酐基、羧酸酯基、氫氧基、環氧基、醯胺基、銨基、腈基、胺基、醯亞胺基、異氰酸酯基、乙醯基、硫代基、醚基、硫代醚基、碸基、膦基、硝基、胺基甲酸乙酯基、鹵素原子等。即使是在這些當中，也最好是羧基、羧酸酐基、羧酸酯基、氫氧基、銨基、胺基、醯亞胺基、異氰酸酯基，更加理想是羧酸酐基、烷氧基甲矽烷基，特別最好是羧酸酐基。As the functional group series, carboxyl group, carboxylic acid anhydride group, carboxylic acid ester group, hydroxyl group, epoxy group, fluorenylamino group, ammonium group, nitrile group, amine group, fluorenimine group, isocyanate group, acetamyl group, sulfur Substituents, ether groups, thioether groups, fluorenyl groups, phosphino groups, nitro groups, urethane groups, halogen atoms, and the like. Even among these, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amine group, an imino group, and an isocyanate group are preferable, and a carboxylic acid anhydride group and an alkoxymethyl group are more preferable. The silane group is particularly preferably a carboxylic anhydride group.

作為環氧系接著性樹脂係列舉以脂肪鏈變體環氧樹脂、環戊二烯變體環氧樹脂和萘變體環氧樹脂等之烴變體環氧樹脂、彈性體變體環氧樹脂、矽酮變體環氧樹脂來作為主成分之接著性樹脂。As the epoxy-based adhesive resin series, there are hydrocarbon modified epoxy resins, elastomer modified epoxy resins such as aliphatic chain modified epoxy resin, cyclopentadiene modified epoxy resin, and naphthalene modified epoxy resin. Silicone-modified epoxy resin as the main component of the adhesive resin.

作為丙烯系接著性樹脂係列舉以具備來自於具有碳數1～20之烴基之（甲基）丙烯酸酯之重複單位和來自於含官能基單體之重複單位之丙烯系共聚物來作為主成分之接著性樹脂。As the main component of the propylene-based adhesive resin series, a propylene copolymer having a repeating unit derived from a (meth) acrylate having a hydrocarbon group of 1 to 20 carbon atoms and a repeating unit derived from a functional group-containing monomer is used as a main component. Adhesive resin.

作為具有碳數1～20之烴基之（甲基）丙烯酸酯係列舉甲基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯、丙基（甲基）丙烯酸酯、n－丁基（甲基）丙烯酸酯、2－乙基己基（甲基）丙烯酸酯、月桂基（甲基）丙烯酸酯、十三烷基（甲基）丙烯酸酯、以及硬脂醯（甲基）丙烯酸酯等。As the (meth) acrylate series having a hydrocarbon group having 1 to 20 carbon atoms, meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

作為含官能基單體係列舉含羥基單體、含羧基單體、含環氧基單體、含胺基單體、含氰基單體、含酮基單體、含烷氧基甲矽烷基單體等。即使是在這些當中，作為含官能基單體係也最好是含羥基單體、含羧基單體。As the functional group-containing monomer series, hydroxyl-containing monomers, carboxyl-containing monomers, epoxy-containing monomers, amine-containing monomers, cyano-containing monomers, ketone-containing monomers, and alkoxysilyl groups Monomer and so on. Even among these, as the functional group-containing monosystem, a hydroxyl-containing monomer and a carboxyl-containing monomer are preferred.

作為含羥基單體係列舉2－羥乙基（甲基）丙烯酸酯、2－羥丙基（甲基）丙烯酸酯、2－羥丁基（甲基）丙烯酸酯、3－羥丁基（甲基）丙烯酸酯、4－羥丁基（甲基）丙烯酸酯等。As the hydroxyl-containing monomer series, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (methyl Group) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

作為含羧基單體係列舉（甲基）丙烯酸、順丁烯二酸、富馬酸、衣康酸等。Examples of carboxyl-containing monomers include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid.

這些接著性樹脂係可以配合需要而含有硬化劑、交聯劑、聚合啟始劑、光安定劑、氧化防止劑、黏著賦予劑、可塑劑、紫外線吸收劑、著色劑、樹脂安定劑、填充劑、顏料、增量劑、帶電防止劑等。These adhesive resins can contain hardeners, crosslinking agents, polymerization initiators, light stabilizers, oxidation inhibitors, adhesion-imparting agents, plasticizers, ultraviolet absorbers, colorants, resin stabilizers, and fillers as required. , Pigment, extender, antistatic agent, etc.

接著劑層之厚度係可以考慮功能性薄膜之使用目的等而適度地進行選定。其厚度係並無特別限定，但是，通常為0.1～1000μm，最好是0.5～500μm，更加理想是1～100μm。The thickness of the adhesive layer is appropriately selected in consideration of the purpose of use of the functional film and the like. The thickness is not particularly limited, but it is usually 0.1 to 1000 μm, preferably 0.5 to 500 μm, and more preferably 1 to 100 μm.

在本發明之功能性薄膜具有接著劑層之時，功能性薄膜係最好是在其使用前之狀態（例如保管時、搬運時），在接著劑層之鄰邊，具有剝離用薄膜。剝離用薄膜係直到使用本發明之功能性薄膜為止之間，保護接著劑層，在使用前，進行剝離及除去，藉此而露出接著劑層。When the functional film of the present invention has an adhesive layer, the functional film preferably has a release film adjacent to the adhesive layer in a state before use (for example, during storage or transportation). The peeling film protects the adhesive layer until the functional film of the present invention is used, and is peeled and removed before use to expose the adhesive layer.

作為剝離用薄膜係列舉在紙或塑膠薄膜等之剝離基材，塗佈剝離劑而設置剝離劑層。As a release film series, a release substrate such as paper or a plastic film is applied, and a release agent is applied to provide a release agent layer.

作為剝離基材係列舉玻璃紙、塗佈紙、上質紙等之紙基材、在這些之紙基材來層壓聚乙烯或聚丙烯等之熱塑性樹脂之層壓紙、在前述基材藉由纖維素、澱粉、聚乙烯醇、丙烯－苯乙烯樹脂等而進行填隙處理之紙基材、或者是聚伸乙基對苯二甲酸酯、聚伸丁基對苯二甲酸酯、聚伸乙基萘二甲酸酯等之聚酯薄膜或聚乙烯或聚丙烯等之聚烯烴薄膜等之塑膠薄膜等。As the release substrate series, paper substrates such as cellophane, coated paper, and high-quality paper, laminated papers made of thermoplastic resins such as polyethylene or polypropylene on these paper substrates, and fibers on the aforementioned substrates are made of fibers. Paper, starch, polyvinyl alcohol, propylene-styrene resin, and other paper substrates, or polyethylene terephthalate, polybutylene terephthalate, and polyethylene Polyester films such as ethyl naphthalate, or plastic films such as polyolefin films such as polyethylene or polypropylene.

作為剝離劑係列舉包含：聚乙烯、聚丙烯等之烯烴系樹脂、異戊二烯系樹脂、丁二烯系樹脂等之橡膠系彈性體、長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂、矽酮系樹脂等。Examples of release agents include rubber-based elastomers such as olefin-based resins such as polyethylene and polypropylene, isoprene-based resins, and butadiene-based resins, long-chain alkyl resins, alkyd resins, and fluorine Resin, silicone resin, etc.

剝離劑層之厚度係並無特別限制，但是，在以溶液狀態來塗佈剝離劑之狀態下，最好是0.02～2.0μm，更加理想是0.05～1.5μm。The thickness of the release agent layer is not particularly limited, but in the state where the release agent is applied in a solution state, it is preferably 0.02 to 2.0 μm, and more preferably 0.05 to 1.5 μm.

作為本發明之功能性薄膜之層構造之例子係列舉以下者，但是，並非限定於這些。The series of examples of the layer structure of the functional film of the present invention are as follows, but they are not limited to these.

（Ⅰ）製程薄膜／樹脂塗佈層／氣體障蔽層 （Ⅱ）製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層 （Ⅲ）製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層／剝離用薄膜 （Ⅳ）製程薄膜／樹脂塗佈層／氣體障蔽層／啟發劑底層／接著劑層／剝離用薄膜(I) process film / resin coating layer / gas barrier layer (II) process film / resin coating layer / gas barrier layer / adhesive layer (III) process film / resin coating layer / gas barrier layer / adhesive layer / Film for peeling (IV) process film / Resin coating layer / Gas barrier layer / Enlightenment primer layer / Adhesive layer / Film for peeling

本發明之功能性薄膜之厚度係並無特別限定，但是，最好是1～1000μm，更加理想是2～200μm，特別最好是5～50μm。The thickness of the functional film of the present invention is not particularly limited, but it is preferably 1 to 1000 μm, more preferably 2 to 200 μm, and particularly preferably 5 to 50 μm.

本發明之功能性薄膜係具有良好之光學等方性。最好是藉由記載於實施例之方法，而在測定面內相位差Re（550）之時，使得其值未滿10nm。The functional film of the present invention has good optical isotropy. It is preferable that the in-plane phase difference Re (550) is measured so that its value is less than 10 nm by the method described in the examples.

本發明之功能性薄膜係具有良好之氣體障蔽性。本發明之功能性薄膜之水蒸氣透過率係最好是在40℃、相對濕度90％之氛圍下，未滿0.2g‧m-2 ‧day-1 。The functional film of the present invention has good gas barrier properties. The water vapor transmission rate of the functional film of the present invention is preferably less than 0.2g‧m -2 ‧day -1 under an atmosphere of 40 ° C and a relative humidity of 90%.

本發明之功能性薄膜係具有良好之耐彎曲性。本發明之功能性薄膜係最好是按照JIS K5600－5，在以直徑6mm來進行心軸彎曲試驗之後，在溫度40℃、相對濕度90％之條件下之水蒸氣透過率，未滿0.2g‧m-2 ‧day-1 。The functional film of the present invention has good bending resistance. The functional film of the present invention preferably has a water vapor transmission rate of less than 0.2 g in accordance with JIS K5600-5 after a mandrel bending test with a diameter of 6 mm at a temperature of 40 ° C and a relative humidity of 90%. ‧M -2 ‧day -1 .

水蒸氣透過率係可以藉由記載於實施例之方法而進行測定。The water vapor transmission rate can be measured by the method described in Examples.

由於具有這些特性，因此，本發明之功能性薄膜係適合使用作為光學裝置用之薄膜。 [裝置]Because of these characteristics, the functional film of the present invention is suitable for use as a film for an optical device. [Device]

本發明之裝置係在本發明之功能性薄膜來貼附於對象物之後，剝離及除去製程薄膜而組成。The device of the present invention is formed by peeling and removing the process film after the functional film of the present invention is attached to an object.

作為本發明之裝置係列舉液晶顯示器、有機EL顯示器、無機EL顯示器、電子紙、太陽能電池等。The device series of the present invention include a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar cell, and the like.

本發明之裝置係具備來自於本發明之功能性薄膜之層積體，因此，不容易發生由於水蒸氣等之浸入而造成之故障，並且，具有良好之耐彎曲性。 [實施例]The device of the present invention is provided with the laminated body of the functional film from the present invention, and therefore, it is unlikely to cause failure due to infiltration of water vapor or the like, and has good bending resistance. [Example]

在以下，列舉實施例而更加詳細地說明本發明。但是，本發明係完全無限定於以下之實施例。Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited to the following examples at all.

各例子中之質量份和％係只要是無特別限制的話，則成為質量基準。 [實施例1]The mass parts and% in each example are mass standards as long as they are not particularly limited. [Example 1]

混合UV硬化性6官能丙烯酸酯樹脂（新中村化學工業公司製、商品名稱：A－DPH）和丙烯基修飾二氧化矽奈米填充物（日產化學公司製、商品名稱：MIBK－2140Z）而成為體積比45：55，在此，加入1％之羥基酮系光聚合啟始劑（BASF公司製、商品名稱：IRGACURE 184），調製硬化性組合物。A mixture of UV-curable 6-functional acrylate resin (produced by Shin Nakamura Chemical Industry Co., Ltd .: A-DPH) and acryl-modified silica dioxide filler (produced by Nissan Chemical Co., Ltd .: trade name: MIBK-2140Z) The volume ratio is 45:55. Here, 1% of a hydroxyketone-based photopolymerization initiator (manufactured by BASF, trade name: IRGACURE 184) is added to prepare a hardenable composition.

藉由在作為製程薄膜之聚伸乙基對苯二甲酸酯薄膜（東洋紡織股份有限公司製、PET50A4100）之平坦面上，塗佈前述硬化性組合物，在得到之塗膜，進行UV照射，而硬化該塗膜，形成厚度3μm之樹脂塗佈層。The aforementioned hardening composition was applied on a flat surface of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., PET50A4100) as a process film, and the obtained coating film was subjected to UV irradiation. Then, the coating film is hardened to form a resin coating layer having a thickness of 3 μm.

藉由在該樹脂塗佈層上，塗佈全氫化聚矽氨烷含有液（Merck Performance Materials 公司製、AZ NL110A－20、溶媒：二甲苯、濃度：20％），在120℃，進行2分鐘之乾燥，而形成厚度200nm之全氫化聚矽氨烷層。A perhydropolysilazane-containing liquid (manufactured by Merck Performance Materials, AZ NL110A-20, solvent: xylene, concentration: 20%) was applied to the resin coating layer at 120 ° C for 2 minutes. It was dried to form a perhydropolysilazane layer having a thickness of 200 nm.

接著，藉由使用電漿離子注入裝置（RF電源：日本電子股份有限公司製、RF56000、高電壓脈衝電源：栗田製作所股份有限公司製、PV－3－HSHV－0835），對於全氫化聚矽氨烷層，以下列之條件，來進行電漿離子注入，形成氣體障蔽層，而得到具有製程薄膜／樹脂塗佈層／氣體障蔽層之層構造之功能性薄膜（1a）。Next, by using a plasma ion implantation device (RF power supply: made by Japan Electronics Co., Ltd., RF56000, high-voltage pulse power supply: made by Kurita Manufacturing Co., Ltd., PV-3-HSHV-0835), the fully hydrogenated polysiliconamine was used. The alkane layer is subjected to plasma ion implantation under the following conditions to form a gas barrier layer, and a functional film (1a) having a layer structure of a process film / resin coating layer / gas barrier layer is obtained.

電漿生成氣體：Ar 氣體流量：100sccm Duty比（功能比）：0.5％ 施加電壓：-6kV RF電源：頻率13.56MHz、施加電力 1000W 處理室內壓：0.2Pa 脈衝幅寬：5μsec 處理時間（離子注入時間）：200秒Plasma generation gas: Ar Gas flow rate: 100 sccm Duty ratio (function ratio): 0.5% Applied voltage: -6kV RF power: Frequency 13.56MHz, applied power 1000W Processing chamber pressure: 0.2Pa Pulse width: 5μsec Processing time (ion implantation Time): 200 seconds

又，藉由在功能性薄膜（1a）之氣體障蔽層上，塗佈丙烯酸酯系黏著劑（Saiden化學公司製、商品名稱：SAIVINOL LT－55），乾燥得到之塗膜，而形成厚度20μm之接著劑層。藉由在該接著劑層上，貼合剝離用薄膜（LINTEC公司製、商品名稱：SP－PET381031），而得到具有製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層／剝離用薄膜之層構造之功能性薄膜（1b）。 [實施例2]In addition, an acrylic adhesive (manufactured by Saiden Chemical Company, trade name: SAIVINOL LT-55) was applied to the gas barrier layer of the functional film (1a), and the resulting coating film was dried to form a thickness of 20 μm. Then the agent layer. A release film (manufactured by LINTEC, trade name: SP-PET381031) was bonded to the adhesive layer to obtain a film having a process film / resin coating layer / gas barrier layer / adhesive layer / release film. Functional film with layer structure (1b). [Example 2]

除了在實施例1，使用氧化鋁填充物（BYK公司製、商品名稱：NANOBYK－3610）來取代丙烯基修飾二氧化矽奈米填充物以外，其餘係相同於實施例1，得到具有製程薄膜／樹脂塗佈層／氣體障蔽層之層構造之功能性薄膜（2a）以及具有製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層／剝離用薄膜之層構造之功能性薄膜（2b）。 [實施例3]Except that in Example 1, an alumina filler (manufactured by BYK, trade name: NANOBYK-3610) was used in place of the acryl-modified silica dioxide filler, and the rest were the same as in Example 1 to obtain a film having a process / Functional film (2a) with layer structure of resin coating layer / gas barrier layer and functional film (2b) with layer structure of process film / resin coating layer / gas barrier layer / adhesive layer / film for peeling. [Example 3]

除了在實施例1，使用氧化鋯填充物（日產化學公司製、商品名稱：ZR－20AS）來取代丙烯基修飾二氧化矽奈米填充物以外，其餘係相同於實施例1，得到具有製程薄膜／樹脂塗佈層／氣體障蔽層之層構造之功能性薄膜（3a）以及具有製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層／剝離用薄膜之層構造之功能性薄膜（3b）。 [實施例4]Except that in Example 1, a zirconia filler (manufactured by Nissan Chemical Co., Ltd., trade name: ZR-20AS) was used in place of the propylene-modified silicon dioxide nano filler, and the rest were the same as in Example 1 to obtain a film having a process / Resin coating layer / Functional film (3a) with layer structure of gas barrier layer and Functional film (3b) with layer structure of process film / resin coating layer / gas barrier layer / adhesive layer / peeling film . [Example 4]

除了在實施例1，在樹脂塗佈層上，藉由以下之方法而形成氣體障蔽層以外，其餘係相同於實施例1，得到具有製程薄膜／樹脂塗佈層／氣體障蔽層之層構造之功能性薄膜（4a）以及具有製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層／剝離用薄膜之層構造之功能性薄膜（4b）。 （氣體障蔽層之形成方法）Except that in Example 1, the gas barrier layer was formed on the resin coating layer by the following method, the rest was the same as in Example 1, and a layer structure having a process film / resin coating layer / gas barrier layer was obtained. Functional film (4a) and functional film (4b) having a layer structure of a process film / resin coating layer / gas barrier layer / adhesive layer / film for peeling. (Formation method of gas barrier layer)

使用電子束加熱方式之真空蒸鍍裝置，藉由電子束之加熱而蒸發氧化矽化學材料（CANON光電公司製之SiO），以製膜中之壓力為0.015Pa之條件，來製造硬化膜厚度50nm之SiOx膜。蒸鍍條件係加速電壓40kV、發射電流0.2A。 [比較例1]A vacuum evaporation device using an electron beam heating method is used to evaporate the silicon oxide chemical material (SiOON manufactured by CANON Optoelectronics Co., Ltd.) under the condition of electron beam heating to produce a hardened film with a thickness of 50 nm under the condition that the pressure during film formation is 0.015 Pa. SiOx film. The deposition conditions were an acceleration voltage of 40 kV and an emission current of 0.2 A. [Comparative Example 1]

除了在實施例1，無形成樹脂塗佈層，在製程薄膜上，直接地形成氣體障蔽層以外，其餘係相同於實施例1，得到具有製程薄膜／氣體障蔽層之層構造之功能性薄膜（5a）以及具有製程薄膜／氣體障蔽層／接著劑層／剝離用薄膜之層構造之功能性薄膜（5b）。 [比較例2]Except that in Example 1, a resin coating layer was not formed, and a gas barrier layer was directly formed on the process film, the rest was the same as in Example 1 to obtain a functional film having a layer structure of the process film / gas barrier layer ( 5a) and a functional film (5b) having a layer structure of a process film / gas barrier layer / adhesive layer / film for peeling. [Comparative Example 2]

在UV硬化性6官能丙烯酸酯樹脂（新中村化學工業公司製、商品名稱：A－DPH），加入1％之羥基酮系光聚合啟始劑（BASF公司製、商品名稱：IRGACURE 184），調製硬化性組合物。A UV-curable 6-functional acrylate resin (produced by Shin Nakamura Chemical Industry Co., Ltd., product name: A-DPH) was added with 1% of a hydroxyketone-based photopolymerization initiator (produced by BASF Corporation, product name: IRGACURE 184) to prepare Hardening composition.

除了使用該硬化性組合物而形成樹脂塗佈層以外，其餘係相同於實施例1，得到具有製程薄膜／樹脂塗佈層／氣體障蔽層之層構造之功能性薄膜（6a）以及具有製程薄膜／樹脂塗佈層／氣體障蔽層／接著劑層／剝離用薄膜之層構造之功能性薄膜（6b）。A functional film (6a) having a layer structure of a process film / resin coating layer / gas barrier layer was obtained in the same manner as in Example 1 except that a resin coating layer was formed using the curable composition, and the process film was obtained. / Resin coating layer / Gas barrier layer / Adhesive layer / Functional film (6b) with a layer structure of a peeling film.

關於在實施例1～4以及比較例1、2得到之功能性薄膜，進行以下之評價試驗。將結果顯示於表1。 [光學等方性之評價]The functional films obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were subjected to the following evaluation tests. The results are shown in Table 1. [Evaluation of optical isotropy]

剝離及除去功能性薄膜（1b）～（6b）之剝離用薄膜，露出接著劑層，在貼合於無鹼玻璃（Eagle XG）之後，剝離及除去製程薄膜。以此作為測定用試料，使用王子測定機器公司製之KOBRA－WR，測定面內相位差Re（550）。 [剝離之評價]The functional films (1b) to (6b) are peeled and removed. The adhesive layer is exposed, and after bonding to an alkali-free glass (Eagle XG), the process film is peeled and removed. Using this as a measurement sample, KOBRA-WR manufactured by Oji Measurement Co., Ltd. was used to measure the in-plane phase difference Re (550). [Evaluation of peeling]

在剝離及除去功能性薄膜（1b）～（6b）之製程薄膜之後，藉由目視而觀察殘餘之層積體，藉由以下之基準而進行評價。After peeling and removing the process films of the functional films (1b) to (6b), the remaining laminated body was visually observed, and evaluated based on the following criteria.

○：在露出面，無產生破壞和破裂。 ╳：在露出面，產生破壞或破裂。 [耐彎曲性評價]○: No damage or crack occurred on the exposed surface. ╳: Damage or cracking occurs on the exposed surface. [Bending resistance evaluation]

剝離及除去功能性薄膜（1b）～（6b）之剝離薄膜，露出接著劑層，在使用手動式層壓機而貼合於聚伸乙基對苯二甲酸酯薄膜（東洋紡織股份有限公司製、商品名稱：PET100A4300、厚度：100μm）之後，剝離及除去製程薄膜。使用這個，來作為測定用試料，依據JIS K5600－5－1：1999，使得樹脂塗佈面，成為外側，以直徑6mm，來進行心軸彎曲試驗。接著，使用MOCON公司製之AQUATRAN，在溫度40℃、相對濕度90％之條件下，測定其水蒸氣透過率。Peel off and remove the peeling film of functional films (1b) to (6b) to expose the adhesive layer, and apply it to a polyethylene terephthalate film using a manual laminator (TOYO TEXTILE CO., LTD.) (Product name: PET100A4300, thickness: 100 μm), and then the process film is peeled and removed. Using this as a measurement sample, a mandrel bending test was performed with a diameter of 6 mm so that the resin-coated surface became the outside in accordance with JIS K5600-5-1: 1999. Next, the water vapor transmission rate of AQUATRAN manufactured by MOCON was measured under the conditions of a temperature of 40 ° C and a relative humidity of 90%.

【表1】 【Table 1】

由表1而得知以下。Table 1 shows the following.

實施例1～4之功能性薄膜係具有良好之光學等方性和耐彎曲性。又，可以對於殘留之層積體不造成不良影響而剝離及除去製程薄膜。The functional films of Examples 1 to 4 have good optical isotropy and bending resistance. In addition, the process film can be peeled off and removed without adversely affecting the remaining laminate.

另一方面，比較例1之功能性薄膜係無法漂亮地剝離製程薄膜，無法進行光學等方性評價和耐彎曲性評價。On the other hand, the functional film of Comparative Example 1 cannot be beautifully peeled from the process film, and optical isotropicity evaluation and bending resistance evaluation cannot be performed.

又，比較例2之功能性薄膜係耐彎曲性呈不良。In addition, the functional film of Comparative Example 2 had poor bending resistance.

無。no.

無。no.

Claims (14)

一種功能性薄膜，具有：製程薄膜、直接地設置於前述製程薄膜上之樹脂塗佈層、以及在前述樹脂塗佈層上呈直接或透過其他層而設置之氣體障蔽層， 其特徵為： 前述樹脂塗佈層係由含有能量硬化性樹脂和無機填充物之硬化性組合物之硬化物而組成的。A functional film includes a process film, a resin coating layer directly provided on the process film, and a gas barrier layer provided on the resin coating layer directly or through other layers, and is characterized in that: The resin coating layer is composed of a cured product of a curable composition containing an energy curable resin and an inorganic filler. 如申請專利範圍第1項之功能性薄膜，其中，前述無機填充物係藉由有機化合物而修飾其表面。For example, the functional thin film of the first patent application range, wherein the surface of the inorganic filler is modified by an organic compound. 如申請專利範圍第2項之功能性薄膜，其中，使用於前述無機填充物之表面修飾之有機化合物係包含：含有反應性不飽和鍵之基。For example, the functional film of claim 2 in the patent application, wherein the surface-modified organic compound used in the aforementioned inorganic filler includes: a group containing a reactive unsaturated bond. 如申請專利範圍第1項之功能性薄膜，其中，前述製程薄膜之樹脂成分係聚酯系樹脂。For example, the functional film of the first patent application range, wherein the resin component of the aforementioned process film is a polyester resin. 如申請專利範圍第1項之功能性薄膜，其中，前述製程薄膜之厚度係10～300μm。For example, the functional film of the first patent application range, wherein the thickness of the aforementioned process film is 10-300 μm. 如申請專利範圍第1項之功能性薄膜，其中，前述樹脂塗佈層之厚度係0.1～10μm。For example, the functional film according to the first patent application range, wherein the thickness of the resin coating layer is 0.1 to 10 μm. 如申請專利範圍第1項之功能性薄膜，其中，前述樹脂塗佈層之相反於接合在製程薄膜之側之相反側之面粗糙曲線之剖面最大高度（Rt）係1～200nm。For example, the functional film of the first patent application range, wherein the cross-section maximum height (Rt) of the surface roughness curve of the resin coating layer opposite to the side bonded to the process film is 1 to 200 nm. 如申請專利範圍第1項之功能性薄膜，其中，前述氣體障蔽層係含有由矽氧化物、矽氮化物、矽氟化物、矽碳化物、金屬氧化物、金屬氮化物、金屬氟化物、金屬碳化物、以及包含構成這些化合物之元素之複合化合物而組成之群組來選出之至少一種。For example, the functional film of the scope of patent application, wherein the gas barrier layer contains silicon oxide, silicon nitride, silicon fluoride, silicon carbide, metal oxide, metal nitride, metal fluoride, metal At least one selected from the group consisting of carbides and composite compounds containing elements constituting these compounds. 如申請專利範圍第1項之功能性薄膜，其中，前述氣體障蔽層係藉由接受重整處理，而對於可以變化成為含有無機化合物之層之層表面，來進行重整而得到的。For example, the functional thin film according to the scope of patent application, wherein the aforementioned gas barrier layer is obtained by reforming the surface of a layer that can be changed into a layer containing an inorganic compound, and is reformed. 如申請專利範圍第1項之功能性薄膜，其中，前述氣體障蔽層之厚度係20～3000nm。For example, the functional thin film of the first patent application range, wherein the thickness of the gas barrier layer is 20-3000 nm. 如申請專利範圍第1項之功能性薄膜，其中，還成為具有接著劑層之功能性薄膜，前述接著劑層係直接或透過其他層而設置在前述氣體障蔽層上。For example, the functional film according to the first patent application range is also a functional film having an adhesive layer, and the adhesive layer is provided on the gas barrier layer directly or through another layer. 如申請專利範圍第1項之功能性薄膜，其中，在依據JIS K5600－5而以直徑6mm來進行心軸彎曲試驗後，在溫度40℃、相對濕度90％條件下之水蒸氣透過率係未滿0.2g‧m-2 ‧day-1 。For example, the functional film under the scope of patent application No. 1, in which after the mandrel bending test with a diameter of 6 mm according to JIS K5600-5, the water vapor transmission rate at a temperature of 40 ° C and a relative humidity of 90% is not Full 0.2g‧m -2 ‧day -1 . 如申請專利範圍第1項之功能性薄膜，其中，使用於光學裝置。For example, the functional film of the scope of patent application No. 1 is used in optical devices. 一種裝置，其特徵為：在如申請專利範圍第1至13項中任一項所述之功能性薄膜來貼附於對象物之後，剝離及除去製程薄膜而組成。A device characterized in that after the functional film according to any one of claims 1 to 13 of the patent application scope is attached to an object, the device is formed by peeling and removing the process film.
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