CN106457785A - Gas barrier film manufacturing method, gas barrier film, electronic device manufacturing method and electronic device - Google Patents

Abstract

The purpose of the present invention is to provide a method of manufacturing a gas barrier film which uses a film substrate material containing a cyclic olefin polymer or a cyclic olefin copolymer and which suppresses the occurrence of breaking and cracking in the film substrate material. This gas barrier film manufacturing method involves providing a clear hard coating layer (3) and a gas barrier layer (5), in that order, on a film substrate (2) that contains a cyclic olefin polymer or a cyclic olefin copolymer, and is characterized by involving a step in which, before providing the clear hard coating layer (3), a protective laminate member (9) is provided on the surface of the film substrate (2) opposite of the surface on which the clear hard coating layer (3) will be provided, and a step in which the ends in the width direction of the laminate body that includes the film substrate (2) and the protective laminate member (9) are cut such that the dimension of the film substrate (2) in the width direction is the same as the dimension of the protective laminate member (9) in the width direction.

Description

The manufacture method of gas barrier film, gas barrier film, the manufacturer of electronic device Method and electronic device

Technical field

The present invention relates to a kind of manufacture method of gas barrier film, gas barrier film, the manufacture method of electronic device And electronic device.More particularly to a kind of manufacture this film using the film base material containing cyclic olefin polymer or cyclic olefine copolymer The generation of the fracture of base material or chap has obtained the method for gas barrier film suppressing, the gas passing through manufactured by the method hinders Every property film, the electronic device that possesses this gas barrier film and its manufacture method.

Background technology

At present, on the surface of plastic base or film to the thin film containing metal-oxides such as aluminium oxide, magnesium oxide, silicon oxides Multiple layers gas barrier film of carrying out lamination and being formed be widely used in needing the various gases to vapor or oxygen etc. to carry out The packaging of the article intercepting, for example, be used for preventing food or industrial goods and the packaging applicationss of pharmaceuticals iso-metamorphism.

This gas barrier film, in addition to packaging applicationss, is urgently expected to the solar cell device with flexibility, is had Organic electro luminescent is (hereinafter also referred to as " organic EL ".) element, launch to flexible electronic such as liquid crystal display cells, and carry out Many researchs.

As the film base material of gas barrier film, various base materials are used according to its purposes.As general gas The film base material of body barrier film, can use PET (polyethylene terephthalate, Polyethylene Terephthalate) Or PEN (PEN, Polyethylene Naphthalate) is (referring for example to patent documentation 1 and patent literary composition Offer 2.), as the film base material of the gas barrier film of display applications, preferably use the low low level difference base material of length of delay, example As COP (cyclic olefin polymer, Cyclo-Olefin Polymer) or COC (cyclic olefine copolymer, Cyclo-Olefin can be used Copolymer).

But, be used COP or COC as gas barrier film film base material when, due to the low intensity of this film base material, because This, in the situation that using rubbing method, hard conating is coated with setting or using CVD (chemical vapor deposition, Chemical Vapor Deposition) method etc. carries out the situation of lamination or carry out under roller form and the work such as batches, extracts out to gas-barrier layer In skill, there is the fracture of this film base material or produce chap and defect.

For this problem, whenever operation of gas-barrier layer etc. is formed on film base material, any process is implemented to film base material When it is considered to be formed on the surface of surface opposite side in film base material and layer, laminating protection laminate member, thus improve film base material Intensity method, but in this approach, process number increases, and cost also can raise.Furthermore, it desired to film base material and protection lamination The high Anawgy accuracy of part, when Anawgy accuracy is low, result can not prevent the generation of the chap of the end of film base material etc..

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 2002-046208 publication

Patent documentation 2：Japanese Unexamined Patent Publication 2007-237588 publication

Content of the invention

Invention problem to be solved

The present invention completes in view of the above problems, and it solves problem and is, provides a kind of use to gather containing cycloolefins The generation of fracture or chap to manufacture this film base material for the film base material of compound or cyclic olefine copolymer has obtained the gas resistance suppressing Every the method for property film, the electronic device that by the gas barrier film manufactured by the method and there is this gas barrier film and Its manufacture method.

For solving the technical scheme of problem

In order to solve the above-mentioned problem of the present invention, to being studied the reason the problems referred to above etc., it is found that：Can carry The barrier properties for gases that the generation of the fracture for the film base material containing cyclic olefin polymer or cyclic olefine copolymer or chap has obtained The manufacture method of film and by the gas barrier film manufactured by the method, the manufacture method of described gas barrier film is to contain There is the gas resistance that transparent hard-coating layer and gas-barrier layer are set gradually on cyclic olefin polymer or the film base material of cyclic olefine copolymer Every the manufacture method of property film, it has following operation：Before arranging described transparent hard-coating layer, in described film base material and setting Have on the surface of surface opposite side of described transparent hard-coating layer, the operation of setting protection laminate member；To comprising described film base The end of the width of laminated body of material and described protection laminate member is cut, and makes the width of described film base material Size and the width of described protection laminate member equivalently-sized operation.

The effect of invention

According to the present invention it is possible to provide the manufacture method of gas barrier film, by the gas barrier manufactured by the method Property film, the electronic device with this gas barrier film and its manufacture method, described gas barrier film is using containing cycloolefins The film base material of polymer or cyclic olefine copolymer is it is suppressed that the generation of the fracture of this film base material or chap.

With regard to the present invention effect manifest mechanism or mechanism of action, as described below.

That is, before setting transparent hard-coating layer, the surface opposite side that arranges with transparent hard-coating layer in film base material in advance Surface on setting protection laminate member, therefore, the intensity of film base material is improved, and is forming other layer such as transparent hard-coating layer When, fracture or chap generation on film base material can be inhibited.In addition, by pre-setting guarantor before setting transparent hard-coating layer Shield laminate member, whenever the surface (being not provided with protecting the face of laminate member) of the opposite side to film base material implements arbitrarily to process When it is not necessary to be respectively provided with protection laminate member every time, the rising of process number or cost can be suppressed.

Further, since cutting out to the end machine containing film base material and the width of the laminated body of protection laminate member Cut, therefore, it can to make film base material identical with the length of the width protecting laminate member and do not improve film base material and protective layer The Anawgy accuracy of splenium part, can make the generation of the chap of film base material end etc. be inhibited with easy composition.

Brief description

Figure 1A is the summary section of an example of the composition of the gas barrier film representing the present invention；

Figure 1B is the summary section of an example of the composition of the gas barrier film representing the present invention；

Fig. 2A is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 B is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 C is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 D is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 E is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 F is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 G is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 H is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 2 I is the outline of an example of the process flow in the manufacture method of the gas barrier film representing the present invention Figure；

Fig. 3 is an example of the discharge plasma processing meanss of the formation representing the gas-barrier layer being suitable to the present invention Schematic diagram.

Description of symbols

1 gas barrier film

2 film base materials

3 transparent hard-coating layer

4 transparent hard-coating layer

5 gas-barrier layers

6 the 2nd gas-barrier layers

7 protection laminate members

8 protecting film

9 protection laminate members

11 outlet rollers

21st, 22,23,24 conveying roller

30 discharge plasma processing meanss

31st, 32 one-tenth deflector rolls

41 gas supply pipes

51 plasma generation power supplys

61st, 62 magnetic field generation device

71 take-up rolls

Specific embodiment

The manufacture method of the gas barrier film of the present invention is in the film containing cyclic olefin polymer or cyclic olefine copolymer On base material, set gradually the manufacture method of the gas barrier film of transparent hard-coating layer and gas-barrier layer it is characterised in that including Following operation：Before above-mentioned transparent hard-coating layer is set, the surface phase that arranges with above-mentioned transparent hard-coating layer in above-mentioned film base material On the surface of anti-side, the operation of setting protection laminate member；Fold to containing above-mentioned film base material and above-mentioned protection laminate member The end of the width of layer body is cut, and makes the size of width of above-mentioned film base material and above-mentioned protection laminate member Width equivalently-sized operation.This feature is the common or corresponding technology of each claim in claim 1～7 Feature.

In the present invention, in the range of the thickness of above-mentioned transparent hard-coating layer is preferably 0.5～1 μm.Thus, transparent hard-coating layer After formation, the intensity of film base material can be further enhanced, can the more effectively fracture to film base material or chap etc. generation Suppressed.

In addition, in the present invention, from the viewpoint of the effect obtaining the present invention, the thickness of preferably above-mentioned film base material is 30 In the range of～100 μm.

In addition, in the present invention, it is preferred to further including, by rubbing method, the 2nd gas is arranged on above-mentioned gas barrier layer The operation of barrier layer.Thus, it is possible to obtain the high gas barrier film of barrier properties for gases further.

Hereinafter, to the present invention and its element and for implementing the form of the present invention, mode is described in detail.Need It is noted that shown in the following description "～" described numerical value before and after it as lower limit and higher limit and is contained Some meanings use.

《Gas barrier film》

Figure 1A and Figure 1B is respectively the summary section of the example of the composition of gas barrier film representing the present invention.

As shown in Figure 1A, the gas barrier film 1 of the present invention has：Containing cyclic olefin polymer or cyclic olefine copolymer Film base material 2, the transparent hard-coating layer 3 being arranged on the two sides of this film base material 2 and transparent hard-coating layer 4, it is arranged on transparent hard-coating layer 3 Gas-barrier layer 5, the 2nd gas-barrier layer 6 being arranged on this gas-barrier layer 5 using rubbing method and be arranged at transparent hard Protection laminate member 7 in coating 4.

In addition, as shown in Figure 1B, the gas barrier film 1 of the present invention can be not provided with transparent hard-coating layer 4, in this situation Under, protection laminate member 7 is set directly on a surface of film base material 2.

It should be noted that the gas barrier film 1 of the present invention shown in Figure 1A or Figure 1B is generally eliminating protective layer Use in the state of splenium part 7.Therefore, after the gas barrier film of the present invention can make stripping protection laminate member Film.

In addition, the gas barrier film 1 of the present invention shown in Figure 1A or Figure 1B is made for thering is the 2nd gas-barrier layer 6 Film, but the film being not provided with the 2nd gas-barrier layer can be made.

《The manufacture method of gas barrier film》

In the present invention, " size of the width of film base material is equivalently-sized with the width of protection laminate member " is Refer to：The size of the width of film base material is roughly the same with the size of the width of protection laminate member, and its difference is 0.5mm Within.

With reference to Fig. 2A～Fig. 2 I, the manufacture method of the gas barrier film of the present invention is illustrated.Fig. 2A～Fig. 2 I is Represent the process chart of an example of the manufacture method of gas barrier film of the present invention.It should be noted that Fig. 2A～Fig. 2 I Shown operation represents to be entered to the gas barrier film being not provided with the 2nd gas-barrier layer 6 in the gas barrier film 1 shown in Figure 1A The operation that row manufactures.

First, as shown in Figure 2 A, prepare the film base material 2 containing cyclic olefin polymer or cyclic olefine copolymer.From until setting From the viewpoint of film base material 2 being protected during putting protection laminate member described later, preferably on a surface of film base material 2 Setting protecting film 8.As protecting film 8, if by can to protect film base material 2 in the way of constituted, it is possible to use arbitrarily protection Film, for example, can be set to the protecting film of the composition same with protection laminate member 9 described later.

Preferably in the subsequent processing in the two sides of film base material 2, the face to setting protection laminate member 9 is (with setting protection The face of the face opposition side of film 8) implement sided corona treatment.Thus, it is possible to improve the adaptation of film base material 2 and transparent hard-coating layer 3.Corona Process can be carried out using commercially available corona surface treatment device.

Then, as shown in Figure 2 B, the table with the surface opposite side of transparent hard-coating layer setting in the two sides of film base material 2 The upper laminating in face (being implemented with the face of sided corona treatment) protection laminate member 9.In illustrated example, the width of protection laminate member 9 The size of the width than film base material 2 for the size constitute shortly, but can be longer than the size of the width of film base material 2, Can be the length roughly the same with the size of the width of film base material 2.

Then, by the laminated body to film base material 2, protecting film 8 and protection laminate member 9 with the dotted line part of such as Fig. 2 B The end of width is cut, and as shown in Figure 2 C, makes the width of film base material 2, protecting film 8 and protection laminate member 9 Equivalently-sized.Due to carrying out this width cutting operation, therefore, it can make film base material 2 and protection laminate member 9 Equivalently-sized and without the Anawgy accuracy improving film base material 2 and protection laminate member 9.It should be noted that in protective layer splenium In the case that the size of the width of the size of the width of part 9 and film base material 2 is roughly the same, it is possible to reduce laminated body Width end the amount cutting, from cost reduce from the viewpoint of, preferably.

Then, as shown in Figure 2 D, protecting film 8 is peeled off from film base material 2, in the table being provided with this protecting film 8 of film base material 2 On face, operate in the same manner as above-mentioned Fig. 2A, implement sided corona treatment.Thus, it is possible to improve the close of film base material 2 and transparent hard-coating layer 4 Conjunction property.

Then, as shown in Figure 2 E, on the surface implementing sided corona treatment of film base material 2, transparent hard-coating layer 4 is set.Make For the forming method of transparent hard-coating layer 4, it is not particularly limited, preferably uses transparent hard-coating layer formation coating fluid, applied with wet type The method that mode for cloth is coated and is dried and is formed.Specifically, transparent hard-coating layer formation is applied with coating fluid Cloth and form coated film, to formed coated film implement cured.For example, transparent hard-coating layer 4 is formed with heat-curing resin In the case of, it is used heater as solidification equipment etc. to give thermal energy and solidified.Or, gel-type resin is with active light In the case that line (such as ultraviolet) forms transparent hard-coating layer 4, it is used the ultraviolet lamp as solidification equipment etc. to irradiate Ultraviolet etc. is solidified, and forms transparent hard-coating layer 4.

It should be noted that the operation (Fig. 2 B, Fig. 2 C) that the laminated body such as above-mentioned film base material 2 are cut can be set to Carry out after forming transparent hard-coating layer 4, but the viewpoint from the generation of the fracture more effectively suppressing film base material 2 or chap etc. goes out Send out, the laminated body such as preferred pair film base material 2 forms transparent hard-coating layer 4 after being cut.

Then, as shown in Figure 2 F, laminating protection laminate member 7 on transparent hard-coating layer 4.In illustrated example, protection lamination The size of the width of part 7 is constituted shortlyer than the size of film base material 2 or the width of transparent hard-coating layer 4, but can With longer than the size in film base material 2 equal in width direction or roughly the same with the size in film base material 2 equal in width direction long Degree.

Then, by the laminated body to film base material 2, protection laminate member 9, transparent hard-coating layer 4 and protection laminate member 7 The end of width is cut, and as shown in Figure 2 G, makes film base material 2, protection laminate member 9, transparent hard-coating layer 4 and protective layer The width of splenium part 7 equivalently-sized.Due to carry out this cut operation, therefore, it can to make film base material 2 and protection lamination The width of part 7 equivalently-sized and without the Anawgy accuracy improving film base material 2 and protection laminate member 7.Need explanation , it is roughly the same situation in the size of the width of protection laminate member 7 with the size of the width of film base material 2 Under, the amount cutting of the width end of laminated body can be reduced, from the viewpoint of cost reduces, preferably.

Then, as illustrated in figure 2h, protection laminate member 9 is peeled off from film base material 2, and be provided with this protection laminate member 9 Surface on arrange transparent hard-coating layer 3.Forming method as transparent hard-coating layer 3, it is possible to use with above-mentioned transparent hard-coating layer 4 Forming method identical method.

It should be noted that the operation (Fig. 2 F, Fig. 2 G) that the laminated body such as above-mentioned film base material 2 are cut can be in shape Carry out after becoming transparent hard-coating layer 3, but the viewpoint being suppressed from the generation of the more effectively fracture to film base material 2 or chap etc. Set out, preferably clear hard conating 3 is formed after the laminated body such as film base material 2 are cut.

In addition, the operation that the laminated body such as above-mentioned film base material 2 are cut can be before peeling off protection laminate member 9 Carry out, but be not limited to this, laminated body can be cut after peeling off protection laminate member 9, form transparent hard-coating layer 3.

Then, as shown in figure 2i, the transparent hard-coating layer 3 being formed forms gas-barrier layer 5, make gas barrier film 1.

As the forming method of gas-barrier layer 5, vapour deposition method or wet coating method can be applied (for example to gather using full hydroxyl Silazane (PHPS), the method being modified by vacuum ultraviolet treatment with irradiation) etc., in the present invention, from can be with institute's phase From the viewpoint of the group hoped is shaped as gas-barrier layer and can accurately control in the layer Elemental redistribution, advantageous applications chemistry Chemical vapour deposition (CVD), and apply discharge plasma chemical vapor deposition method as chemical vapor deposition method (wait from Daughter CVD).The details such as plasma CVD carry out aftermentioned.

As set forth above, it is possible to manufacture gas barrier film.

It should be noted that in the process chart shown in Fig. 2A～Fig. 2 I, being set to transparent hard in the setting of the two sides of film base material 2 Coating 3 and transparent hard-coating layer 4, but only transparent hard-coating layer can be set in the one side of film base material 2.In this case, until Fig. 2A Similarly carry out each operation till～Fig. 2 E, after Fig. 2 E, gas-barrier layer 5 is formed on transparent hard-coating layer 4.

In addition, in the process chart shown in Fig. 2A～Fig. 2 I, being not provided with the 2nd gas-barrier layer, but gas resistance can formed Form the 2nd gas-barrier layer further with wet coating method after interlayer 5.In such a case it is possible to manufacture have higher The gas barrier film of gas barrier property.

In addition, in the example of above-mentioned manufacture method, as shown in figure 2i, by the film after newly formed gas-barrier layer 5 It is set to gas barrier film 1, protection laminate member 7 can be peeled off, and will be peeled off after gas-barrier layer 5 is formed Film be set to gas barrier film.Only in the case of the one side setting transparent hard-coating layer of film base material 2, preferably in transparent hard-coating layer After forming gas-barrier layer 5 on 4, the film that the film of protection laminate member 9 is stripped and is formed is set to gas barrier film.Separately Outward, in the case of gas-barrier layer 5 forming the 2nd gas-barrier layer, preferably will protect after the 2nd gas-barrier layer is formed Laminate member 9 or 7 is peeled off.

《Each element of gas barrier film》

[film base material]

The film base material of the present invention contains cyclic olefin polymer (COP) or cyclic olefine copolymer (COC) as main constituent, here Described main constituent refers to：Constitute in the resinous principle of film base material, the component ratio of COP and COC is more than 60 mass %, preferably More than 80 mass %, more than more preferably 90 mass %, particularly preferably constituted by more than 95 mass %.

The film base material being formed by cyclic olefin polymer or the cyclic olefine copolymer of the present invention is poly- with the past widely used Ethylene glycol terephthalate film is compared, and has relatively low water vapour permeability, and it is (transparent to have excellent light transmittance Property), when possessing in organic EL element, there is the feature improving luminous efficiency.And, birefringence is low, possess in organic EL element When, possess the little feature of the visual field angle dependency of color.

Generally, due to impact of steric hindrance etc. is difficult to cyclic olefin be carried out with homopolymerization and accordingly, there exist and α-alkene Hydrocarbon etc. carries out method A of addition polymerization and the method B both approaches of the ring-opening polymerisation based on cyclic olefin, by the former method The polymer of A is referred to as cyclic olefine copolymer (COC), and the polymer of method B of the latter is referred to as cyclic olefin polymer (COP).

The cyclic olefin polymer being applicable to the present invention comprises the fluoropolymer resin containing ester ring type structure.As preferred Cyclic olefin polymer is：Cyclic olefin has been carried out with polymerization or the resin of copolymerization sum.As cyclic olefin, can enumerate for example：Fall Bornylene, dicyclopentadiene, tetracyclododecane, ethyltetracyclo dodecylene, ethidine tetracyclododecane, Fourth Ring The unsaturated hydrocarbons and their derivates of the multiring structures such as [7.4.0.110,13.02,7] 13 carbon -2,4,6,11- tetraene；Cyclobutane, Cyclopentenes, cyclohexene, 3,4- dimethylcyclopentene, 3- methylcyclohexene, 2- (2- methyl butyl) -1- cyclohexene, cyclo-octene, The unsaturated hydrocarbons of the single ring architectures such as 3a, 5,6,7a- tetrahydrochysene -4,7- methylene -1H- indenes, cycloheptene, cyclopentadiene, cyclohexadiene And its derivant etc..These cyclic olefins can have polar group as substituent group.As polar group, can enumerate for example： Hydroxyl, carboxyl, alkoxyl, epoxy radicals, glycidyl, oxygen carbonyl, carbonyl, amino, ester group, carboxylic carboxylic anhydride group etc., particularly preferably Ester group, carboxyl or carboxylic carboxylic anhydride group.

Preferably cyclic olefin polymer can be the cycloolefins that the monomer beyond cyclic olefin is carried out with addition copolymerization Copolymer.As can addition copolymerization monomer, can enumerate for example：Ethylene or the alpha-olefins such as ethylene, propylene, 1-butylene, 1- amylene； 1,4- hexadiene, 4- methyl isophthalic acid, 4- hexadiene, 5- methyl isophthalic acid, diene such as 4- hexadiene, 1,7- octadiene etc..

Cyclic olefin can be obtained by polyaddition reaction or metathesis ring-openning polymerization.Polyreaction generally exists Carry out in the presence of catalyst.

Cyclic olefin polymer preferably makes cyclic olefin be polymerized or copolymerization, then, carries out hydrogenation and by molecule In unsaturated bond be converted to the material of saturated bond.Hydrogenation is blown into hydrogen in the presence of known hydrogenation catalyst And carry out.

In addition, as cyclic olefin polymer, following norbornene resins can be enumerated.Norbornene resin preferably has There is norborene skeleton as repetitives, as its concrete example, can enumerate for example：Japanese Unexamined Patent Application 62-252406 publication, Japanese Unexamined Patent Application 62-252407 publication, Japanese Unexamined Patent Publication 2-133413 publication, Japanese Unexamined Patent Application 63-145324 publication, Japanese Unexamined Patent Application 63-264626 publication, Japanese Unexamined Patent Publication 1-240517 publication, Japanese Patent Publication 57-8815 publication, day This Unexamined Patent 5-2108 publication, Japanese Unexamined Patent Publication 5-39403 publication, Japanese Unexamined Patent Publication 5-43663 publication, Japanese Unexamined Patent Publication Flat 5-43834 publication, Japanese Unexamined Patent Publication 5-70655 publication, Japanese Unexamined Patent Publication 5-279554 publication, Japanese Unexamined Patent Publication 6- No. 206985 publications, Japanese Unexamined Patent Publication 7-62028 publication, Japanese Unexamined Patent Publication 8-176411 publication, Japanese Unexamined Patent Publication 9- No. 241484 publications, Japanese Unexamined Patent Publication 2001-277430 publication, Japanese Unexamined Patent Publication 2003-139950 publication, Japanese Unexamined Patent Publications 2003-14901 publication, Japanese Unexamined Patent Publication 2003-161832 publication, Japanese Unexamined Patent Publication 2003-195268 publication, Japanese Unexamined Patent Publication 2003-211588 publication, Japanese Unexamined Patent Publication 2003-211589 publication, Japanese Unexamined Patent Publication 2003-268187 publication, Japan are special Open 2004-133209 publication, Japanese Unexamined Patent Publication 2004-309979 publication, Japanese Unexamined Patent Publication 2005-121813 publication, Japan JP 2005-164632 publication, Japanese Unexamined Patent Publication 2006-72309 publication, Japanese Unexamined Patent Publication 2006-178191 publication, Japan In JP 2006-215333 publication, Japanese Unexamined Patent Publication 2006-268065 publication, Japanese Unexamined Patent Publication 2006-299199 publication etc. Described cyclic olefin polymer, but it is not limited to these.In addition, these materials both can be used alone it is also possible to combine Using two or more.

As the cyclic olefin polymer of the present invention, can obtain as commercially available product, for example, preferably use hydrops chemical industry ZEONEX, ZEONOR that エ ッ シ Na (trade name) that Co., Ltd. manufactures, Japanese Zeon Co., Ltd. manufacture (more than, commodity Name), JSR Corp. manufacture ARTON (trade name), Hitachi Chemical Co., Ltd. manufacture OPTOREZ (trade name), three wells KCC manufacture Apelle (trade name, APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) etc..

COP film as the present invention or the manufacture method of COC film, for example, can use common blow moulding, T modulus method, pressure Prolong the autofrettage of method, cutting method, the tape casting, emulsion technique, pressure sintering etc., as film film-forming method, can select known Solution curtain coating masking method or melting casting film method.

From the viewpoint of the effect obtaining the present invention, preferably film base material thickness be 30～100 μm in the range of.

[protection laminate member]

In the manufacture method of the gas barrier film of the present invention, before film base material forms transparent hard-coating layer, at this Setting protection laminate member on the surface with the surface opposite side forming transparent hard-coating layer of film base material.In addition, this protective layer Splenium part and film base material are cut by the end of the width to its laminated body, and the size of both widths becomes Identical.

In general, weak as the film base material intensity of main constituent containing COP or COC, other functions are formed on film base material During layer, there is a problem of producing fracture or chap of film base material etc..In addition, when only on film base material, protecting film is set, according to film Base material and the Anawgy accuracy of protecting film, the end of film base material can not be completely capped, thus producing chap on the end of film base material Split etc. bad.

In the present invention, by before forming transparent hard-coating layer on film base material setting protection laminate member to its lamination The end of the width of body is cut, and the intensity of film base material can be improved, and can be to protect laminate member complete The end of all standing film base material.Therefore, it can reduce manufacture gas barrier film when, particularly formed transparent hard-coating layer or Loss to film base material during gas-barrier layer, the generation of the fracture of suppression film base material or chap etc. effectively.

In addition, protection laminate member preferably has thermostability.In this case, when manufacturing gas barrier film, relatively For film base material, by applying the process of excessive thermal energy, for example, form coating during transparent hard-coating layer using rubbing method Heat drying afterwards is processed, and when the materials'use heat-curing resin as transparent hard-coating layer 4 or ultraviolet curing resin Heat cure process or ultraviolet treatment with irradiation etc., with respect to each process that the thermal energy giving can reduce that film base material is subject to damage Wound, usually can make the excellent film base material of flatness.

In addition, when the discharge plasma processing meanss shown in the Fig. 3 stating after a procedure form gas-barrier layer, in conveying During film base material, scratch that the contact with each roller class of rear-face contact mode of a surface of film base material leads to etc. can be prevented.

It should be noted that when there is in organic EL element the gas barrier film of the present invention, to protect laminate member Removed mode and use.

The protection laminate member of the present invention mainly has heat-resistant film, adhesive layer and stripping film etc. and constitutes, when using, right Stripping film is peeled off, and adhesive layer is fitted with the film base material of the present invention and uses.

As constitute protection laminate member heat-resistant film, be not particularly limited, constitute film base material cyclic olefin polymer or About 100～160 DEG C about of the glass transition temperature of cyclic olefine copolymer, preferably by having the fusing point higher than it or glass The membrane material changing transition temperature (Tg) is formed.As heat-resistant film used in protection laminate member, can enumerate for example： Poly (ethylene naphthalate) film (Q83 (trade name), Tg that for example Di Ren DuPont Co., Ltd. manufactures：262 DEG C), poly- to benzene Naphthalate film (Co., Ltd.'s manufacture is spun by such as Japan, Polyester (registered trade mark) film (trade name) spins in Japan, Fusing point：260 DEG C), polyimide film (for example Rhizoma Sparganii Gas Co., Ltd. manufacture NEOPULIM L-3430 (Tg：303℃)、L- 1000(Tg：260℃)、L-9000(Tg：315 DEG C)), polyamide membrane (UNITIKA Co., Ltd. manufacture Tg：280 DEG C) etc..

In addition, as the composition of the adhesive layer being applicable to the present invention, being not particularly limited, for example dry laminating agent, wet layer Pressure agent, binding agent, sealant, hot solvent etc. all can use.As binding agent, for example, can use polyester resin, polyurethane Resinoid, polyvinyl acetate esters resin, acrylic resin, nitrile rubber etc..In addition, can enumerate by macromolecular compound with have The gel of machine solvent or oil formation or colloidal sol, the water based emulsion of macromolecular compound, macromolecular compound and water soluble polymer It is dissolved in hydrophilic solvent and carried out colloidal sol or gel of dispersion etc..

In addition, as stripping film, for example can using acrylic film or piece, polycarbonate membrane or piece, polyacrylate film or The plastic foil such as piece, poly (ethylene naphthalate) film or piece, polyethylene terephthalate film or piece, fluorine film or piece or mixed Enter to have the resin film of titanium oxide, silicon dioxide, aluminium powder, copper powder etc. or piece, the resin being mixed into these materials is implemented coating or The metals such as aluminum are carried out with resin film or sheet material that metal evaporation etc. implements Surface Machining.

In addition in the present invention it is possible to commercially available product directly be used as protection laminate member.Such as rattan lumber industry can be enumerated Heat-resisting protective film MASDAC (registered trade mark) PC that Co., Ltd. manufactures is (such as product name Normal Type PC-542PA, viscous Mixture low mobile model PC-751, PC-801).This heat-resisting protective film is that the low thermal shrinkage polyester film superimposed layer being 50 μm in thickness has Adhesive phase (4～10 μm of thickness) and the composition of stripping film (40 μm of thickness).In addition, can enumerate in the same manner by rattan lumber's industry strain formula Commercial firm manufacture optics with surface protection film MASDAC (registered trade mark) TFB (such as product name ZBO-0421, NBO-0424, TFB-4T3-367AS).

[transparent hard-coating layer]

In the manufacture method of the gas barrier film of the present invention, on the film base material of setting matcoveredn splenium part, shape Become transparent hard-coating layer.By arranging transparent hard-coating layer on film base material, gas-barrier layer, gas are arranged on this transparent hard-coating layer Barrier layer can be configured well with respect to film base material adaptation.

The gel-type resin used in formation as the transparent hard-coating layer of the present invention, can enumerate thermohardening type resin or Active energy ray-curable resin, it may be preferred to use active energy ray-curable resin from the aspect of shaping readily.

(1) thermohardening type resin

Thermohardening type resin is not particularly limited, and specifically, can enumerate：Epoxy resin, cyanate ester resin, phenolic aldehyde tree The various heat cures such as fat, bismaleimide-triazine resin, polyimide resin, acrylic resin, vinyl benzyl resin Property resin.

As epoxy resin, as long as averagely every 1 molecule has the epoxy radicals of more than 2, specifically, can lift Go out：Bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol type epoxy resin, naphthalene type ring Oxygen tree fat, bisphenol f type epoxy resin, phosphorous epoxy resin, bisphenol-s epoxy resin, aromatic series glycidyl amine epoxy tree Fat (specifically, is four glycidyl group diaminodiphenyl-methane, triglycidyl group-para-aminophenol, 2-glycidyl Base toluidines, diglycidylaniline etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol aldehyde type varnish type ring Oxygen tree fat, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, there is the asphalt mixtures modified by epoxy resin of butadiene structure Fat, phenol aralkyl type epoxy resin, the epoxy resin with dicyclopentadiene structure, the diglycidyl ether of bis-phenol Thing, the diglycidyl ether compound of naphthalene glycol, the glycidyl etherified thing of phenol and the diglycidyl ether of alcohols The alkyl of compound and these epoxy resin replaces body, halogenide and hydride etc..These materials can be using a kind or combination Using two or more.

(2) active energy ray-curable resin

Can preferably use in the present invention active energy ray-curable resin refer to such by ultraviolet or electron beam Active wire irradiate, thus through cross-linking reaction etc. solidification resin.As active energy ray-curable resin, preferably use Composition containing the monomer with ethylenical unsaturated double bonds, and make it solid by active wire as irradiation ultraviolet radiation or electron beam Change, form active energy ray-curable resin bed.As active energy ray-curable resin, purple can be enumerated as the resin representing Outside line gel-type resin or electronic beam solidified resin etc., the ultraviolet hardening tree preferably irradiated by ultraviolet and solidify Fat.

(2.1) ultraviolet curing resin

Hereinafter, the ultraviolet curing resin of the transparent hard-coating layer suitably forming the present invention is illustrated.

As ultraviolet curing resin, can enumerate for example：Ultraviolet hardening urethane acrylate resinoid, purple Outside line curing type polyester acrylic esters resin, ultraviolet hardening Epoxy Acrylates resin, ultraviolet hardening polyol Acrylic resin or ultraviolet hardening epoxy resin etc..

Ultraviolet hardening acroleic acid polyurethane resinoid generally speaking can be by making isocyanate-monomer or prepolymer With polyester polyol react obtained from product further with acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, third Olefin(e) acid 2- hydroxy propyl ester etc. has the monomer reaction of esters of acrylic acid of hydroxyl and is readily derived.For example can be special using Japan Open the resin described in clear 59-151110 publication.

Make acrylic acid 2- hydroxyl second as ultraviolet hardening polyester acrylic esters resin it is however generally that can enumerate Ester, the monomer of 2- hydroxy acrylic acid esters are reacted with polyester polyol, thus the resin being readily formed, it is possible to use Japanese Unexamined Patent Publication Resin described in clear 59-151112 publication.

As the concrete example of ultraviolet hardening Epoxy Acrylates resin, can enumerate and epoxy acrylate is made Oligomer, wherein adds reactive diluent, photoreaction initiator the resin making it react and generating, it is possible to use Japan is special Open the resin described in flat 1-105738 publication.

In addition, in the present invention, it is preferred to using ultraviolet hardening polyol acrylic resin, as this chemical combination Thing, can enumerate such as polyfunctional acrylic ester resin etc..Here, polyfunctional acrylic ester resin refer to have in molecule 2 with On acryloxy or methacryloxy compound.

As the monomer of polyfunctional acrylic ester resin, can enumerate for example：Glycol diacrylate, diethylene glycol dipropyl Olefin(e) acid ester, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, three hydroxyl first Base ethane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, five glycerol three acrylic acid Ester, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, glycerol tri-acrylate, two Pentaerythritol triacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol six propylene Acid esters, three (acryloyl-oxyethyl) isocyanuric acid ester, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate Ester, 1,6-HD dimethylacrylate, neopentylglycol dimethacrylate, trimethylol propane trimethyl acrylic acid Ester, trimethylolethane trimethacrylate methacrylate, tetramethylol methane trimethyl acrylic ester, tetramethylol methane tetramethyl third Olefin(e) acid ester, five glycerol trimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, season Penta tetrol tetramethyl acrylate, glycerol trimethacrylate, dipentaerythritol trimethyl acrylic ester, dipentaerythritol four Methacrylate, dipentaerythritol pentamethacrylates, dipentaerythritol hexamethacrylate.These compounds are permissible Individually using or be mixed with two or more.Furthermore it is possible to be the oligomer such as the dimer of above-mentioned monomer, trimer.

As the commercially available product of ultraviolet curing resin adoptable in the present invention, can suitably select and utilize, for example Adekaoptomer KR, Adekaoptomer BY series：KR-400、KR-410、KR-550、KR-566、KR-567、BY- 320B (more than, ADEKA Corp. manufactures)；Koei hard A-101-KK、Koei hard A-101-WS、Koei hard C-302、Koei hard C-401-N、Koei hard C-501、Koei hard M-101、Koei hard M-102、Koei hard T-102、Koei hard D-102、Koei hard NS-101、Koei hard FT-102Q8、Koei hard MAG- 1-P20, Koei hard AG-106, Koei hard M-101-C (more than, Guang Rong KCC manufacture)；SEIKABEAM PHC2210(S)、SEIKABEAM PHC X-9(K-3)、SEIKABEAM PHC2213、SEIKABEAM DP-10、SEIKABEAM DP-20、SEIKABEAM DP-30、SEIKABEAM P1000、SEIKABEAM P1100、SEIKABEAM P1200、 SEIKABEAM P1300、SEIKABEAM P1400、SEIKABEAM P1500、SEIKABEAM P1600、SEIKABEAM SCR900 (more than, Dainichiseika Color Chem manufactures)；KRM7033、KRM7039、KRM7130、KRM7131、 UVECRYL29201, UVECRYL29202 (more than, Daicel UCB Co., Ltd. manufactures)；RC-5015、RC-5016、RC- 5020、RC-5031、RC-5100、RC-5102、RC-5120、RC-5122、RC-5152、RC-5171、RC-5180、RC-5181 (more than, Dainippon Ink Chemicals manufactures)；OLEX No.340KURIYA (more than, Chinese paint company manufacture)；SANRAD H-601、 SANRAD RC-750、SANRAD RC-700、SANRAD RC-600、SANRAD RC-500、SANRAD RC-611、SANRAD RC-612 (more than, Sanyo Chemical Industries, Ltd. manufactures)；SP-1509, SP-1507 (more than, Showa Highpolymer Co., Ltd Manufacture)；RCC-15C (Grace Japan KK's manufacture), ARONIX M-6100, M-8030, M-8060 (more than, East Asia close Co., Ltd. is become to manufacture) etc..

(2.2) Photoepolymerizationinitiater initiater

In addition, for the solidification promoting ultraviolet curing resin, preferably with respect to ultraviolet curing resin 2～30 Photoepolymerizationinitiater initiater is contained in the range of quality %.As Photoepolymerizationinitiater initiater, one group of the double salt of particularly preferred salt, it is put Go out to cause the lewis acid of cationic polymerization due to light irradiation.

As this salt, it is particularly effective for particularly using aromatic series salt as cationic polymerization initiators, Wherein preferably Japanese Unexamined Patent Application 50-151996 publication, with the aromatic series halogeno salt described in 50-158680 publication etc., Japanese Unexamined Patent Application 50-151997 publication, with 52-30899 publication, with 59-55420 publication, with 55-125105 publication Deng described in Group VIA aromatic series salt, Japanese Unexamined Patent Application 56-8428 publication, with 56-149402 publication, same to 57- Aromatic diazonium salt described in oxygen sulfonium salt described in No. 192429 publications etc., Japanese Patent Publication 49-17040 publication etc., Thiopyrylium salts described in No. 4139655 description of U.S. Patent No. etc. etc..Furthermore it is possible to enumerate aluminium complex or light divides Solution property silicon compound Type of Collective initiator etc..Above-mentioned cationic polymerization initiators and benzophenone, benzoin can be applied in combination The photosensitizing agents such as diisopropyl ether, thiaxanthone.

(2.3) various additives

In addition, in order to adjust traumatic resistance, lubricity or refractive index, inorganic compound can be contained on transparent hard-coating layer Or the microgranule of organic compound.

As the inorganic particles used in transparent hard-coating layer, can enumerate：Silicon oxide, titanium oxide, aluminium oxide, oxidation Stannum, Indium sesquioxide., tin indium oxide (ITO；Tin-doped indium oxide (Indium Tin Oxide)), zinc oxide, zirconium oxide, magnesium oxide, Calcium Carbonate, Calcium Carbonate, Talcum, clay, calcined kaolin, baked calcium silicate, afwillite, aluminium silicate, magnesium silicate and phosphoric acid Calcium.Particularly preferably use silicon oxide, titanium oxide, aluminium oxide, zirconium oxide, magnesium oxide etc..

In addition, as organic filler, polymethyl methacrylate acrylate powder, acrylic acid benzene second can be added Vinyl resin powder, poly methyl methacrylate toner, silicone toner, polystyrene resins powder, poly- Carbonate resin powder, benzoguanamine resinoid powder, melamine class toner, polyolefin resin powder, polyesters The ultraviolet such as toner, polyamide-based resin powder, polyimide based resin powder or poly- ethylene fluoride resinoid powder are solid The property changed resin combination.Particularly preferably enumerate crosslinked polystyrene particle and (for example comprehensive grind chemistry SX-130H, SX-200H, SX- processed 350H), poly methyl methacrylate class particle (for example comprehensive grind chemistry processed MX150, MX300), fluoroacrylic resin microgranule. As fluoroacrylic resin microgranule, for example Japanese paint system can be enumerated：The commercially available products such as FS-701.In addition, as acrylic acid grain Son, can enumerate for example Japanese paint system：S-4000, as acrylicstyrene particle, can enumerate for example Japanese paint system： S-1200, MG-251 etc..

In addition, for the thermostability improving transparent hard-coating layer, can select not suppressing the antioxidant of photocuring reaction and Use.

Solvent can not contained in the transparent hard-coating layer formation coating fluid of the formation for transparent hard-coating layer it is also possible to Suitably contain as needed, can be the solvent being diluted.As contained organic solvent in transparent hard-coating layer formation masking liquid, For example from hydro carbons (such as toluene, dimethylbenzene etc.), alcohols (such as methanol, ethanol, isopropanol, butanol, Hexalin etc.), ketone (such as acetone, methyl ethyl ketone, methylisobutylketone etc.), esters (such as methyl acetate, ethyl acetate, methyl lactate etc.), second Suitably select in glycol ethers, other organic solvent, or by these material mixings and can utilize.Preferably use containing propylene glycol (carbon number as alkyl is for monoalky lether (carbon number as alkyl is 1～4) or propylene-glycol monoalky lether acetass 1～4) etc. more than 5 mass %, above-mentioned organic solvent more than more preferably 5～80 mass %.

Silicone-based surfactant or polyoxy ether compound can be contained further in transparent hard-coating layer.In addition, saturating Fluoro- silicone grafted polymers can be contained in bright hard conating.

These transparent hard-coating layer can be using transparent hard-coating layer formation coating fluid, for example with gravure coating machine, dipping painting The known wet methods such as deposited machine, reverse coating machine, bar coating machine, dispensing coating machine, ink-jet method are coated with.

For the coating weight of hard coat layer coating solution, as wet layer thickness, 0.1～40 μm is suitable for, preferably 0.5～30 μ m.In addition, as thickness, being 0.1～30 μm, preferably 1～10 μm.

(2.4) solidification processing method of transparent hard-coating layer

After film base material forms transparent hard-coating layer, active energy ray, preferred ultraviolet are irradiated to this transparent hard-coating layer, Transparent hard-coating layer is solidified the most at last.

Make ultraviolet curing resin solidification, the light for forming the transparent hard-coating layer of solidification as by photocuring reaction Source, as long as produce the light source of ultraviolet it is possible to use without limitation.It is, for example possible to use low pressure mercury lamp, middle pressure water Silver-colored lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp etc..Irradiation condition is because of respective lamp Difference, the irradiation dose of active energy ray is preferably 5～350mJ/cm²In the range of, particularly preferably 250～300mJ/cm²Model In enclosing.

[gas-barrier layer]

In the manufacture method of the gas barrier film of the present invention, gas-barrier layer is formed on above-mentioned transparent hard-coating layer.

For the gas-barrier layer of the present invention, by the vapor being determined according to the method for JIS-K-7129-1992 Transmission (25 ± 0.5 DEG C, 90 ± 2%RH) is preferably 0.01g/ (m²24 hours) below.In addition, by according to JIS-K- The oxygen transmission that the method for 7126-1987 determines is preferably 1 × 10^-3ml/(m²24 hours atm) below, vapor is saturating Degree of penetrating is preferably 1 × 10-5g/ (m²24 hours) below.

As the material forming gas-barrier layer, it is possible to use film base material or there is suppression lead to possess this barrier properties for gases The material of the function of immersion of the element such as the moisture of the performance degradation of the organic EL element of film or oxygen, such as silicon oxide, oxynitriding Silicon, silicon dioxide, silicon nitride etc..

The forming method of gas-barrier layer is not particularly limited, for example, can use vacuum vapour deposition, sputtering method, reaction Property sputtering method, molecular line epitaxy, ion beam method, ion plating method, Plasma Polymerization, atmospheric pressure plasma polymerization The forming method by dry technique of method, plasma CVD method, laser CVD method, thermal cvd etc. or using there being wet side The forming method of formula.

As the forming method of the gas-barrier layer using wet mode, it is using wet side on film base material After formula is coated with the coating fluid containing polysilazane compounds such as full hydroxyl polysilazanes, irradiate vacuum ultraviolet (quasi-molecule Light), the inoranic membranes such as silicon oxide, silicon oxynitride, silicon nitride are modified process and the method that forms gas-barrier layer.

With regard to using have quasi-molecule light as above wet mode gas-barrier layer forming method detailed Carefully, for example may be referred to Japanese Unexamined Patent Publication 2012-024933 publication, Japanese Unexamined Patent Publication 2012-121149 publication, Japanese Unexamined Patent Publication 2013-022799 publication, Japanese Unexamined Patent Publication 2013-039786 publication, Japanese Unexamined Patent Publication 2013-052561 publication, Japan are special Open 2013-086445 publication etc. to record.

In the present invention, from the viewpoint of being stably formed high-grade gas-barrier layer, preferably by chemistry The method that chemical vapour deposition (CVD) forms gas-barrier layer, from the viewpoint of can forming more accurate gas-barrier layer, More preferably as discharge plasma chemical vapor deposition method (plasma CVD method) of chemical vapor deposition method.

And then, from the Elemental redistribution that can be contained with the formation of arbitrary pattern in the thickness direction of the gas-barrier layer being formed Profile from the viewpoint of, as discharge plasma chemical vapor deposition method (plasma CVD method), particularly preferably in resin On one face of base material using the unstrpped gas containing organo-silicon compound and oxygen, using comprising Fig. 3 described later being applied with The discharge plasma chemical vapor deposition method formation between the roller in the magnetic field of shown composition with discharge space has gas resistance The method of interlayer.

Hereinafter, as one of gas-barrier layer of the present invention, being applied between the roller in the magnetic field shown in Fig. 3 using having The forming method being formed with the gas-barrier layer of discharge plasma processing meanss of discharge space illustrates.

(1) element outline of gas-barrier layer

Even if the gas-barrier layer just constituting gas barrier film is used in having between the roller being applied with the magnetic field shown in Fig. 3 For the gas-barrier layer that the discharge plasma processing meanss of discharge space are formed, as its element outline, preferably by layer Thick direction has the distribution of refractive index, has the inoranic membrane composition of more than one extreme value in this index distribution.Gas hinders Interlayer is made up of the material containing silicon, oxygen and carbon, has the multiple layer lamination knot that formed different by the containing ratio of silicon, oxygen and carbon Structure.

And, for gas-barrier layer, can be by the distance on the surface away from gas-barrier layer on thickness direction and upper The relational design stating the ratio (atomic ratio) of the atomic weight of each element (silicon, oxygen or carbon) becomes arbitrary element outline.

In addition, gas-barrier layer is in addition to silicon, oxygen and carbon, nitrogen can be contained further.By containing nitrogen, gas can be controlled The refractive index of body barrier layer.For example, SiO₂Refractive index be 1.5, on the other hand, the refractive index of SiN is 1.8～2.0 about.Cause This, by containing nitrogen in gas-barrier layer, form SiON in gas-barrier layer, can be set to as preferred refractive index The 1.6～1.8 of value.So, by being suitable for above-mentioned discharge plasma processing meanss, the content of nitrogen can be adjusted, can control The refractive index of gas-barrier layer.

(2) thickness of gas-barrier layer

The thickness of the gas-barrier layer preferably scope of 5～3000nm, the more preferably scope of 10～2000nm, especially excellent Elect the scope of 100～1000nm as.

In addition, in the case of forming gas-barrier layer by multiple layers, the thickness of the entirety of gas-barrier layer is set as 10 The scope of～10000nm, but the preferably scope of 10～5000nm, the more preferably scope of 100～3000nm, particularly preferably The scope of 200～2000nm.

(3) forming method of gas-barrier layer：Plasma enhanced chemical vapor is grown up

In the present invention, it is preferred to be the layer forming gas-barrier layer using plasma enhanced chemical vapor flop-in method.As profit The gas-barrier layer being formed with plasma enhanced chemical vapor flop-in method, more preferably for example by using the electric discharge shown in Fig. 3 Plasma processing apparatus, the film base material being formed with transparent hard-coating layer on one face are configured in a pair of one-tenth deflector roll, at this Discharged between a pair of one-tenth deflector roll and produced the layer that the plasma enhanced chemical vapor flop-in method of plasma is formed.Plasma Chemical vapor deposition method can be the plasma enhanced chemical vapor flop-in method of penning discharge plasma mode.In addition, at a pair Become between deflector roll when being discharged, preferably make a pair of one-tenth deflector roll alternating polarity invert.

Sky in plasma enhanced chemical vapor flop-in method, when producing plasma, preferably between multiple one-tenth deflector rolls Between produce plasma discharge.

In addition, as the forming method of gas-barrier layer, preferably using using to the plasma chemistry gas to roller mode Phase flop-in method.In the present invention, refer to using to the plasma enhanced chemical vapor flop-in method of roller mode：Using a pair of film forming Roller, and this pair of one-tenth deflector roll each on configuration be formed with the film base material of transparent hard-coating layer, discharged between a pair of one-tenth deflector roll And produce plasma, thus carry out the formation of gas-barrier layer.

So, there is by configuration in a pair of one-tenth deflector roll the film base material of transparent hard-coating layer, put between this one-tenth deflector roll Electricity, can carry out film forming on being present in a film base material becoming in deflector roll.Meanwhile, become on the film base material in deflector roll at another Film forming can also be carried out.Therefore, it can double film forming speed, can effectively manufacture thin film.And then, can be in a pair of film forming The film of identical structure is formed on the respective film base material on roller.

In addition, above-mentioned plasma enhanced chemical vapor flop-in method preferably uses the film forming gas containing organo-silicon compound and oxygen Body.The content of the oxygen in film forming gas preferably makes the total amount complete oxidation of the organo-silicon compound in film forming gas need Below theoretical oxygen amount.

The layer that gas-barrier layer is formed preferably by continuous film-forming process.

(4) manufacture device of gas-barrier layer

As described above, from the viewpoint of productivity ratio, preferably the film base material of transparent hard-coating layer is had in roll-to-roll mode Upper formation gas-barrier layer.As the device that can manufacture gas-barrier layer using plasma enhanced chemical vapor flop-in method, do not have Especially limit, preferably become and possess at least one pair of one-tenth deflector roll and plasma electrical source, and can be in the structure becoming electric discharge between deflector roll The device becoming.

For example, using can be applied between the roller in the magnetic field shown in Fig. 3 formed discharge space discharge plasma at During reason device, from can also be using plasma enhanced chemical vapor flop-in method, while being continuously manufactured by roll-to-roll mode Viewpoint is set out, preferably.

Hereinafter, with reference to Fig. 3, while illustrating to the manufacture method of gas-barrier layer 5.

Fig. 3 is showing of of the discharge plasma processing meanss of the formation representing the gas-barrier layer being suitable to the present invention It is intended to.

Discharge plasma processing meanss 30 shown in Fig. 3 are can to form discharge space being applied between the roller in magnetic field Discharge plasma processing meanss, possess：Outlet roller 11, conveying roller 21,22,23,24, become deflector roll 31 and 32, gas supply pipe 41st, plasma generation power supply 51, the magnetic field generation device 61 of inside being arranged at into deflector roll 31 and 32 and 62 and take-up roll 71.In addition, in discharge plasma processing meanss 30, at least becoming deflector roll 31 and 32, gas supply pipe 41, plasma to produce It is configured at not shown vacuum with power supply 51 and magnetic field generation device 61 and 62 indoor.And then, process in discharge plasma In device 30, vacuum chamber is connected to vacuum pump (not shown), it is possible to use this vacuum pump adjusts the indoor pressure of vacuum.

《2nd gas-barrier layer》

In the manufacture method of the gas barrier film of the present invention, form the 2nd gas preferably on above-mentioned gas barrier layer Barrier layer.

2nd gas-barrier layer passes through, after forming above-mentioned gas barrier layer, to contain to being coated with this gas-barrier layer The coating fluid of polysilazane and the vacuum-ultraviolet light below film illumination wavelength 200nm that formed simultaneously carry out modification and are formed Method (rubbing method) being formed.By arranging the 2nd gas-barrier layer, the barrier properties for gases of gas barrier film can be improved Energy.In addition, in the case of setting the 2nd gas-barrier layer, above-mentioned gas barrier layer is preferably by the formation side beyond rubbing method Method is formed, thus, it is possible to make forming method different in gas-barrier layer and the 2nd gas-barrier layer, can obtain gas barrier The gas barrier film of excellent performance.

(coating fluid containing polysilazane)

In the coating fluid containing polysilazane, from the defects such as film property, crack are few, residual organic matter few from the viewpoint of, For example contain polysiloxanes such as the polysilazanes such as Perhydropolysilazane, organopolysilazane, silsesquioxane etc..Wherein, from gas Body barrier property is high, also maintain gas barrier property in bending and under the conditions of hot and humid from the aspect of, more preferably poly- silicon nitrogen Alkane, particularly preferred Perhydropolysilazane.

Polysilazane is the polymer with silicon-nitrogen key, for having the SiO of the keys such as Si-N, Si-H, N-H₂、Si₃N₄, and two The ceramic precursor inorganic polymer such as intermediate solid solution SiOxNy of person.More preferably enumerate Japanese Unexamined Patent Publication 2013-022799 publication The polysilazane described in paragraph 0051～0058.

(modification)

The modification of the 2nd gas-barrier layer being formed using rubbing method refers to silicon compound to silicon oxide or oxynitriding The conversion reaction of silicon etc., specifically, is that the film obtained from the coating fluid containing polysilazane instigating the coating present invention becomes Chemical conversion can manifest the process of the inorganic thin film of the degree of barrier properties for gases.

As the modification for making silicon compound carry out to the conversion reaction of silicon oxide or silicon oxynitride etc., can enumerate Such as corona treatment, ultraviolet treatment with irradiation, heat treated etc., in the manufacture method of the gas barrier film of the present invention In, the treatment with irradiation of the vacuum-ultraviolet light of below wavelength 200nm can be used.

[other composition layer]

On the gas barrier film of the present invention, in addition to each composition layer of described above, in the mesh not damaging the present invention Effect in the range of other functional layer can also be set.Can enumerate and for example prevent oozing out layer, smooth layer, antiglare layer etc..

《Electronic device and the manufacture method of electronic device》

The gas barrier film of the above-mentioned present invention is preferably disposed on such as organic EL element, solar cell device, liquid The electronic components such as crystal display element and constitute electronic device.

The manufacture method of the electronic device of the present invention is to have to be set in turn in be total to containing cyclic olefin polymer or cycloolefins The manufacture method of the electronic device of the gas barrier film of the transparent hard-coating layer on the film base material of polymers and gas-barrier layer, it is special Levy and be, there is following operation：Before setting transparent hard-coating layer, contrary with the surface of setting transparent hard-coating layer in film base material On the surface of side, the operation of setting protection laminate member；To the width containing film base material and the laminated body of protection laminate member The end in direction is cut, and makes the size of width of film base material and the size phase of the width of protection laminate member With the operation cutting；The operation that protection laminate member is peeled off from film base material and removed；Film base material is arranged at electronic component Operation.

In addition, the electronic device of the present invention is characterised by, by the manufacture method of the electronic device of the invention described above Lai Manufacture.

Embodiment

Hereinafter, enumerate embodiment, specifically describe the present invention, but the present invention is not limited to these embodiments.Need Bright, use the expression of " % " in embodiment, as long as no specified otherwise, represent " quality % ".

《The making of gas barrier film 101》

(preparation of film base material)

Prepare film base material (50 μm of thickness, width that there is protecting film in single-sided lamination in advance, being made up of cyclic olefin polymer Roller 1350mm).

(laminating of protection laminate member, the surface treatment of film base material)

Implement sided corona treatment on above-mentioned ready film base material with the face of the opposition side in the face of setting protecting film, at this The protection laminate member -1 (50 μm of thickness, width 1300mm) of laminating PET in process face.Then, with the width side of film base material To size and the size of width of protection laminate member -1 become the mode of identical (width 1280mm) and cut laminated body Width end and wind.

Then, protecting film is peeled off from film base material, implements sided corona treatment in being fitted with the face of this protecting film of film base material. Obtain will be implemented with sided corona treatment film base material winding, two sides implement sided corona treatment, single-sided lamination matcoveredn splenium part- 1 film base material.

(formation of transparent hard-coating layer -1)

Then, on the face being not provided with protecting laminate member -1 in the two sides of film base material, using nick version, to become dry The mode that 0.7 μm of thickness is coated with containing the ultraviolet curing resin (JSR with acrylate and amorphous silica as main constituent Society OPSTAR Z7527) and surfactant (AGC Seimichemical society Surflon S-651) transparent hard-coating layer Formation coating fluid is simultaneously dried.

Then, using high-pressure mercury-vapor lamp, to this film with light quantity 270mJ/cm under air²Carrying out ultraviolet irradiation makes it Solidification, forms transparent hard-coating layer -1.

(formation of gas-barrier layer -1)

Then, according to following methods, gas-barrier layer is formed on transparent hard-coating layer -1 and wind.

To the film base material being formed with above-mentioned transparent hard-coating layer -1, using can be applied between the roller in the magnetic field shown in Fig. 3 Formed discharge space discharge plasma processing meanss, install have above-mentioned transparent hard-coating layer -1 film base material roller, under State, under film forming condition, on the transparent hard-coating layer -1 of film base material, gas-barrier layer -1 is formed with thickness 100nm, make gas barrier Property film 101.

＜ membrance casting condition ＞

The quantity delivered of unstrpped gas (HMDSO)：50sccm(Standard Cubic Centimeterper Minute)

Oxygen (O₂) quantity delivered：500sccm

The indoor vacuum of vacuum：3Pa

Applying electric power from plasma generation power supply：1.2kW

The frequency of plasma generation power supply：80kHz

The transporting velocity of film：0.5m/min

《The making of gas barrier film 102》

In the making of above-mentioned gas barrier film 101, except the table being carried out as follows the laminating protecting laminate member, film base material Beyond face is processed, similarly operate, make gas barrier film 102.

That is, cut the width end of film base material in the way of ready film base material becomes width 1280mm.Cutting out Implement sided corona treatment, PET system of fitting on reason face in this place on the face of the opposition side in face of setting protecting film of the film base material after cutting Protection laminate member -1 (50 μm of thickness, width 1275mm) and wind.

Then, protecting film is peeled off from film base material, implements sided corona treatment in being fitted with the face of this protecting film of film base material. Winding implements the film base material of sided corona treatment, obtains implementing sided corona treatment on two sides, in single-sided lamination matcoveredn splenium part -1 Film base material.

《The making of gas barrier film 103》

In the making of above-mentioned gas barrier film 101, except arranging as described below further on gas-barrier layer -1 Beyond gas-barrier layer -2, similarly operate, make gas barrier film 103.

(formation of gas-barrier layer -2)

After forming above-mentioned gas barrier layer -1, gas-barrier layer -1 forms gas barrier with following wet coating method Layer -2.

First, as the coating fluid containing polysilazane, prepare Perhydropolysilazane (PHPS：AnamikaNN120-10、 No catalyst type, AZ electronic material (strain) system) 10 mass % dibutyl ethers solution.

On above-mentioned gas barrier layer -1, preparation is coated with by dip-coating in the way of dried average thickness becomes 300nm The coating fluid containing polysilazane, under 85 DEG C of temperature, the atmosphere of humidity 55%RH be dried 1 minute.And then, in temperature 25 DEG C, keep 10 minutes under the atmosphere of humidity 10%RH (- 8 DEG C of dew point temperature), carry out dehumidification treatments and formed containing polysilazane Coated film.Thereafter carry out Excimer light irradiation process under conditions of following, gas-barrier layer -1 is formed as the 2nd gas The gas-barrier layer -2 of the application type of body barrier layer.

It should be noted that the condition that Excimer light irradiation is processed is as described below.

Illumination wavelength：172nm

Gas enclosed by lamp：Xe

Excimer lamp light intensity：130mW/cm²(172nm)

Sample and the distance of light source：1mm

Film heating-up temperature：70℃

Oxygen concentration in irradiation unit：1.0%

Excimer lamp irradiation time：5 seconds

《The making of gas barrier film 104》

In the making of above-mentioned gas barrier film 101, when forming transparent hard-coating layer -1,0.5 μ is become with dry layer thickness The mode of m is coated with transparent hard-coating layer formation coating fluid, in addition, similarly operates, and has made gas barrier film 104.

《The making of gas barrier film 105》

In the making of above-mentioned gas barrier film 104, on gas-barrier layer -1, with above-mentioned gas barrier film 103 Making similarly operate, arrange gas-barrier layer -2, in addition, similarly operate, made gas barrier film 105.

《The making of gas barrier film 106,107》

In the making of above-mentioned gas barrier film 103, when forming transparent hard-coating layer -1, respectively become with dry layer thickness 0.3 μm, 1.0 μm of mode be coated with transparent hard-coating layer formation coating fluid, in addition, similarly operate, made gas resistance Every property film 106,107.

《The making of gas barrier film 108》

In the making of above-mentioned gas barrier film 101, when forming transparent hard-coating layer -1,2.0 μ are become with dry layer thickness The mode of m is coated with transparent hard-coating layer formation coating fluid, in addition, similarly operates, and has made gas barrier film 108.

《The making of gas barrier film 109》

In the making of above-mentioned gas barrier film 108, on gas-barrier layer -1, with above-mentioned gas barrier film 103 Making similarly operate, arrange gas-barrier layer -2, in addition, similarly operate, made gas barrier film 109.

《The making of gas barrier film 110》

In the making of above-mentioned gas barrier film 101, setting transparent hard-coating layer -1 after, film base material another Further transparent hard-coating layer -2 are set as described below on face, in addition, similarly operate, make gas barrier film 110.

It should be noted that gas-barrier layer -1 is arranged on transparent hard-coating layer -2.

(formation of transparent hard-coating layer -2)

After setting transparent hard-coating layer -1, protection laminate member -1 is peeled off from film base material, transparent hard-coating layer -1 pastes Close the protection laminate member -2 (50 μm of thickness, width 1250mm) of PET.Then, with the size of the width of film base material and The mode that the size of the width of protection laminate member -2 becomes identical (width 1230mm) cuts the width of laminated body End.

On the face of the laminating matcoveredn splenium part -1 of film base material, it is coated with the way of becoming 0.7 μm of dried film thickness and uses Formed in the transparent hard-coating layer that the transparent hard-coating layer formation coating fluid of the formation of above-mentioned transparent hard-coating layer -1 is prepared as and use Coating fluid is simultaneously dried.Thus, form transparent hard-coating layer -2 and (in table 1, be set to " method A ".).

《The making of gas barrier film 111》

In the making of above-mentioned gas barrier film 110, change the forming method of transparent hard-coating layer -2 as described below, remove Outside this, similarly operate, made gas barrier film 111.

That is, after setting transparent hard-coating layer -1, protection laminate member -1 is not peeled off from film base material, and in transparent hard painting The protection laminate member -2 (50 μm of thickness, width 1250mm) of laminating PET on layer -1.Then, with the width of film base material Size and the size of width of protection laminate member -2 become the mode of identical (width 1230mm) and cut laminated body Width end simultaneously winds.

Protection laminate member -1 is peeled off from film base material, on the face being fitted with this protection laminate member -1, to become dry The mode that 0.7 μm of thickness is coated with the same manner as the transparent hard-coating layer formation coating fluid of the formation for above-mentioned transparent hard-coating layer -1 The transparent hard-coating layer formation coating fluid of preparation is simultaneously dried.It is consequently formed transparent hard-coating layer -2 and (in table 1, be set to " method B”.).

《The making of gas barrier film 112》

In the making of above-mentioned gas barrier film 101, the thickness of film base material is changed to 100 μm, in addition, equally Ground operation, has made gas barrier film 112.

《The making of gas barrier film 113》

In the making of above-mentioned gas barrier film 101, protection laminate member -1 do not fitted on film base material and carries out The formation of bright hard conating -1, in addition, similarly operates, and has made gas barrier film 113.

《The making of gas barrier film 114》

In the making of above-mentioned gas barrier film 102, protection laminate member -1 do not fitted on film base material and carries out The formation of bright hard conating -1, in addition, similarly operates, and has made gas barrier film 114.

《The evaluation of gas barrier film 101～114》

Each gas barrier film to above-mentioned making, with following viewpoint evaluation as gas barrier film function.

(1) evaluation of the degree of the breakage of gas barrier film

The gas barrier film of making is cut into length 100mm, width 1230mm, at both ends in the width direction to 10mm In the range of, confirm by visual observation to have or not the loss such as chap or fracture.Confirm result according to following benchmark evaluations.

3：Do not see chap on the whole in the width of film base material and rupture, it is possible to use.

2：It can be seen that chapping or rupturing in a part in the range of from the both ends of film base material to 10mm.

1：It can be seen that chapping or rupturing in major part in the range of from the both ends of film base material to 10mm.

(2) it is equipped on the evaluation that the generation of skin dark stain during organic EL element has or not

First, the gas barrier film 101～114 of use, makes organic EL element as described below.

(making of organic EL element)

Remove protection laminate member -1 or protection laminate member -2 from each gas barrier film 101～114, from away from width side It is cut into the size specified to the region of end 20mm.This gas barrier film is fixed on the base material of commercially available vacuum deposition apparatus On support, o.10 following compound Ns are put on the resistance heating plate of tungsten, these substrate holders and resistance heating plate are installed In the 1st vacuum tank of vacuum deposition apparatus.In addition, silver-colored (Ag) is put on the resistance heating plate of tungsten, and it is installed on vacuum In 2nd vacuum tank of evaporation coating device.

1st vacuum tank of vacuum deposition apparatus is decompressed to 4 × 10^-4After Pa, to being placed with compound N heating o.10 Plate is energized and is heated, and arranges the basal layer of the 1st electrode with thickness 10nm with evaporation rate 0.1～0.2nm/ second.Will The gas barrier film being formed with basal layer moves to the 2nd vacuum tank in the state of vacuum, and the 2nd vacuum tank is decompressed to 4 × 10^{- 4}After Pa, the heating plate being placed with silver is energized and is heated.Thus, formed with evaporation rate 0.1～0.2nm/ second The 1st electrode being made up of the silver of thickness 8nm.

Then, it is decompressed to vacuum 1 × 10 using commercially available vacuum deposition apparatus^-4After Pa, make barrier properties for gases Film moves, and is deposited with following compound HT-1, the sky of setting 20nm with the evaporation rate 0.1nm/ second on the 1st electrode being formed Cave transfer layer (HTL).

Then, using following compound A-3 (blue-light-emitting dopant), following compound A-1 (green emitting dopant), Following compound A-2 (emitting red light dopant) and following compound H-1 (main compound), form the common evaporation of thickness 70nm Luminescent layer so that compound A-3 in the way of the inclined concentration that containing ratio becomes 35%～5% with respect to thickness direction with linear Evaporation rate is made to change, compound A-1 and compound A-2 does not rely on thickness, to respectively become the finite concentration of 0.2 mass % Mode, so that evaporation rate is changed with the evaporation rate 0.0002nm/ second, compound H-1 becomes with containing ratio in thickness direction The mode of 64.6%～94.6% inclined concentration makes evaporation rate change.

Thereafter, following compound ET-1 are deposited with luminescent layer, form the electron supplying layer of thickness 30nm, enter one Walk electron injecting layer potassium fluoride (KF) being deposited with and being formed thickness 2nm.And, aluminum is deposited with and is formed thickness 2nd electrode of 110nm.

It should be noted that for above-mentioned each organic function layer formation compound N o.10, compound HT-1, chemical combination Thing A-1～3, compound H-1 and compound ET-1 are compound shown below.

[chemical formula 1]

Then, use the aluminium foil of 25 μm of thickness as seal member, use following seal member in the one side of this aluminium foil：With 20 μm of thickness is fitted with the lamellar bonding agent (epoxylite) of thermohardening type as sealing resin layer, is overlapped in the 2nd electrode On the resin base material making.Now, make seal member bonding agent formed face and element organic functionses aspect continuously overlapping, And so that the end of the wiring lead of the 1st electrode and the 2nd electrode is exposed in outside.

Then, the sample containing gas barrier film is configured in decompressor, in the reduced pressure of 90 DEG C, 0.1MPa Under, keep 5 minutes in the state of pressure is applied to overlapping sample and seal member.Then, make containing gas barrier film Sample return to atmospheric pressure environment, further at 120 DEG C heating 30 minutes and make bonding agent solidify.

Above-mentioned sealing process is carried out with following condition, under atmospheric pressure, under the nitrogen atmosphere of below moisture content 1ppm, according to JIS B 9920, the cleannes of mensure are grade 100, and dew point temperature is less than -80 DEG C, the air of below oxygen concentration 0.8ppm Pressure.

By above operation, make organic EL element.It should be noted that the area of light-emitting zone become 5cm × 5cm.

(evaluation of each organic EL element)

1mA/cm is applied to the organic EL element making²Electric current make its light.Then, after just applying, 50 DEG C, As fluorescent lifetime in the environment of 80%RH, to the luminance after 300 hours and 500 hours continuous luminous, with 100 times Optical microscope (M Co., Ltd. ORITEX manufacture MS-804, lens MP-ZE25-200) amplify one of organic EL element Divide and shot.Then, shooting image is cut into 2mm square, each image viewing is had or not with skin dark stain and produces.Asked by observed result Go out the generation area ratio that skin dark stain is with respect to light-emitting area, according to following benchmark evaluation skin dark stain patience.

5：Even if not seeing the generation of skin dark stain in the sample after luminous at 500 hours completely yet.

4：Even if in the sample after luminous at 300 hours, also do not see the generation of skin dark stain completely, but luminous at 500 hours Somewhat it can be seen that the generation (produce area 0.1% less than 3.0%) of skin dark stain in sample afterwards

3：At 300 hours luminous after sample in somewhat it can be seen that skin dark stain generation (produce area 0.1% less than 3.0%)

2：At 300 hours luminous after sample in it can be seen that the generation of obvious skin dark stain (produces area more than 3.0% and low In 6.0%)

1：The generation (producing area more than 6.0%) of many skin dark stains is can be seen that at 300 hours in sample after lighting

Result described in table 1 shows：By the gas barrier film of method manufacture specified in the present invention with compare The gas barrier film of example is compared, and can suppress damaged generation.In addition learn：By possessing with this in organic EL element The gas barrier film that method manufactures, suppresses to the generation skin dark stain causing such as being peeled off by film.

It can thus be stated that manufacturing method according to the invention, it is possible to use containing cyclic olefin polymer or cycloolefin copolymer The film base material of thing suppresses the fracture of this film base material or the generation of chap.

In addition learn：In the case of being provided with the 2nd gas-barrier layer, do not damage the fracture of film base material or the product of chap yet Raw inhibition.

In addition learn：When the thickness of transparent hard-coating layer is 0.5～1.0 μm, carrying organic EL unit of gas barrier film During part, the generation of suppression skin dark stain.This is considered because by being set in the range of this thickness of transparent hard-coating layer, can enter one Step improves the intensity of film base material.

In addition learn：It is also possible to suppress film base material in the case of the two sides that transparent hard-coating layer is arranged at film base material Fracture or the generation chapped.In addition learn：In the case of being somebody's turn to do, to laminated body such as film base materials after the transparent hard-coating layer of ground floor is formed The time being cut both can be to arrange the moment of protection laminate members or only in film base in two surface sides of film base material The moment of the one side side setting protection laminate member of material.

Industrial practicality

As described above, the present invention is adapted to provide for using the film base material containing cyclic olefin polymer or cyclic olefine copolymer right The manufacture method of the gas barrier film that the generation of the fracture of this film base material or chap is suppressed, by manufactured by the method Gas barrier film, the electronic device possessing this gas barrier film and its manufacture method.

Claims (7)

1. a kind of manufacture method of gas barrier film, wherein, described gas barrier film includes：Containing cyclic olefin polymer or The film base material of cyclic olefine copolymer and be set in turn in the transparent hard-coating layer on described film base material and gas-barrier layer,

The manufacture method of described gas barrier film includes following operation：

Before arranging described transparent hard-coating layer, in described film base material contrary with the surface being provided with described transparent hard-coating layer one On the surface of side, the operation of setting protection laminate member；

The end of the width of the laminated body comprising described film base material and described protection laminate member is cut, and makes institute State the size of width of film base material and the width of described protection laminate member equivalently-sized operation.

2. the manufacture method of gas barrier film as claimed in claim 1, wherein,

In the range of the thickness of described transparent hard-coating layer is 0.5～1 μm.

3. the manufacture method of gas barrier film as claimed in claim 1 or 2, wherein,

In the range of the thickness of described film base material is 30～100 μm.

4. the manufacture method of the gas barrier film as any one of claims 1 to 3, it also includes existing by rubbing method The operation of the 2nd gas-barrier layer is arranged on described gas-barrier layer.

5. a kind of gas barrier film, it is the manufacturer by the gas barrier film any one of Claims 1 to 4 Method manufactures.

6. a kind of manufacture method of electronic device, wherein, described electronic device has gas barrier film, described barrier properties for gases Film includes：Film base material containing cyclic olefin polymer or cyclic olefine copolymer and be set in turn in saturating on described film base material Bright hard conating and gas-barrier layer,

The manufacture method of described electronic device includes following operation：

Before arranging described transparent hard-coating layer, in described film base material contrary with the surface being provided with described transparent hard-coating layer one On the surface of side, the operation of setting protection laminate member；

The end of the width of the laminated body comprising described film base material and described protection laminate member is cut, and makes institute State the size of width of film base material and the width of described protection laminate member equivalently-sized operation；

The operation that described protection laminate member is peeled off from described film base material and removed；

Described film base material is arranged at the operation of electronic component.

7. a kind of electronic device, it is to be manufactured by the manufacture method of the electronic device described in claim 6.