WO2019230280A1

WO2019230280A1 - Gas barrier film and method for producing gas barrier film

Info

Publication number: WO2019230280A1
Application number: PCT/JP2019/017426
Authority: WO
Inventors: 美帆宮▲崎▼; 昇太広沢
Original assignee: コニカミノルタ株式会社
Priority date: 2018-05-31
Filing date: 2019-04-24
Publication date: 2019-12-05
Also published as: JP7173138B2; JPWO2019230280A1

Abstract

The present invention provides a method for producing a gas barrier film, which is capable of suppressing decrease in adhesion between a base material film and a gas barrier layer, and which is also capable of suppressing decrease in the gas barrier properties. According to the present invention, a gas barrier film is produced by a step wherein a gas barrier layer is formed on a base material film by a vapor-phase film formation method, said base material film containing a resin, organic fine particles and a halogenated hydrocarbon that serves as an organic solvent. The content of the halogenated hydrocarbon in the base material film before the formation of the gas barrier layer is from 10 ppm to 1,000 ppm (inclusive).

Description

Gas barrier film and method for producing gas barrier film

The present invention relates to a gas barrier film and a method for producing the gas barrier film.

Conventionally, gas barrier films in which a gas barrier layer is formed on a base film are known. In this gas barrier film, a resin film is used as a base film, and the flexibility of the gas barrier film can be imparted by setting the thickness of the base film to 50 μm or less.

As a base film of a gas barrier film, a resin film containing a resin, an organic solvent, and fine particles formed using a solution casting method is known (for example, see Patent Document 1 and Patent Document 2). This resin film includes inorganic fine particles and organic fine particles as a matting agent. Moreover, the halogenated hydrocarbon solvent is used as the organic solvent of the base film using the solution casting method.

JP 2006-264118 A JP 2007-76207 A

However, in a base film containing an organic solvent and fine particles, the fine particles intervening between the base film and the gas barrier layer are likely to fall off, and the adhesion between the base film and the gas barrier layer is likely to deteriorate. Furthermore, the fine particles intervening between the base film and the gas barrier layer tend to cause cracks and defects in the gas barrier layer, and the gas barrier property of the gas barrier film is likely to be lowered.

In order to solve the above-described problems, in the present invention, a gas barrier film capable of suppressing a decrease in adhesion between the base film and the gas barrier layer and a decrease in gas barrier property, and a method for producing the gas barrier film are provided. provide.

The method for producing a gas barrier film of the present invention includes a step of forming a gas barrier layer by a vapor deposition method on a substrate film containing a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent. And content of the halogenated hydrocarbon in the base film before forming a gas barrier layer is 10 ppm or more and 1000 ppm or less.

The gas barrier film of the present invention includes a base film and a gas barrier layer formed on the base film. And a base film contains halogenated hydrocarbon as resin, organic particulates, and an organic solvent, and content of halogenated hydrocarbon in a base film is 1 ppm or more and 90 ppm or less.

According to the present invention, it is possible to provide a gas barrier film capable of suppressing a decrease in adhesion between the base film and the gas barrier layer and a decrease in gas barrier property, and a method for producing the gas barrier film.

It is a figure which shows schematic structure of a gas barrier film. It is a schematic diagram of a vacuum plasma CVD apparatus. It is a schematic diagram which shows an example of the discharge plasma CVD apparatus between rollers. It is a schematic diagram of a roll-to-roll type sputtering apparatus.

Hereinafter, although the example of the form for implementing this invention is demonstrated, this invention is not limited to the following examples.
The description will be given in the following order.
1. 1. Gas barrier film Method for producing gas barrier film

<1. Gas barrier film>
Hereinafter, specific embodiments of the gas barrier film of the present invention will be described.
In FIG. 1, schematic structure of a gas barrier film is shown. A gas barrier film 10 shown in FIG. 1 includes a base film 11 and a gas barrier layer 12.

[Base film]
The base film 11 includes a resin 13 serving as a base and organic fine particles 14. Furthermore, the base film 11 contains a halogenated hydrocarbon as an organic solvent, and the content (mass) of the halogenated hydrocarbon is 1 ppm or more and 90 ppm or less with respect to the total mass of the base film 11. The base film 11 is preferably a resin film manufactured by a so-called solution casting method, in which a dope in which a resin, an additive, or the like is dissolved or dispersed in a solvent is cast on a casting support. .

The base film 11 used for the gas barrier film 10 is not particularly limited in material, thickness and the like as long as it can hold the gas barrier layer 12 and can be appropriately selected according to the purpose of use. As the base film 11, a conventionally known resin film can be used. The base film 11 may be formed from a plurality of materials. Examples of the base film 11 include resin films described in paragraphs [0124] to [0136] of JP2013-226758A, paragraphs [0044] to [0047] of WO2013 / 002026, and the like. Can do.

The base film 11 may be a single resin film or a plurality of resin films, or may be formed of a plurality of layers. Although the base film 11 is not limited to a single wafer shape and a roll shape, the roll shape which can respond | correspond to a roll to roll system from a viewpoint of productivity is preferable. The thickness of the base film 11 is not particularly limited, but is preferably 5 to 100 μm, more preferably 5 to 40 μm.

[resin]
Although it does not specifically limit as resin 13 which comprises the base film 11, It is preferable to contain a thermoplastic resin. Here, the “thermoplastic resin” is a resin that softens when heated to a glass transition temperature or a melting point. The thermoplastic resin is easy to manufacture and is preferably optically transparent. Transparent means that the total light transmittance of visible light is 60% or more. The substrate film 11 preferably has a total light transmittance of visible light of 80% or more, and more preferably 90% or more.

Specific examples of the resin 13 constituting the base film 11 include cellulose acylate resins such as cellulose (di, tri) acetate, cellulose acetate propionate, and cellulose acetate butyrate, and acrylic resins such as polymethyl methacrylate. Resins, Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene terephthalate, polyphenylene sulfide, polyphenylene oxide, polycaprolactone, polycarbonate resins, norbornene resins, monocyclic cyclic olefin resins, cyclic conjugated diene systems Resins, vinyl alicyclic hydrocarbon resins, cyclic polyolefin resins such as hydrides thereof, polyarylate resins, polysulfones (polyethers) (Including Lufone) resin, polyethylene, polypropylene, ABS resin, polylactic acid, cellophane, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene resin, polymethylpentene, polyether ketone, polyether ketone imide, Examples thereof include polyamide resins such as nylon, fluorine resins, polyarylate, thermoplastic elastomers, and silicones. Among these, norbornene resins, cellulose acylate resins (hereinafter also referred to as cellulose acylates), acrylic resins (hereinafter also referred to as acrylic resins), or mixed resins thereof can be given.

(Norbornene resin)
The resin 13 constituting the base film 11 preferably includes a norbornene resin. In particular, a norbornene-based resin having a polar group is preferably included. The norbornene resin is not particularly limited as long as it has a structural unit derived from norbornene. Even if it is a norbornene homopolymer, it is a copolymer of norbornene and another monomer (a monomer that can be polymerized with norbornene). There may be. In particular, a norbornene homopolymer is preferable. In the base film 11, the norbornene-based resin can be used alone or in combination of two or more.

Examples of the monomer constituting the norbornene resin film include norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, and 5-methoxy. Carbonyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5 -Methyl-2-norbornene and the like.

Further, the norbornene resin constituting the base film 11 is a homopolymer or copolymer of a monomer represented by the following general formula (A-1) or the following general formula (A-2). It is preferable.

In general formula (A-1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or Represents a polar group. However, except for the case where all of R ¹ to R ⁴ are hydrogen atoms, the structure in which R ¹ and R ² are simultaneously hydrogen atoms and the structure in which R ³ and R ⁴ are simultaneously hydrogen atoms are excluded. p represents an integer of 0 to 2.

In the monomer represented by the general formula (A-1), at least one of R ¹ to R ⁴ is a polar group from the viewpoint of ensuring solubility during solution film formation of a norbornene resin. Is preferred. Further, from the viewpoint of improving the heat resistance of the base film 11, p is preferably 1 to 2. When p is from 1 to 2, the resulting resin becomes bulky and the glass transition temperature tends to be improved.

In the monomer represented by the general formula (A-1), the halogen atom represented by R ¹ to R ⁴ is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms. Examples of polar groups represented by R ¹ to R ⁴ include a carboxy group, a hydroxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, a cyano group, and these groups such as a methylene group. Examples include a hydrocarbon group in which a divalent organic group having polarity such as a group bonded through a linking group, a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group. It is done. R ¹ to R ⁴ are preferably a carboxy group, a hydroxy group, an alkoxycarbonyl group or an allyloxycarbonyl group. In particular, R ¹ to R ⁴ are preferably an alkoxycarbonyl group or an allyloxycarbonyl group from the viewpoint of ensuring solubility during solution film formation of a norbornene resin.

In general formula (A-2), R ⁵ represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. R ⁶ represents a polar group or a halogen atom. p represents an integer of 0 to 2.

In the monomer represented by the general formula (A-2), R ⁵ is preferably a hydrocarbon group having 1 to 3 carbon atoms. R ⁶ is preferably a polar group. The polar group represented by R ⁶ is preferably a carboxy group, a hydroxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, or a cyano group, and a hydroxy group, an alkoxycarbonyl group, or allyloxy. A carbonyl group is more preferable. In particular, R ⁶ is preferably an alkoxycarbonyl group or an allyloxycarbonyl group from the viewpoint of ensuring solubility during solution film formation of a norbornene-based resin.
The halogen atom represented by R ⁶ is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
The norbornene resin constituting the base film 11 contains a homopolymer or copolymer of the monomer represented by the general formula (A-2), thereby lowering the molecular symmetry and evaporating the solvent. It is easy to promote the diffusion movement of the molecules.

Specific examples (1 to 34) of the monomers represented by the general formula (A-1) and the general formula (A-2) are shown below.

Examples of the copolymerizable monomer copolymerizable with the monomer represented by the general formula (A-1) or (A-2) include those represented by the general formula (A-1) or the general formula (A-2). And a copolymerizable monomer capable of ring-opening copolymerization with the monomer represented, and a copolymerizable monomer capable of addition copolymerization with the monomer represented by formula (A-1) or (A-2). It is done.

Examples of the copolymerizable monomer capable of ring-opening copolymerization with the monomer represented by the general formula (A-1) or (A-2) include monomers such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. Can be mentioned.
Examples of the copolymerizable monomer that can be addition copolymerized with the monomer represented by formula (A-1) or (A-2) include unsaturated double bond-containing compounds, vinyl-based cyclic hydrocarbon compounds, (Meth) acrylate is mentioned.

Examples of the unsaturated double bond-containing compound include olefin compounds having 2 to 12 carbon atoms. The olefinic compound preferably has 2 to 8 carbon atoms. Examples of these olefinic compounds include ethylene, propylene, and butene.
Examples of the vinyl-based cyclic hydrocarbon compound include vinylcyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene. Examples of (meth) acrylates include alkyl (meth) acrylates having 1 to 20 carbon atoms such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate.

In the polymer constituting the norbornene resin, the content of the structural unit derived from the monomer represented by the general formula (A-1) or the general formula (A-2) is the structural unit constituting the norbornene resin. It is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and particularly preferably 70 to 100 mol%, based on the total of the above.

Examples of the norbornene-based resin include homopolymers or copolymers of the monomer represented by the general formula (A-1) or (A-2). For example, the following (1) to (7) ). As these polymers, the polymers (1) to (3) and the polymer (5) are preferable, and the polymer (3) and the polymer (5) are more preferable.

(1) Ring-opening polymer of monomer represented by general formula (A-1) or general formula (A-2) (2) General formula (A-1) or general formula (A-2) (3) Hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) (4) (1) ) Or (2) ring-opened (co) polymer cyclized by Friedel-Craft reaction and then hydrogenated (co) polymer (5) General formula (A-1) or general formula (A-2) (6) Copolymer of monomer represented by unsaturated double bond and compound containing unsaturated double bond (6) Addition type (co) of monomer represented by general formula (A-1) or general formula (A-2) Polymer and hydrogenated (co) polymer thereof (7) Monomer and methacrylate or acrylic represented by general formula (A-1) or general formula (A-2) Alternating copolymer of the over door

Further, the norbornene resin constituting the base film 11 is a homopolymer or copolymer of a monomer represented by the following general formula (B-1) or general formula (B-2). Is preferred. The norbornene-based resin constituting the base film 11 is a polymer containing a structural unit represented by the general formula (B-2) from the viewpoint of easily obtaining a resin film having a high glass transition temperature and a high transmittance. Alternatively, a copolymer having a structural unit represented by the general formula (B-1) and a structural unit represented by the general formula (B-2) is preferable.

X in the general formula (B-1) is a group represented by —CH═CH— or a group represented by —CH ₂ CH ₂ —. R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group. However, except for the case where all of R ¹ to R ⁴ are hydrogen atoms, the structure in which R ¹ and R ² are simultaneously hydrogen atoms and the structure in which R ³ and R ⁴ are simultaneously hydrogen atoms are excluded. p represents an integer of 0 to 2.

In the monomer represented by the general formula (B-1), at least one of R ¹ to R ⁴ is a polar group from the viewpoint of ensuring solubility during solution film formation of a norbornene resin. Is preferred. Further, from the viewpoint of improving the heat resistance of the base film 11, p is preferably 1 to 2. When p is from 1 to 2, the resulting resin becomes bulky and the glass transition temperature tends to be improved.
Examples of the halogen atom represented by R ¹ to R ⁴ , the hydrocarbon group having 1 to 30 carbon atoms, and the polar group in the monomer represented by the general formula (B-1) include: Examples thereof are the same as R ¹ to R ^{4 in} (A-1).

X in the general formula (B-2) is a group represented by —CH═CH— or a group represented by —CH ₂ CH ₂ —. R ⁵ represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. R ⁶ represents a polar group or a halogen atom. p represents an integer of 0 to 2.

In the general formula (B-2), R ⁵ is preferably a hydrocarbon group having 1 to 3 carbon atoms. Examples of the polar group represented by R ⁶ and the halogen atom include the same groups as those in the general formula (A-2).

The intrinsic viscosity [eta] inh of norbornene-based resin, for example, preferably 0.2 ~ ^5cm 3 / g, more preferably 0.3 ~ ^{3cm 3} / g, particularly preferably 0.4 ~ 1.5cm ³ / g .
The number average molecular weight (Mn) of the norbornene resin is, for example, preferably 8000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 12,000 to 50,000.
The weight average molecular weight (Mw) of the norbornene resin is preferably, for example, 20000 to 300000, more preferably 30000 to 250,000, and particularly preferably 40000 to 200000.

The norbornene-based resin has heat resistance, water resistance, chemical resistance, mechanical properties, and film formability when the intrinsic viscosity [η] inh, number average molecular weight, and weight average molecular weight are in the above ranges. Becomes better. The intrinsic viscosity [η] inh of the norbornene resin can be measured by gel permeation chromatography (GPC). The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the norbornene-based resin can be measured in terms of polystyrene by gel permeation chromatography (GPC).

The glass transition temperature (Tg) of the norbornene resin is preferably 110 ° C. or higher. The glass transition temperature (Tg) of the norbornene resin is preferably 110 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 220 ° C. If Tg is 120 degreeC or more, the deformation | transformation at the time of secondary processing, such as coating and printing, when used under high temperature conditions can be suppressed. On the other hand, if Tg is 350 ° C. or lower, it is possible to suppress difficulty in molding due to an increase in the softening temperature of the resin.

Also, as the norbornene resin, a commercially available product can be used. Examples of commercially available norbornene-based resins include Arton (registered trademark) G, Arton F, Arton R, and Arton RX manufactured by JSR.

[Organic fine particles]
The organic fine particles 14 are mainly used for improving the slipperiness of the surface of the base film 11. The organic fine particles 14 constituting the base film 11 are not particularly limited. The organic fine particles 14 preferably have a high affinity with the resin 13 and the organic solvent constituting the base film 11. The higher the affinity with the resin 13 and the organic solvent, the more the organic fine particles 14 can be prevented from falling off the base film 11.

Further, since the organic fine particles 14 are higher in flexibility than the inorganic fine particles, the organic fine particles 14 can easily follow the stretching of the base film 11. Even when the film-like material for producing the base film 11 is stretched, the stretching tension applied to the periphery of the organic fine particles can be isotropically dispersed. For this reason, falling off of the organic fine particles 14 from the base film 11 can be suppressed. By suppressing the falling off of the organic fine particles 14, it is possible to suppress a decrease in adhesion between the base film 11 and the gas barrier layer 12. Furthermore, in the process of forming the gas barrier layer 12, etc., contamination of the device due to particle dropping can be suppressed.

Examples of the organic fine particles 14 include (meth) acrylic acid esters, itaconic acid diesters, maleic acid diesters, vinyl esters, olefins, styrenes, (meth) acrylamides, allyl compounds, vinyl ethers, and vinyl ketones. Polymers containing structural units derived from at least one selected from the group consisting of vinyl heterocyclic compounds, unsaturated nitriles, unsaturated monomers, and unsaturated carboxylic acids, silicone resins, fluorine resins, polyphenylene sulfide Etc. In addition, (meth) acryl means acryl or methacryl. Hereinafter, the particles made of the above polymer are referred to as polymer particles.

(Meth) acrylic acid esters constituting the polymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and ethylene glycol di (meth) acrylate. , Trimethylolpropane tri (meth) acrylate and the like. Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dipropyl itaconate. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dipropyl maleate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like. . Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene. Styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, trifluoromethyl styrene, vinyl benzoic acid. Examples include methyl ester and divinylbenzene. (Meth) acrylamides include (meth) acrylamide, methyl (meth) acrylamide, ethyl (meth) acrylamide, propyl (meth) acrylamide, butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and phenyl (meth) acrylamide. , Dimethyl (meth) acrylamide, methylenebisacrylamide and the like. Examples of allyl compounds include allyl acetate, allyl caproate, allyl laurate, and allyl benzoate. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like. Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone and the like. Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone and the like. Examples of unsaturated nitriles include acrylonitrile and methacrylonitrile. Examples of the unsaturated carboxylic acids include (meth) acrylic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester and the like.

Organic fine particles 14 are composed of (meth) acrylic acid esters because they have high affinity with norbornene-based resins, are flexible to stress, are less likely to generate anisotropic voids, and are easy to improve adhesion to the gas barrier layer 12. It is preferable to include a polymer containing a structural unit derived from one or more selected from vinyl esters, styrenes and olefins. Furthermore, the organic fine particle 14 includes a polymer containing a structural unit derived from (meth) acrylic acid esters, a polymer containing a structural unit derived from styrenes, a structural unit derived from (meth) acrylic acid esters and styrene. More preferably, it is a copolymer containing a structural unit derived from a class. In particular, the organic fine particles 14 are preferably a copolymer including a structural unit derived from (meth) acrylic acid esters and a structural unit derived from styrene.

The organic fine particles 14 may be particles (core-shell particles) having a core-shell structure including a core layer (inner particle core) and a shell layer (particle outer shell). Examples of such organic fine particles 14 include core-shell particles having a low Tg core layer containing a (meth) acrylic acid ester homopolymer or copolymer and a high Tg shell layer.

The polymer particles constituting the organic fine particles 14 can be produced by an arbitrary method. For example, it can be produced by a method such as emulsion polymerization, suspension polymerization, dispersion polymerization or seed polymerization. In particular, since it is easy to obtain particles having a uniform particle diameter, it is preferable to produce the particles by seed polymerization or emulsion polymerization under an aqueous medium.

Examples of the method for producing the organic fine particles 14 include the following polymerization methods (1) to (3). The polymerization method can be appropriately selected according to the average particle diameter of the organic fine particles 14 to be produced. In addition, the monomer for producing seed particles is not particularly limited, and a monomer for producing the above-described organic fine particles 14 can be used.
(1) One-stage polymerization method in which a monomer mixture is dispersed in an aqueous medium for polymerization (2) After the monomer is polymerized in an aqueous medium to obtain seed particles, the monomer mixture is absorbed into the seed particles -Stage polymerization method in which polymerization is performed (3) Multi-stage polymerization method that repeats the process of producing seed particles of the two-stage polymerization method

The absolute value Δn of the refractive index difference between the organic fine particles 14 and the resin 13 is preferably 0.1 or less, and preferably 0.085 or less in order to suppress an increase in haze of the gas barrier film 10 or the base film 11. More preferably, it is 0.065 or less.

The average particle size of the organic fine particles 14 is preferably 0.04 to 2 μm, and more preferably 0.08 to 1 μm. When the average particle diameter of the organic fine particles 14 is 0.04 μm or more, it becomes easy to impart sufficient slipperiness to the gas barrier film 10 and the base film 11. When the average particle diameter of the organic fine particles 14 is 2 μm or less, an increase in haze is easily suppressed.

The average particle diameter of the organic fine particles 14 can be obtained as the average value of the equivalent circle diameters of 100 particles obtained by SEM imaging or TEM imaging of the surface of the substrate film 11 and the section. The equivalent circle diameter can be obtained by converting the projected area of particles obtained by photographing into the diameter of a circle having the same area. SEM imaging or TEM imaging is performed at a magnification of 5000 times. The average particle size of the organic fine particles 14 in the dispersion can be measured with a zeta potential / particle size measurement system (ELSZ-1000Z manufactured by Otsuka Electronics Co., Ltd.). The average particle size of the organic fine particles 14 means the average size (average secondary particle size) of the aggregate if it is agglomerated particles, and the size of one particle if it is non-aggregated particles. Mean measured value.

The content of the organic fine particles 14 is preferably 0.03 to 1.0% by mass, more preferably 0.05 to 0.6% by mass, based on the total mass of the base film 11. More preferably, the content is 0.08 to 0.4% by mass. If the content of the organic fine particles 14 is 0.03% by mass or more, sufficient slipperiness is easily imparted to the base film 11, and an increase in haze can be suppressed if the content is 1.0% by mass or less.

[Organic solvent]
The base film 11 contains 1 ppm to 90 ppm of halogenated hydrocarbon as an organic solvent. Since the base film 11 contains the halogenated hydrocarbon, the affinity between the resin 13 and the organic fine particles 14 is improved, so that the organic fine particles 14 are less likely to drop off from the base film 11. Further, the presence of the halogenated hydrocarbon on the surface of the base film 11 improves the affinity between the base film 11 and the gas barrier layer 12 and improves the adhesion between the base film 11 and the gas barrier layer 12. .

(Halogenated hydrocarbon)
As the halogenated hydrocarbon, it is preferable that the resin 13 constituting the base film 11 has high solubility. Examples of the halogenated hydrocarbon include alkyl fluorides such as fluoromethane, fluoroethane, fluorobenzene, chloromethane, dichloromethane, trichloromethane (chloroform), tetrachloromethane, chloroethane, chloroethene, 1-chloropropane, 2-chloropropane, Alkyl chlorides such as 1-chlorobutane, 1-chloro-2-methylpropane, 2-chlorobutane, 2-chloro-2-methylpropane, chlorobenzene, chlorophenylbenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, Examples thereof include alkyl bromides such as bromomethane, tribromomethane, bromoethane and bromobenzene, and alkyl iodides such as iodomethane, triiodomethane, iodoethane and iodobenzene.
Since the base film 11 has high solubility of the norbornene-based resin, the base film 11 preferably contains alkyl chloride as the halogenated hydrocarbon, and particularly preferably contains methylene chloride.

(Other organic solvents)
The base film 11 may contain an organic solvent other than the halogenated hydrocarbon together with the halogenated hydrocarbon. The other organic solvent preferably contains a non-halogen organic solvent such as methyl acetate, ethyl acetate, acetone, tetrahydrofuran, etc., in which the resin 13 constituting the base film 11, in particular, a norbornene resin is highly soluble.

The base film 11 preferably contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms as another solvent. When the base film 11 contains alcohol, when a resin film is produced using the solution casting method, the film-like material is easily gelled, and the film-like material is easily peeled from the support. Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like. In particular, the base film 11 preferably contains ethanol as the other solvent because the dope has high stability, the boiling point is relatively low, and the drying property is good.

(Measurement method of organic solvent content)
The measurement of the content of the organic solvent and the content of the halogenated hydrocarbon in the base film 11 can be performed using headspace gas chromatography. The measurement of the content of the organic solvent and halogenated hydrocarbon by headspace gas chromatography can be performed under the following conditions.

(Measurement condition)
Headspace device: HP7694 Head Space Sampler (manufactured by Hewlett-Packard Company)
-Temperature conditions: transfer line 200 ° C, loop temperature 200 ° C
-Sample amount: 0.8g / 20ml vial-GC: HP5890 (manufactured by Hewlett-Packard Company)
・ MS: HP5971 (manufactured by Hewlett-Packard Company)
-Column: HP-624 (30m x 0.25mm ID)
Oven temperature: initial temperature 40 ° C. (holding time 3 minutes), temperature rising rate 10 ° C./minute, ultimate temperature 200 ° C. (holding time 5 minutes)

[Physical properties of base film]
(Haze)
The haze of the base film 11 is preferably 4.0% or less, more preferably 2.0% or less, and further preferably 1.0% or less. The haze of the base film 11 should be measured in accordance with JIS K-6714 using a haze meter (HGM-2DP, Suga Test Instruments) under conditions of 25 ° C. and 60% RH for a sample having a size of 40 mm × 80 nm. Can do.

(Phase difference Ro and Rt)
The base film 11 preferably has an in-plane retardation Ro of 20 to 120 nm, more preferably 30 to 100 nm, measured in an environment of a measurement wavelength of 550 nm and 23 ° C. and 55% RH. The thickness direction retardation Rt of the base film 11 is preferably 70 to 350 nm, and more preferably 100 to 320 nm. The phase differences Ro and Rt of the base film 11 can be adjusted mainly by the draw ratio. In order to increase the phase differences Ro and Rt of the base film 11, it is preferable to increase the draw ratio.

Ro and Rt of the base film 11 are respectively defined by the following formulas.
Formula (1): Ro = (nx−ny) × d
Formula (2): Rt = ((nx + ny) / 2−nz) × d
In the formula, nx represents the refractive index in the in-plane slow axis direction (direction in which the refractive index is maximum) of the base film. ny represents the refractive index in the direction orthogonal to the in-plane slow axis of the base film. nz represents the refractive index in the thickness direction of the base film. d represents the thickness (nm) of the base film.

The in-plane slow axis of the substrate film 11 refers to an axis having the maximum refractive index on the film surface. The in-plane slow axis of the substrate film 11 can be confirmed by an automatic birefringence meter Axoscan (Axo Scan Mueller Polarimeter: manufactured by Axometrics).

The measurement of Ro and Rt of the base film 11 can be performed by the following method.
(1) The substrate film is conditioned for 24 hours in an environment of 23 ° C. and 55% RH. The average refractive index of the substrate film is measured with an Abbe refractometer, and the thickness d is measured using a commercially available micrometer.
(2) Retardation Ro and Rt at a measurement wavelength of 550 nm of the substrate film after humidity adjustment are each 23 ° C. and 55% by using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics). Measure under RH environment.

[Gas barrier layer]
The gas barrier film 10 includes a gas barrier layer 12 (hereinafter also referred to as a vapor deposition gas barrier layer) 12 formed on a base film 11 by a vacuum film formation method. The gas barrier layer 12 constituting the gas barrier film 10 has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method in accordance with the above is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferable to have.

(Gas phase gas barrier layer)
The gas barrier layer 12 formed by the vacuum film forming method is not particularly limited as long as it has a barrier property, and a conventionally known configuration can be applied. For example, a layer formed by vapor deposition of a general inorganic compound can be used.

Although it does not specifically limit as an inorganic compound contained in a vapor-phase film-forming gas barrier layer, For example, the oxide, nitride, carbide, oxynitride, and carbide of an inorganic material or a metal material are mentioned. Inorganic compounds include oxides, nitrides, and carbides including one or more inorganic or metal materials selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, and Ta in terms of gas barrier performance. Oxynitrides, oxycarbides, and the like are preferable. In particular, examples of the inorganic compound suitable for the gas-phase film-forming gas barrier layer include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, and aluminum silicate. Can be mentioned. The gas-phase film-forming gas barrier layer containing an inorganic compound may contain an element other than the inorganic compound as a secondary component.

The film thickness of the vapor deposition gas barrier layer is not particularly limited, but is preferably 5 to 1000 nm. Within this range, the gas barrier layer is excellent in high gas barrier performance, bending resistance, and suitability for cutting. Further, the vapor deposition gas barrier layer may be a single layer or may have a structure in which two or more layers are laminated.

Examples of the vacuum film forming method for forming the gas barrier layer 12 include a vacuum deposition method, a sputtering method, an ion plating method, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method. Examples include growth methods.
As the vacuum film-forming method, it is preferable to use chemical vapor deposition (CVD). The chemical vapor deposition method is a method in which a source gas containing a target thin film component is supplied onto a substrate, and the film is deposited by a chemical reaction on the surface of the substrate or in the gas phase. The chemical vapor deposition method includes a method of generating plasma or the like for the purpose of activating a chemical reaction. For example, thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD using plasma as an excitation source Examples thereof include vacuum plasma CVD, which is a method (PECVD method).

[Vacuum plasma CVD method]
As a vacuum film forming method for forming the gas barrier layer 12, it is preferable to use a vacuum plasma CVD method. In the vacuum plasma CVD method, material gas flows into a vacuum vessel equipped with a plasma source, and power is supplied from the power source to the plasma source to generate discharge plasma in the vacuum vessel. The reactive species deposited on the substrate. A gas-phase film-forming gas barrier layer obtained by a vacuum plasma CVD method is preferable because a target compound can be produced by selecting conditions such as a raw material compound, decomposition gas, decomposition temperature, and input power.

As a raw material compound, it is preferable to use a compound containing silicon or a compound containing metal, such as a silicon compound, a titanium compound, and an aluminum compound. For these, a conventionally known compound applied to the vacuum plasma CVD method can be used. For example, examples of known compounds include those described in paragraphs [0028] to [0031] of JP2013-063658A, paragraphs [0078] to [0081] of JP2013 / 047002A, and the like. it can. Preferably, silane, tetramethoxysilane, tetraethoxysilane, hexamethyldisiloxane, etc. are mentioned.
These raw material compounds may be used alone or in combination of two or more.

Decomposition gases for decomposing the raw material gas to obtain inorganic compounds include hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide gas, nitrogen oxide gas, Nitrogen gas, oxygen gas, water vapor, etc. are mentioned. Further, the decomposition gas may be used by mixing with an inert gas such as argon gas or helium gas. A desired vapor deposition gas barrier layer can be obtained by appropriately selecting a source gas containing a raw material compound and a decomposition gas.

[Vacuum plasma CVD equipment]
Hereinafter, the vacuum plasma CVD method will be specifically described. FIG. 2 shows an example of a schematic diagram of a vacuum plasma CVD apparatus applied to the vacuum plasma CVD method.

The vacuum plasma CVD apparatus 40 shown in FIG. 2 has a vacuum chamber 42, and a susceptor 44 is disposed on the bottom surface inside the vacuum chamber 42. An anode electrode 41 is disposed on the susceptor 44. A cathode electrode 43 is disposed on the ceiling side inside the vacuum chamber 42 at a position facing the susceptor 44. A heat medium circulation system 46, a vacuum exhaust system 47, a gas introduction system 48, and a high-frequency power source 49 are disposed outside the vacuum chamber 42. A heat medium is disposed in the heat medium circulation system 46. The heat medium circulation system 46 includes a pump that moves the heat medium, a heating device that heats the heat medium, a cooling device that cools the heat medium, a temperature sensor that measures the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 45 having a storage device for storing the information is provided.

The heating / cooling device 45 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 44. Details of the vacuum plasma CVD apparatus 40 shown in FIG. 2 can be referred to paragraphs [0080] to [0098] of International Publication No. 2012/090644.

[Vacuum plasma CVD method: roll-to-roll]
Next, as another form of the vacuum plasma CVD apparatus, a gas barrier layer deposition method by a roll-to-roll method will be described. The gas barrier layer formed by the roll-to-roll method contains carbon atoms, silicon atoms, and oxygen atoms, the composition continuously changes in the layer thickness direction, and satisfies the following requirements (1) and (2) simultaneously. Is preferred.

(1) In the gas barrier layer, among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy, the distance from the gas barrier layer surface in the layer thickness direction of the gas barrier layer, silicon atoms, The carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount of oxygen atoms and carbon atoms (100 at%) (carbon atom ratio (at%)) has an extreme value, and the carbon atoms of the carbon distribution curve The difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the ratio is 3 at% or more.

(2) In the region of 90% or more of the total thickness of the gas barrier layer, the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms is the following formula (A) or (B) It has the relationship represented by.
Formula (A): (carbon average atomic ratio) <(silicon average atomic ratio) <(oxygen average atomic ratio)
Formula (B): (oxygen average atomic ratio) <(silicon average atomic ratio) <(carbon average atomic ratio)

Note that the measurement accuracy in the interface region between the gas barrier layer and the base material is slightly reduced due to noise of constituent atoms of the base material. Therefore, in the requirement (2), the total thickness of the gas barrier layer is 90 to 95. It is preferable to satisfy the relationship defined by the above formula (A) or formula (B) in a region within the range of%. Here, at least 90% or more of the film thickness of the gas barrier layer does not have to be a continuous part in the gas barrier layer, but is simply the above formula (A) or formula (B) in a part of 90% or more in the gas barrier layer. It only has to satisfy the relationship specified in.

(Measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy)
The average value of the carbon atom content ratio in the gas barrier layer can be determined by the following XPS depth profile measurement.

The silicon distribution curve, oxygen distribution curve, silicon distribution curve, etc. in the thickness direction of the gas barrier layer are measured by X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon. In combination, it can be created by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve having the horizontal axis as the etching time, the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer. For this reason, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed when measuring the XPS depth profile is adopted as the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”. can do. Moreover, it is preferable to set it as the following measurement conditions as a sputtering method employ | adopted in such XPS depth profile measurement.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval

It is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous, specifically, the distance from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer (x, unit: nm) calculated from the etching rate and the etching time. ) And the atomic ratio of carbon (C, unit: at%), the condition represented by [(dC / dx) ≦ 0.5] is satisfied.

(Carbon atom profile in gas barrier layer)
The gas barrier layer contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements. The composition continuously changes in the layer thickness direction, and the carbon distribution curve satisfies the requirement (1) among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy. In addition, it is preferable that the carbon atom ratio has a configuration in which the concentration gradient continuously changes in a specific region of the gas barrier layer from the viewpoint of achieving both gas barrier properties and flexibility.

In the gas barrier layer having such a carbon atom profile, it is more preferable that the carbon distribution curve in the layer has at least one extreme value. Furthermore, it is more preferred that the carbon distribution curve has at least two extreme values, and particularly preferred that it has at least three extreme values. When the carbon distribution curve has an extreme value, sufficient gas barrier properties can be ensured even when a film having a gas barrier layer is bent. When the carbon distribution curve has at least two or three extreme values, the absolute value of the difference in the thickness direction distance between one extreme value and another extreme value adjacent thereto is 200 nm or less. Is more preferable, 100 nm or less is more preferable, and 75 nm or less is particularly preferable.

The extreme value of the above distribution curve is the maximum or minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer. The maximum value is an inflection point at which the value of the atomic ratio of the element changes from increase to decrease when the distance from the surface of the gas barrier layer is changed, and 4 points in the thickness direction from the position of the inflection point. It means that the atomic ratio value of the element at a position changed by ˜20 nm decreases by 3 at% or more. The minimum value is an inflection point at which the atomic ratio value of the element changes from decrease to increase when the distance from the surface of the gas barrier layer is changed, and the thickness direction from the position of the inflection point In other words, the atomic ratio value of the element at the position changed by 4 to 20 nm is increased by 3 at% or more. That is, the maximum value and the minimum value are points where the atomic ratio value of the element decreases or increases by 3 at% or more in any range when the position in the thickness direction is changed in the range of 4 to 20 nm.

(Each atomic profile in the gas barrier layer)
The gas barrier layer is characterized by containing carbon atoms, silicon atoms and oxygen atoms as constituent elements. Preferred embodiments of the ratio of each atom and the maximum and minimum values of the ratio of each atom will be described below. To do.

(Relationship between maximum and minimum carbon atom ratio)
In the gas barrier layer, the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio in the carbon distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. preferable. By setting the difference between the maximum value and the minimum value of the carbon atom ratio to 3 at% or more, sufficient gas barrier properties can be obtained when the manufactured gas barrier layer is bent. When the difference between the maximum value and the minimum value is 5 at% or more, the gas barrier property when the film having the gas barrier layer is bent is further improved.

(Relationship between maximum and minimum oxygen atom ratio)
In the gas barrier layer, the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) in the oxygen distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. preferable.

(Relationship between maximum and minimum silicon atom ratio)
In the gas barrier layer, the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) in the silicon distribution curve is preferably less than 10 at%, and more preferably less than 5 at%. preferable. If the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) is less than 10 at%, sufficient gas barrier properties and mechanical strength can be obtained for the gas barrier layer.

In order to improve the uniformity of the entire film surface and the gas barrier property, it is preferable that the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer). The gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon total are measured at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. When the distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve Are the same as each other or a difference within 5 at%.

The gas barrier layer preferably includes at least one gas barrier layer that simultaneously satisfies the above requirements (1) and (2), but may include two or more layers that satisfy such a condition. Furthermore, when two or more gas barrier layers are provided, the materials of the plurality of gas barrier layers may be the same or different.

In the silicon distribution curve, oxygen distribution curve and carbon distribution curve, the silicon atom ratio to the total amount of silicon atoms, oxygen atoms and carbon atoms is preferably in the range of 19 to 40 at%, and in the range of 30 to 40 at%. It is more preferable that The oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably in the range of 33 to 67 at%, more preferably in the range of 41 to 62 at%. Furthermore, the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably in the range of 1 to 19 at%, more preferably in the range of 3 to 19 at%.

Other configurations of the gas barrier layer described above are described in paragraphs [0025] to [0047] of International Publication No. 2012/046767, paragraphs [0029] to [0040] of JP 2014-000782 A, and the like. Can be referred to and adopted as appropriate.

(Gas barrier layer thickness)
The thickness of the gas barrier layer is preferably in the range of 5 to 1000 nm, more preferably in the range of 10 to 800 nm, and particularly preferably in the range of 100 to 500 nm. When the thickness of the gas barrier layer is within the above range, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are excellent, and good gas barrier properties can be obtained even in a bent state. Further, when the total thickness of the gas barrier layers is within the range, desired flatness can be realized in addition to the above effects.

(Method for forming gas barrier layer)
A method for forming a gas barrier layer that simultaneously satisfies the above requirements (1) and (2) is not particularly limited, and a known method can be used. For example, paragraphs [0049] to [2012] of International Publication No. 2012/046767 can be used. The method described in [0069] etc. can be referred to.

In addition, from the viewpoint of forming a gas barrier layer whose element distribution is precisely controlled, a discharge plasma having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound and an oxygen gas. It is preferable to use chemical vapor deposition.

More specifically, plasma chemistry is performed by using a discharge plasma treatment apparatus between rollers to which a magnetic field is applied, winding a substrate around a pair of film forming rollers, and performing plasma discharge while supplying a film forming gas between the pair of film forming rollers. It is preferable to form the gas barrier layer by a vapor deposition method. Further, when discharging while applying a magnetic field between a pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately. Thus, by winding a base material on a pair of film forming rollers and performing plasma discharge between the pair of film forming rollers, the distance between the base material and the discharge space changes, and plasma on the surface of the base material changes. By continuously changing the strength, it is possible to form a gas barrier layer in which the carbon atom ratio has a concentration gradient and the carbon atom ratio continuously changes in the layer.

In addition, during film formation, the film is formed on the surface of the base material existing on one film forming roller, and simultaneously formed on the surface of the base material existing on the other film forming roller as a pair. It becomes possible. That is, since the film formation efficiency can be doubled and a film having the same configuration can be formed, the extreme value of the carbon distribution curve can be doubled, and the above requirements (1) and (2) can be efficiently performed simultaneously. A filled gas barrier layer can be formed.

(Roller discharge plasma CVD equipment)
The film forming apparatus used when manufacturing the gas barrier layer by the above-mentioned plasma CVD method is not particularly limited. For example, when the manufacturing apparatus shown in FIG. 3 is used, the gas barrier layer can be manufactured by the roll-to-roll method while using the plasma CVD method. Hereinafter, the manufacturing method of the gas barrier layer will be described in detail with reference to FIG. FIG. 3 is a schematic view showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field is applied, which can be suitably used in the production of a gas barrier layer.

An inter-roller discharge plasma CVD apparatus (hereinafter also simply referred to as a plasma CVD apparatus) 50 to which a magnetic field shown in FIG. 3 is applied mainly includes a feeding roller 51, a transport roller 52, a transport roller 54, a transport roller 55, and a transport. Roller 57, film formation roller 53 and film formation roller 56, film formation gas supply pipe 59, plasma generation power supply 63, magnetic field generator 61 installed inside film formation roller 53, film formation roller 56 Are provided with a magnetic field generator 62 and a take-up roller 58. In such a plasma CVD manufacturing apparatus, at least the

film forming rollers

53 and 56, the film forming gas supply pipe 59, the plasma generating power source 63, and the magnetic

field generating apparatuses

61 and 62 are not shown in the vacuum. Located in the chamber. In FIG. 3, electrode drums connected to a plasma generating power source 63 are installed on the

film forming rollers

53 and 56. Further, in such a plasma CVD manufacturing apparatus, a vacuum chamber (not shown) is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by this vacuum pump. Yes.

In such a plasma CVD manufacturing apparatus, each film forming roller generates plasma so that a pair of film forming rollers (film forming roller 53 and film forming roller 56) can function as a pair of counter electrodes. The power supply 63 is connected. By supplying electric power from the plasma generation power source 63 to the film formation roller 53 and the film formation roller 56, it is possible to generate plasma by discharging into the space between the film formation roller 53 and the film formation roller 56. In such a plasma CVD manufacturing apparatus, the pair of

film forming rollers

53 and 56 are preferably arranged so that their central axes are substantially parallel on the same plane. Thus, by arranging the pair of

film forming rollers

53 and 56, the film forming rate can be doubled, and a film having the same configuration can be formed.

Also, a magnetic field generator 61 and a magnetic field generator 62 fixed so as not to rotate even when the film forming roller rotates are provided inside the film forming roller 53 and the film forming roller 56, respectively.

As the film formation roller 53 and the film formation roller 56, known rollers can be used as appropriate. As the film forming roller 53 and the film forming roller 56, it is preferable to use rollers having the same diameter from the viewpoint of efficiently forming a thin film. Further, as the feed roller 51 and the

transport rollers

52, 54, 55, 57 used in such a plasma CVD manufacturing apparatus, known rollers can be appropriately selected and used. The take-up roller 58 is not particularly limited as long as it can take up the base material 60 on which the gas barrier layer is formed, and a known roller can be appropriately used.

As the film forming gas supply pipe 59, one capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be appropriately used. Further, as the plasma generating power source 63, a conventionally known power source of a plasma generating apparatus can be used. As such a plasma generation power source 63, since it is possible to efficiently perform the plasma CVD method, a power source (AC power source or the like) capable of alternately reversing the polarity of the pair of film forming rollers is used. It is preferable to use it. Further, it is more preferable that such a plasma generating power source 63 is one that can apply electric power in a range of 100 W to 10 kW and an AC frequency in a range of 50 Hz to 500 kHz. . As the

magnetic field generators

61 and 62, a known magnetic field generator can be used as appropriate.

Using the plasma CVD apparatus 50 shown in FIG. 3, for example, the type of source gas, the power of the electrode drum of the plasma generator, the strength of the magnetic field generator, the pressure in the vacuum chamber (decompression degree), the diameter of the film forming roller, A desired gas barrier layer can be produced by appropriately adjusting the conveyance speed of the substrate.

In the plasma CVD apparatus 50 shown in FIG. 3, a film forming gas (raw material gas or the like) is supplied into the vacuum chamber, and plasma discharge is performed while a magnetic field is generated between the pair of

film forming rollers

53 and 56. A film gas (a raw material gas or the like) is decomposed by plasma, and a gas barrier layer is formed on the surface of the substrate 60 held by the film forming roller 53 and on the surface of the substrate 60 held by the film forming roller 56. . In such film formation, the substrate 60 is conveyed by the feed roller 51, the

conveyance rollers

52, 54, 55, 57, the take-up roller 58, the

film formation rollers

53, 56, etc. The gas barrier layer can be formed by a continuous film forming process using a to-roll method.

(Deposition gas)
As a film forming gas used in the plasma chemical vapor deposition method, a raw material gas containing an organosilicon compound and an oxygen gas are used, and the content of the oxygen gas in the film forming gas is the same as that of the organic silicon compound in the film forming gas. It is preferable that the amount is less than the theoretical oxygen amount necessary for complete oxidation of the whole amount.

It is preferable to use an organosilicon compound containing at least silicon as a raw material gas constituting the film forming gas used for producing the gas barrier layer. Examples of the organosilicon compound applicable to the production of the gas barrier layer include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, and dimethylsilane. , Trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. . Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the resulting gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

The film forming gas can contain oxygen gas as a reaction gas in addition to the source gas. Oxygen gas is a gas that reacts with a raw material gas to become an inorganic compound such as an oxide. Further, as a film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

When the film forming gas contains a source gas containing an organosilicon compound and an oxygen gas, the ratio of the source gas to the oxygen gas is the oxygen gas that is theoretically necessary for completely reacting the source gas and the oxygen gas. It is preferable not to make the oxygen gas ratio excessively higher than the ratio of the amount. About this, description, such as international publication 2012/046767, can be referred, for example.

(Degree of vacuum)
The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 100 Pa.

(Roller film formation)
In the plasma CVD method using the plasma CVD apparatus 50 shown in FIG. 3, the electric power applied to the electrode drum connected to the plasma generating power source 63 for discharging between the

film forming rollers

53 and 56 is the kind of the source gas. And can be adjusted as appropriate according to the pressure in the vacuum chamber. The power applied to the electrode drum is preferably in the range of 0.1 to 10 kW, for example. If the applied power is in such a range, the generation of particles (illegal particles) can be suppressed, and the amount of heat generated during film formation is within the control range. Further, thermal deformation of the substrate, performance deterioration due to heat, and generation of wrinkles during film formation can be suppressed.

In the plasma CVD apparatus 50, the conveyance speed (line speed) of the substrate 60 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is within the range of 0.25 to 100 m / min. Preferably, it is more preferably in the range of 0.5 to 20 m / min. If the line speed is within the range, wrinkles due to the heat of the base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.

[Second gas barrier layer; wet coating method]
The gas barrier layer 12 is a layer formed by a method other than the vacuum film formation method (second gas barrier layer) together with the vapor phase film formation gas barrier layer (first gas barrier layer) formed by the vacuum film formation method described above. May be provided. In this case, the first gas barrier layer formed by the vacuum film formation method is provided on the base film 11 side, and the second gas barrier layer formed by a method other than the vacuum film formation method is provided on the first gas barrier layer. It is preferable. That is, it is preferable that the gas barrier film 10 has a laminated structure of [base film 11 / gas phase deposition gas barrier layer (first gas barrier layer) / second gas barrier layer].

Examples of the gas barrier layer formed by a method other than the vacuum film forming method include a gas barrier layer formed by a wet coating method using a coating solution containing a silicon compound. Examples of the gas barrier layer formed by this wet coating method include a polysilazane modified layer formed by coating a coating liquid containing a polysilazane compound by a known wet coating method and then modifying the coating film.

(Polysilazane modified layer)
The polysilazane compound used for forming the polysilazane modified layer is a polymer that is a precursor of silicon oxynitride having a silicon-nitrogen bond in the structure. As the polysilazane compound, those having the structure of the following general formula (1) are preferably used.

In the formula, each of R ¹ , R ² , and R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

From the viewpoint of denseness as a film of the polysilazane modified layer, it is preferable to use perhydropolysilazane in which all of R ¹ , R ² and R ³ are hydrogen atoms. In addition, for details of polysilazane, paragraphs [0024] to [0040] of JP2013-255910A, paragraphs [0037] to [0043] of JP2013-188942A, and JP2013-151123A. Paragraphs [0014] to [0021], Paragraphs [0033] to [0045] of JP 2013-052569 A, Paragraphs [0062] to [0075] of JP 2013-129557 A, JP 2013-226758 A. Paragraphs [0037] to [0064] and the like can be referred to.

Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as a polysilazane-containing coating solution as it is. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials.

(Polysilazane modified layer forming method)
A coating film using a solution containing a polysilazane compound can be formed by applying a solution containing a polysilazane compound and an additive on a substrate. Any appropriate method can be adopted as the solution coating method. Examples thereof include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, and gravure printing. After applying the solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. Regarding the method for forming a coating film, paragraphs [0058] to [0064] of JP-A No. 2014-151571, paragraphs [0052] to [0056] of JP-A No. 2011-183773, and the like can be referred to.

(Modification process)
The modification treatment is treatment for performing a conversion reaction of the polysilazane compound to silicon oxide or silicon oxynitride. For the modification treatment, a known method for the conversion reaction of the polysilazane compound can be used. As the reforming treatment, a conversion reaction using plasma, ozone, or ultraviolet rays that can be converted at a low temperature is preferable. A conventionally known method can be used for the conversion reaction using plasma, ozone, or ultraviolet rays. The modification treatment is preferably performed by irradiating the coating film of the polysilazane compound-containing liquid with vacuum ultraviolet rays (VUV) having a wavelength of 200 nm or less.

The thickness of the polysilazane modified layer formed by the wet coating method is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. The entire polysilazane modified layer or only the surface layer may be a modified layer, and the thickness of the modified layer may be 1 to 50 nm, preferably 1 to 10 nm.

(Vacuum UV treatment)
In the step of irradiating the coating film containing the polysilazane compound with VUV, it is preferable that at least a part of the polysilazane is modified to silicon oxynitride. In VUV irradiation step, it is preferable that the illuminance of VUV in the coating film surface for receiving the coating film containing a polysilazane compound is in the range of 30 ~ 200mW / cm ^2, and more preferably in the range of 50 ~ 160mW / cm ² . By setting the illuminance of the VUV to 30 mW / cm ² or more, sufficient reforming efficiency can be obtained, and when it is 200 mW / cm ² or less, the rate of damage to the coating film is extremely suppressed and damage to the substrate is also reduced. Can be made.

Irradiation energy amount of VUV in the surface of the coating film containing the polysilazane compound is preferably in the range of 200 ~ 10000mJ / cm ^2, and more preferably in the range of 500 ~ 5000mJ / cm ^2. The polysilazane is sufficiently modified by setting the irradiation energy amount of VUV to 200 mJ / cm ² or more. Moreover, by setting it as 10,000 mJ / cm < ² > or less, it can suppress the excessive modification | reformation and can suppress the generation | occurrence | production of the crack of a polysilazane modified layer and the thermal deformation of a base material as much as possible.

A rare gas excimer lamp is preferably used as the vacuum ultraviolet light source.
Since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. Therefore, it is preferable to perform VUV irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of VUV irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, still more preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm.

Further, as the gas satisfying the irradiation atmosphere used at the time of VUV irradiation, dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

These reforming treatments are, for example, paragraphs [0055] to [0091] of JP2012-086394A, paragraphs [0049] to [0085] of JP2012-006154A, JP2011-251460A. The contents described in paragraphs [0046] to [0074] of FIG.

(Middle layer)
When laminating a polysilazane modified layer, it is preferable to provide an intermediate layer between the polysilazane modified layers. As the intermediate layer, it is preferable to apply a polysiloxane modified layer. The polysiloxane-modified layer is formed by applying a coating solution containing polysiloxane onto the polysilazane-modified layer using a wet coating method and then drying, and then irradiating the dried coating film with vacuum ultraviolet rays. be able to.

Examples of the coating method for the coating liquid for forming the intermediate layer include spin coating, dipping, roller blades, and spraying methods. As the vacuum ultraviolet ray, it is preferable to use the same VUV irradiation as the above-described polysilazane compound modification treatment.

The coating solution used for forming the intermediate layer mainly contains polysiloxane and an organic solvent. The polysiloxane applicable to the formation of the intermediate layer is not particularly limited, but an organopolysiloxane represented by the following general formula (2) is particularly preferable.

In the general formula (2), R ⁴ to R ⁹ each represent the same or different organic group having 1 to 8 carbon atoms. Here, at least one group of R ⁴ to R ⁹ includes either an alkoxy group or a hydroxyl group. m is an integer of 1 or more.

In the organopolysiloxane represented by the general formula (2), it is particularly preferable that m is 1 or more and the weight average molecular weight in terms of polystyrene is 1000 to 20000. If the weight average molecular weight in terms of polystyrene of the organopolysiloxane is 1000 or more, the intermediate layer to be formed is hardly cracked and the gas barrier property can be maintained, and if it is 20000 or less, the formed intermediate layer is cured. And sufficient hardness as an intermediate layer can be obtained.

The dry film thickness of the intermediate layer is preferably in the range of 100 nm to 10 μm, more preferably 50 nm to 1 μm. If the thickness of the intermediate layer is 100 nm or more, sufficient gas barrier properties can be ensured. Moreover, if the film thickness of the intermediate layer is 10 μm or less, stable coating properties can be obtained when forming the intermediate layer.

In addition, for details of polysiloxane, paragraphs [0028] to [0032] in JP2013-151123A, paragraphs [0050] to [0064] in JP2013-086501A, and JP2013-059927A. Paragraphs [0063] to [0081], Paragraphs [0119] to [0139] of JP 2013-226673 A, and the like can be referred to.

[Second gas barrier layer; transition metal-containing layer]
The second gas barrier layer is preferably a laminated form of a transition metal (M2) -containing layer and an inorganic element (M1) -containing layer other than the transition metal. The inorganic element (M1) -containing layer is preferably a layer formed by a wet coating method using a coating solution containing the above-described silicon compound. That is, the second gas barrier layer preferably has a laminated structure of a polysilazane modified layer and a transition metal-containing layer.

The second gas barrier layer composed of the laminated form of the transition metal-containing layer and the inorganic element-containing layer other than the transition metal has a mixed region containing the inorganic element M1 and the transition metal M2 at least in the thickness direction. It is preferable to have a region in which the value of the atomic ratio of the transition metal M2 to the inorganic element M1 in (M2 / M1) is in the range of 0.02 to 49 continuously in the thickness direction of 5 nm or more.

Further, in the second gas barrier layer, the transition metal-containing layer includes a region A containing a transition metal of Group 3 to Group 11 as the main component a, and an inorganic element of Group 12 to Group 14 as the main component b. It is preferable to have a mixed region containing a compound derived from the main component a and the main component b between the B region to be contained.

In the mixed region containing the inorganic element M1 and the transition metal M2, it is preferable that oxygen is contained in addition to the transition metal M2 and the inorganic element M1. The mixed region preferably contains at least one of a mixture of an oxide of a transition metal and an oxide of an inorganic element, or a composite oxide of a transition metal M2 and an inorganic element M1, and the transition metal M2 and It is more preferable to contain a composite oxide with the inorganic element M1.

(Transition metal (M2) -containing layer: A region)
The A region in the transition metal (M2) -containing layer refers to a region containing the transition metal M2 as a main component a as a metal.
The transition metal M2 is not particularly limited, and any transition metal may be used alone or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, Au, and the like.

Examples of the transition metal M2 that can provide good barrier properties include Nb, Ta, V, Zr, Ti, Hf, Y, La, and Ce. Among these, Nb, Ta, and V, which are Group 5 elements, are particularly preferable from the viewpoint of various examination results from the viewpoint of easy bonding to the inorganic element M1.

In particular, when the transition metal M2 is a Group 5 element (particularly Nb) and the inorganic element M1 whose details will be described later is Si, a significant barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal M2 is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

The thickness of the A region is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, and more preferably in the range of 5 to 15 nm from the viewpoint of achieving both barrier properties and optical characteristics. More preferably.

(Inorganic element (M1) containing layer: B region)
The B region in the inorganic element (M1) -containing layer refers to a region containing an inorganic material other than the transition metal as the main component b. As the inorganic element M1, an inorganic element selected from metals of Group 12 to Group 14 of the long-period periodic table is preferable. The inorganic element M1 is not particularly limited, and any inorganic element of Group 12 to Group 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. . The inorganic element M1 preferably contains Si, Sn or Zn, more preferably contains Si, and particularly preferably Si alone.
The thickness of the region B is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm, and in the range of 50 to 300 nm from the viewpoint of achieving both barrier properties and productivity. Is particularly preferred.

(Mixed area)
The mixed region contains an inorganic element M1 selected from Group 12 to Group 14 inorganic elements of the long-period periodic table and a transition metal M2 selected from Group 3 elements to Group 11 metals. A region in which the value of the atomic ratio of the transition metal M2 to the inorganic element M1 (M2 / M1) is within the range of 0.02 to 49, and has a thickness of 5 nm or more continuously in the thickness direction. It is an area. Here, the mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed. .

(Oxygen deficient composition)
In the mixed region, part of the composition is preferably a non-stoichiometric composition (oxygen deficient composition) in which oxygen is deficient. The oxygen deficient composition means that the condition defined by the following relational expression (2) is satisfied when the composition of the mixed region is expressed by the following chemical composition formula (1).
Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
As an oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, [(2y + 3z) / (a + bx)] in the mixed region when the composition of the mixed region is expressed by the chemical composition formula (1) is calculated. Use the minimum value obtained.

In the following composition formula (1) and relational formula (2), M1 represents an inorganic element, M2 represents a transition metal, O represents oxygen, and N represents nitrogen. x, y, and z are stoichiometric coefficients, respectively, a represents the maximum valence of M1, and b represents the maximum valence of M2. Moreover, in the following description, when special distinction is not necessary, the composition represented by the chemical composition formula (1) is simply referred to as the composition of the mixed region.

As described above, the composition of the mixed area of the inorganic elements M1 and the transition metal M2, represented by a formula _{(1) [(M1) (} M2) x O y N z]. As is clear from this composition, the composition of the mixed region may partially include a nitride structure, and it is preferable from the viewpoint of barrier properties to include a nitride structure.

Assuming that the maximum valence of the inorganic element M1 is a, the maximum valence of the transition metal M2 is b, the valence of O is 2, and the valence of N is 3, the composition of the mixed region (part of which is nitride) May be stoichiometric composition, [(2y + 3z) / (a + bx) = 1.0]. In this case, this formula means that the total number of bonds of the inorganic element M1 and the transition metal M2 is equal to the total number of bonds of O and N, and both the inorganic element M1 and the transition metal M2 are It is combined with either O or N. In addition, when two or more kinds are used together as the inorganic element M1, or when two or more kinds are used together as the transition metal M2, the maximum valence of each element is calculated by weighted averaging with the abundance ratio of each element. The combined valence is adopted as the value of a and b of each “maximum valence”.

On the other hand, in the mixed region, when [(2y + 3z) / (a + bx) <1.0] shown by the relational expression (2), O, with respect to the total number of bonds of the inorganic element M1 and the transition metal M2 This means that the total number of N bonds is insufficient. Such a state is the above-mentioned “oxygen deficiency”. In the oxygen deficient state, the remaining bonds of the inorganic element M1 and the transition metal M2 have a possibility of bonding to each other. When the metals of the inorganic element M1 and the transition metal M2 are directly bonded to each other, a denser and higher-density structure is formed than when the metals are bonded via O or N. As a result, it is considered that the barrier property is improved.

The mixed region is a region where the value of x satisfies [0.02 ≦ x ≦ 49, (0 <y, 0 ≦ z)]. This has the same meaning as defining the region where the value of the atomic ratio of transition metal M2 / inorganic element M1 is in the range of 0.02 to 49 and the thickness is 5 nm or more.

In this region, both the inorganic element M1 and the transition metal M2 are involved in direct bonding between metals. For this reason, it is considered that the presence of a mixed region satisfying this condition with a thickness of a predetermined value or more (5 nm) contributes to an improvement in barrier properties. In addition, it is considered that the closer the abundance ratio of the inorganic element M1 and the transition metal M2 is, the more the barrier region is improved. Preferably, the region satisfying [0.2 ≦ x ≦ 5] is included in a thickness of 5 nm or more, and the region satisfying [0.3 ≦ x ≦ 4] is included in a thickness of 5 nm or more. More preferably.

Here, if there is a region satisfying the relationship of [(2y + 3z) / (a + bx) <1.0] represented by the relational expression (2) within the range of the mixed region described above, the effect of improving the barrier property is exhibited. It is confirmed that The mixed region preferably has at least part of its composition satisfying [(2y + 3z) / (a + bx) ≦ 0.9], more preferably satisfying [(2y + 3z) / (a + bx) ≦ 0.85], It is more preferable to satisfy [(2y + 3z) / (a + bx) ≦ 0.8]. Here, the smaller the value of [(2y + 3z) / (a + bx)] in the mixed region, the higher the barrier effect, but the greater the absorption of visible light. Therefore, when used in applications where transparency is desired, [(2y + 3z) / (a + bx) ≧ 0.2] is preferable, and [(2y + 3z) / (a + bx) ≧ 0.3]. Is more preferable, and [(2y + 3z) / (a + bx) ≧ 0.4] is more preferable.

In addition, the thickness of the mixed region in which good barrier properties can be obtained is 5 nm or more as the sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and this thickness is preferably 8 nm or more, preferably 10 nm. More preferably, it is more preferably 20 nm or more. The thickness of the mixed region is not particularly limited from the viewpoint of barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 30 nm or less from the viewpoint of optical characteristics. .

(Composition analysis by XPS analysis and measurement of the thickness of the mixed region)
In the second gas barrier layer composed of the laminated form of the transition metal-containing layer and the inorganic element-containing layer other than the transition metal, the mixed region of the inorganic element M1 and the transition metal M2, the composition distribution in the A region and the B region, The thickness and the like can be obtained by XPS depth profile measurement using the above-described X-ray photoelectron spectroscopy (abbreviation: XPS).

[Other layers; protective layer]
The gas barrier film 10 may have a protective layer containing an organic compound or the like on the upper portion (outermost surface portion) of the gas barrier layer 12. As the organic compound used in the protective layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. it can. Furthermore, it is particularly preferable to use the above-described modified polysiloxane layer as the intermediate layer as a protective layer.

The protective layer is prepared by mixing an organic resin or an inorganic material with other components in a dilution solvent as necessary to prepare a coating solution. After coating this coating solution on the substrate surface by a conventionally known coating method, ionization is performed. It is preferable to form by irradiating and curing.

[Other layers; smooth layers]
The gas barrier film 10 may have a smooth layer (underlayer, primer layer) between the base film 11 and the gas barrier layer 12. A smooth layer is provided in order to planarize the rough surface of the base film 11 in which protrusions and the like exist. The material for forming such a smooth layer is not limited, but preferably contains a curable resin.

The curable resin is not particularly limited, and examples thereof include an active energy ray curable resin that is cured by irradiation with active energy rays such as ultraviolet rays, and a thermosetting resin that is cured by heating. The curable resins may be used alone or in combination of two or more. Conventionally known materials can be used as materials for the active energy ray-curable resin and the thermosetting resin.

The method for forming the smooth layer is not particularly limited, but a coating solution containing a curable material may be applied by a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method or other wet coating method, or a vapor deposition method. After coating by dry coating method to form a coating film, the coating film is formed by irradiation with active energy rays such as visible light, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron beams, heating, etc. A curing method is preferred.

The smoothness of the smooth layer is a surface roughness value defined by JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. The surface roughness is measured using an AFM (Atomic Force Microscope). The AMF includes a detector having a stylus with a very small tip radius, and the surface roughness is calculated from a cross-sectional curve of unevenness continuously measured by this detector. The thickness of the smooth layer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

For details of the smooth layer, paragraphs [0125] to [0143] of JP-A No. 2014-141056, paragraphs [0138] to [0150] of JP-A No. 2014-141555, and paragraphs of JP-A No. 2013-226757 It can be adopted with reference to [0131] to [0143].

[Other layers; Bleed-out layer]
The gas barrier film 10 may have a bleed-out prevention layer. The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that unreacted oligomers migrate to the surface of the resin film by heating and contaminate the contact surface when the smooth layer is formed on the resin film. It is provided on the opposite surface of the base film 11 having a layer. As long as the bleed-out preventing layer has this function, the same configuration as that of the smoothing layer described above can be applied.

[Other layers; Anchor coat layer]
The gas barrier film 10 may have an anchor coat layer on the base film 11 for the purpose of improving the adhesion (adhesion) between the base film 11 and the gas barrier layer. The anchor coating agent used in this anchor coat layer includes polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene / vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Etc. can be used singly or in combination of two or more. Conventionally known additives can be added to these anchor coating agents. A commercially available product may be used as the anchor coating agent. Specifically, as the siloxane-based UV curable polymer solution, a 3% isopropyl alcohol solution of “X-12-2400” manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

The above-mentioned anchor coat layer is obtained by coating an anchor coat agent on a substrate by a known method such as roll coat, gravure coat, knife coat, dip coat, spray coat, etc., and drying and removing the solvent, diluent, etc. Can be formed.

[Other layers; Desiccant layer]
The gas barrier film 10 may have a desiccant layer (moisture adsorption layer). Examples of the material used for the desiccant layer include calcium oxide and organometallic oxide. Calcium oxide is preferably used after being dispersed in a binder resin or the like, and as a commercially available product, for example, AqvaDry series manufactured by SAES Getter Co., Ltd. is preferable. Moreover, as an organometallic oxide, OleDry (registered trademark) series manufactured by Futaba Electronics Co., Ltd. or the like can be used.

<2. Manufacturing method of gas barrier film>
Next, the manufacturing method of a gas barrier film is demonstrated.
In addition, in the manufacturing method of the following gas barrier films, the manufacturing method of the gas barrier film 10 of the structure shown in the above-mentioned FIG. 1 is demonstrated as an example of the manufactured gas barrier film. About each structure of the gas barrier film 10, the structure similar to embodiment of the above-mentioned gas barrier film is applicable.

The gas barrier film 10 can be manufactured by forming the gas barrier layer 12 on the base film 11. Therefore, the method for manufacturing the gas barrier film 10 includes a step of preparing the base film 11 and a step of forming the gas barrier layer 12 on the base film 11.

As a step of preparing the base film 11, a base film 11 containing a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent capable of producing the gas barrier film 10 is prepared. Alternatively, a commercially available resin film containing a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent capable of producing the gas barrier film 10 is prepared as the base film 11. The above-mentioned various resin films can be used as the resin film. In addition, a conventionally known method for producing a resin film can be applied to the production of the base film 11.

[Process for producing base film]
The manufacturing method of the base film 11 is not particularly limited, and a conventionally known method for manufacturing a resin film is applied as long as the base film 11 containing a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent can be manufactured. be able to. In particular, in the base film 11 before forming the gas barrier layer 12, if the production method can adjust the content (mass) of the halogenated hydrocarbon to 10 ppm or more and 1000 ppm or less with respect to the total mass of the base film 11, Conventionally known methods for producing resin films can be applied.

The base film 11 containing a resin, organic fine particles, and halogenated hydrocarbon as an organic solvent in an amount of 10 ppm to 1000 ppm is preferably produced by a solution film forming method (cast method). That is, the method for producing the base film 11 preferably has the following steps 1 to 3.
1. 1. A step of obtaining a dope containing a resin, organic fine particles, and a halogenated hydrocarbon. 2. A step of casting a dope on a support, drying and peeling to obtain a film-like material. Step of stretching a film

(1. Obtaining dope containing resin, organic fine particles, and halogenated hydrocarbon)
In the step of obtaining a dope containing resin, organic fine particles, and halogenated hydrocarbon (dope preparation step), the resin and organic fine particles are dissolved in an organic solvent to prepare a dope.

As the resin for preparing the dope, the above-mentioned various resins can be used. As the resin for preparing the dope, the polarities represented by the above general formula (A-1), general formula (A-2), general formula (B-1), or general formula (B-2) It is preferable to include a norbornene-based resin having a group.

The organic solvent for dissolving the resin is not particularly limited as long as it contains at least a halogenated hydrocarbon and can dissolve the resin constituting the base film 11. Preferably, a mixed solvent of the above-mentioned various halogenated hydrocarbons and another organic solvent is used as the organic solvent.

The method for dissolving the resin in the organic solvent is not particularly limited, and the desired resin may be dissolved in the organic solvent, or various monomers may be polymerized in the organic solvent to dissolve the resin in the organic solvent. . The resin concentration in the dope is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and particularly preferably 10 to 30% by mass. If the concentration of the resin in the dope is too low, the viscosity becomes low, and it becomes difficult to adjust the thickness of the base film 11. Moreover, when too high, film-forming property will be bad, and the nonuniformity of the thickness and surface shape of the base film 11 will become large.

The method for adding the organic fine particles into the dope is not particularly limited, and the organic fine particles may be added directly to the solvent, or an aggregate of organic fine particles may be prepared and then added to the solvent. In particular, when the organic fine particles are particles (polymer particles) made of the above-mentioned polymer, it is preferable to add the polymer particles to a solvent after preparing an aggregate of the polymer particles. The aggregate of polymer particles is obtained by spray drying a slurry containing polymer particles, a surfactant, an inorganic powder, and an aqueous medium. The aggregate of polymer particles can be prepared, for example, by the method described in JP 2010-138365 A. The aggregate of polymer particles is composed of a plurality of polymer particles whose mutual connection (fusion) is suppressed. For this reason, since the aggregate of polymer particles is easily separated into polymer particles when the aggregate is dispersed in a resin or an organic solvent, it is excellent in handleability and dispersibility.

(2. Casting a dope on a support, drying and peeling to obtain a film-like product)
In the step of casting a dope on a support, drying and peeling to obtain a film-like material, the dope prepared by the above method is cast on the support. Then, after the dope cast on the support is dried, it is peeled off from the support to obtain a film-like material.

The method of casting the dope is not particularly limited, and a method of discharging from a casting die and casting on a support, a bar coater, a T die, a T die with a bar, a doctor blade, a roll coat, a die coat, etc. And a method of casting on a support.

Next, the solvent in the dope cast on the support is evaporated and dried. Then, the dried dope is peeled from the support to obtain a film. The residual solvent amount of the entire organic solvent containing the halogenated hydrocarbon when peeling the film-like material from the support (residual solvent amount at the time of peeling) is preferably 10 to 150% by mass, and 20 to 40% by mass It is more preferable that When the amount of residual solvent at the time of peeling is 10% by mass or more, the cycloolefin resin easily flows and becomes non-oriented at the time of drying or stretching, so it is easy to reduce Ro and Rt of the obtained base film. If the amount of residual solvent at the time of peeling is 150% by mass or less, the force required for peeling off the dope is not excessively increased, so that the dope breakage can be easily suppressed.
The residual solvent amount of the dope is defined by the following formula. The same applies to the following.
Residual solvent amount of dope (% by mass) = (mass before dope drying process−mass after dope drying process) / mass after dope drying process × 100

(3. Step of stretching a film-like product)
In the step of stretching the obtained film-like material, the film-like material may be stretched only in one direction (uniaxial stretching) or in two orthogonal directions (biaxial stretching). Preferably, the film-like material is stretched by biaxial stretching that extends in two directions of the width direction (TD direction) of the film-like material and the transport direction (MD direction) orthogonal to the width direction (TD direction).

The stretching ratio is preferably, for example, [TD stretching ratio / MD stretching ratio] of 1.0 to 3.0. The draw ratios in the TD direction and MD direction are each preferably 1.01 to 3.5 times, more preferably 1.01 to 1.3 times. The higher the draw ratio, the greater the residual stress of the obtained base film. The draw ratio is defined as [(size of stretched film after stretching) / (size of stretched film before stretching)].

The stretching temperature is preferably (Tg−65) ° C. or more and (Tg + 60) ° C. or less, and (Tg−50) ° C. or more (Tg + 50), where Tg is the glass transition temperature of the resin constituting the substrate film 11. It is more preferable that the temperature is not higher than ° C, and it is more preferable that the temperature be (Tg-30) ° C or higher and (Tg + 50) ° C or lower. When the stretching temperature is (Tg-30) ° C. or higher, the film-like product tends to have flexibility suitable for stretching, and excessive tension is not easily applied to the film-like product during stretching. For this reason, it is difficult for excessive residual stress to remain on the base film 11, and it is difficult for Ro and Rt to increase excessively. Further, when the stretching temperature is (Tg + 60) ° C. or less, moderate residual stress tends to remain on the stretched base film 11, and generation of bubbles due to evaporation of the solvent in the film-like material can be suppressed. As a specific example of the stretching temperature, when a norbornene resin is used, the temperature is preferably 100 to 220 ° C.

Stretching of the film-like material in the MD direction can be performed, for example, by a method (roll method) in which a difference in peripheral speed is applied to a plurality of rolls and the difference in the peripheral speed of the roll is used between them. Stretching of the film-like material in the TD direction can be performed by, for example, a method (tenter method) in which both ends of the film-like material are fixed with clips or pins and the distance between the clips or pins is increased in the traveling direction.

Through the above steps, the base film 11 containing a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent can be produced. The content of the halogenated hydrocarbon in the base film 11 is adjusted to 10 ppm or more and 1000 ppm or less by controlling the residual amount of the organic solvent in the step of evaporating the solvent in the dope cast on the support. can do. When the content of the halogenated hydrocarbon in the base film 11 is 10 ppm or more and 1000 ppm or less, the content of the halogenated hydrocarbon contained in the base film 11 after forming the gas barrier layer is 1 ppm or more and 90 ppm or less. Easy to adjust. In addition, content of the organic solvent of the base film 11 can be performed using the measuring method by the above-mentioned head space gas chromatography, and measuring conditions.

[Production method of gas barrier layer]
Next, the gas barrier layer 12 is produced on the surface side of the base film 11 produced by the method described above. The base film 11 before forming the gas barrier layer 12 contains 10 ppm or more and 1000 ppm or less of a halogenated hydrocarbon as an organic solvent. The base film 11 before forming the gas barrier layer 12 contains halogenated hydrocarbons in the range of 10 ppm to 1000 ppm, thereby suppressing the removal of organic fine particles contained in the base film 11 in the production apparatus for the gas barrier layer 12. can do. In addition, in the gas barrier film 10 formed by forming the gas barrier layer 12 when the base film 11 before forming the gas barrier layer 12 contains 10 to 1000 ppm of halogenated hydrocarbon, It becomes easy to adjust the content of the halogenated hydrocarbon to 1 ppm or more and 90 ppm or less.

In the gas barrier film 10, at least a gas barrier layer 12 formed by a vacuum film forming method is formed. For this reason, since the base film 11 is exposed to the heating environment and the reduced pressure environment during the production of the gas barrier layer 12, the organic solvent contained in the base film 11 is vaporized, and the base film 11 The content of the organic solvent decreases. For this reason, the halogenated hydrocarbon content of the base film 11 before forming the gas barrier layer 12 needs to be sufficiently larger than the halogenated hydrocarbon content of the base film 11 in the gas barrier film 10. Therefore, in order to adjust the halogenated hydrocarbon content in the base film 11 of the gas barrier film 10 to 1 ppm or more and 90 ppm or less, the halogenated hydrocarbon content of the base film 11 before the gas barrier layer 12 is formed. Must be 10 ppm or more and 1000 ppm or less.

As the type and the film forming method of the gas barrier layer 12 manufactured by the vacuum film forming method, an arbitrary configuration may be selected from the various gas barrier layers 12 described above, and layers other than the various gas barrier layers 12 described above may be manufactured.
Moreover, as a vacuum film-forming method for producing the gas barrier layer 12 on the base film 11, a roll-to-roll manufacturing device that unwinds the base film 11 from a roller and forms the gas barrier layer 12 on the film forming roller, It is preferable to use a manufacturing method. As a film forming method of the gas barrier layer 12 using a roll-to-roll manufacturing apparatus, for example, a plasma CVD film forming apparatus using the roll-to-roll method having the configuration shown in FIG. 3 is preferably used.

Further, a first gas barrier layer (gas phase deposition gas barrier layer) is formed by combining a layer (second gas barrier layer) formed by a method other than the vacuum deposition method with a vacuum deposition method (first gas barrier layer). ) And a second gas barrier layer (a gas barrier layer other than the vacuum film forming method) is preferably produced. For the film formation of the second gas barrier layer, other film formation methods such as the wet coating method described above can be applied.

Through the above steps, the base film 11 having the resin 13 and the organic fine particles 14 and containing 1 to 90 ppm of halogenated hydrocarbon as an organic solvent, and the gas barrier layer 12 formed by a vapor deposition method. Can be produced. In addition, it is not necessary to perform preparation of the base film 11 and preparation of the gas barrier layer 12 continuously. For example, a long base film 11 wound in a roll shape is produced using a solution film forming method, and the roll-like base film 11 is transferred from the production place of the base film 11 to another place. The gas barrier layer 12 may be formed.

The present invention will be specifically described by way of examples, but the present invention is not limited thereto.

<Preparation of Gas Barrier Film of Sample 101>
A base film was prepared by the following method (solution film forming method), and a gas barrier layer was formed on the base film to prepare a gas barrier film of Sample 101.

[Preparation of base film]
(Preparation of fine particle dispersion)
1.0 part by mass of polyphenylene sulfide particles (Torepal PPS manufactured by Toray Industries Inc.) (fine particles A) having an average particle size of 0.3 μm and 100 parts by mass of methylene chloride were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin. Thus, a fine particle dispersion A was obtained.

(Preparation of dope)
Next, a main dope having the following composition was prepared.
First, methylene chloride and ethanol were added to the pressure dissolution tank. Next, Topas 5013 (manufactured by Polyplastics Co., Ltd.) (resin A) was added as a norbornene resin to the pressurized dissolution tank with stirring. Next, the fine particle dispersion A prepared above was added, and this was heated to 60 ° C., and the resin was completely dissolved while stirring. The heating temperature was raised from room temperature at 5 ° C./min, dissolved in 30 minutes, and then lowered at 3 ° C./min.
The viscosity of the obtained solution was 7000 cp, and the water content was 0.50%. This was filtered using a filter cartridge SHP150 (manufactured by Loki Techno Co.) at a filtration flow rate of 300 L / m ² · h and a filtration pressure of 1.0 × 10 ⁶ Pa to obtain a main dope.

(Main dope composition)
Norbornene-based resin (Topas 5013; resin A, no polar group): 100 parts by mass Methylene chloride (MC): 270 parts by mass Ethanol (EtOH): 20 parts by mass Fine particle dispersion A (polyphenylene sulfide particles; fine particles A): 30 parts by mass

(Film formation)
Next, an endless belt casting apparatus was used to uniformly cast the main dope on a stainless steel belt support at a temperature of 31 ° C. and a width of 1800 mm. The temperature of the stainless steel belt was controlled at 28 ° C. The conveyance speed of the stainless steel belt was 20 m / min.

On the stainless steel belt support, the solvent was evaporated until the methylene chloride (MC) in the cast film was 680 ppm and ethanol (EtOH) was 150 ppm. Next, the film-like material was peeled from the stainless steel belt support with a peeling tension of 128 N / m. The peeled film was stretched 1.2 times in the transport direction at 120 ° C. (Tg−45 ° C.) while being transported by many rollers. Next, the film-like material was stretched 1.5 times in the width direction under a condition of 150 ° C. (Tg−15 ° C.) with a tenter. Then, the edge part pinched | interposed with the tenter clip was slit with the laser cutter, and it wound up after that, and obtained the base film with a film thickness of 40 micrometers.

[Formation of gas barrier layer]
A gas barrier layer having a thickness of 100 nm was formed on the base film produced by the above method by the following method (sputtering method: condition 1).

For the formation of the gas barrier layer, a roll-to-roll type sputtering apparatus 70 shown in FIG. 4 was used. A sputtering apparatus 70 shown in FIG. A drum 73 for contacting and cooling the surface of the base film 76 is disposed at the center of the vacuum chamber 72. Further, a feeding roller 74 and a winding roller 75 for winding the base film 76 are arranged in the vacuum chamber 72. The base film 76 wound around the feed roller 74 is conveyed onto the drum 73 via the guide roll 77, and the base film 76 is further wound around the take-up roller 75 via the guide roll 78. The vacuum chamber 72 has a vacuum pump 71 as a vacuum exhaust system, and the vacuum chamber 72 is exhausted from the exhaust port 79 by the vacuum pump 71. The vacuum chamber 72 includes a direct current discharge power source 81 to which pulse power can be applied as a film forming system, and a cathode 82 connected to the discharge power source 81, and a target (not shown) is mounted on the cathode 82. Is done. The discharge power supply 81 is connected to the controller 83. The controller 83 is connected to the gas flow rate adjustment unit 84. The gas flow rate adjustment unit 84 is connected to the gas flow rate adjustment unit 84 that supplies the reaction gas to the vacuum chamber 72 via the pipe 85 while adjusting the amount of reaction gas introduced into the vacuum chamber 72. The vacuum chamber 72 is configured to be supplied with a constant flow rate of discharge gas (not shown). Hereinafter, specific conditions of the gas barrier layer forming method using the sputtering method (condition 1) will be described.

Si was set as a target, and a pulse application type DC power source was prepared as a discharge power source 81. The substrate film 76 was hung on the feeding roller 74 and passed to the take-up roller 75. After completing the preparation of the substrate to the sputtering apparatus 70, the door of the vacuum chamber 72 was closed, the vacuum pump 71 was started, and vacuuming and cooling of the drum were started. When the ultimate pressure reached 4 × 10 ⁻⁴ Pa and the drum temperature reached 5 ° C., the conveyance of the base film 76 was started. Argon was introduced as a discharge gas, the discharge power supply 81 was turned on, plasma was generated on the Si target at a discharge power of 5 kW and a film formation pressure of 0.3 Pa, and pre-sputtering was performed for 3 minutes. Thereafter, oxygen was introduced as a reaction gas. After the discharge was stabilized, the amounts of argon and oxygen gas were gradually reduced to lower the film forming pressure to 0.1 Pa. After confirming the stability of discharge at 0.1 Pa, a silicon oxide film was formed for a certain period of time. After the film formation was completed, the vacuum chamber 72 was returned to atmospheric pressure, and the film on which the silicon oxide film was formed was taken out.

<Preparation of Gas Barrier Film of Sample 102>
A gas barrier film of Sample 102 was produced in the same manner as Sample 101 described above, except that the method for forming the gas barrier layer was changed to the following method (CVD method: Condition 2).

[Production of gas barrier layer]
Sample No. described in the examples of WO2016 / 009801 was formed on the base film. A gas barrier layer was formed in the same manner as in No. 28. Specifically, a roll-to-roll type structure in which two apparatuses each having a film forming roll facing the film forming part illustrated in FIG. 3 are connected (having a first film forming part and a second film forming part). An inter-roller discharge plasma CVD apparatus was used. An effective film formation width was 1000 mm, and a gas barrier layer having a thickness of 100 nm was produced under the following film formation conditions.

(Plasma CVD film formation conditions)
-Conveying speed: 6.0 m / min,
-Source gas (HMDSO) supply amount of the first film forming unit: 150 sccm (Standard Cubic Centimeter per Minute)
-Oxygen gas supply amount of the first film forming unit: 400 sccm
-Vacuum degree of the first film forming part: 2.0 Pa
-Applied power of the first film forming unit: 4.0 kW
-Source gas (HMDSO) supply amount of the second film forming unit: 150 sccm
-Oxygen gas supply amount of the second film forming unit: 400 sccm
-Vacuum degree of the second film forming part: 2.0 Pa
-Applied power of the second film forming unit: 4.0 kW
・ Power supply frequency: 84 kHz
-Temperature of all film forming rolls: 30 ° C

<Preparation of Gas Barrier Film of Sample 103>
In the production of the base film, the method for preparing the fine particle dispersion was changed to the following method (fine particles B), and the drying conditions of the film cast on the stainless belt support were changed, and methylene chloride ( A gas barrier film of Sample 103 was produced in the same manner as Sample 101 described above except that the solvent was evaporated until MC was 640 ppm and ethanol (EtOH) was 175 ppm.

[Preparation of fine particle dispersion]
1.0 part by mass of core-shell particles having an average particle size of 0.3 μm (Stabiloid made by Aika Kogyo) (fine particles B) and 100 parts by mass of methylene chloride were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin. Thus, a fine particle dispersion B was obtained.

<Preparation of Gas Barrier Film of Sample 104>
A gas barrier film of Sample 104 was produced in the same manner as Sample 103 described above, except that the method for forming the gas barrier layer was changed to the following method (CVD method + PHPS modified layer: Condition 3).

[Production of gas barrier layer]
Sample No. described in the examples of WO2016 / 009801 was formed on the base film. A gas barrier layer was formed in the same manner as in No. 28. Specifically, a roll-to-roll type structure in which two apparatuses each having a film forming roll facing the film forming part illustrated in FIG. 3 are connected (having a first film forming part and a second film forming part). An inter-roller discharge plasma CVD apparatus was used. A first gas barrier layer having a thickness of 100 nm and a film thickness of 100 nm was prepared under the following film formation conditions.

Furthermore, the polysilazane-containing liquid prepared by the following method was applied on the first gas barrier layer prepared by the above method so that the dry film thickness was 300 nm, and the atmosphere (dew point 5 ° C.) was 80 ° C. for 2 minutes. Dried. And the modification | reformation process of the modification energy 6.0J / cm < ² > was performed to the coating film after drying, and the 2nd gas barrier layer which consists of a polysilazane modified layer was produced.

(Preparation of polysilazane-containing liquid)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS) (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diamino) Hexane (TMDAH))-containing perhydropolysilazane 20% by mass dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1 (mass ratio), and further dried film thickness For adjustment, the solution was appropriately diluted with dibutyl ether to prepare a polysilazane-containing liquid.

<Preparation of Gas Barrier Film of Sample 105>
In the production of the base film, polymer particles (acrylic / styrene polymer particles: fine particles C) produced by the following method were produced, and the drying conditions of the film cast (cast) on the stainless steel belt support were changed. A gas barrier film of Sample 105 was prepared in the same manner as Sample 104 described above, except that the solvent was evaporated until methylene chloride (MC) was 610 ppm and ethanol (EtOH) was 143 ppm.

[Preparation of fine particle dispersion]
(Manufacture of seed particles)
In a polymerization vessel equipped with a stirrer and a thermometer, 1000 g of deionized water was added, 200 g of methyl methacrylate and 6 g of t-dodecyl mercaptan were added, and the mixture was heated to 70 ° C. while purging with nitrogen under stirring. The temperature of the solution was maintained at 70 ° C., and 20 g of deionized water in which 1 g of potassium persulfate was dissolved was added as a polymerization initiator, and then polymerization was performed for 10 hours. The average particle size of the polymer particles in the obtained emulsion was 0.44 μm.

(Manufacture of polymer particles)
A polymerization vessel equipped with a stirrer and a thermometer was charged with 800 g of deionized water in which 3 g of polyoxyethylene tridecyl ether ammonium sulfate was dissolved, and 144 g of methyl acrylate, 22 g of styrene, and 34 g of ethylene glycol dimethacrylate as a monomer mixture. And 1 g of azobisisobutyronitrile as a polymerization initiator was added. Next, the mixed solution is T.P. The mixture was stirred with a K homomixer (manufactured by Koki Kogyo Co., Ltd.) to obtain a dispersion.

Further, 60 g of the above emulsion containing seed particles was added to the dispersion, and the mixture was stirred at 30 ° C. for 1 hour to allow the seed particles to absorb the monomer mixture. Next, the seed particles that have absorbed the monomer mixture are polymerized by heating at 50 ° C. for 5 hours under a nitrogen stream, and then cooled to room temperature (about 25 ° C.) to obtain a slurry containing polymer particles. Obtained. The average particle diameter of the obtained polymer particles (organic fine particles) was 0.3 μm.

(Manufacture of polymer particle aggregates)
After cooling, 50 g of Snowtex O-40 (manufactured by Nissan Chemical Industries, Ltd .: 40% solid content as colloidal silica (inorganic powder), particle size: 0.02-0.03 μm) was added to the resulting slurry. The mixture was stirred for 10 minutes with a K homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). This slurry was spray-dried under the following conditions using a spray dryer (model: atomizer take-up method, model number: TRS-3WK) manufactured by Sakamoto Giken Co., Ltd. as a spray dryer to obtain a polymer particle aggregate. . The average particle diameter of the polymer particle aggregate was 30 μm.
・ Supply speed: 25ml / min
・ Atomizer speed: 11000 rpm
・ Air volume: 2m ³ / min
-Slurry inlet temperature of spray dryer: 130 ° C
-Polymer particle aggregate outlet temperature: 70 ° C

<Preparation of Gas Barrier Film of Sample 106>
In the production of the base film of the sample 101 described above, the main dope was produced by changing the resin to be used to Arton-G7810 (manufactured by JSR) (resin B, with polar group). Furthermore, the drying conditions of the film cast on the stainless steel belt support were changed, and the solvent was evaporated until the methylene chloride (MC) was 610 ppm and ethanol (EtOH) was 143 ppm, thereby producing a base film. did. Further, the gas barrier layer was formed under the same condition 2 (CVD method) as that of the sample 102 described above. Except for these conditions, a gas barrier film of Sample 106 was produced in the same manner as Sample 105 described above.

<Preparation of Gas Barrier Film of Sample 107>
In the preparation of the base film of the sample 101 described above, the sample 107 was prepared in the same manner as the sample 106 described above except that the resin used was changed to Arton-R5000 (manufactured by JSR) (resin C, with polar group). A gas barrier film was prepared.

<Preparation of Gas Barrier Film of Sample 108>
In the production of the base film, the sample 107 and the sample 107 described above were used except that the fine particles used were changed to fine particles D (acrylic / styrene polymer particles, 0.8 μm), and the content of the organic solvent was changed as follows. A gas barrier film of Sample 108 was produced in the same manner.

The fine particles D were produced by changing the average particle diameter of the polymer particles (organic fine particles) to 0.8 μm in the production of the polymer particles (fine particles C) of the sample 105.
In the preparation of the main dope, methylene chloride (MC), ethanol (EtOH), methane, and toluene (Tol) were used as organic solvents, and the drying conditions of the cast film on the stainless steel belt support were changed. The solvent was evaporated until methylene chloride (MC) was 610 ppm, ethanol (EtOH) was 143 ppm, and toluene (Tol) was 10 ppm.

<Preparation of Gas Barrier Film of Sample 109>
In the production of the base film, the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until methylene chloride (MC) was 930 ppm and ethanol (EtOH) was 720 ppm. Prepared a gas barrier film of Sample 109 in the same manner as Sample 108 described above.

<Preparation of Gas Barrier Film of Sample 110>
In the production of the base film, the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until the methylene chloride (MC) was 210 ppm and the ethanol (EtOH) was 90 ppm. Prepared a gas barrier film of Sample 110 in the same manner as Sample 109 described above.

<Preparation of Gas Barrier Film of Sample 111>
In production of the base film, the wound film is unwound and transported by a number of rollers at 160 ° C., and the transport speed is adjusted until methylene chloride (MC) is 55 ppm and ethanol (EtOH) is 30 ppm. A gas barrier film of Sample 111 was produced in the same manner as Sample 110 described above, except that the sample was dried.

<Preparation of Gas Barrier Film of Sample 112>
In production of the base film, the wound film is unwound and transported by a number of rollers at 180 ° C., and the transport speed is adjusted until methylene chloride (MC) is 13 ppm and ethanol (EtOH) is 12 ppm. A gas barrier film of Sample 112 was produced in the same manner as Sample 111 described above except that the sample was dried and then wound up.

<Preparation of Gas Barrier Film of Sample 113>
A gas barrier film of Sample 113 was prepared in the same manner as Sample 112 described above, except that the gas barrier layer was formed under the same conditions (CVD method + PHPS modified layer: Condition 3) as Sample 104 described above.

<Preparation of Gas Barrier Film of Sample 114>
A gas barrier film of Sample 114 was produced in the same manner as Sample 112 described above, except that the method for forming the gas barrier layer was changed to the following method (CVD method: Condition 4).

[Production of gas barrier layer]
Except for changing the vacuum degree of the first film forming unit to 2.5 Pa and changing the vacuum degree of the second film forming unit to 2.5 Pa, the same method as the formation conditions (CVD method: condition 2) of the gas barrier layer of the sample 102 Thus, a gas barrier layer was formed on the base film.

<Preparation of Gas Barrier Film of Sample 115>
In the preparation of the main dope, except that chloroform was used as the organic solvent, the drying conditions of the film cast (cast) on the stainless belt support were changed, and the solvent was evaporated until chloroform reached 55 ppm. A gas barrier film of Sample 115 was produced in the same manner as Sample 114.

<Preparation of Gas Barrier Film of Sample 116>
In preparing the main dope, use chlorobenzene (MCB) as the organic solvent, change the drying conditions of the cast film on the stainless steel belt support, and evaporate the solvent until the chlorobenzene (MCB) reaches 55 ppm. A gas barrier film of Sample 116 was produced in the same manner as Sample 114 described above, except that it was changed.

<Preparation of Gas Barrier Film of Sample 117>
A base film (resin D; cellulose acetate propionate, fine particles A; polyphenylene sulfide, organic solvent; methylene chloride (MC), methanol (MtOH) in the same manner as the optical film 106 described in Examples of Japanese Patent No. 6264373 )), And the drying conditions of the cast film on the stainless steel belt support were changed, and the solvent was evaporated until methylene chloride (MC) was 15 ppm and methanol (MtOH) was 8 ppm. Except for the above, a gas barrier film of Sample 117 was produced in the same manner as Sample 114 described above.

<Preparation of Gas Barrier Film of Sample 118>
A base film (resin E; mixed resin of acrylic resin and cellulose acetate propionate, fine particles A; polyphenylene sulfide, organic solvent; methylene chloride) in the same manner as the optical film 206 described in Examples of Japanese Patent No. 6264373 (MC)), and the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until methylene chloride (MC) was 15 ppm and ethanol (EtOH) was 15 ppm. A gas barrier film of Sample 118 was produced in the same manner as Sample 114 described above, except that it was changed.

<Preparation of Gas Barrier Film of Sample 119>
A gas barrier film of Sample 119 was produced in the same manner as Sample 114 described above, except that the gas barrier layer formation conditions were changed to the following conditions (CVD method: Condition 5).

[Production of gas barrier layer]
Except for changing the vacuum degree of the first film forming unit to 1.5 Pa and the vacuum degree of the second film forming unit to 1.5 Pa, the same method as the formation conditions (CVD method: condition 2) of the gas barrier layer of the sample 102 Thus, a gas barrier layer was formed on the base film.

<Preparation of Gas Barrier Film of Sample 120>
In the production of the base film, the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until the methylene chloride (MC) was 10 ppm and the ethanol (EtOH) was 10 ppm. Prepared a gas barrier film of Sample 120 by the same method as Sample 109 described above.

<Preparation of Gas Barrier Film of Sample 121>
In the production of the base film, a gas barrier film of Sample 121 was produced in the same manner as Sample 102 described above, except that the method for preparing the fine particle dispersion was changed to the following method (fine particles E).

[Preparation of fine particle dispersion]
Silica particles having an average particle size of 0.3 μm (SiO ₂ manufactured by CIK Nanotech) (fine particles E) 1.0 part by mass and 100 parts by mass of methylene chloride were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin. Thus, a fine particle dispersion E was obtained.

<Preparation of Gas Barrier Film of Sample 122>
In the production of the base film, the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until the methylene chloride (MC) was 2900 ppm and the ethanol (EtOH) was 2500 ppm. Prepared a gas barrier film of Sample 122 by the same method as Sample 107 described above.

<Preparation of Gas Barrier Film of Sample 123>
In the production of the base film, the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until the methylene chloride (MC) was 5 ppm and the ethanol (EtOH) was 5 ppm. Prepared a gas barrier film of Sample 123 by the same method as Sample 107 described above.

<Preparation of Gas Barrier Film of Sample 124>
In the preparation of the main dope, polymer particles (fine particles C) produced by the same method as sample 105 are used as the fine particles, toluene (Tol) is used as the organic solvent, and cast onto a stainless belt support (cast). A gas barrier film of Sample 124 was produced in the same manner as Sample 115 described above, except that the drying conditions of the film were changed and the solvent was evaporated until toluene (Tol) was 55 ppm.

<Preparation of gas barrier film of sample 125>
In the preparation of the main dope, toluene (Tol) was used as the organic solvent, the drying conditions of the cast film on the stainless belt support were changed, and the solvent was evaporated until toluene (Tol) was 55 ppm. Except for the above, a gas barrier film of Sample 125 was produced in the same manner as Sample 115 described above.

<Evaluation methods>
[Content of organic solvent in base film after barrier film formation]
The solvent content of the base film after drying the dope and the solvent content in the base film after forming the gas barrier layer were quantified using headspace gas chromatography. Headspace gas chromatography measurement was performed under the following conditions.

(conditions)
Headspace device: HP7694 Head Space Sampler (manufactured by Hewlett-Packard Company)
-Temperature conditions: transfer line 200 ° C, loop temperature 200 ° C
-Sample amount: 0.8g / 20ml vial-GC: HP5890 (manufactured by Hewlett-Packard Company)
・ MS: HP5971 (manufactured by Hewlett-Packard Company)
-Column: HP-624 (30m x 0.25mm ID)
Oven temperature: initial temperature 40 ° C. (holding time 3 minutes), temperature rising rate 10 ° C./minute, ultimate temperature 200 ° C. (holding time 5 minutes)

[Adhesion]
The produced gas barrier film was cross-cut by 100 squares by a method according to JIS K 5600-5-6. And in the gas barrier film after cross-cutting, the adhesion state of the base film of each mass and the gas barrier layer was confirmed. The gas barrier layer was peeled by 1/3 or less of the mass, and the adhesion of the gas barrier film was evaluated according to the following criteria (rank) from the number x of the acceptable mass in 100 masses.
4: x is 90 or more 3: x is 80 or more and less than 90 2: x is 70 or more and less than 80 1: x is less than 70

[Water vapor transmission rate (WVTR)]
Calcium (Ca: corrosive metal) was vapor-deposited on an area of 20 mm × 20 mm on a glass substrate using a vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd. to produce a Ca layer having a thickness of 80 nm. Next, the produced gas barrier film was bonded and sealed on the glass substrate on which the Ca layer was formed using an adhesive (manufactured by ThreeBond 1655) to produce a Ca method evaluation sample. In addition, the gas barrier film bonded with the adhesive was left in a glove box (GB) for one day and night in order to remove moisture of the adhesive and adsorbed water on the surface of the gas barrier film.

Next, the produced Ca method evaluation sample was stored in a 60 ° C. and 90% RH environment. Then, light was incident on the Ca method evaluation sample after storage for 20 hours from the normal direction on the glass surface side and photographed from the opposite surface side using an area-type CCD camera to obtain an evaluation image of the Ca layer. .

Next, the average density | concentration of Ca vapor deposition part of the obtained evaluation image was digitized. This evaluation was also performed on the Ca method evaluation sample after storage for 40, 60, 80, or 100 hours in a 60 ° C. and 90% RH environment, and the average of the slope with respect to the average concentration of the Ca vapor deposition portion in 20 to 100 hours. From the value, the average value (g / m ² / day) of the water vapor transmission rate (WVTR) was calculated. And the average value of this WVTR was converted into the water vapor transmission rate (WVTR) in 40 degreeC and 90% RH environment, and the following reference | standard (rank) evaluated. The conversion factor used at this time is 1/25.
4: 1 × 10 ^{−4 or} less 3: 1 × 10 ⁻⁴ or more, 1 × 10 ^{−3 or} less 2: 1 × 10 ⁻³ or more, 1 × 10 ^{−2 or} less 1: 1 × 10 ⁻² or more

[Flexibility]
The sample size of the gas barrier film is 3 cm x 13 cm, and the gas barrier film is bent 100,000 times into a curved surface with a diameter of 6 mm with the U-shaped stretch tester DLDMMLH-FS manufactured by Yuasa System Equipment Co. I let you. Thereafter, using the bent central portion of the gas barrier film, a measurement sample of the Ca method was produced in the same manner as the evaluation of the water vapor permeability described above. Furthermore, after storing in a 60 ° C. and 90% RH environment for 200 hours, it is considered that the gas barrier layer has been damaged (cracked), and the gas barrier film is cracked (cracked) according to the following criteria. The occurrence of was evaluated.
4: No corrosion streaking (no cracking)
3: 1 or more corrosion streaks are generated and less than 3 (crack generation is 1 or more and less than 3)
2: Corrosion streaks 3 or more and less than 10 (crack generation is 3 or more and less than 10)
1: 10 or more corrosion lines (10 or more cracks)

[Device contamination]
Under the gas barrier layer formation conditions of samples 101 to 125 described above, after forming the gas barrier layer with a base film length of 100 m, the apparatus was opened to the atmosphere, the CVD roll and the inner wall of the apparatus were confirmed, The presence or absence of contamination was confirmed. The case where there was no contamination in the apparatus was evaluated as ○, and the case where there was contamination was evaluated as ×. When there was contamination (x), the substance detected as contamination was analyzed.

The main configuration of the gas barrier films of the samples 101 to 125 and the evaluation results are shown in Table 1 below. The forming conditions 1 to 5 of the resins A to E, the fine particles A to E, and the gas barrier layer constituting the base film shown in Table 1 are as follows.

[resin]
Resin A: Polyplastic Topas 513 (no polar group)
Resin B: Arton-G7810 manufactured by JSR (with polar group)
Resin C: Arton-R5000 (with polar group) manufactured by JSR
Resin D: Cellulose (non-norbornene)
Resin E: Acrylic resin / cellulose acylate mixture (non-norbornene)

[Fine particles]
Fine particle A: polyphenylene sulfide fine particle (0.3 μm)
Fine particle B: Core shell fine particle (0.3 μm)
Fine particle C: acrylic / styrene polymer fine particle (0.3 μm)
Fine particle D: acrylic / styrene polymer fine particle (0.8 μm)
Fine particles E: inorganic fine particles (SiO ₂ )

[Gas barrier layer]
・ Condition 1: Sputtering method ・ Condition 2: CVD method (deposition unit vacuum 2.0 Pa)
・ Condition 3: CVD method + PHPS modified layer ・ Condition 4: CVD method (deposition unit vacuum 2.5 Pa)
Condition 5: CVD method (deposition unit vacuum degree 1.5 Pa)

As shown in Table 1, the base film contains a resin, organic fine particles, and halogenated hydrocarbon of 1 ppm or more and 90 ppm or less (after gas barrier layer film formation) as an organic solvent, and is formed by a vapor phase film formation method. In addition, the gas barrier films of Sample 101 to Sample 120 having the gas barrier layer all obtained results of 2 or more in each of the evaluation items of adhesion, water vapor transmission rate (WVTR), and bending resistance. Further, the gas barrier films of Sample 101 to Sample 120 were not confirmed to be contaminated in the evaluation of device contamination. In addition, as a gas barrier film, each evaluation should just be 2 or more, and it is preferable that it is 3 or more.

On the other hand, in the gas barrier film of the sample 121 having only inorganic fine particles without organic fine particles, all evaluations are 1 in each of the items of adhesion, water vapor permeability (WVTR), and bending resistance. . In addition, contamination within the device has also occurred. As a result of analyzing this pollutant, it was confirmed that SiO ₂ which is a material of inorganic fine particles was mainly.

The inorganic fine particles used in the gas barrier film of the sample 121 have a lower affinity with the resin of the base film than the organic fine particles. For this reason, like the gas barrier film of the sample 121, when only inorganic fine particles are included, the particles easily fall off from the base film, and the base film and the gas barrier layer easily peel off. In addition, the removal of the inorganic fine particles tends to cause cracks in the gas barrier layer, so that the gas barrier property is likely to deteriorate. Furthermore, contamination in the apparatus due to dropping off of the inorganic fine particles tends to occur.
Further, since the inorganic fine particles are more rigid than the organic fine particles, the flexibility of the base film is likely to be reduced, and the flex resistance of the base film is likely to be reduced.

When the amount of the organic solvent contained in the base film is excessive like the gas barrier film of the sample 122, the gas barrier property tends to be lowered. When the base film contains an excessive organic solvent, the film formation (gas phase film formation method) of the gas barrier layer is likely to be hindered by the organic solvent present in a large amount at the interface between the base film and the gas barrier layer. For this reason, the gas barrier property tends to be lowered.

Also, like the gas barrier film of the sample 123, when the amount of the organic solvent contained in the base film is too small, the gas barrier property tends to be lowered. When the organic film contained in the base film is small (less than 1 ppm; below the detection limit), the affinity between the resin and the organic fine particles is reduced in the base film, and the organic fine particles are likely to fall off. As a result, the base film and the gas barrier layer easily peel off due to the removal of the organic fine particles. In addition, cracking of the gas barrier layer is likely to occur due to the removal of the organic fine particles, so that the gas barrier property is likely to be lowered.

When the halogenated hydrocarbon is not contained as the organic solvent like the gas barrier film of the sample 124 and the gas barrier film of the sample 125, the gas barrier property and the bending resistance are likely to be lowered. Furthermore, contamination in the apparatus due to the dropping of the fine particles is likely to occur.
In the base film, in a configuration that does not contain a halogenated hydrocarbon as an organic solvent, the affinity between the resin and the organic fine particles is less likely to be higher than when a halogenated hydrocarbon is included. For this reason, in the structure which does not contain a halogenated hydrocarbon as an organic solvent, the affinity between the resin and the organic fine particles tends to decrease, and the organic fine particles are likely to fall off. As a result, the removal of the organic fine particles tends to cause cracks in the gas barrier layer, and the gas barrier properties are also likely to deteriorate.

The gas barrier film of the sample 101 and the gas barrier film of the sample 102 differ in the formation method of the gas barrier layer between the sputtering method (condition 1) and the CVD method (condition 2), but the gas barrier film formed by any method is sufficient. It has a good gas barrier property. Therefore, in the gas barrier film, the gas barrier layer can be formed by applying an arbitrary vapor deposition method such as sputtering or CVD. However, since the gas barrier film (condition 2; CVD method) of the sample 102 has a higher gas barrier property, it is preferable to apply a vacuum deposition method such as a CVD method as a method for forming the gas barrier layer.

The gas barrier film of sample 103 and the gas barrier film of sample 104 were formed by any method, although the method of forming the gas barrier layer was different between the CVD method (condition 2) and the CVD method + PHPS modified layer (condition 3). The gas barrier film also has sufficient gas barrier properties. Therefore, if the gas barrier film has a gas barrier layer (first gas barrier layer) formed by a vapor deposition method such as a CVD method, the gas barrier layer formed by another method on the gas barrier layer. You may have.

The gas barrier film of sample 105 has an acrylic / styrene polymer (particle C) as fine particles. The gas barrier film (particle C; acrylic / styrene polymer) of the sample 105 has a higher gas barrier property than the gas barrier film (particle B; core shell) of the sample 104. Therefore, it is preferable that a gas barrier film has a polymer containing the structural unit derived from a (meth) acrylic-type monomer and the structural unit derived from a styrene-type monomer as organic fine particles used for a base film. Polymer fine particles containing structural units derived from (meth) acrylic monomers and structural units derived from styrene monomers tend to have a high affinity with halogenated hydrocarbons, which are organic solvents. Is less likely to occur, and the film-forming property and adhesion of the gas barrier layer are likely to be improved. For this reason, it is thought that the gas barrier property of a gas barrier film becomes easy to improve.

The gas barrier film of the sample 106 and the gas barrier film of the sample 107 are norbornene resins (resin B or resin C) having a polar group as a resin constituting the base film. The gas barrier film (resin B) of the sample 106 and the gas barrier film (resin C) of the sample 107 are more closely attached to the base film and the gas barrier layer than the gas barrier film of sample 105 (resin A: norbornene-based resin having no polar group). Improved. By using a norbornene-based resin having a polar group as a resin constituting the base film, the affinity between the resin and the organic fine particles is likely to be higher than when a norbornene-based resin having no polar group is used. It is considered that the film formation and adhesion of the gas barrier layer are likely to be improved because the fine particles do not easily fall off.

The gas barrier film of the sample 108 contains methylene chloride (MC), ethanol (EtOH), and toluene (Tol) as organic solvents. The gas barrier film of the sample 108 has the same result as the gas barrier film (MC + EtOH) of the sample 106. From this result, even when the base film contains an organic solvent other than the halogenated hydrocarbon as well as the halogenated hydrocarbon, a gas barrier film having the same characteristics can be obtained. Therefore, the gas barrier film may contain any organic solvent other than the halogenated hydrocarbon as long as it contains a halogenated hydrocarbon as the organic solvent used for the base film.

The gas barrier film of Sample 109, the gas barrier film of Sample 110, the gas barrier film of Sample 111, and the gas barrier film of Sample 112 are each an amount of organic solvent contained in the base film (methylene chloride (MC) content; 5 ppm to 85 ppm) is different. In each gas barrier film, the gas barrier film (5 ppm) of the sample 112 is the best, and the gas barrier film (9 ppm) of the sample 111 is the next best. Moreover, the gas barrier film (9 ppm) of the sample 111 is the best for the barrier property. From this result, the gas barrier film tends to have better adhesion and barrier properties as the amount of the halogenated hydrocarbon contained in the base film is closer to the lower limit (1 ppm).

The gas barrier film of the sample 113 and the gas barrier film of the sample 114 have all the evaluation results of 4, and the best result is obtained among all the samples. The gas barrier film of the sample 113 and the gas barrier film of the sample 114 are formed from the gas barrier film of the sample 112 (condition 2; CVD method vacuum degree 2.0 Pa), the formation conditions of the gas barrier layer (condition 3; CVD method + PHPS modified layer, or Condition 4: CVD method, degree of vacuum 1.5 Pa) is changed. Therefore, as the gas barrier layer of the gas barrier film, the condition 3 (CVD method + PHPS modified layer) for forming the second gas barrier layer on the first gas barrier layer formed by the vapor deposition method or a vacuum with a low vacuum degree is used. It is preferable to use condition 4 (CVD method vacuum degree 1.5 Pa) formed by vapor deposition.

The gas barrier film of sample 115 and the gas barrier film of sample 116 use chloroform or chlorobenzene, which is a halogenated hydrocarbon, as an organic solvent for the base film. In any gas barrier film, two or more results were obtained in each evaluation. From this result, the gas barrier film can use arbitrary halogenated hydrocarbons as the organic solvent of the base film. However, the gas barrier film of sample 114 (organic solvent; methylene chloride) has better evaluation results. Accordingly, the gas barrier film preferably contains methylene chloride among the halogenated hydrocarbons as the organic solvent.

The gas barrier film of the sample 117 and the gas barrier film of the sample 118 are cellulose resin (resin D) or acrylic resin / cellulose resin (resin E) in which the resin constituting the base film is not a norbornene resin. . As for the gas barrier film containing any resin, a result of 3 or more was obtained in each evaluation. From this result, the base film of the gas barrier film is not limited to the norbornene-based resin, and may be composed of a resin other than the norbornene-based resin. However, the gas barrier film of the sample 114 (resin C: norbornene-based resin having a polar group) has better results of each evaluation. From this result, it is preferable that the resin constituting the base film of the gas barrier film is a norbornene resin.

The gas barrier film of sample 119 has a gas barrier layer formed under condition 5 (CVD method vacuum degree 1.5 Pa), which is lower than condition 4 (CVD method vacuum degree 2.0 Pa). As for the gas barrier film of the sample 119, the same result as the gas barrier film of the sample 112 and the sample 113 in which the gas barrier layer was formed on condition 4 (CVD method vacuum degree 2.0 Pa) was obtained. Therefore, the gas barrier film can form a gas barrier layer under any conditions as long as it is a vapor deposition method. In particular, if it is a vacuum deposition method such as a CVD method, a gas barrier layer having a good gas barrier property can be formed under arbitrary conditions.

In the gas barrier film of sample 120, the amount of organic solvent (MC content) contained in the base film is 3 ppm, and the organic solvent contained in the base film than the gas barrier film of sample 112 (MC content; 5 ppm). The amount of is small. The gas barrier film of the sample 120 has lower adhesion and flex resistance than the gas barrier film of the sample 112. From this result, in the gas barrier film in which the amount of the organic solvent contained in the base film is reduced to 5 ppm, each evaluation result becomes good, but when the amount of the organic solvent is reduced to 3 ppm, each evaluation result starts to decrease. Therefore, in the gas barrier film, the amount of the organic solvent contained in the base film is preferably 3 ppm or more. However, even if the amount of the organic solvent contained in the base film is 3 ppm, each evaluation result is 3 or more, so that the content of the organic solvent can be further reduced. On the other hand, when the amount of the organic solvent contained in the base film is equal to or lower than the detection limit value (less than 1 ppm) like the gas barrier film of the sample 123, the base film is If the organic solvent is contained at 1 ppm or more, it is considered that the gas barrier film has sufficient characteristics.

The present invention is not limited to the configuration described in the above embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

DESCRIPTION OF SYMBOLS 10 ...

Gas barrier film

11, 76 ... Base film, 12 ... Gas barrier layer, 13 ... Resin, 14 ... Organic fine particle, 40 ... Vacuum plasma CVD apparatus, 41 ... Anode electrode, 42, 72 ... vacuum chamber, 43 ... cathode electrode, 44 ... susceptor, 45 ... heating / cooling device, 46 ... heat medium circulation system, 47 ... vacuum exhaust system, 48 ... Gas introduction system, 49 ... High frequency power supply, 50 ... Plasma CVD apparatus, 51,74 ... Feeding roller, 52,54,55,57 ... Conveying roller, 53,56 ... Deposition roller, 58, 75 ... take-up roll, 59 ... Deposition gas supply pipe, 60 ... Base material, 61, 62 ... Magnetic field generator, 63 ... Power source for plasma generation , 70 ... Sputtering device, 7 ... Vacuum pump, 73 ... Drum, 77,78 ... Guide roll, 79 ... Exhaust port, 81 ... Discharge power source, 82 ... Cathode, 83 ... Controller, 84. ..Gas flow rate adjustment unit, 85 ... Piping

Claims

A step of forming a gas barrier layer by a vapor deposition method on a base film containing a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent;
The manufacturing method of the gas barrier film whose content of the said halogenated hydrocarbon in the said base film before forming the said gas barrier layer is 10 ppm or more and 1000 ppm or less.
The method for producing a gas barrier film according to claim 1, wherein the organic fine particles have a polymer containing a structural unit derived from a (meth) acrylic monomer and a structural unit derived from a styrene monomer.
The method for producing a gas barrier film according to claim 1 or 2, wherein the halogenated hydrocarbon contains methylene chloride.
As the vacuum film forming method for forming the gas barrier layer, one kind selected from a vacuum vapor deposition method, a sputtering method, an ion plating method, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method. The manufacturing method of the gas barrier film in any one of Claim 1 to 3 using the above method.
The method for producing a gas barrier film according to any one of claims 1 to 4, wherein the resin includes a norbornene-based resin having a polar group.
The method for producing a gas barrier film according to any one of claims 1 to 5, wherein a content of the halogenated hydrocarbon in the base film after forming the gas barrier layer is 1 ppm or more and 90 ppm or less.
A base film;
A gas barrier layer formed on the base film,
The base film contains a resin, organic fine particles, and a halogenated hydrocarbon as an organic solvent,
A gas barrier film, wherein the content of the halogenated hydrocarbon in the substrate film is 1 ppm or more and 90 ppm or less.
The gas barrier film according to claim 7, wherein the organic fine particles have a polymer containing a structural unit derived from a (meth) acrylic monomer and a structural unit derived from a styrene monomer.
The gas barrier film according to claim 7 or 8, comprising methylene chloride as the halogenated hydrocarbon.
The gas barrier film according to any one of claims 7 to 9, comprising a norbornene-based resin having a polar group as the resin.