WO2018003274A1

WO2018003274A1 - Method for producing gas barrier film

Info

Publication number: WO2018003274A1
Application number: PCT/JP2017/016809
Authority: WO
Inventors: 鈴木　一生; 河村　朋紀
Original assignee: コニカミノルタ株式会社
Priority date: 2016-06-28
Filing date: 2017-04-27
Publication date: 2018-01-04
Also published as: JPWO2018003274A1; CN109415805B; CN109415805A; JP6888623B2

Abstract

The present invention provides a method for producing a gas barrier film that has excellent gas barrier properties and is highly transparent. The present invention pertains to a method for producing a gas barrier film, which comprises forming a gas barrier layer on a base material by plasma chemical vapor deposition using a composition that contains an organic siloxane compound and 0.1-10 μg/L of at least one metal element selected from the group consisting of Sn, Pt, and Au.

Description

Method for producing gas barrier film

The present invention relates to a method for producing a gas barrier film by a plasma chemical vapor deposition method.

Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for. By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.

By the way, in recent years, gas barrier films that prevent permeation of water vapor, oxygen, and the like as described above are also used in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL). It's getting on. In order to apply a gas barrier film to an electronic device, a particularly high gas barrier property is required.

As a method for producing a gas barrier film, a method of forming an inorganic barrier layer on a base film by a vapor deposition method such as a vapor deposition method, a sputtering method, or a CVD method is known. The vapor phase film forming method is generally advantageous in that the gas barrier layer to be formed has particularly excellent barrier performance. For example, Japanese Unexamined Patent Application Publication No. 2011-73430 (corresponding to US Patent Application Publication No. 2012/040107) discloses a thin film layer in which a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve of a gas barrier layer satisfy a predetermined condition. An invention relating to a gas barrier laminate film formed by chemical vapor deposition is disclosed. It is described that the gas barrier laminated film described in the document has a sufficient gas barrier property, and even when the film is bent, it is possible to sufficiently suppress a decrease in the gas barrier property.

When a gas barrier film is used in an image display device such as a liquid crystal display element (LCD) or organic electroluminescence (EL), it is required to satisfy both high gas barrier properties and transparency (visible light transmission). However, the present inventors have found that it is difficult to achieve both gas barrier properties and optical characteristics in the invention described in Japanese Patent Application Laid-Open No. 2011-73430.

Therefore, an object of the present invention is to provide a method for producing a gas barrier film having excellent gas barrier properties and excellent transparency.

The present inventors have conducted intensive research to solve the above problems. As a result, a plasma chemical vapor deposition (plasma CVD) method is used, using as a raw material a composition containing a predetermined amount of at least one metal element selected from the group consisting of Sn, Pt, and Au and an organosiloxane compound. It has been found that the above problems can be solved by forming a silicon-containing layer (gas barrier layer), and the present invention has been completed.

FIG. 1 is a schematic view showing an example of a manufacturing apparatus used for forming a gas barrier layer by plasma enhanced chemical vapor deposition.

One aspect of the present invention provides a plasma chemical vapor phase using a composition comprising 0.1 to 10 μg / L of at least one metal element selected from the group consisting of Sn, Pt, and Au, and an organosiloxane compound. The present invention relates to a method for producing a gas barrier film, comprising forming a gas barrier layer on a substrate by a vapor deposition method. According to such a method for producing a gas barrier film, the obtained gas barrier film has excellent gas barrier properties and excellent transparency. Although the details of the reason why such an effect is obtained are unknown, the following mechanism is conceivable. Note that the following mechanism is based on speculation, and the present invention is not limited to the following mechanism.

The present inventors have found that when a silicon-containing layer is formed by a plasma CVD method using an organic siloxane compound as a raw material, there is a problem that the obtained gas barrier film does not have sufficient transparency. At the time of film formation by the plasma CVD method, a byproduct derived from an organic group of the organosiloxane compound and containing a unsaturated bond (for example, a double bond) can be generated. Based on this, the present inventors speculated that light may be absorbed by the by-product and the transparency may not be sufficient. In particular, the method of forming a gas barrier layer with a plasma CVD apparatus having a counter roll electrode with a magnetic field generator inside is excellent in productivity, but on the principle of generating plasma by trapping electrons with magnetic lines of force. Distribution occurs in the plasma density in the deposition zone between the electrodes (deposition rolls). For this reason, it is considered that when a film is formed by such a manufacturing apparatus, a by-product containing an unsaturated bond is likely to be generated particularly in a portion where the plasma density is low because the bond decomposition energy is small. For the above problems, the transparency of the obtained gas barrier film can be improved by using a composition containing a certain amount or more of a metal element in addition to the organosiloxane compound as a plasma CVD raw material. The present inventors have found out. This is because the metal element exerts a catalytic action to activate the organosiloxane compound before gasification, thereby suppressing the formation of unsaturated bonds and the progress of breaking of unsaturated bonds that occur. It is considered that a gas barrier film excellent in transparency can be obtained by reducing the light absorption due to. Moreover, the present inventors have found that when the metal element contained in the composition is excessively large, the gas barrier property of the gas barrier film is deteriorated. This is considered to be because when the metal element contained in the composition is excessively large, decomposition and polymerization of the organosiloxane compound proceed, and the denseness of the resulting gas barrier layer decreases. In the present invention, a gas barrier film having both gas barrier properties and transparency can be obtained by using a composition containing an appropriate amount of a metal element in addition to an organosiloxane compound as a plasma CVD raw material.

Hereinafter, preferred modes of the gas barrier film of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

In this specification, “X to Y” indicating a range means “X or more and Y or less”. In the present specification, unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

The substrate that can be used in the present invention is not particularly limited, and specific examples include polyester resins (for example, polyethylene terephthalate resin), acrylic resins, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent resins. Fluorine resin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, poly Ether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring-modified polycarbonate resin, fluorene ring-modified polyester resin, acryloyl compound, etc. Like substrate comprising a thermoplastic resin. These thermoplastic resins can be used alone or in combination of two or more. Among these, it is preferable that it is a base material (polyester film) containing a polyester resin, and it is more preferable that it is a base material (polyethylene terephthalate film) containing a polyethylene terephthalate resin. Moreover, this base material can be used individually or in combination of 2 or more types.

In the base material including the thermoplastic resin, the content of the thermoplastic resin is preferably 70% by mass or more, more preferably 90% by mass or more, and 95% by mass with respect to the total mass of the base material. More preferably, the upper limit is 100% by mass.

Since the gas barrier film obtained by the production method according to the present invention can be used as an electronic device such as a solar cell or an organic EL, the substrate is preferably transparent. That is, preferably, the light transmittance of the substrate is usually 80% or more, preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 91% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

Further, the above-mentioned base material may be an unstretched film or a stretched film. The said base material can be manufactured by a conventionally well-known general method. Regarding the method for producing these base materials, the items described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

The surface of the base material may be subjected to various known treatments for improving adhesion, such as easy adhesion treatment, corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatment as necessary. May be performed in combination.

The base material may be a single layer or a laminated structure of two or more layers. When the substrate has a laminated structure of two or more layers, the respective substrates may be the same type or different types.

The thickness of the substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 500 μm, and more preferably 20 to 200 μm.

In the production method according to the present invention, in addition to the following organosiloxane compound, at least one metal element selected from the group consisting of Sn, Pt, and Au (hereinafter, selected from the group consisting of “Sn, Pt, and Au”). The composition containing 0.1 to 10 μg / L of “at least one metal element” is also simply referred to as “metal element”) is used for film formation by plasma enhanced chemical vapor deposition. With metal elements (for example, Ag and Cu) other than Sn, Pt, and Au, it is difficult to achieve both gas barrier performance and transparency. On the other hand, if the content of the metal element in the composition is less than 0.1 μg / L or exceeds 10 μg / L, it is difficult to achieve both gas barrier performance and transparency. The amount of metal elements in the composition (total amount of metal elements in the volume of the entire composition) may be 0.1 to 10 μg / L, but from the viewpoint of a further balance between gas barrier performance and transparency, 1 It is preferably ˜8 μg / L, more preferably 2 to 5 μg / L, and even more preferably 3 to 5 μg / L. Among these, Sn is preferable as the metal element. In the present invention, a metal element may be contained in the composition for supplying a source gas used for forming a gas barrier layer by plasma enhanced chemical vapor deposition, and the formed gas barrier layer contains the metal element. It does not have to be.

The composition may contain one kind of metal element selected from the group consisting of Sn, Pt and Au, or may contain two or more kinds. When the composition contains two or more kinds of metal elements, the amount of the above metal elements is the total amount of these two or more kinds.

The metal element may be present in the composition as a single metal of Sn, Pt, and / or Au, but may be present in the form of a metal ion or the like from the viewpoint of the uniformity of the composition. For example, a composition may be prepared by adding a salt or complex of Sn, Pt, and / or Au to an organosiloxane compound, such as dibutyltin dilaurate, dibutyltin diacetate, etc. , Tin compounds such as dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide; tetrachloroplatinum (II) acid, hexachloroplatinum (IV) acid, hexachloroplatinum (IV) acid Ammonium, platinum chloride (II), platinum chloride (IV), platinum oxide (II), platinum hydroxide (II), platinum dioxide (IV), platinum oxide (IV), platinum disulfide (IV), platinum sulfide (IV) ), Potassium tetrachloroplatinate (II), potassium hexachloroplatinate (IV) A platinum compound of: gold (I) chloride, gold (III) chloride, gold (III) bromide, tetrachloroauric acid, tetrachloroaurate, sodium tetrachloroaurate, chloro (trimethylphosphine) gold (I), Chloro (triethylphosphine) gold (I), chloro (triphenylphosphine) gold (I), chlorodimethylsulfidegold (I), chloro (tris (p-trifluoromethylphenyl) phosphine) gold, tetrachlorogold (III) Although gold compounds, such as an acid, can be illustrated, it is not limited to these. Here, dibutyltin dilaurate is preferable as the tin compound, hexachloroplatinum (IV) acid is preferable as the platinum compound, and chloro (triphenylphosphine) gold (I) is preferable as the gold compound. These salts or complexes can be used alone or in combination of two or more.

Note that the amount of the metal element contained in the composition can be measured by ICP mass spectrometry.

The addition of the metal compound to the composition can be carried out by a conventionally known method such as adding a predetermined amount of a metal compound to the following organosiloxane compound and heating or stirring as necessary.

In the manufacturing method according to the present invention, the gas barrier layer is formed by plasma enhanced chemical vapor deposition. The plasma chemical vapor deposition method (plasma-enhanced chemical vapor deposition), which is a method for forming a gas barrier layer, is not particularly limited, but is a plasma CVD method at or near atmospheric pressure described in International Publication No. 2006/033233. And a plasma CVD method using a plasma CVD apparatus having a counter roll electrode.

In particular, since the productivity is high, the formation of the gas barrier layer by the plasma CVD method is preferably performed by a plasma CVD apparatus having a counter roll electrode, and is performed by a plasma CVD apparatus having a counter roll electrode provided with a magnetic field generator inside. It is more preferable. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

Hereinafter, a method for forming a gas barrier layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode will be described. However, the technical scope of the present invention is not limited to this form.

When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a film is applied to each of the pair of film forming rollers. More preferably, the plasma is generated by discharging between the pair of film forming rollers. Thus, by using a pair of film forming rollers, placing a film on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller is placed on the film forming roller. While forming an existing film, it is possible to form a film on the surface of the substrate on the other film forming roller at the same time, so that a thin film can be produced efficiently and a normal roller is not used. Compared with the plasma CVD method, the film formation rate can be doubled, and a film having a substantially identical structure can be formed.

Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, as a film forming gas used in such a plasma CVD method, a gas containing an organosiloxane compound and oxygen is preferable.

Hereinafter, a preferred specific example of an apparatus for forming a gas barrier layer by plasma chemical vapor deposition will be described with reference to FIG. 1, but the present invention is not limited in any way. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

1 includes a feed roller 32,

transport rollers

33, 34, 35, and 36,

film forming rollers

39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller 39. And 40,

magnetic field generators

43 and 44 installed inside 40, and a take-up roller 45 are provided. In such a manufacturing apparatus, at least the

film forming rollers

39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic

field generating units

43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge the space between the film formation roller 39 and the film formation roller 40 by supplying electric power from the plasma generation power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. According to such a manufacturing apparatus, it is possible to form a gas barrier layer by a CVD method. While depositing the gas barrier layer component on the film forming roller 39, the gas barrier layer component is also formed on the film forming roller 40. Therefore, the gas barrier layer can be formed efficiently.

In the film forming roller 39 and the film forming roller 40, magnetic

field generating units

43 and 44 are provided, which are fixed so as not to rotate even when the film forming roller rotates.

The

magnetic field generators

43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating part 43 provided on one film forming roller 39 and a magnetic field generating part provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generators 44 and the

magnetic field generators

43 and 44 form a substantially closed magnetic circuit. By providing such

magnetic field generators

43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surfaces of the

film forming rollers

39 and 40, and the plasma is converged on the bulges. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

The

magnetic field generators

43 and 44 provided in the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic

field generation units

43 and 44, the opposing space along the length direction of the roller axis without straddling the magnetic field generation unit on the roller side where the lines of magnetic force oppose each other. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. It is excellent in that a deposited film can be efficiently formed on a material or the like.

As the film formation roller 39 and the film formation roller 40, known rollers can be used as appropriate. As such

film forming rollers

39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. The diameters of the

film forming rollers

39 and 40 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity is less likely to deteriorate, and the total amount of heat of the plasma discharge is applied to the substrate in a short time. Since this can be avoided, damage to the substrate and the like can be reduced, which is preferable. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

In such a manufacturing apparatus 31, the base material etc. are arrange | positioned on a pair of film-forming roller (the film-forming roller 39 and the film-forming roller 40) so that the surfaces of the base material face each other. By disposing the substrate and the like in this way, when the plasma is generated by performing discharge in the facing space between the film forming roller 39 and the film forming roller 40, the base existing between the pair of film forming rollers is present. It becomes possible to form films on the surfaces of the materials and the like simultaneously. That is, according to such a manufacturing apparatus, the gas barrier layer component is deposited on the surface of the substrate or the like on the film forming roller 39 by the plasma CVD method, and the gas barrier layer component is further deposited on the film forming roller 40. Therefore, the gas barrier layer can be efficiently formed on the surface of the substrate or the like.

As the feed roller 32 and the

transport rollers

33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. Further, the take-up roller 45 is not particularly limited as long as it can take up a film having a gas barrier layer formed on a substrate or the like, and a known roller can be used as appropriate.

Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.

The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the

magnetic field generators

43 and 44, known magnetic field generators can be used as appropriate.

Using such a manufacturing apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film (base material, etc.) The gas barrier layer can be formed by appropriately adjusting the transport speed. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. As a result, the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer is formed on the surface of the base material on the film forming roller 39 and the surface of the base material on the film forming roller 40 by plasma CVD. It is formed by. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the

film forming rollers

39 and 40, and the plasma is converged on the magnetic field. For this reason, when a base material etc. pass the A point of the film-forming roller 39 in FIG. 1, and the B point of the film-forming roller 40, the maximum value of a carbon distribution curve is formed in a gas barrier layer. On the other hand, when the substrate or the like passes through the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. It is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the gas barrier layer (the difference between the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (conveying speed of the substrate or the like). In such film formation, the substrate and the like are conveyed by the delivery roller 32 and the film formation roller 39, respectively, so that they are formed on the surface of the substrate and the like by a roll-to-roll continuous film formation process. Then, the gas barrier layer 3 is formed.

As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas can be used alone or in combination of two or more. In the present invention, the source gas in the film forming gas used for forming the gas barrier layer contains an organosiloxane compound. The source gas may contain at least one metal element selected from the group consisting of Sn, Pt, and Au described later.

The above-described organosiloxane compound is a compound having an organic group and a siloxane bond (Si—O). The organic group contained in the siloxane compound is not particularly limited. For example, the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group) N-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl Group, isohexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethyl group Butyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2- A butyl group, a cyclohexyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group, a naphthyl group) and the like. These organic groups include halogen, an alkyl group having 1 to 6 carbon atoms, It may be substituted with a further substituent such as an alkoxy group having 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group, an amino group, a carboxyl group, a hydroxyl group or an acyl group.

More specifically, examples of the organosiloxane compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane (HMDSO), octamethyltrisiloxane, decamethyltetrasiloxane (DMTSO), tetramethoxy, and the like. Acyclic siloxane compounds such as silane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; 1,3,5- Trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl Black hexasiloxane, and the like tetradecanoyl methyl cyclotetradecane hept siloxane, siloxane bond (Si-O) by cyclic siloxane compound having a cyclized structure (cyclic organosiloxane compound) the like can be exemplified, without limitation. As the organosiloxane compound, those having no carbon-carbon unsaturated bond such as alkenylene group, alkynylene group or vinyl group in the molecule are preferable from the viewpoint of transparency. As the organosiloxane compound, those having a Si—O—Si structure in the molecule are preferable from the viewpoint of gas barrier properties. Furthermore, the organic siloxane compound is more preferably a cyclic siloxane compound from the viewpoint of achieving both gas barrier properties and transparency. This is because, in the case of a cyclic siloxane compound (cyclic organic siloxane compound), since there are more siloxane bonds per molecule than a non-cyclic organic siloxane compound, the gas barrier layer tends to be dense even with a small bond decomposition energy. This is presumably because the activation effect of the organosiloxane compound by the metal element is further increased. These organosiloxane compounds can be used alone or in combination of two or more.

Further, as the source gas, for example, an organic compound gas of methane, ethane, ethylene, or acetylene may be used in combination with the above organic siloxane compound.

The supply amount of the raw material gas can be arbitrarily set. For example, it is preferably 1 to 1000 sccm (Standard Cubic Centimeter per Minute), and more preferably 10 to 200 sccm.

Further, as the film forming gas, a reactive gas may be used in addition to the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination. The gas flow rate ratio of the reaction gas to the source gas is, for example, preferably source gas: reaction gas = 1: 1 to 20, more preferably 1: 1 to 10.

As the 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, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

Further, 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 0.1 to 50 Pa.

The film conveyance speed (line speed) can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in a range of ˜20 m / min.

As described above, as a more preferable aspect of the present embodiment, a plasma using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode having a magnetic field generator inside as a gas barrier layer as shown in FIG. The film is formed by the CVD method. This is superior in flexibility (flexibility) when mass-produced using the above-mentioned plasma CVD apparatus (roll-to-roll method), and mechanical strength, especially when transported by roll-to-roll. This is because it is possible to efficiently produce a gas barrier layer having both durability and barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

The gas barrier layer may be a single layer or a laminated structure of two or more layers. When the gas barrier layer has a laminated structure of two or more layers, the metals contained in each gas barrier layer may be the same or different. When the gas barrier layer has a laminated structure of two or more layers, the total thickness of the gas barrier layer is the thickness of the gas barrier layer.

From the viewpoint of gas barrier performance, the thickness of the gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is the thickness of the second gas barrier layer (the total thickness of the laminated structure of two or more layers). ) Is preferably 10 to 1000 nm, more preferably 25 to 600 nm, and even more preferably 50 to 300 nm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The thickness of the gas barrier layer can be measured by TEM observation.

The composition analysis of the gas barrier layer can analyze the composition in the depth direction of the film by performing a depth profile using X-ray photoelectron spectroscopy (XPS: Xray Photoelectron Spectroscopy). That is, while etching the surface of the gas barrier layer of the gas barrier film, the composition in the depth (thickness) direction from the surface is measured.

The composition analysis of the gas barrier layer is obtained by XPS depth profile measurement. The obtained distribution curve of silicon, oxygen, carbon, etc. can be created with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance (L) from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer in the film thickness direction. As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, use the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. Can do.

<< XPS analysis conditions >>
・ Device: QUANTERASXM (manufactured by ULVAC-PHI Co., Ltd.)
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, Al2p, Nb3d, Ta4d, Hf4d, Ti2p, Zr3d, Ru3d, Y3p, C1s, N1s, O1s
・ Irradiated X-ray: Single crystal spectroscopy AlKα
・ X-ray spot and its size: 800 × 400 μm oval shape ・ Sputtering ion: Ar (2 keV)
Depth profile: Repeat measurement after sputtering for 1 minute.

Sputtering conditions;
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
・ Data processing: MultiPak (manufactured by ULVAC-PHI)
Quantification: The background is obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.

In the production method according to the present invention, layers (functional layers) having various functions may be provided on the gas barrier film.

In addition, when providing a functional layer in a gas barrier film, since it is utilized as electronic devices, such as a solar cell and an organic EL element, it is preferable that a functional layer is also transparent. That is, preferably, the light transmittance of the functional layer is usually 80% or more, preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 91% or more.

(Anchor coat layer)
An anchor coat layer may be formed on the surface of the base material on the side where the gas barrier layer is formed for the purpose of improving the adhesion between the base material and the gas barrier layer.

As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

Also, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Hard coat layer)
A hard coat layer may be provided on the surface (one side or both sides) of the substrate. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. A layer containing a cured product of the functional resin, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. You may use the commercially available base material in which the hard-coat layer is formed previously. As the ultraviolet curable resin, for example, Z-731L (manufactured by Aika Industry Co., Ltd.), Opstar (registered trademark) Z7527 (manufactured by JSR Corporation), which is an acrylic ultraviolet curable resin, is preferably used.

The method for forming the hard coat layer is not particularly limited, but it may be formed by a wet coating method (coating method) such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as a vapor deposition method. Is preferred.

The drying temperature of the coating film when forming the hard coat layer is not particularly limited, but is preferably 40 to 120 ° C.

The active energy ray used when curing the hard coat layer is preferably ultraviolet rays.
Although it does not restrict | limit especially as an ultraviolet irradiation device, For example, a high pressure mercury lamp etc. are mentioned. Although ultraviolet irradiation conditions are not specifically limited, For example, performing under air is mentioned. The amount of ultraviolet irradiation energy is not particularly limited, but is preferably 0.3 to 5 J / cm ² .

The thickness of the hard coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Smooth layer)
The gas barrier film may form a smooth layer between the base material and the gas barrier layer. The smooth layer is provided in order to flatten the rough surface of the substrate on which protrusions and the like exist, or to fill the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the substrate. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

Specific examples of thermosetting materials include Tutprom Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

The method for forming the smooth layer is not particularly limited, but may be formed by a wet coating method (coating method) such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as a vapor deposition method. preferable.

In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm, from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. Is preferred.

The smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601: 2001, and the 10-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a barrier layer is apply | coated with an application | coating form, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability will be impaired. In addition, it is easy to smooth the unevenness after coating.

The water vapor permeability of the gas barrier film is preferably less than 5 × 10 ⁻³ g / (m ² · day), more preferably less than 1 × 10 ⁻³ g / (m ² · day), More preferably, it is less than 5 × 10 ⁻⁴ g / (m ² · day). In the present specification, a value measured by a method based on JIS K 7129-1992 is adopted as the value of “water vapor permeability”. The measurement conditions are temperature: 38 ± 0.5 ° C. and relative humidity (RH): 90 ± 2%.

The light transmittance of the gas barrier film at a wavelength of 450 nm is preferably 88% or more, more preferably 90% or more, and further preferably 91% or more (upper limit 100%). In this specification, the value of “light transmittance at a wavelength of 450 nm” is a value obtained by measuring a transmission spectrum of a gas barrier film using a spectrocolorimeter CM-3700A (manufactured by Konica Minolta Co., Ltd.). And

The gas barrier film obtained by the production method according to the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the electronic device main body include an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV).

The effect of the present invention will be described using the following examples and comparative examples. In the following examples, “parts” and “%” mean “parts by mass” and “mass%”, respectively, unless otherwise specified, and each operation is performed at room temperature (25 ° C.). In addition, this invention is not limited to a following example.

[Example 1]
<Preparation of Sample 1>
(Preparation of base material)
A 100 μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both sides was used as a base material. A hard coat layer having an anti-blocking function with a thickness of 0.5 μm was formed on the surface of the substrate opposite to the surface on which the gas barrier layer was formed. That is, an ultraviolet (UV) curable resin (manufactured by Aika Industry Co., Ltd., product number: Z731L) was applied to a substrate so that the dry film thickness was 0.5 μm, then dried at 80 ° C., and then in the air. Curing was performed using a high-pressure mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm ² .

Next, a hard coat layer having a thickness of 2 μm was formed on the surface of the substrate on which the gas barrier layer was to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a substrate so that the dry film thickness was 2 μm, and then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a substrate with a hard coat layer was obtained. Hereinafter, in this example and comparative examples, for convenience, this base material with a hard coat layer is simply referred to as a base material.

(Preparation of CVD raw materials)
Dibutyltin dilaurate is mixed with 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS) to prepare a tin (Sn) concentration of 1 μg / L (ratio of tin to the total volume of the mixture). A plasma CVD raw material was prepared.

(Formation of gas barrier layer)
The substrate was set in a plasma CVD apparatus as represented by the schematic diagram of FIG. 1 and evacuated. Thereafter, a gas barrier layer mainly composed of SiOC is formed with a film thickness of 60 nm on one surface of the substrate (on the hard coat layer having a thickness of 2 μm formed above) using the plasma CVD raw material. Sample 1 was prepared by plasma CVD. At this time, a source gas of 100 sccm (Standard Cubic Centimeter per Minute) vaporized by baking the plasma CVD source and oxygen gas of 300 sccm were supplied into the apparatus, and the pressure in the apparatus during film formation was set to 1 Pa. A 100 kHz high frequency power source was used as the plasma generating power source. The film conveyance speed (line speed) was 5 m / min.

[Example 2]
<Preparation of Sample 2>
Sample 2 was produced in the same manner as in Example 1 except that the plasma CVD raw material was prepared so that the tin concentration was 0.1 μg / L.

[Example 3]
<Preparation of Sample 3>
Sample 3 was prepared in the same manner as in Example 1 except that the plasma CVD raw material was prepared so that the tin concentration was 3 μg / L.

[Example 4]
<Preparation of Sample 4>
Sample 4 was produced in the same manner as in Example 1 except that the plasma CVD raw material was prepared so that the tin concentration was 5 μg / L.

[Example 5]
<Preparation of Sample 5>
Sample 5 was produced in the same manner as in Example 1 except that the plasma CVD material was prepared so that the tin concentration was 10 μg / L.

[Comparative Example 1]
<Preparation of Sample 6>
Sample 6 was produced in the same manner as in Example 1 except that the plasma CVD material was prepared so that the tin concentration was 11 μg / L.

[Example 6]
<Preparation of Sample 7>
Example 1 except that TMCTS and hexachloroplatinum (IV) acid were mixed and a plasma CVD raw material prepared so that the platinum (Pt) concentration was 3 μg / L (the ratio of platinum to the total volume of the mixture) was used. Sample 7 was produced in the same manner as described above.

[Example 7]
<Preparation of Sample 8>
Other than using TCMTS and chloro (triphenylphosphine) gold (I), and using a raw material for plasma CVD prepared so that the gold (Au) concentration is 3 μg / L (ratio of gold to the total volume of the mixture) A sample 8 was prepared in the same manner as in Example 1.

[Comparative Example 2]
<Preparation of Sample 9>
Sample 9 was prepared in the same manner as in Example 1 except that the plasma CVD raw material was changed to TMCTS without adding a metal compound.

[Comparative Example 3]
Example 1 except that TMCTS and silver acetate (I) were mixed and the raw material for plasma CVD was prepared so that the silver (Ag) concentration was 3 μg / L (ratio of silver to the total volume of the mixture). Sample 10 was produced in the same manner.

[Comparative Example 4]
Example except that TMCTS, tetrachlorocopper (II) and acid were mixed and the raw material for plasma CVD was prepared so that the copper (Cu) concentration was 3 μg / L (the ratio of copper to the total volume of the mixture). Sample 11 was prepared in the same manner as in Example 1.

[Example 8]
<Preparation of Sample 12>
Example 1 except that dibutyltin dilaurate was mixed with HMDSO (hexamethyldisiloxane) and the plasma CVD raw material was changed to a tin concentration of 1 μg / L (ratio of tin to the total volume of the mixture). Sample 12 was prepared in the same manner as described above.

[Example 9]
<Preparation of Sample 13>
Sample 13 was produced in the same manner as in Example 8 except that the plasma CVD raw material was prepared so that the tin concentration was 3 μg / L.

[Example 10]
<Preparation of Sample 14>
Sample 14 was produced in the same manner as in Example 8 except that the plasma CVD material was prepared so that the tin concentration was 5 μg / L.

[Example 11]
<Preparation of Sample 15>
Sample 15 was produced in the same manner as in Example 8 except that the plasma CVD raw material was prepared so that the tin concentration was 10 μg / L.

[Comparative Example 5]
<Preparation of Sample 16>
Sample 16 was prepared in the same manner as in Example 8 except that the plasma CVD raw material was prepared so that the tin concentration was 11 μg / L.

[Example 12]
<Preparation of Sample 17>
Sample 17 was prepared in the same manner as in Example 8 except that HMDSO and hexachloroplatinic (IV) acid were mixed and a plasma CVD raw material prepared so that the platinum concentration was 3 μg / L was used.

[Example 13]
<Preparation of Sample 18>
Sample 18 was prepared in the same manner as in Example 8 except that HMDSO and chloro (triphenylphosphine) gold (I) were mixed and the plasma CVD raw material prepared so that the gold concentration was 3 μg / L was used. .

[Comparative Example 6]
<Preparation of Sample 19>
A sample 19 was produced in the same manner as in Example 8 except that the plasma CVD raw material was changed to HMDSO without adding a metal compound.

[Example 14]
<Preparation of Sample 20>
Sample 20 was produced in the same manner as in Example 1 except that DMTSO (decamethyltetrasiloxane) was mixed with dibutyltin dilaurate and the plasma CVD raw material was prepared so that the tin concentration was 3 μg / L.

[Example 15]
<Preparation of Sample 21>
Sample 21 was produced in the same manner as in Example 1 except that TEOS (tetraethoxysilane) was mixed with dibutyltin dilaurate and the plasma CVD raw material was prepared so that the tin concentration was 3 μg / L.

[Evaluation methods]
<Gas barrier property evaluation>
Using a water vapor transmission rate measuring apparatus AQUATRAN2 (manufactured by MOCON), the water vapor permeability [g / (m ² · 24h)] ([g / (m ² -Day)]) was measured.

From the measured water vapor transmission rate, the gas barrier property was ranked according to the following evaluation criteria. As the water vapor permeability is smaller, the gas barrier property is higher, and ranks 1 to 3 are practical gas barrier properties.

(Evaluation criteria)
Rank 1 ◎: Water vapor permeability is less than 5 × 10 ⁻⁴ g / (m ² · 24 h) Rank 2 ○: Water vapor permeability is 5 × 10 ⁻⁴ g / (m ² · 24 h) or more 1 × 10 ⁻ Rank less than ³ g / (m ² · 24h) 3 ○ △: Water vapor permeability is 1 × 10 ⁻³ g / (m ² · 24 h) or more and less than 5 × 10 ⁻³ g / (m ² · 24 h) Rank 4 Δ: Water vapor permeability is 5 × 10 ⁻³ g / (m ² · 24 h) or more and less than 1 × 10 ⁻² g / (m ² · 24 h) Rank 5 Δ ×: Water vapor permeability is 1 × 10 ⁻² g / (m ² · 24h) or more and less than 5 × 10 ⁻² g / (m ² · 24h) Rank 6 ×: Water vapor permeability is 5 × 10 ⁻² g / (m ² · 24 h) or more.

<Optical characteristics>
The transmission spectrum was measured using a spectrocolorimeter CM-3700A (manufactured by Konica Minolta Co., Ltd.), and the transparency was ranked based on the light transmittance (%) at a wavelength of 450 nm for samples 1 to 21 according to the following evaluation criteria. Ranks 1 to 3 are practical transparency.
Rank 1 ◎: Light transmittance at a wavelength of 450 nm is 91% or more Rank 2 ○: Light transmittance at a wavelength of 450 nm is 90% or more and less than 91% Rank 3 ○ Δ: Light transmittance at a wavelength of 450 nm is 88% or more 90 Rank less than% 4 Δ: Light transmittance at a wavelength of 450 nm is 85% or more and less than 88% Rank 5 Δ ×: Light transmittance at a wavelength of 450 nm is 80% or more and less than 85% Rank 6 ×: Light transmittance at a wavelength of 450 nm Less than 80%.

This application is based on Japanese Patent Application No. 2016-127952 filed on June 28, 2016, the disclosure of which is incorporated by reference in its entirety.

1 gas barrier film,
2 base material,
3 gas barrier layer,
31 manufacturing equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 Take-up roller.

Claims

Using a composition containing 0.1 to 10 μg / L of at least one metal element selected from the group consisting of Sn, Pt, and Au and an organosiloxane compound, the gas barrier layer is formed by plasma enhanced chemical vapor deposition. The manufacturing method of a gas-barrier film including forming on a material.
The method for producing a gas barrier film according to claim 1, wherein the organosiloxane compound has a Si-O-Si structure in the molecule.
The method for producing a gas barrier film according to claim 2, wherein the organic siloxane compound is a cyclic siloxane compound.
The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the amount of the metal element in the composition is 2 to 5 µg / L.
The production of a gas barrier film according to any one of claims 1 to 4, wherein the formation of the gas barrier layer by the plasma chemical vapor deposition method is performed by a plasma CVD apparatus having a counter roll electrode provided with a magnetic field generator therein. Method.