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WO2018003274A1 - Procédé de production de film formant une barrière aux gaz - Google Patents

Procédé de production de film formant une barrière aux gaz Download PDF

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Publication number
WO2018003274A1
WO2018003274A1 PCT/JP2017/016809 JP2017016809W WO2018003274A1 WO 2018003274 A1 WO2018003274 A1 WO 2018003274A1 JP 2017016809 W JP2017016809 W JP 2017016809W WO 2018003274 A1 WO2018003274 A1 WO 2018003274A1
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WO
WIPO (PCT)
Prior art keywords
gas barrier
film
gas
barrier layer
plasma
Prior art date
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PCT/JP2017/016809
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English (en)
Japanese (ja)
Inventor
鈴木　一生
河村　朋紀
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to CN201780040108.5A priority Critical patent/CN109415805B/zh
Priority to JP2018524920A priority patent/JP6888623B2/ja
Publication of WO2018003274A1 publication Critical patent/WO2018003274A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes

Definitions

  • the present invention relates to a method for producing a gas barrier film by a plasma chemical vapor deposition method.
  • 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.
  • a gas barrier film By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.
  • 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.
  • LCD liquid crystal display elements
  • PV solar cells
  • EL organic electroluminescence
  • a method for producing a gas barrier film 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.
  • 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.
  • a gas barrier film 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).
  • LCD liquid crystal display element
  • EL organic electroluminescence
  • 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.
  • 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.
  • plasma CVD plasma chemical vapor deposition
  • 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 ⁇ g / 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.
  • 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.
  • 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.
  • 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.
  • X to Y indicating a range means “X or more and Y or less”.
  • 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.
  • polyester resins for example, polyethylene terephthalate resin
  • acrylic resins for example, polyethylene terephthalate resin
  • 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.
  • this base material 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.
  • this base material can be used individually or in combination of 2 or more types.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, and more preferably 20 to 200 ⁇ m.
  • 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 ⁇ g / 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.
  • metal elements for example, Ag and Cu
  • the amount of metal elements in the composition may be 0.1 to 10 ⁇ g / L, but from the viewpoint of a further balance between gas barrier performance and transparency, 1 It is preferably ⁇ 8 ⁇ g / L, more preferably 2 to 5 ⁇ g / L, and even more preferably 3 to 5 ⁇ g / L. Among these, Sn is preferable as the metal element.
  • 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.
  • 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.
  • 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
  • dibutyltin dilaurate is preferable as the tin compound
  • hexachloroplatinum (IV) acid is preferable as the platinum compound
  • chloro (triphenylphosphine) gold (I) is preferable as the gold compound.
  • 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.
  • 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.
  • 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.
  • a plasma discharge in a space between a plurality of film forming rollers 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.
  • the plasma is generated by discharging between the pair of film forming rollers.
  • the film formation rate can be doubled, and a film having a substantially identical structure can be formed.
  • a film forming gas used in such a plasma CVD method a gas containing an organosiloxane compound and oxygen is preferable.
  • the first roller 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.
  • 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.
  • 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.
  • a pair of film-forming roller film-forming rollers 39 and 40
  • position a pair of film-forming roller film-forming rollers 39 and 40
  • the film forming rate can be doubled and a film having the same structure can be formed.
  • 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.
  • 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.
  • 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 mm ⁇ , particularly in the range of 300 to 700 mm ⁇ , from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mm ⁇ 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 mm ⁇ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.
  • the base material etc. are arrange
  • the substrate and the like 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.
  • 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.
  • 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.
  • the plasma generating power source 42 a known power source of a plasma generating apparatus can be used as appropriate.
  • 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.
  • 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.
  • the magnetic field generators 43 and 44 known magnetic field generators can be used as appropriate.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • source 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.
  • 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.
  • 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-
  • 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.
  • organosiloxane compound examples 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
  • 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.
  • the organosiloxane compound those having a Si—O—Si structure in the molecule are preferable from the viewpoint of gas barrier properties.
  • the organic siloxane compound is more preferably a cyclic siloxane compound from the viewpoint of achieving both gas barrier properties and transparency.
  • 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.
  • a reactive gas may be used in addition to the source 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.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • 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.
  • a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • 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.
  • 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 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.
  • a plasma using a plasma CVD apparatus 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.
  • the metals contained in each gas barrier layer may be the same or different.
  • the total thickness of the gas barrier layer is the thickness of the gas barrier layer.
  • 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.
  • XPS Xray Photoelectron spectroscopy
  • 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).
  • 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.
  • 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-K ⁇ Measurement area: Si2p, Al2p, Nb3d, Ta4d, Hf4d, Ti2p, Zr3d, Ru3d, Y3p, C1s, N1s, O1s
  • Irradiated X-ray Single crystal spectroscopy AlK ⁇ ⁇ X-ray spot and its size: 800 ⁇ 400 ⁇ m oval shape
  • ⁇ Sputtering ion Ar (2 keV)
  • Depth profile Repeat measurement after sputtering for 1 minute.
  • layers (functional layers) having various functions may be provided on the gas barrier film.
  • a functional layer 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.
  • 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.
  • polyester resins 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.
  • 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).
  • the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition.
  • a vapor phase method such as physical vapor deposition or chemical vapor deposition.
  • an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
  • 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.
  • 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 ⁇ m.
  • a hard coat layer may be provided on the surface (one side or both sides) of the substrate.
  • 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.
  • 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.
  • 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.
  • 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.
  • a wet 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
  • 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 ⁇ m.
  • 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.
  • a resin composition containing an acrylate compound having a radical reactive unsaturated compound for example, 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.
  • 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.
  • 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.
  • 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.
  • a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method
  • a dry coating method such as a vapor deposition method. preferable.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary.
  • 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 ⁇ m, more preferably in the range of 2 to 7 ⁇ m, 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
  • 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).
  • 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%).
  • 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.).
  • 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.
  • 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).
  • Example 1 ⁇ Preparation of Sample 1> (Preparation of base material) A 100 ⁇ m-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 ⁇ m 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 ⁇ m, 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 .
  • UV ultraviolet
  • a hard coat layer having a thickness of 2 ⁇ m 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 ⁇ m, 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.
  • this base material with a hard coat layer is simply referred to as a base material.
  • Dibutyltin dilaurate is mixed with 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS) to prepare a tin (Sn) concentration of 1 ⁇ g / L (ratio of tin to the total volume of the mixture).
  • TCTS 2,4,6,8-tetramethylcyclotetrasiloxane
  • 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 ⁇ m formed above) using the plasma CVD raw material.
  • Sample 1 was prepared by plasma CVD.
  • 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.
  • 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 ⁇ g / L.
  • 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 ⁇ g / L.
  • 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 ⁇ g / L.
  • 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 ⁇ g / L.
  • 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 ⁇ g / 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 ⁇ g / 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 ⁇ g / L (ratio of gold to the total volume of the mixture) A sample 8 was prepared in the same manner as in Example 1.
  • 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.
  • 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 ⁇ g / L (ratio of silver to the total volume of the mixture). Sample 10 was produced in the same manner.
  • 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 ⁇ g / 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 ⁇ g / L (ratio of tin to the total volume of the mixture). Sample 12 was prepared in the same manner as described above.
  • HMDSO hexamethyldisiloxane
  • 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 ⁇ g / L.
  • 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 ⁇ g / L.
  • 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 ⁇ g / L.
  • 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 ⁇ g / L.
  • 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 ⁇ g / L was used.
  • 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 ⁇ g / L was used. .
  • 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 ⁇ g / L.
  • DMTSO decamethyltetrasiloxane
  • 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 ⁇ g / L.
  • TEOS tetraethoxysilane
  • 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.
  • 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 ⁇ ⁇ Light transmittance at a wavelength of 450 nm is 88% or more 90 Rank less than% 4 ⁇ : Light transmittance at a wavelength of 450 nm is 85% or more and less than 88% Rank 5 ⁇ ⁇ : 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%.

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Abstract

La présente invention concerne un procédé de production d'un film formant une barrière aux gaz, qui présente d'excellentes propriétés de barrière aux gaz et qui est hautement transparent. La présente invention concerne un procédé de production d'un film formant une barrière aux gaz, qui comprend la formation d'une couche formant une barrière aux gaz sur un matériau de base par dépôt chimique en phase vapeur par plasma à l'aide d'une composition qui contient un composé organique de type siloxane et 0,1-10 μg/l d'au moins un élément métallique choisi dans le groupe constitué par Sn, Pt et Au.
PCT/JP2017/016809 2016-06-28 2017-04-27 Procédé de production de film formant une barrière aux gaz WO2018003274A1 (fr)

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JP2003089163A (ja) * 2001-09-17 2003-03-25 Dainippon Printing Co Ltd バリアフィルムとこれを用いた積層材、包装用容器、画像表示媒体およびバリアフィルムの製造方法
WO2006033233A1 (fr) * 2004-09-21 2006-03-30 Konica Minolta Holdings, Inc. Film barriere contre les gaz transparent
JP2011073430A (ja) * 2009-09-01 2011-04-14 Sumitomo Chemical Co Ltd ガスバリア性積層フィルム

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WO2011052764A1 (fr) * 2009-10-30 2011-05-05 住友化学株式会社 Processus de production d'un film multicouche
JP6156388B2 (ja) * 2012-10-19 2017-07-05 コニカミノルタ株式会社 ガスバリアー性フィルムの製造方法、ガスバリアー性フィルム及び電子デバイス
JP6252493B2 (ja) * 2013-01-11 2017-12-27 コニカミノルタ株式会社 ガスバリア性フィルム
WO2015060394A1 (fr) * 2013-10-24 2015-04-30 コニカミノルタ株式会社 Film barrière contre les gaz
US9620150B2 (en) * 2014-11-11 2017-04-11 Seagate Technology Llc Devices including an amorphous gas barrier layer

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JP2003089163A (ja) * 2001-09-17 2003-03-25 Dainippon Printing Co Ltd バリアフィルムとこれを用いた積層材、包装用容器、画像表示媒体およびバリアフィルムの製造方法
WO2006033233A1 (fr) * 2004-09-21 2006-03-30 Konica Minolta Holdings, Inc. Film barriere contre les gaz transparent
JP2011073430A (ja) * 2009-09-01 2011-04-14 Sumitomo Chemical Co Ltd ガスバリア性積層フィルム

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