WO2015025783A1 - Dispositif de production de film barrière contre les gaz et procédé de production de film barrière contre les gaz - Google Patents

Dispositif de production de film barrière contre les gaz et procédé de production de film barrière contre les gaz Download PDF

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Publication number
WO2015025783A1
WO2015025783A1 PCT/JP2014/071357 JP2014071357W WO2015025783A1 WO 2015025783 A1 WO2015025783 A1 WO 2015025783A1 JP 2014071357 W JP2014071357 W JP 2014071357W WO 2015025783 A1 WO2015025783 A1 WO 2015025783A1
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Prior art keywords
gas barrier
gas
film forming
film
barrier film
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PCT/JP2014/071357
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English (en)
Japanese (ja)
Inventor
千明 門馬
大石　清
浩了 有田
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コニカミノルタ株式会社
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Priority to JP2015532832A priority Critical patent/JP6341207B2/ja
Publication of WO2015025783A1 publication Critical patent/WO2015025783A1/fr

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    • 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
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • 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
    • C23C16/308—Oxynitrides
    • 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
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3266—Magnetic control means
    • H01J37/32669—Particular magnets or magnet arrangements for controlling the discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32733—Means for moving the material to be treated
    • H01J37/32752—Means for moving the material to be treated for moving the material across the discharge
    • H01J37/32761—Continuous moving
    • H01J37/3277—Continuous moving of continuous material

Definitions

  • the present invention relates to a gas barrier film manufacturing apparatus and a gas barrier film manufacturing method. More specifically, an apparatus for manufacturing a transparent gas barrier film having excellent flexibility, used for gas blocking of electronic devices such as liquid crystals, organic electroluminescence (organic EL), solar cells, and electronic paper, and manufacturing of a gas barrier film Regarding the method.
  • an apparatus for manufacturing a transparent gas barrier film having excellent flexibility used for gas blocking of electronic devices such as liquid crystals, organic electroluminescence (organic EL), solar cells, and electronic paper, and manufacturing of a gas barrier film Regarding the method.
  • a resin base material such as a transparent plastic has a problem that the gas barrier property is inferior to a glass base material. It has been found that when a base material with poor gas barrier properties is used, water vapor or oxygen penetrates and, for example, the function in the electronic device is deteriorated.
  • a layer having a gas barrier property (hereinafter referred to as a gas barrier layer) is formed on a resin base material, and these laminates are used as a gas barrier film.
  • gas barrier films used for packaging materials and liquid crystal display elements that require gas barrier properties are known in which silicon oxide is vapor-deposited on a resin substrate, and in which aluminum oxide is vapor-deposited. Yes.
  • an inter-roller discharge plasma chemical vapor deposition method (hereinafter also referred to as a roller CVD method) to which a magnetic field is applied has been proposed as a method for forming a gas barrier layer that can achieve both high gas barrier properties and high productivity.
  • a roller CVD method an inter-roller discharge plasma chemical vapor deposition method to which a magnetic field is applied has been proposed as a method for forming a gas barrier layer that can achieve both high gas barrier properties and high productivity.
  • FIG. 8 shows a film forming apparatus (hereinafter referred to as a roller CVD apparatus) 100 to which the roller CVD method is applied.
  • a roller CVD apparatus 100 to which the roller CVD method is applied.
  • the roller CVD apparatus 100 along the transport direction X of the resin base material K, the feed roller 101, the transport roller 102, the film forming roller 103, the transport rollers 104 and 105, the film forming roller 106, the transport A roller 107 and a take-up roller 108 are arranged in this order, and the resin base material K is transported in the transport direction X while applying a predetermined tension to the resin base material K sent from the feed roller 101. ing.
  • the pair of film forming rollers 103 and 106 are arranged close to each other with their peripheral surfaces facing each other, and are connected to the plasma generation power source 110 so as to function as a pair of counter electrodes, respectively.
  • plasma can be generated by discharging into a space 109 (also referred to as a discharge space) between the film forming roller 103 and the film forming roller 106.
  • Magnetic field generators 111 and 112 are provided inside the film forming roller 103 and the film forming roller 106, respectively, and are fixed so as to follow the rotation of the film forming rollers 103 and 106 and do not rotate themselves.
  • a gas supply port 113 for supplying a film forming gas (raw material gas or the like) into the discharge space 109 at a predetermined speed and a vacuum pump 116 are connected to the gas from the discharge space 109.
  • the gas discharge port 114 for discharging the gas and the gas supplied from the gas supply port 113 and the film forming material formed due to the gas pass through the discharge space 109 and then the gas. It is discharged from the discharge port 114.
  • the vacuum chamber 120 Is placed inside.
  • a plasma discharge is generated between the pair of film forming rollers 103 and 106 while supplying a film forming gas (such as a raw material gas) into the discharge space 109.
  • a film forming gas (raw material gas or the like) is decomposed by plasma, and a gas barrier layer is formed on the surface of the resin base material K on the film forming roller 103 and the surface of the resin base material K on the film forming roller 106 by a roller CVD method. It is formed.
  • the film formation efficiency of the gas barrier layer is improved by the magnetic field generated by the magnetic field generators 111 and 112, and the concentration gradient of each element component such as carbon atoms continuously changes in the gas barrier layer. Adhesion, flexibility and gas barrier properties are improved.
  • the film forming material to be discharged from the gas discharge port 114 through the discharge space 109 between the film forming rollers 103 and 106 diffuses into the vacuum chamber 120.
  • Such a film forming material adheres and accumulates on the film forming rollers 103 and 106.
  • the dielectric constant of the electrode changes when the film forming roller and the resin base material K are integrally regarded as electrodes, and plasma is generated. Therefore, the concentration gradient of each element component in the gas barrier layer cannot be provided as designed, and the gas barrier property of the gas barrier film is lowered.
  • Such a problem becomes prominent when film formation is performed continuously, and becomes particularly remarkable in the region of the end portion of the resin base material that is fed from the feed roller 101 and formed into a film.
  • the present invention has been made in view of the above-described problems and situations, and a solution to the problem is to provide a gas barrier film manufacturing apparatus and a gas barrier film manufacturing method capable of preventing deterioration of the quality of the gas barrier film. It is to be.
  • the present inventors have found that the problems of the present invention can be solved by preventing adhesion / deposition of the film forming material to the film forming roller in the process of examining the cause of the above problems, etc.
  • the present invention has been reached.
  • a vacuum chamber having at least a pair of inner wall surfaces facing each other; A pair of resin bases that are arranged to extend between the pair of inner wall surfaces so as to form a facing space with each other and that are wound while being conveyed are opposed to each other through the facing space.
  • a film forming roller A magnetic field generating member that is provided inside each film forming roller and generates a swelled magnetic field in the vicinity of a region facing the facing space of the peripheral surface of the film forming roller, A plasma generating power source connected to the pair of film forming rollers and generating plasma by causing discharge in the facing space; A gas supply port that is disposed on one of the upper side and the lower side of the opposing space and supplies a film forming gas to the opposing space; A gas exhaust port disposed on the other of the upper side and the lower side of the opposing space, for exhausting the gas in the opposing space to the outside of the vacuum chamber; With In a gas barrier film manufacturing apparatus for forming a gas barrier layer on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied, Of the peripheral surface of the film forming roller, it is exposed without contacting the resin base material, and covers an exposed region adjacent to the contact region with the resin base material in the circumferential
  • An apparatus for producing a gas barrier film comprising a covering member.
  • the covering member is 2.
  • the covering member is The apparatus for producing a gas barrier film according to any one of claims 1 to 4, wherein the apparatus is disposed at a position separated from the exposed region by 0.1 to 100 mm. 6).
  • the covering member is 6.
  • the covering member is 7.
  • the covering member is 8.
  • the apparatus for producing a gas barrier film according to any one of claims 1 to 8, further comprising a partition wall surrounding a space from the facing space to the gas discharge port. 10.
  • the pair of film forming rollers disposed outside the space between the pair of inner wall surfaces of the vacuum chamber and including the facing space and surrounded by the partition wall and the resin base material.
  • a supply port for supplying non-reactive gas is provided on the side of each roller including 10.
  • a method for producing a gas barrier film using the apparatus for producing a gas barrier film according to any one of Items 1 to 10 The film-forming gas supplied from the gas supply port to the facing space is a film-forming gas containing an organosilicon compound, Forming a gas barrier layer containing carbon atoms, silicon atoms and oxygen atoms on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied.
  • a method for producing a gas barrier film is a film-forming gas containing an organosilicon compound, Forming a gas barrier layer containing carbon atoms, silicon atoms and oxygen atoms on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied.
  • the quality of the gas barrier film can be prevented by the above means of the present invention.
  • the covering member covers the exposed area of the peripheral surface of the film forming roller, it is considered that the film forming material diffused in the vacuum chamber is prevented from adhering and depositing on the film forming roller. Therefore, it is considered that the concentration gradient of each element component in the gas barrier layer can be provided as designed, and the quality deterioration of the gas barrier film can be prevented.
  • An apparatus for producing a gas barrier film of the present invention includes a vacuum chamber having at least a pair of inner wall surfaces facing each other, and an extended space between the pair of inner wall surfaces so as to form an opposing space therebetween.
  • a pair of film-forming rollers that are disposed and conveyed while being opposed to each other through the facing space; and provided inside each film-forming roller, of the peripheral surfaces of the film-forming rollers Near the region facing the facing space, a magnetic field generating member that generates a swelled magnetic field, a plasma generation power source that is connected to the pair of film forming rollers and discharges the facing space to generate plasma, and
  • a gas supply port that is disposed on one of the upper and lower sides of the facing space and supplies a film forming gas containing an organosilicon compound to the facing space; on the other of the upper and lower sides of the facing space
  • a gas exhaust port for exhausting the gas in the facing space to the outside of the vacuum chamber, and one of the resin substrates by plasma chemical vapor deposition while
  • the covering member is formed to be curved along the peripheral surface of the film forming roller in the circumferential direction of the film forming roller.
  • the manufacturing apparatus of a gas barrier film is provided with the temperature control part which maintains the said coating
  • the covering member is preferably disposed at a position separated from the exposed region by 0.1 to 100 mm, preferably 0.1 to 50 mm, more preferably 0.1 to 25 mm.
  • the said covering member is provided with respect to the manufacturing apparatus of the said gas barrier film so that attachment or detachment is possible.
  • the “gas barrier property” referred to in the present invention is a water vapor permeability (temperature: 60 ⁇ 0.5 ° C., relative humidity (RH): 90 ⁇ 2%) measured by a method according to JIS K 7129-1992. ) Is 3 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 mL / m 2 ⁇ 24 h ⁇ atm or less. It means that.
  • vacuum ultraviolet light specifically mean light having a wavelength of 100 to 200 nm.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • ⁇ Basic structure of gas barrier film ⁇ 1A and 1B are schematic cross-sectional views showing an example of the basic configuration of the gas barrier film of the present invention.
  • the gas barrier film 1 of this invention is the resin base material 2 as a support body, the smoothing layer 3 formed in the one surface of the said resin base material 2, and between rollers.
  • a second gas barrier layer 5 formed by subjecting a polysilazane coating film to vacuum ultraviolet irradiation (VUV) treatment is disposed on the gas barrier layer 4 as required (FIG. 1B).
  • the surface on which the gas barrier layer 4 is formed has a surface free energy dispersion component of 30 to 40 mN / min in an environment of 23 ° C. and 50% RH.
  • the smoothing layer 3 within the range of m is formed.
  • the dispersion component of the surface free energy is in the range of 33 to 38 mN / m because adhesion and gas barrier properties are improved.
  • many carbon atom components can be oriented in a portion close to the resin substrate 2, and as a result, the adhesion between the resin substrate 2 and the gas barrier layer 4 is improved, and the gas barrier property is also improved.
  • the surface free energy dispersion component in the smoothing layer 3 is 30 to 40 mN / m or more, a surface having good wettability with the gas barrier layer 4 by the inter-roller discharge plasma chemical vapor deposition method can be obtained.
  • the carbon atom component in the peripheral part of the base material 2 can be controlled to a predetermined condition, and as a result, excellent adhesion and barrier properties can be realized.
  • the dispersion component of the surface free energy is less than 30 mN / m or greater than 40 mN / m, the carbon atom component around the resin base material 2 decreases, and as a result, the adhesion and barrier properties deteriorate. .
  • the dispersion component ⁇ SD value of the surface free energy is measured by the following method. Measure the contact angle between the surface of the smoothing layer 3 and three kinds of solvents, water, nitromethane, and diiodomethane as standard liquids, using an automatic contact angle measuring device CA-V (manufactured by Kyowa Interface Chemical Co., Ltd.) Then, the ⁇ SH value was calculated based on the following formula, and the dispersion component ⁇ SD and the hydrogen bond component ⁇ SH value (mN / m) of the surface free energy of the smoothing layer 3 were obtained. In addition, the contact angle was 3 ⁇ l of the solvent dropped on the surface of the smoothing layer 3 in an environment of 23 ° C. and 50% RH, and a value 100 ms after the landing was used.
  • ⁇ L ⁇ (1 + cos ⁇ ) / 2 ( ⁇ SD ⁇ ⁇ LD) 1/2 + ( ⁇ SP ⁇ ⁇ LP) 1/2 + ( ⁇ SH ⁇ ⁇ LH) 1/2
  • ⁇ L surface tension of liquid
  • ⁇ contact angle between liquid and solid ⁇ SD
  • ⁇ SP dispersion of solid surface free energy
  • polarity hydrogen bonding component
  • ⁇ LD surface free energy
  • ⁇ LP dispersion of surface free energy of liquid, polarity
  • hydrogen Binding component ⁇ L ⁇ LD + ⁇ LP + ⁇ LH
  • ⁇ S ⁇ SD + ⁇ SP + ⁇ SH
  • the surface free energy ( ⁇ SD, ⁇ SP, ⁇ SH) of the three components of the standard liquid can be obtained by solving the ternary simultaneous equations from the respective contact angle values using the following values.
  • Each component value ( ⁇ sd, ⁇ sp, ⁇ sh) was determined. [Water (29.1, 1.3, 42.4), Nitromethane (18.3, 17.7, 0), Diiodomethane (46.8, 4.0, 0)]
  • the smoothing layer 3 is not particularly limited as long as it has the above surface free energy, but contains a resin having a radical reactive unsaturated bond, inorganic particles, a photoinitiator, a solvent, and a reactive diluent. Further, it is preferable that the reactive diluent is contained in an amount of 0.1 to 10% by mass as the content ratio in the smoothing layer 3.
  • the composition ratio of the resin having a radical reactive unsaturated bond, the inorganic particles, the photoinitiator, the solvent, and the reactive diluent, and the structure and size of each constituent material are appropriately adjusted. Therefore, it is preferable from the viewpoint of adjusting to a desired surface free energy.
  • Resin having a radical-reactive unsaturated bond examples include epoxy resins, acrylic resins, urethane resins, polyester resins, silicone resins, and ethylene vinyl. Examples thereof include acetate (EVA) resin. By using these, the light transmittance of the resin composition can be further enhanced.
  • a photocurable or thermosetting resin type having a radical-reactive unsaturated bond is preferable, among them, from the viewpoint of productivity, obtained film hardness, smoothness, transparency, etc.
  • an ultraviolet curable resin is preferable.
  • any resin that can be cured by ultraviolet irradiation to form a transparent resin composition can be used without limitation. From the viewpoint of the hardness, smoothness, and transparency of the resulting smoothing layer 3. It is preferable to use acrylic resin, urethane resin, polyester resin, and the like.
  • acrylic resin composition examples include acrylate compounds having a radical reactive unsaturated bond, mercapto compounds having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate, and the like. What dissolved the polyfunctional acrylate monomer etc. are mentioned. Moreover, it is also possible to use it as a mixture which mixed the above resin compositions in arbitrary ratios, and resin containing the reactive monomer which has one or more photopolymerizable unsaturated bonds in a molecule
  • Preferable specific examples include UV curable resin unidic V-4025, A-BPEF (fluorene-containing acrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) manufactured by DIC Corporation, and LCH1559 (manufactured by Toyochem: hybrid hard coat agent containing silica).
  • A-BPEF fluorene-containing acrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.
  • LCH1559 manufactured by Toyochem: hybrid hard coat agent containing silica
  • LCH1559 containing inorganic particles is preferable.
  • photopolymerization initiator known ones such as Irgacure 184 (manufactured by BASF Japan) can be used, and one or a combination of two or more can be used.
  • the reactive diluent applicable to the smoothing layer 3 is a monofunctional reactive monomer having one acryloyl group or one methacryloyl group per molecule, and is originally a highly viscous oligomer. In this embodiment, it also serves to adjust the surface free energy dispersion component.
  • the reactive diluent has a role of adjusting the dispersion component of the surface free energy, and therefore preferably has a polar group or a hydrophobic group.
  • the polar group include an epoxy group, an ethylene oxide group, a carbonyl group, a hydroxy group, a carboxy group, a phosphate group, and a primary, secondary, or tertiary amino group.
  • the hydrophobic group includes a methylene group. , Isobonyl groups, penteniol groups, and the like. By combining both structures, the surface free energy can be appropriately adjusted by adjusting the addition amount.
  • the addition amount of the reactive diluent is 0.1 to 10% by mass as a mass ratio with respect to the smoothing layer 3 from the viewpoint of the obtained surface free energy dispersion component, formation of a cured coating film, surface hardness, and the like. Is preferred. More preferably, it is 1 to 5% by mass.
  • an appropriate surface free energy dispersion component can be obtained on the surface of the smoothing layer 3, and sufficient adhesion to the gas barrier layer 4 and gas barrier properties can be obtained. preferable. In addition, sufficient smoothness and hardness can be obtained, and it is preferable that the roller contact when performing the inter-roller discharge plasma chemical vapor deposition method is not damaged.
  • preferred reactive diluents include fluorine oligomers manufactured by AGC Seimi Chemical Co., Ltd .: Surflon S-651, hydroxyethyl methacrylate, FA-512M (dicyclopentenyloxyethyl methacrylate (Hitachi Chemical Co., Ltd.)), Phosphoric acid acrylate: Light acrylate P-1A (Kyoeisha Chemical Co., Ltd.), GMA (Light Ester G glycidyl methacrylate (Kyoeisha Chemical Co., Ltd.)), and isobornyl methacrylate: Light Ester IB-X (Kyoeisha Chemical) However, it is not limited to these.
  • inorganic particles applicable to the smoothing layer 3 include silica fine particles such as dry silica and wet silica, titanium oxide, zirconium oxide, zinc oxide, tin oxide, cerium oxide, antimony oxide, and indium tin.
  • examples include metal oxide fine particles such as mixed oxide and antimony tin mixed oxide, and organic fine particles such as acrylic and styrene.
  • silica fine particles in the range of 10 to 50 nm are dispersed in an organic solvent from the viewpoint of transparency and hardness. The dispersed nano-dispersed silica particles are preferable.
  • the inorganic particles are preferably blended in the range of 5 to 50 parts by weight, particularly in the range of 10 to 40 parts by weight with respect to 100 parts by weight of the curable resin constituting the smoothing layer 3. Is preferred.
  • the addition amount is also appropriately determined according to the arithmetic average roughness described later.
  • the smoothing layer 3 is a composition (smooth) using the above-described resin having a radical-reactive unsaturated bond, inorganic particles, a photoinitiator, a solvent, and a reactive diluent.
  • resin having a radical-reactive unsaturated bond
  • inorganic particles having a radical-reactive unsaturated bond
  • a photoinitiator for example, doctor blade method, spin coating method, dipping method, table coating method, spray method, applicator method, curtain coating method, die coating method, ink jet method, dispenser method, etc., if necessary It can be formed by adding a curing agent and curing the resin composition by heating or ultraviolet irradiation.
  • an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is used, and a range of 100 to 400 nm emitted from these light sources, preferably 200
  • the irradiation can be performed by irradiating ultraviolet rays in a wavelength region within a range of ⁇ 400 nm or irradiating an electron beam in a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.
  • the thickness of the smoothing layer 3 is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m, particularly preferably in the range of 0.5 to 5 ⁇ m. Further, the smoothing layer 3 may be composed of two or more layers.
  • additives such as an antioxidant, a plasticizer, another matting agent, and a thermoplastic resin can be added as necessary.
  • distributed resin in the solvent Well-known alcohol solvent, aromatic carbonization It can be used by appropriately selecting from conventionally known organic solvents such as hydrogen solvents, ether solvents, ketone solvents, ester solvents and the like. Among these, MEK (methyl ethyl ketone) can be preferably used.
  • the smoothing layer 3 preferably has a surface arithmetic average roughness Ra value in the range of 0.5 to 2.0 nm, more preferably in the range of 0.8 to 1.5 nm.
  • the arithmetic average roughness Ra of the smoothing layer 3 is in the range of 0.5 to 2.0 nm, the surface of the smoothing layer 3 has an appropriate roughness, and the gas barrier layer is caused by friction with the roller. 4 is stable, and the gas barrier layer 4 can be formed with high accuracy by the inter-roller discharge plasma chemical vapor deposition method. Therefore, the uniform gas barrier layer 4 can be formed.
  • the arithmetic average roughness Ra of the surface of the smoothing layer 3 can be measured by the following method. ⁇ Method of measuring surface arithmetic average roughness Ra; AFM measurement> The arithmetic average roughness Ra is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus having a minimum tip radius, and the minimum tip Measurement is made many times in a section whose measuring direction is several tens of ⁇ m with a radius stylus, and it is obtained as roughness relating to the amplitude of fine irregularities.
  • AFM Anamic Force Microscope
  • Gas barrier layer 4 The gas barrier layer 4 is formed on the surface of the smoothing layer 3 by an inter-roller discharge plasma chemical vapor deposition method to which a magnetic field is applied.
  • the gas barrier layer 4 in the present invention uses a raw material gas containing an organosilicon compound and a reaction gas as a film forming gas, and contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements. It is a more preferable embodiment that all the conditions of the carbon atom distribution profile defined by “)” to “Condition (4)” are satisfied.
  • Carbon atom ratio of the gas barrier layer 4 is within a distance range of 90 to 95% of the layer thickness in the vertical direction from the surface of the gas barrier layer 4 in the layer thickness direction (adjacent to the resin base material 2). Within a distance range of 5 to 10% from the surface to be continuous).
  • Carbon atom ratio of the gas barrier layer 4 is within a distance range of 90 to 95% of the layer thickness in the direction perpendicular to the surface of the gas barrier layer 4 in the layer thickness direction (resin substrate 2) within a distance range of 5 to 10% in the vertical direction from the surface adjacent to 2.
  • the average value of the carbon atom content ratio and the carbon atom distribution profile in the gas barrier layer 4 can be obtained by measurement of an XPS depth profile described later.
  • the gas barrier layer 4 contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements, and the distance from the surface in the layer thickness direction of the gas barrier layer 4 and silicon
  • the carbon atom content profile has the above-mentioned “condition (1)” to “condition ( It is preferable that all the conditions of “4)” are satisfied from the viewpoint of obtaining the gas barrier film 1 having further excellent flexibility (flexibility) and adhesion.
  • the carbon atom ratio has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the gas barrier layer 4 from the viewpoint of achieving both gas barrier properties and flexibility.
  • the carbon distribution curve in the layer has at least one extreme value. Furthermore, it is more preferable to have at least two extreme values, and it is particularly preferable to have at least three extreme values.
  • the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film 1 is bent is insufficient. Further, in the case of having at least two or three extreme values as described above, the gas in the thickness direction of the gas barrier layer 4 with respect to one extreme value and the extreme value adjacent to the extreme value included in the carbon distribution curve.
  • the absolute value of the difference in distance from the surface of the barrier layer 4 is preferably 200 nm or less, and more preferably 100 nm or less.
  • the extreme value refers to the maximum value or the minimum value of the atomic ratio of each element.
  • the local maximum value means that the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer 4 is changed.
  • the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the gas barrier layer 4 is changed, and the atomic ratio of the element at that point
  • the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer 4 in the layer thickness direction of the gas barrier layer 4 from the above point is further changed by 20 nm is increased by 3 at% or more.
  • the maximum value of the carbon atom ratio within a distance range of 89% in the vertical direction from the surface (the surface opposite to the surface in contact with the resin base material 2) is less than 20 at%.
  • the maximum value of the carbon atom ratio within the distance range of 90 to 95% perpendicular to the surface (within the distance range of 5 to 10% from the surface adjacent to the resin base material 2) is 20 at % Or more is a preferred embodiment.
  • the gas barrier layer 4 has (2) a carbon atom ratio having a concentration gradient within a distance range of 89% in the vertical direction from the surface. And (4) in the range of 90 to 95% in the vertical direction from the surface, in other words, from the surface adjacent to the resin substrate 2 toward the surface portion, It is a preferred embodiment that the carbon atom ratio continuously increases in the range of 5 to 10% in the direction of the layer thickness.
  • the concentration gradient of the carbon atom ratio continuously changes means that the carbon distribution ratio in the carbon distribution curve does not include a portion where the carbon atom ratio changes discontinuously.
  • the following formula It means that the condition represented by F1) is satisfied.
  • the gas barrier layer 4 is characterized by containing carbon atoms, silicon atoms and oxygen atoms as constituent elements, and the ratio, maximum value and minimum value of each atom. A preferred embodiment for the value is described below.
  • the absolute value of the difference between the maximum value and the minimum value of carbon atom ratio in the carbon distribution curve is 5 at% or more. preferable.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, and particularly preferably 7 at% or more.
  • the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve is preferably 5 at% or more. % Or more is more preferable, and 7 at% or more is particularly preferable. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film 1 is bent is sufficient.
  • the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve is preferably less than 5 at%. % Is more preferable, and it is particularly preferable that it is less than 3 at%. If the absolute value is less than 5 at%, the gas barrier film 1 obtained has sufficient gas barrier properties and mechanical strength.
  • the total amount of silicon atoms, oxygen atoms and carbon atoms means silicon.
  • the total number of atoms, oxygen atoms and carbon atoms is meant, and “amount of carbon atoms” means the number of carbon atoms.
  • at% means the atomic number ratio of each atom when the total atom number of a silicon atom, an oxygen atom, and a carbon atom is 100 at%.
  • Elemental composition distribution analysis (depth profile) in the layer thickness direction by XPS Silicon distribution curve, oxygen distribution curve, and carbon distribution curve, and oxygen-carbon total distribution curve in the layer thickness direction of the gas barrier layer 4 Is a so-called XPS depth profile measurement that uses Xray Photoelectron Spectroscopy (XPS) measurement and rare gas ion sputtering such as argon to perform surface composition analysis sequentially while exposing the inside of the sample. Can be created.
  • XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time is generally correlated with the distance from the surface of the gas barrier layer 4 in the layer thickness direction of the gas barrier layer 4. “Distance from the surface of the gas barrier layer 4 in the thickness direction of the barrier layer 4” as a distance from the surface of the gas barrier layer 4 calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. Can be adopted.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • the gas barrier layer 4 is formed in the layer surface direction (parallel to the surface of the gas barrier layer 4) from the viewpoint of forming a gas barrier layer 4 that is uniform over the entire layer surface and has excellent gas barrier properties. In the same direction) is preferably substantially uniform.
  • the gas barrier layer 4 is substantially uniform in the layer surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the surface of the gas barrier layer 4 by XPS depth profile measurement.
  • the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the atomic ratio of carbon in each carbon distribution curve is the same.
  • the absolute value of the difference between the maximum value and the minimum value is the same or within 5 at%.
  • the gas barrier film 1 of the present invention preferably includes at least one gas barrier layer 4 that satisfies all of the above-mentioned “condition (1)” to “condition (4)”.
  • Two or more layers may be provided. Further, when two or more such gas barrier layers 4 are provided, the materials of the plurality of gas barrier layers 4 may be the same or different. Further, when two or more such gas barrier layers 4 are provided, such a gas barrier layer 4 may be formed on one surface of the resin base material 2, It may be formed on the surface. Moreover, as such a plurality of gas barrier layers 4, a gas barrier layer 4 that does not necessarily have a gas barrier property may be included.
  • the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atom ratio, the oxygen atom ratio, and the carbon atom ratio are within a distance range from the surface of the gas barrier layer 4 to 89% of the layer thickness.
  • the maximum value of the silicon atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms is preferably in the range of 19 to 40 at%, and more preferably in the range of 25 to 35 at%. More preferred.
  • the maximum value of the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 4 is preferably in the range of 33 to 67 at%, more preferably in the range of 41 to 62 at%.
  • the maximum value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 4 is preferably in the range of 1 to 19 at%, and preferably in the range of 3 to 19 at%. More preferred.
  • the thickness of the gas barrier layer 4 is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and more preferably in the range of 100 to 1000 nm. It is particularly preferable that it is within the range.
  • the gas barrier properties such as oxygen gas barrier property and water vapor barrier property are excellent, and the gas barrier property is not deteriorated by bending.
  • the total thickness of the gas barrier layers 4 is usually in the range of 10 to 10000 nm and in the range of 10 to 5000 nm. It is preferably in the range of 100 to 3000 nm, more preferably in the range of 200 to 2000 nm.
  • gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are sufficient, and the gas barrier properties tend not to decrease due to bending.
  • the gas barrier layer 4 is formed on the surface of the smoothing layer 3 on the resin substrate 2 by an inter-roller discharge plasma chemical vapor deposition method to which a magnetic field is applied.
  • the gas barrier layer 4 in the present invention uses a discharge plasma treatment apparatus between rollers to which a magnetic field is applied, conveys the resin base material 2 while being wound around a pair of film forming rollers, and between the pair of film forming rollers.
  • a film forming gas is supplied while applying a magnetic field to perform plasma discharge, and the film is formed by a plasma chemical vapor deposition method.
  • a film forming gas used in such a plasma chemical vapor deposition method a raw material gas containing an organosilicon compound and a reactive gas are used, and the content of the reactive gas in the film forming gas is set in the film forming gas.
  • the total amount of the organosilicon compound is preferably less than the theoretical amount necessary for complete reaction.
  • the gas barrier layer 4 is a layer formed by the continuous film-forming process.
  • roller CVD method In the discharge plasma chemical vapor deposition method between rollers to which a magnetic field is applied (hereinafter, also simply referred to as “roller CVD method”), formation is performed while applying a magnetic field between a plurality of film forming rollers when generating plasma. It is preferable to generate a plasma discharge in the discharge space, and in the present invention, a pair of film forming rollers is used, and the resin base material 2 is conveyed while being wound around each of the pair of film forming rollers. It is preferable to generate plasma by discharging in a state where a magnetic field is applied between the rollers.
  • the film formation rate can be doubled, and since a film having the same structure can be formed, it is possible to at least double the extreme value in the carbon distribution curve, It is possible to efficiently form a layer satisfying all of the above “condition (1)” to “condition (4)”.
  • the gas barrier layer 4 on the surface of the resin base material 2 by a roll-to-roll method.
  • An apparatus that can be used when manufacturing the gas barrier film 1 by such a plasma chemical vapor deposition method is not particularly limited, but includes a film forming roller including at least a pair of magnetic field applying apparatuses, a plasma, and the like. It is preferable that the apparatus includes a power source and is configured to be capable of discharging between a pair of film forming rollers. For example, when the manufacturing apparatus shown in FIG. The gas barrier film 1 can be produced by a roll-to-roll method while utilizing the growth method.
  • the resin base material 2 in the following description means the resin base material which has the smoothing layer 3 on the surface.
  • FIG. 2 is a schematic diagram illustrating an example of an inter-roller discharge plasma CVD apparatus (hereinafter also referred to as a roller CVD apparatus 20) to which a magnetic field is applied.
  • the roller CVD apparatus 20 is a gas barrier film manufacturing apparatus according to the present invention. As shown in FIG. 2, the long strip-shaped resin substrate 2 having a predetermined width is conveyed by a plurality of rollers in the conveyance direction X. However, the gas barrier film 1 is manufactured by forming the gas barrier layer 4 on the resin substrate 2 by the CVD method.
  • This roller CVD apparatus 20 includes a box-shaped vacuum chamber 200.
  • the vacuum chamber 200 is connected to a vacuum pump 370 so that the internal pressure is appropriately adjusted.
  • the vacuum chamber 200 in the present embodiment has two pairs of inner wall surfaces facing each other.
  • a delivery roller (original winding roller) 25 around which the resin base material 2 is wound is rotatably disposed on the upstream side in the transport direction X, and the resin is disposed on the downstream side in the transport direction X.
  • a winding roller 26 for winding the substrate 2 is rotatably disposed.
  • the feed roller 25 and the take-up roller 26 are a pair of inner wall surfaces facing each other (not shown in FIG. Between the inner wall surfaces of the first and second inner walls).
  • the winding roller 26 is connected to a driving source (not shown) such as a motor for rotating the winding roller 26.
  • a known roller can be appropriately used as long as the resin base material 2 on which the gas barrier layer 4 is formed can be wound.
  • the transport roller 21, the film formation roller 31, the transport rollers 22 and 23, the film formation roller 32, the transport roller from the upstream side to the downstream side in the transport direction X. 24 are arranged in this order.
  • the transport rollers 21 to 24 and the film forming rollers 31 and 32 are rotatably disposed in a state of extending substantially horizontally between the pair of inner wall surfaces in the vacuum chamber 200, respectively.
  • the resin base material 2 is transported in the transport direction X while applying a predetermined tension to 2.
  • the pair of film forming rollers 31 and 32 is disposed so as to form an opposing space (hereinafter also referred to as a discharge space H) between them, and is a resin base wound around itself while being conveyed.
  • the material 2 is made to oppose through the discharge space H.
  • the pair of film forming rollers 31 and 32 are respectively connected to a plasma generating power source 33 and function as a pair of counter electrodes.
  • the plasma generating power source 33 can generate a plasma by causing electric discharge to discharge the discharge space H between the film forming roller 31 and the film forming roller 32.
  • a power source of a known plasma generation apparatus can be used as appropriate.
  • the polarities of the film forming rollers 31 and 32 are alternately set. It is preferable to use one that can be reversed (such as an AC power supply).
  • the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. More preferably, it can be in the range of -500 kHz.
  • the film-forming rollers 31 and 32 that can be used as electrodes, known rollers can be used as appropriate.
  • the film forming rollers 31 and 32 those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently.
  • the diameter of the film forming rollers 31 and 32 is preferably in the range of 100 to 1000 mm ⁇ , particularly in the range of 100 to 700 mm ⁇ , from the viewpoint of discharge conditions, the space of the vacuum chamber 200 described later, and the like.
  • the diameter is 100 mm ⁇ or more, the plasma discharge space H will not be reduced, so there is no decrease in productivity, and it is possible to avoid that the total heat of plasma discharge is applied to the film in a short time, and the residual stress is less likely to increase. .
  • it is 1000 mm ⁇ or less, it is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space H and the like.
  • the pair of film forming rollers 31 and 32 as described above are arranged so that the central axes are substantially parallel to each other.
  • the film forming rate can be doubled and a film having the same structure can be formed.
  • the extreme value can be at least doubled.
  • a magnetic field generator 34 and a magnetic field generator 35 are provided inside the film forming roller 31 and the film forming roller 32, respectively, and are fixed so as to follow the rotation of the film forming rollers 31 and 32 and do not rotate themselves. It is in the state. These magnetic field generators 34 and 35 have no lines of magnetic force between the magnetic field generator 34 provided on one film forming roller 31 and the magnetic field generator 35 provided on the other film forming roller 32, The magnetic poles are preferably arranged so that each magnetic field generator 34, 35 forms a substantially closed magnetic circuit. By providing such magnetic field generators 34 and 35, it is possible to generate a magnetic field in which magnetic lines of force swell in the vicinity of the region facing the discharge space H in the peripheral surfaces of the film forming rollers 31 and 32. Since the plasma is easily converged on the exit portion, this is excellent in that the film formation efficiency of the gas barrier layer 4 can be improved.
  • these magnetic field generators 34 and 35 are provided with racetrack-shaped magnetic poles that are long in the axial direction of the film forming rollers 31 and 32, respectively. It is preferable that one magnetic field generator 34 and the other magnetic field generator 35 are arranged so that the opposite magnetic poles have the same polarity.
  • the magnetic field generators 34 and 35 are formed such that the magnetic field lines do not straddle the magnetic field generators 34 and 35 on the opposing film forming rollers 31 and 32 side.
  • a racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the discharge space H along the axial direction of 31 and 32, and the plasma can be converged on the magnetic field.
  • the gas barrier layer 4 as a vapor deposition film can be efficiently formed on the surface of the resin base material 2 wound along.
  • magnetic field generators 34 and 35 well-known magnetic field generators, such as a permanent magnet and an electromagnet, can be used suitably, for example.
  • a gas supply port 36 for supplying a film forming gas containing an organosilicon compound to the discharge space H at a predetermined speed and a gas in the discharge space H connected to the vacuum pump 370.
  • a gas discharge port 37 for discharging a film forming material formed due to the gas to the outside of the vacuum chamber 200 is provided.
  • the gas supply port 36 is disposed at an equal distance from the film forming rollers 31 and 32 and above the discharge space H, and the gas discharge port 37 is formed by the film forming rollers 31 and 32. At the same distance from the bottom surface 201 of the vacuum chamber 200 and in the lower region of the discharge space H. Thereby, the gas supplied from the gas supply port 36 passes through the discharge space H between the film forming rollers 31 and 32 and is discharged from the gas discharge port 37.
  • a covering member 38 that covers the exposed region R of the film forming rollers 31 and 32 is disposed in the vicinity of the film forming rollers 31 and 32.
  • the exposed region R is exposed without contacting the resin base material 2 on the peripheral surfaces of the film forming rollers 31 and 32, and the film forming roller with respect to the contact region with the resin base material 2.
  • 31 and 32 are adjacent regions in the circumferential direction.
  • the covering member 38 extends substantially horizontally between the pair of inner wall surfaces in the vacuum chamber 200, and the film forming rollers 31, 32 in the circumferential direction of the film forming rollers 31, 32. It is curved and formed in a round bracket shape so as to follow the peripheral surface.
  • the covering member 38 is preferably disposed at a distance of 0.1 to 100 mm from the exposed region R, more preferably at a distance of 0.1 to 50 mm from the exposed region R. Preferably, it is spaced from the exposed region R by 0.1 to 25 mm.
  • the covering member 38 in the present embodiment is detachably attached to the pair of inner wall surfaces in the vacuum chamber 200.
  • the covering member 38 is formed of a material that does not affect the film formation, and at least the surface on the opposite side of the film forming rollers 31 and 32 of the surface of the covering member 38 is roughened.
  • materials that do not affect the film formation include metal materials such as stainless steel, copper, and aluminum that have been subjected to insulation treatment, and non-materials such as SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, and MgO.
  • Examples thereof include synthetic resin materials such as metal materials, polyether ether ketone, polyphenylene sulfide, polyimide, polyamide, and polytetrafluoroethylene.
  • the covering member 38 is roughened means that the arithmetic average roughness (center average roughness) defined by JIS B0601-1994 is 1 ⁇ m or more.
  • arithmetic average roughness center average roughness
  • polishing can be used.
  • a temperature control unit 375 that maintains the covering member 38 at a predetermined temperature is connected to the covering member 38.
  • the temperature control unit 375 is configured to easily attach the film forming material to the surface of the covering member 38 by maintaining the temperature of the covering member 38 at a predetermined temperature.
  • the temperature controller 375 may control the temperature of the covering member 38 by heat conduction or by radiation.
  • a potential control unit that controls the potential of the covering member 38 may be connected. This potential control unit controls the potential of the covering member 38 to make it easy to attach the film forming material to the covering member 38.
  • the roller CVD apparatus 20 As described above, plasma discharge is performed while applying a magnetic field between the pair of film forming rollers 31 and 32 while supplying a film forming gas (such as a source gas) into the discharge space H.
  • a film forming gas such as a source gas
  • the film forming gas raw material gas or the like
  • the covering member 38 covers the exposed region R on the peripheral surface of the film forming rollers 31 and 32
  • the film forming material diffused in the vacuum chamber 200 adheres and accumulates on the film forming rollers 31 and 32. Is prevented.
  • the covering member 38 is formed to be curved along the peripheral surface of the film forming rollers 31 and 32 in the circumferential direction of the film forming rollers 31 and 32, the film forming material diffused into the vacuum chamber 200 is formed. Adhering and depositing on the film forming rollers 31 and 32 is reliably prevented. Further, since the surface of the covering member 38 opposite to the film forming rollers 31 and 32 is roughened, the film forming material diffused into the vacuum chamber 200 is opposite to the film forming rollers 31 and 32 of the covering member 38. As a result, the film forming material diffused in the vacuum chamber 200 is more reliably prevented from adhering and depositing on the film forming rollers 31 and 32.
  • the temperature control unit 375 maintains the covering member 38 at a predetermined temperature, the film forming material is more easily attached to the covering member 38. As a result, the film forming material diffused in the vacuum chamber 200 is formed on the film forming roller 31. It is more reliably prevented from adhering to and depositing on 32. Further, since the covering member 38 is disposed at a distance of 0.1 to 100 mm, preferably 0.1 to 50 mm, particularly preferably 0.1 to 25 mm from the exposed region R of the film forming rollers 31 and 32, The film forming material diffused in the chamber 200 is more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.
  • the feeding roller 25, the winding roller 26, and the film forming roller 31 transport the resin base material 2 in the transport direction X, so that the region of the resin base material 2 on which the gas barrier layer 4 is formed becomes the winding roller 26, a new region of the resin base material 2 in which the gas barrier layer 4 is not formed is fed from the feed roller 25 and conveyed onto the film forming rollers 31 and 32.
  • the gas barrier layer 4 is formed on the surface of the resin substrate 2 by a roll-to-roll continuous film forming process.
  • the type of source gas, the power of the plasma generating power source 33, the strength of the magnetic field generators 34 and 35, the pressure in the vacuum chamber, the diameters of the film forming rollers 31 and 32, the conveyance speed of the resin base material 2, etc. are appropriately selected. Can be adjusted.
  • Source gas constituting the film forming gas for forming the gas barrier layer 4 is preferably an organosilicon compound containing at least silicon.
  • organosilicon compound applicable to the present invention examples include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl.
  • examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer 4. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • the film forming gas may contain a reactive gas in addition to the source gas.
  • a reactive gas a gas that reacts with the raw material gas to form 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 reaction gas for forming a nitride for example, nitrogen or ammonia can be used.
  • 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 nitride are formed. The reaction gas can be used in combination.
  • a carrier gas may be used as necessary.
  • 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, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.
  • the ratio of the raw material gas and the reactive gas is a theoretically required reactive gas for completely reacting the raw material gas and the reactive gas. It is preferable that the ratio of the reaction gas is not excessively increased rather than the ratio of the amount. If the ratio of the reaction gas is excessively increased, it is difficult to obtain the target gas barrier layer 4 in the present invention. Therefore, in order to obtain the desired performance as a barrier film, it is preferable that the total amount of the organosilicon compound in the film-forming gas be less than the theoretical oxygen amount necessary for complete oxidation.
  • a film-forming gas containing hexamethyldisiloxane (HMDSO, (CH 3 ) 6 Si 2 O) as a source gas and oxygen (O 2 ) as a reaction gas is reacted by a roller CVD method to produce silicon-oxygen.
  • HMDSO, (CH 3 ) 6 Si 2 O hexamethyldisiloxane
  • O 2 oxygen
  • a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film made of silicon dioxide SiO 2 is formed.
  • Reaction Formula (1) (CH 3 ) 6Si 2 O + 12O 2 ⁇ 6CO 2 + 9H 2 O + 2SiO 2
  • the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed.
  • the ratio is controlled to a flow rate equal to or less than the raw material ratio of the complete reaction, which is the theoretical ratio, and the incomplete reaction is performed. That is, it is necessary to set the amount of oxygen to less than 12 moles of the stoichiometric ratio with respect to 1 mole of hexamethyldisiloxane.
  • the raw material hexamethyldisiloxane and the reaction gas, oxygen are supplied from the gas supply unit to the film formation region to form a film. Even if the molar amount (flow rate) of oxygen is 12 times the molar amount (flow rate) of hexamethyldisiloxane as a raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio.
  • the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. .
  • the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane.
  • the amount is more than 0.5 times.
  • the pressure (degree of vacuum) in the vacuum chamber 200 can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 100 Pa.
  • the conveyance speed (line speed) of the resin base material 2 can be appropriately adjusted according to the type of raw material 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 within the range of 0.5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material 2 hardly occur, and the thickness of the formed gas barrier layer 4 can be sufficiently controlled.
  • FIG. 3 is a graph showing an example of the silicon distribution curve, oxygen distribution curve, and carbon distribution curve of the gas barrier layer 4.
  • symbols A to D represent A as a carbon distribution curve, B as a silicon distribution curve, C as an oxygen distribution curve, and D as an oxygen-carbon distribution curve.
  • the gas barrier layer has a maximum carbon atom ratio within a distance range of 89% vertically from the surface and less than 20 at%, and a distance of 89% vertically from the surface. It can be seen that the carbon atom ratio within the range has a concentration gradient and a structure in which the concentration changes continuously (corresponding to the above-mentioned “condition (1)” and “condition (2)”). ).
  • the gas barrier layer 4 has a carbon atom ratio within a distance range of 90 to 95% in the vertical direction (within a distance range of 5 to 10% in the vertical direction from the surface adjacent to the resin base material 2). It can be seen that the maximum value of is 20 at% or more and the carbon atom ratio continuously increases (corresponding to the above-mentioned “condition (3)” and “condition (4)”). ).
  • FIG. 4 is a graph showing an example of a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve of a gas barrier layer of a comparative example.
  • the gas barrier layer formed by a flat electrode (horizontal transport) type discharge plasma CVD method A carbon atom distribution curve A, a silicon atom distribution curve B, an oxygen atom distribution curve C, and an oxygen-carbon distribution curve D are shown.
  • the gas barrier layer of the comparative example has a configuration in which a continuous change in the concentration gradient of the carbon atom component does not occur.
  • Resin substrate 2 Here, the resin base material 2 constituting the gas barrier film 1 will be described.
  • the resin base material 2 is not particularly limited as long as it is formed of an organic material capable of holding the gas barrier layer 4 having the above gas barrier properties.
  • Examples of the resin substrate 2 applicable to the present invention include methacrylic acid ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, poly
  • Examples of the resin film include ether ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and a laminated film formed by laminating two or more layers of the above resins.
  • resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used.
  • the thickness of the resin base material 2 is preferably in the range of 5 to 500 ⁇ m, more preferably in the range of 25 to 250 ⁇ m.
  • the resin base material 2 in the present invention is preferably transparent.
  • the resin base material 2 is transparent and the layer formed on the resin base material 2 is also transparent, it becomes a transparent gas barrier film 1 and is used as a transparent substrate for electronic devices (for example, organic EL). It is also possible.
  • the resin base material 2 using the above resin or the like may be an unstretched film or a stretched film.
  • a stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.
  • a phase difference etc. can also be adjusted by extending
  • the resin substrate 2 in the present invention can be manufactured by a conventionally known general film forming method.
  • an unstretched resin base material 2 that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the resin as a material is dissolved in a solvent, cast on an endless metal resin support, dried, and peeled to form an unstretched film that is substantially amorphous and not oriented.
  • the resin base material 2 can also be manufactured.
  • the flow of the resin base material 2 (vertical axis, MD) is applied to the unstretched resin base material 2 by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. )
  • Direction or a direction perpendicular to the flow direction of the resin base material 2 (horizontal axis, TD), can be used to produce a stretched resin base material.
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the resin base material 2, but is preferably in the range of 2 to 10 times in the MD direction and TD direction, respectively.
  • the resin base material 2 in the present invention may be subjected to relaxation treatment or off-line heat treatment in terms of dimensional stability.
  • the relaxation treatment is preferably carried out in the process from the heat setting during the stretching film forming step in the above-described film forming method to the winding after the tenter is drawn out in the TD direction.
  • the relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C., and more preferably at a treatment temperature in the range of 100 to 180 ° C.
  • it does not specifically limit as a method of off-line heat processing For example, the method of conveying by the roller conveyance method by a several roller group, the air conveyance which blows and blows air to a film, etc.
  • the conveyance tension of the heat treatment is made as low as possible to promote thermal shrinkage, whereby the resin base material 2 with good dimensional stability is obtained.
  • the treatment temperature is preferably in the temperature range of (Tg + 50) to (Tg + 150) ° C. Tg here refers to the glass transition temperature of the resin substrate 2.
  • the resin base material 2 in the present invention can be applied with an undercoat layer coating solution inline on one or both sides in the course of film formation.
  • undercoating during the film forming process is referred to as in-line undercoating.
  • resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used.
  • a conventionally well-known additive can also be added to these undercoat layers.
  • the undercoat layer can be formed using a known coating method such as roller coating, gravure coating, knife coating, dip coating, or spray coating.
  • the coating amount of the undercoat layer is preferably in the range of 0.01 to 2 g / m 2 (dry state).
  • Second gas barrier layer 5 In the gas barrier film 1 of the present invention, a polysilazane-containing liquid is applied and dried on the gas barrier layer 4 by a wet application method, and the formed coating film is irradiated with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. Then, it is preferable to form the second gas barrier layer 5 by subjecting the formed coating film to a modification treatment.
  • VUV light vacuum ultraviolet light
  • a second defect constituted by polysilazane imparted from above on the minute defect portion generated when the gas barrier layer 4 that has already been formed is formed. It is preferable from the viewpoint of being able to be filled with the gas barrier layer components, efficiently preventing gas purging, and further improving gas barrier properties and flexibility.
  • the thickness of the second gas barrier layer 5 is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. If the thickness of the second gas barrier layer 5 is 1 nm or more, desired gas barrier performance can be exhibited. If the thickness is 500 nm or less, film quality deterioration such as generation of cracks in a dense silicon oxynitride film Can be prevented.
  • the polysilazane in the present invention is a polymer having a silicon-nitrogen bond in the molecular structure and is a polymer that is a precursor of silicon oxynitride, and the polysilazane to be applied is not particularly limited, A compound having a structure represented by the following general formula (1) is preferable.
  • R 1 , R 2 and R 3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.
  • perhydropolysilazane in which all of R 1 , R 2 and R 3 are composed of hydrogen atoms is particularly preferable.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6-membered and 8-membered rings, and its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance.
  • Mn number average molecular weight
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as a polysilazane-containing coating solution as it is.
  • Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.
  • the second gas barrier layer 5 is formed by applying and drying a coating liquid containing polysilazane on the gas barrier layer 4 formed by the inter-roller discharge plasma CVD method to which a magnetic field is applied, and then irradiating with vacuum ultraviolet rays. be able to.
  • organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.
  • organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers.
  • organic solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the second gas barrier layer-forming coating solution containing polysilazane varies depending on the layer thickness of the second gas barrier layer 5 and the pot life of the coating solution, but is preferably 0.2 to 35 masses. %.
  • the second gas barrier layer forming coating solution contains an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, Rh acetylacetonate, etc.
  • a metal catalyst such as an Rh compound can also be added.
  • Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.
  • the amount of these catalysts added to the polysilazane is preferably in the range of 0.1 to 10% by mass, preferably in the range of 0.2 to 5% by mass with respect to the total mass of the second gas barrier layer forming coating solution. More preferably, it is more preferably in the range of 0.5 to 2% by mass.
  • any appropriate wet coating method can be adopted as a method of coating the second gas barrier layer forming coating solution containing polysilazane.
  • Specific examples include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the thickness of the coating film can be appropriately set according to the purpose.
  • the thickness of the coating film is preferably in the range of 50 nm to 2 ⁇ m as the thickness after drying, more preferably in the range of 70 nm to 1.5 ⁇ m, and in the range of 100 nm to 1 ⁇ m. Is more preferable.
  • the second gas barrier layer 5 is a step of irradiating a layer containing polysilazane with vacuum ultraviolet (VUV), and at least a part of the polysilazane is modified into silicon oxynitride.
  • VUV vacuum ultraviolet
  • perhydropolysilazane will be described as an example of the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and becomes a specific composition of SiO x N y .
  • x and y are basically in the range of 2x + 3y ⁇ 4.
  • the coating film contains silanol groups, and there are cases where 2 ⁇ x ⁇ 2.5.
  • Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet irradiation and the like. It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, the cured as SiN y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H 2 .
  • Si—O—Si Bonds by Hydrolysis and Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH.
  • Two Si—OH are dehydrated and condensed to form a Si—O—Si bond and harden. This is a reaction that occurs in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated as outgas from the resin base material 2 by the heat of irradiation becomes the main moisture source.
  • Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO 2.1 to SiO 2.3 is obtained.
  • Adjustment of the composition of silicon oxynitride in the layer obtained by subjecting the polysilazane-containing layer to vacuum ultraviolet irradiation can be performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (1) to (4) described above. .
  • the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane layer coating is preferably in the range of 30 to 200 mW / cm 2 , and preferably in the range of 50 to 160 mW / cm 2. More preferred. If it is 30 mW / cm 2 or more, there is no concern about the reduction of the reforming efficiency, and if it is 200 mW / cm 2 or less, the coating film is not ablated and the substrate is not damaged.
  • Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200 ⁇ 10000mJ / cm 2, and more preferably in a range of 500 ⁇ 5000mJ / cm 2. If it is 200 mJ / cm 2 or more, the modification can be sufficiently performed, and if it is 10000 mJ / cm 2 or less, it is not excessively reformed, and cracking and thermal deformation of the resin substrate 2 can be prevented. it can.
  • a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source.
  • Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.
  • excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms.
  • the rare gas is xenon, e + Xe ⁇ Xe * Xe * + 2Xe ⁇ Xe 2 * + Xe Xe 2 * ⁇ Xe + Xe + h ⁇ (172 nm)
  • excimer light of 172 nm is emitted.
  • ⁇ Excimer lamps are characterized by high efficiency because radiation concentrates on one wavelength and almost no other light is emitted. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
  • Dielectric barrier discharge is a gas space created by placing a gas space between both electrodes via a dielectric such as transparent quartz and applying a high frequency high voltage of several tens of kHz to the electrode.
  • the discharge is called a thin micro discharge.
  • the micro discharge streamer reaches the tube wall (derivative)
  • electric charges accumulate on the dielectric surface, and the micro discharge disappears.
  • This micro discharge is a discharge that spreads over the entire tube wall and repeats generation and extinction. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.
  • Electrodeless electric field discharge by capacitive coupling, also called RF discharge.
  • the lamp and electrodes and their arrangement may be basically the same as those of dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.
  • the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to cause discharge in the entire discharge space. Must be a thing.
  • an electrode in which fine metal wires are meshed is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.
  • the outer diameter of the double-cylindrical lamp is about 25 mm, the difference in distance to the irradiation surface cannot be ignored directly below the lamp axis and on the side of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.
  • the biggest feature of the capillary excimer lamp is its simple structure.
  • the quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.
  • the outer diameter of the tube of the thin tube lamp is about 6 nm to 12 mm. If it is too thick, a high voltage is required for starting.
  • the electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power.
  • light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed.
  • it is suitable for flexible film materials such as PET that are easily affected by heat.
  • oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 to 4500 ppm.
  • the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • each functional layer In the gas barrier film 1 of the present invention, each functional layer can be provided as necessary in addition to the above-described constituent layers.
  • Overcoat layer may be formed on the second gas barrier layer 5 for the purpose of further improving the flexibility.
  • the organic material used for forming the overcoat layer is preferably an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group. Can be used.
  • These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed from the organic resin composition coating solution to be cured.
  • the gas barrier film 1 of the present invention is preferably provided as a film for an electronic device.
  • Examples of the electronic device include an organic electroluminescence panel (organic EL panel), an organic electroluminescence element (organic EL element), an organic photoelectric conversion element, and a liquid crystal display element.
  • organic EL panel organic electroluminescence panel
  • organic EL element organic electroluminescence element
  • organic photoelectric conversion element organic photoelectric conversion element
  • liquid crystal display element liquid crystal display element
  • the gas barrier film 1 having the configuration shown in FIGS. 1A and 1B is used as a sealing film for sealing solar cells, liquid crystal display elements, organic EL elements, and the like, for example. be able to.
  • FIG. 1 An example of an organic EL panel P that is an electronic device using the gas barrier film 1 as a sealing film is shown in FIG.
  • the organic EL panel P is formed on the gas barrier film 1, the transparent electrode 6 such as ITO formed on the gas barrier film 1, and the transparent electrode 6. And an organic EL element 7 that is a main body of the electronic device, and a counter film 9 disposed via an adhesive layer 8 so as to cover the organic EL element 7.
  • the transparent electrode 6 may form part of the organic EL element 7.
  • a transparent electrode 6 and an organic EL element 7 are formed on the surface of the gas barrier film 1 on the gas barrier layer 4 side and the second gas barrier layer 5 side.
  • the organic EL element 7 is suitably sealed so as not to be exposed to water vapor, and the organic EL element 7 is not easily deteriorated. Therefore, the organic EL panel P can be used for a long time. It becomes possible and the lifetime of the organic EL panel P is extended.
  • the opposing film 9 may be a gas barrier film 1 in addition to a metal film such as an aluminum foil.
  • a metal film such as an aluminum foil.
  • the covering member 38 covers the exposed region R on the peripheral surface of the film forming rollers 31 and 32, the film forming material diffused in the vacuum chamber 200 adheres to the film forming rollers 31 and 32. -It can prevent that it accumulates. Therefore, the concentration gradient of each element component in the gas barrier layer 4 can be provided as designed, and the deterioration of the quality of the gas barrier film 1 can be prevented.
  • the covering member 38 is formed to be curved along the peripheral surface of the film forming rollers 31 and 32 in the circumferential direction of the film forming rollers 31 and 32, the film forming material diffused into the vacuum chamber 200 is formed. It is possible to reliably prevent adhesion and deposition on the film forming rollers 31 and 32.
  • the film forming material diffused into the vacuum chamber 200 is opposite to the film forming rollers 31 and 32 of the covering member 38. It becomes easy to adhere to the surface. Therefore, the film forming material diffused in the vacuum chamber 200 can be more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.
  • the temperature control unit 375 maintains the covering member 38 at a predetermined temperature, the film forming material can be more easily attached to the covering member 38. Therefore, the film forming material diffused in the vacuum chamber 200 can be more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.
  • the covering member 38 is disposed at a distance of 0.1 to 100 mm, preferably 0.1 to 50 mm, particularly preferably 0.1 to 25 mm from the exposed region R of the film forming rollers 31 and 32, It is possible to more reliably prevent the film forming material diffused in the chamber 200 from adhering to and depositing on the film forming rollers 31 and 32.
  • the covering member 38 is detachably attached to the inner wall surface of the vacuum chamber 200, when a large amount of film forming material adheres to the covering member 38, the covering member 38 is exchanged and is again formed. Can be easily adhered. Therefore, the film forming material diffused in the vacuum chamber 200 can be more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.
  • roller CVD apparatus 20 has been described as transporting the resin base material 2 in the X direction in FIG. 2, it may be transported in the opposite direction.
  • roller CVD apparatus 20 has been described as transporting the resin base material 2 in the X direction in FIG. 2, it may be transported in the opposite direction.
  • FIG. 1
  • roller CVD apparatus 20 has been described as having the gas discharge port 37 on the bottom surface 201 of the vacuum chamber 200, it may be provided at a position other than the bottom surface.
  • the roller CVD apparatus 20 has been described as having the gas supply port 36 above the discharge space H and the gas discharge port 37 below, but has the gas supply port 36 below and the gas discharge port 37 above. It's also good.
  • the covering member 38 has been described as a shape curved in a parenthesis, the shape may be, for example, as shown in FIGS. 6A to 6C as long as the exposed region R of the film forming rollers 31 and 32 is covered.
  • the covering member 38 shown in FIG. 6A has a shape bent in an L shape when viewed from the axial direction of the film forming rollers 31 and 32.
  • the covering member 38 shown in FIG. 6B has a shape bent in a turtle shell shape when viewed from the axial direction of the film forming rollers 31 and 32.
  • the covering member 38 shown in FIG. 6C has a linear shape when viewed from the axial direction of the film forming rollers 31 and 32.
  • roller CVD Equipment (1) As an example of the apparatus for producing a gas barrier film according to the present invention, a roller CVD apparatus (1) similar to the roller CVD apparatus 20 in the above embodiment was produced. Specifically, in this roller CVD apparatus (1), a covering member similar to that in the above embodiment is provided.
  • roller CVD Equipment (2) As a comparative example of the gas barrier film production apparatus according to the present invention, a roller CVD apparatus (2) similar to the conventional one was produced. Specifically, in this roller CVD apparatus (2), the same covering member as in the above embodiment is not provided.
  • ⁇ Film formation conditions Source gas: hexamethyldisiloxane (organosilicon compound: HMDSO: (CH 3 ) 6 Si 2 O) ⁇ Raw gas supply: 50 sccm (Standard Cubic Centimeter per Minute) ⁇ Supply amount of oxygen gas (O 2 ): 500 sccm ⁇ Degree of vacuum in the vacuum chamber: 3Pa ⁇ Applied power from the power source for plasma generation: 0.8 kW ⁇ Power supply frequency for plasma generation: 80 kHz -Film transport speed: 1.5 m / min
  • each sample material of each gas barrier film is 12 mm ⁇ 12 mm in size through a mask, and the metal calcium ( (Metal that corrodes by reacting with moisture) was deposited.
  • metal aluminum ( ⁇ 3 to 5 mm, granular, water vapor impermeable metal) was vapor-deposited on the entire surface of one side of the sheet, and temporarily sealed.
  • the obtained sample was stored for 100 hours in a constant temperature and humidity oven (Yamato Humberic Chamber IG47M) adjusted to a high temperature and high humidity of 60 ° C. and 90% RH, and stored based on the method described in JP-A-2005-283561.
  • the amount of moisture permeated into the sample was calculated from the amount of corrosion of the metallic calcium before and after.
  • the evaluation value of the amount of permeated water in the sample in the region on the top side (the side on which the gas barrier layer was first formed) in each gas barrier film was set to the reference value “1”. Moreover, the value of the ratio of the permeated water amount in the samples in the intermediate region and the tail region in each gas barrier film to the permeated water amount in the head region was calculated and used as an evaluation value. Each evaluation value was as shown in Table 1 below.
  • X-ray photoelectron spectrometer manufactured by Thermo Fisher Scientific, model name “VG Theta Probe”
  • XPS depth profiles were measured for samples in each region of each gas barrier film.
  • the irradiation X-ray of the X-ray photoelectron spectrometer was set to single crystal spectroscopy AlK ⁇ , and the X-ray spot shape and size were set to an 800 ⁇ 400 ⁇ m ellipse.
  • the etching ion species was set to argon (Ar + ), the etching rate was set to 0.05 nm / sec in terms of SiO 2 thermal oxide film, and the etching interval was set to 10 nm in terms of SiO 2 .
  • the evaluation value of the carbon element ratio (absolute value of the difference between the maximum value and the minimum value) in the sample of the region on the top side (the side on which the gas barrier layer was first formed) in each gas barrier film is used as a reference.
  • the value was “1”.
  • the ratio of the carbon element ratio (absolute value of the difference between the maximum value and the minimum value) in the sample in the intermediate region and the end region of each gas barrier film to the carbon element ratio in the start region was calculated as an evaluation value.
  • Each evaluation value was as shown in Table 1 above.
  • the roller CVD apparatus as an example of the present invention, that is, the roller CVD apparatus (1) provided with the covering member, is more gas than the roller CVD apparatus (2) of the comparative example. It can be seen that the degree of decrease in the gas barrier property is small in the region on the front side, the region on the middle side and the region on the end side of the barrier film, and the degree of change in the carbon element ratio in the XPS depth profile is small. From this, it can be seen that in the roller CVD apparatus (1), even if the gas barrier film is continuously produced, the quality deterioration of the gas barrier film can be prevented.
  • the film forming material diffused in the vacuum chamber 200 which is the object of the above embodiment, is prevented from adhering and depositing on the film forming rollers 31 and 32, and each element component in the gas barrier layer 4 is prevented from being deposited.
  • a concentration gradient as designed, for example, between the film forming rollers 31 and 32 as shown in FIG. It is erected from the bottom surface 201 of the vacuum chamber 200 to below the film forming rollers 31 and 32 so that the resin base material 2 is interposed, and cooperates with a pair of inner wall surfaces of the vacuum chamber 201 to face each other (discharge space).
  • a partition wall 39 surrounding the space from H to the gas discharge port 37 can be provided.
  • a partition wall 39 is disposed on the side of the gas outlet 37 along the gas outlet 37.
  • the partition wall 39 is erected from the bottom surface 201 of the vacuum chamber 200 to at least below the film forming rollers 31 and 32 so that the resin base material 2 is interposed between the film forming rollers 31 and 32.
  • 200 is configured so as to surround the space from the discharge space H to the gas discharge port 37 in cooperation with the pair of inner wall surfaces (front and rear inner wall surfaces not shown in FIG. 7).
  • the partition wall 39 is provided to rise from the bottom surface 201 of the vacuum chamber 200 to below the film forming rollers 31 and 32, and to bend from the upper end of the rising portion 390.
  • a bent portion 391 that extends in a direction away from the outlet 37 and faces a partial region of the resin base material 2, and a support that stands from the bottom surface of the vacuum chamber 200 and supports the tip of the bent portion 391 from below. Part 392.
  • the bent portion 391 preferably has a length of 5 cm or more, more preferably a length of 20 cm or more, in a plane perpendicular to the axial direction of the film forming rollers 31 and 32 (for example, the paper surface of FIG. 7). Particularly preferably, it has a length of 45 cm or more. In addition, in this vertical surface, it is preferable that the bending part 391 opposes the resin base material 2 over the full length.
  • the bent portion 391 is preferably disposed away from the resin base material 2 by 0.1 to 100 mm, more preferably from the resin base material 2 by 0.1 to 50 mm. Particularly preferably, the resin substrate 2 is arranged at a distance of 0.1 to 25 mm.
  • the partition wall 39 is detachably provided on the bottom surface of the vacuum chamber 200.
  • the partition wall 39 is preferably made of a material that does not affect the film formation, and the surface on the gas discharge port 37 side is preferably roughened.
  • materials that do not affect the film formation include metal materials such as stainless steel, copper, and aluminum that have been subjected to insulation treatment, and non-materials such as SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, and MgO.
  • Examples thereof include synthetic resin materials such as metal materials, polyether ether ketone, polyphenylene sulfide, polyimide, polyamide, and polytetrafluoroethylene.
  • the roughening of the partition walls 39 means that the arithmetic average roughness (center average roughness) defined by JIS B0601-1994 is 1 ⁇ m or more.
  • sandblasting or polishing can be used.
  • a temperature control unit 395 that maintains the partition wall 39 at a predetermined temperature is connected to the partition wall 39.
  • the temperature control unit 395 makes it easy for the film forming material to adhere to the surface of the partition wall 39 by maintaining the temperature of the partition wall 39 at a predetermined temperature.
  • the temperature control unit 395 may control the temperature of the partition wall 39 by heat conduction or by radiation.
  • a potential control unit for controlling the potential of the partition wall 39 may be connected. This potential control unit controls the potential of the partition wall 39 so that the film forming material is easily attached to the partition wall 39.
  • the pair of inner wall surfaces of the vacuum chamber 200 (the pair of inner wall surfaces extending the film forming rollers 31 and 32 between) and the partition wall 39 cooperate to discharge. Since the space from the space H to the gas discharge port 37 is surrounded, the film forming material to be discharged from the gas discharge port 37 may go around from below the film forming rollers 31 and 32 and diffuse into the vacuum chamber 200. Is prevented. Further, the partition wall 39 is provided with a bent portion 391 provided so as to be bent from the upper end of the rising portion 390 and extending in a direction away from the gas discharge port 37 and facing a partial region of the resin base material 2.
  • the bent portion 391 has a length of 5 cm or more, preferably 20 cm or more, particularly preferably 45 cm or more on the surface perpendicular to the axial direction of the film forming rollers 31 and 32, and is 0.1 to 100 mm from the resin substrate 2;
  • the film-forming material is more difficult to pass between the partition wall 39 and the film-forming rollers 31 and 32 because the distance is preferably 0.1 to 50 mm, particularly preferably 0.1 to 25 mm.
  • the surface of the partition wall 39 on the gas discharge port 37 side is roughened, and the temperature control unit 395 maintains the partition wall 39 at a predetermined temperature, so that the film forming material is likely to adhere to the partition wall 39, It becomes more difficult for the film forming material to pass between the partition wall 39 and the film forming rollers 31 and 32.
  • the internal space of the vacuum chamber 200 shown in FIGS. 2 and 7 is disposed outside the space surrounded by the partition wall 38, the resin base material 2 and the like, including the plasma discharge space H.
  • a supply port (not shown) for supplying a non-reactive gas on the side of each roller, that is, on the side of the feed roller 25, the take-up roller 26, the transport rollers 21, 24, and the film forming rollers 31, 32, It is possible to supply the non-reactive gas from the supply port so as not to impair the exhaust capability of the vacuum pump 370.

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  • Chemical Vapour Deposition (AREA)

Abstract

La présente invention empêche la diminution de qualité d'un film barrière contre les gaz. Un dispositif DCPV à rouleaux (20) est pourvu : d'une chambre à vide (200) comportant une paire de surfaces de paroi internes opposées ; des rouleaux de formation de film disposés de manière à former un espace de décharge électrique (H) entre eux et qui amènent entre eux un substrat de résine enroulé (2) à s'opposer à l'espace de décharge électrique (H) ; des dispositifs de formation de champ magnétique (34, 35) qui génèrent un champ magnétique au niveau de la surface périphérique des rouleaux de formation de film (31, 32) ; une source électrique de génération de plasma (33) qui provoque une décharge électrique au niveau de l'espace de décharge électrique (H) ; une ouverture d'alimentation en gaz (36) qui est disposée au-dessus de l'espace de formation de film et qui fournit un gaz de formation de film à l'espace de décharge électrique (H) ; une ouverture d'échappement de gaz (37) qui est disposée au niveau de la région située au-dessous de l'espace de décharge électrique (H) et qui évacue le gaz de l'espace de décharge électrique (H) vers l'extérieur de la chambre à vide (200) ; et un élément de recouvrement (38) qui recouvre une région exposée (R) de la surface périphérique des rouleaux de rotation de film (31, 32) qui ne sont pas en contact avec le substrat de résine (2) et qui avoisinent dans le sens périphérique la région de contact avec le substrat de résine (2).
PCT/JP2014/071357 2013-08-21 2014-08-13 Dispositif de production de film barrière contre les gaz et procédé de production de film barrière contre les gaz WO2015025783A1 (fr)

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WO2015151680A1 (fr) * 2014-04-01 2015-10-08 株式会社神戸製鋼所 Dispositif de formation de film par cvd plasma

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JPH0372083A (ja) * 1989-08-14 1991-03-27 Canon Inc マイクロ波プラズマｃｖｄ法により大面積の機能性堆積膜を連続的に形成する方法及び装置
JP2001131755A (ja) * 1996-09-10 2001-05-15 Hitachi Maxell Ltd プラズマｃｖｄ装置
JP2008196001A (ja) * 2007-02-13 2008-08-28 Kobe Steel Ltd プラズマｃｖｄ装置
JP2011084780A (ja) * 2009-10-15 2011-04-28 Kobe Steel Ltd プラズマｃｖｄ装置
JP2011208191A (ja) * 2010-03-29 2011-10-20 Fujifilm Corp 成膜装置

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JP6580829B2 (ja) * 2014-04-01 2019-09-25 株式会社神戸製鋼所 プラズマｃｖｄ成膜装置

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Publication number Priority date Publication date Assignee Title
JPH0372083A (ja) * 1989-08-14 1991-03-27 Canon Inc マイクロ波プラズマｃｖｄ法により大面積の機能性堆積膜を連続的に形成する方法及び装置
JP2001131755A (ja) * 1996-09-10 2001-05-15 Hitachi Maxell Ltd プラズマｃｖｄ装置
JP2008196001A (ja) * 2007-02-13 2008-08-28 Kobe Steel Ltd プラズマｃｖｄ装置
JP2011084780A (ja) * 2009-10-15 2011-04-28 Kobe Steel Ltd プラズマｃｖｄ装置
JP2011208191A (ja) * 2010-03-29 2011-10-20 Fujifilm Corp 成膜装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015151680A1 (fr) * 2014-04-01 2015-10-08 株式会社神戸製鋼所 Dispositif de formation de film par cvd plasma
JP2015200011A (ja) * 2014-04-01 2015-11-12 株式会社神戸製鋼所 プラズマｃｖｄ成膜装置

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