WO2014175029A1 - Procédé de fabrication d'un film de barrière aux gaz et procédé de modification de surface - Google Patents

Procédé de fabrication d'un film de barrière aux gaz et procédé de modification de surface Download PDF

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Publication number
WO2014175029A1
WO2014175029A1 PCT/JP2014/059796 JP2014059796W WO2014175029A1 WO 2014175029 A1 WO2014175029 A1 WO 2014175029A1 JP 2014059796 W JP2014059796 W JP 2014059796W WO 2014175029 A1 WO2014175029 A1 WO 2014175029A1
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Prior art keywords
gas barrier
excimer
barrier film
polysilazane
surface modification
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PCT/JP2014/059796
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English (en)
Japanese (ja)
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浩了 有田
廣瀬　達也
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コニカミノルタ株式会社
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Priority to JP2015513653A priority Critical patent/JP6222224B2/ja
Publication of WO2014175029A1 publication Critical patent/WO2014175029A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere

Definitions

  • the present invention relates to a method for producing a gas barrier film produced by irradiating a polysilazane layer containing a polysilazane compound with an excimer lamp to form a gas barrier layer by surface modification, and a surface modification used in the method for producing a gas barrier film. It relates to the processing method.
  • a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles that require blocking of various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals.
  • a metal oxide thin film such as aluminum oxide, magnesium oxide, or silicon oxide
  • packaging articles that require blocking of various gases such as water vapor and oxygen
  • gases such as water vapor and oxygen
  • liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and the like are used in liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and the like.
  • organic EL elements, and the like are required to have high gas barrier properties (gas barrier properties) because internal penetration of water vapor or air causes deterioration in quality.
  • VUV vacuum ultraviolet light
  • Patent Document 1 proposes a method of producing a silicon oxide film by applying vacuum ultraviolet light irradiation to a coating film coated with a silazane compound solution.
  • This method uses light energy in the range of 100 to 200 nm as a wavelength called vacuum ultraviolet light, which is larger than the interatomic bonding force in the silazane compound.
  • This allows the formation of a silicon oxide film (gas barrier layer) at a relatively low temperature by advancing an oxidation reaction with active oxygen or ozone while directly breaking the atomic bonds by the action of only photons called photon processes. It can be carried out.
  • a method of converting a part or all of a silazane compound coating film into a silicon oxide film by irradiating an excimer lamp of a VUV light source having an illuminance of 40 mW / cm 2 for 3 to 10 minutes is disclosed.
  • Patent Document 2 discloses a method of irradiating an excimer lamp in an environment that does not contain water vapor and oxygen, in which the water vapor concentration is 140 ppm or less and the oxygen concentration is 0.5 vol% or less. .
  • Patent Documents 1 and 2 there is no description regarding a method of forming a silicon oxide film while continuously transporting a substrate or the like. There is no mention of the related production stability.
  • Patent Document 3 discloses a film base coated with polysilazane in an environment where the water vapor concentration is 1000 to 4000 ppm and the oxygen concentration is 0.05 to 21% by volume while the substrate is continuously conveyed by a roll-to-roll method.
  • a method for producing a gas barrier film by irradiating a material with vacuum ultraviolet light to perform a modification treatment is disclosed.
  • Patent Document 3 makes no mention of the excimer lamp life in continuous production and production stability related thereto.
  • excimer lamps are not only reduced in illuminance due to long-time lighting, but also excimer lamp tubes are fragile due to vacuum ultraviolet light emitted from the lamps themselves, which causes excimer lamp damage. Yes. The time at which this excimer lamp breaks is not uniform and there is no sign of breakage, and it is difficult to predict when the excimer lamp breaks.
  • JP 2009-255040 A International Publication No. 2011/007543 Special table 2009-503157
  • the present invention has been made in view of the above-mentioned problems, and the problem to be solved is to use a surface modification treatment method by excimer lamp irradiation performed in a continuous production method, and to reduce the life of the excimer lamp (for example, decrease in lamp illuminance or By providing a method for producing a gas barrier film capable of stably forming a gas barrier layer even in a continuous production system, and a surface modification method used therefor, by suppressing damage to the excimer lamp) is there.
  • the present inventor has developed a substrate having a polysilazane layer formed by applying a coating liquid having a polysilazane compound on at least one surface side of the substrate.
  • Gas barrier film manufactured by carrying out a surface modification process for modifying the gas barrier layer by continuously transporting the inside of the surface modification process equipped with an excimer lamp emitting light and irradiating the polysilazane layer with excimer light
  • the life of the excimer lamp is reduced by applying a gas barrier film manufacturing method that controls the average water vapor concentration in the space region between the excimer lamp and the substrate during the surface modification treatment to a specific range.
  • a polysilazane layer formed by applying a coating liquid having a polysilazane compound on at least one surface side on a substrate is continuously conveyed in a surface modification step including an excimer lamp that emits excimer light,
  • a method for producing a gas barrier film, wherein the polysilazane layer is irradiated with the excimer light to perform a surface modification treatment for modifying the gas barrier layer A method for producing a gas barrier film, wherein an average water vapor concentration in a space region between the excimer lamp and the base material during the surface modification treatment is in a range of 150 to 930 ppm.
  • a surface modification treatment method which is used in the method for producing a gas barrier film according to any one of items 1 to 7.
  • a method for producing a gas barrier film having suitability for continuous production capable of suppressing a decrease in lamp illuminance of an excimer lamp and a decrease in lifetime of an excimer lamp, and capable of stably forming a gas barrier layer And a surface modification treatment method used therefor.
  • the technical feature of the present invention is that the average water vapor concentration in the space region between the excimer lamp and the substrate during the surface modification treatment (hereinafter also referred to as the treatment space) is controlled within the range of 150 to 930 ppm. If the average water vapor concentration during the surface modification treatment is 150 ppm or more, the illuminance caused by the reaction between the ammonia component generated from the polysilazane layer by the excimer light and the excimer lamp tube A decrease can be prevented. On the other hand, if the average water vapor concentration during the surface modification treatment is 930 ppm or less, the excimer lamp activated by the excimer light reacts with moisture in the atmosphere to prevent the excimer lamp from becoming weak. Can do. Therefore, the illuminance stability and fragility resistance of the excimer lamp tube can be improved by performing the surface modification treatment in a treatment space having an average water vapor concentration in the range of 150 to 930 ppm.
  • the method for producing a gas barrier film of the present invention comprises a polysilazane layer formed by applying a coating liquid having a polysilazane compound on at least one side of a substrate, and a surface having an excimer lamp that emits excimer light.
  • a method for producing a gas barrier film which is produced by carrying out a surface modification treatment for continuously conveying the inside of a reforming process, irradiating the excimer light to the polysilazane layer, and modifying the gas barrier layer,
  • An average water vapor concentration in a space region between the excimer lamp and the base material during the surface modification treatment is in a range of 150 to 930 ppm.
  • the peak irradiance of the lamp tube surface of the excimer lamp it is 50 mW / cm 2 or more, further 80 mW / cm 2 or more It is preferable from the viewpoint of excellent illuminance stability during continuous irradiation of the lamp.
  • the shortest distance between the surface of the lamp tube of the excimer lamp and the polysilazane layer surface on the base material in the facing position within the range of 0.1 to 9.0 mm, stable base material transportability and This is preferable from the viewpoint of excellent illuminance stability during continuous irradiation of the lamp.
  • a plurality of excimer lamps are installed from the viewpoint of productivity, and more than 10 excimer lamps are arranged in parallel in the transport direction of the base material. It is preferable that
  • the “gas barrier property” as used in the present invention means suppression of permeation of gas such as water molecules and oxygen molecules, and water vapor permeability (temperature: measured by a method based on JIS K 7129-1992). 40 ⁇ 0.5 ° C., relative humidity (RH): 90 ⁇ 2%) is 1 ⁇ 10 ⁇ 1 g / (m 2 ⁇ 24 h) or less, and oxygen measured by a method according to JIS K 7126-1987 It means that the permeability is 1 mL / m 2 ⁇ 24 h ⁇ atm or less.
  • the average water vapor concentration in the space region between the excimer lamp and the base material during the surface modification treatment referred to in the present invention is a capacitance type for 10 places in the space region in a state where the excimer lamp is caused to emit light.
  • the water vapor concentration is measured using a dew point meter or a mirror-cooled dew point meter, and the arithmetic average value is defined as the average water vapor concentration in the spatial region referred to in the present invention.
  • the measured temperature cannot be generally defined because the temperature in the space region varies depending on the irradiation conditions of the excimer lamp.
  • vacuum ultraviolet light specifically mean light having a wavelength in the range 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.
  • the method for producing a gas barrier film of the present invention comprises a polysilazane layer formed by applying a coating liquid having a polysilazane compound on at least one side of a substrate, and a surface having an excimer lamp that emits excimer light.
  • a method for producing a gas barrier film which is produced by carrying out a surface modification treatment for modifying a gas barrier layer by continuously conveying the inside of a modification step and irradiating the excimer light to the polysilazane layer.
  • An average water vapor concentration in a space region between the excimer lamp and the base material during the reforming treatment is in a range of 150 to 930 ppm.
  • a layer obtained by modifying a polysilazane layer formed by applying a coating liquid having a polysilazane compound is referred to as a gas barrier layer.
  • the spatial region in which the average water vapor concentration defined in the present invention is controlled within the range of 150 to 930 ppm during the surface modification treatment is specifically the spatial region S shown in FIG. 1B described later.
  • an excimer light irradiation region 7 irradiated from the excimer lamp 3 is defined.
  • the method for producing a gas barrier film of the present invention comprises a substrate having an excimer lamp that emits excimer light on a substrate having a polysilazane layer formed by applying a coating liquid having a polysilazane compound on at least one surface side.
  • the polysilazane layer is subjected to surface modification treatment under the condition that the inside of the reforming process is continuously conveyed and the average water vapor concentration in the space region between the excimer lamp and the substrate is in the range of 150 to 930 ppm. It is characterized by being modified into a gas barrier layer.
  • the average water vapor concentration during the surface modification treatment is 150 ppm or more, it is possible to prevent a decrease in illuminance due to the reaction between the ammonia component generated from the polysilazane layer by the excimer light and the excimer lamp tube. it can.
  • the average water vapor concentration during the surface modification treatment is 930 ppm or less, the excimer lamp activated by the excimer light reacts with moisture in the atmosphere to prevent the excimer lamp from becoming weak. Can do. Therefore, the illuminance stability and fragility resistance of the excimer lamp tube can be improved by performing the surface modification treatment within the range of 150 to 930 ppm as the water vapor concentration.
  • the shortest distance between the surface of the lamp tube of the excimer lamp at the facing position and the polysilazane layer surface on the substrate is in the range of 0.1 to 9.0 mm.
  • the surface modification step according to the present invention is a preferred embodiment in which a plurality of excimer lamps, preferably 10 or more excimer lamps are arranged in parallel with respect to the substrate transport direction.
  • FIG. 1A is an external view showing an example of a xenon excimer irradiation unit that can be used in the method for producing a gas barrier film of the present invention.
  • the xenon excimer irradiation unit 1 includes an excimer lamp holder 2, an excimer lamp 3, and a plurality of nitrogen gas and water vapor supply pipe inlets 4.
  • FIG. 1B is a cross-sectional view taken along the line AA of the xenon excimer light irradiation unit 1 shown in FIG. 1A.
  • the excimer lamp holder 2 is supplied with nitrogen gas (N 2 ) and water vapor (H 2 O) containing a predetermined water vapor concentration from a nitrogen gas and water vapor supply pipe inlet 4.
  • N 2 nitrogen gas
  • H 2 O water vapor
  • concentration were controlled toward 9 can be injected.
  • the excimer lamp 3 irradiates the excimer light 7 toward the lower substrate 9.
  • the water vapor concentration in the vicinity of the excimer lamp 3 according to the present invention can be measured in the space region S shown in FIG. 1B by directly arranging a water vapor concentration measuring sensor or sampling with a tube or the like.
  • region said by this invention is defined as the excimer light irradiation area
  • the number of samplings in the excimer light irradiation area 7 is set to 10 and the average value is obtained, and this is set as the average water vapor concentration in the excimer light irradiation area 7 which is the space area S.
  • a method of controlling the water vapor concentration in the mixed gas supplied from the nitrogen gas and water vapor supply pipe inlet 4 so as to obtain a desired water vapor concentration is preferable.
  • a plurality of groups are provided in the excimer irradiation region of the excimer lamp at an appropriate interval inside the excimer light irradiation unit 34 having a structure in which the periphery is sealed as shown in FIG.
  • the water vapor concentration measurement sensor is arranged, an average value of a plurality of measurement data is obtained, and the excimer light irradiation is performed by the humidification or dehumidification by the water vapor concentration adjusting device provided in the excimer light irradiation unit 34 from the measurement result.
  • a method for controlling the water vapor concentration inside the unit 34 and the excimer irradiation area of the excimer lamp to a predetermined condition is also a suitable method.
  • a commercially available capacitance type dew point meter or mirror cooled dew point meter can be preferably used.
  • the shortest distance h between the lamp tube surface of the excimer lamp 3 and the surface of the polysilazane layer 8 on the substrate is in the range of 0.1 to 9.0 mm. Is preferred.
  • the excimer light vacuum ultraviolet light
  • the substrate surface can be irradiated.
  • FIG. 2 is a schematic cross-sectional view showing a configuration of a gas barrier film manufacturing apparatus that has a surface modification treatment unit according to the present invention and can continuously convey and manufacture a gas barrier film, and is laminated as an example.
  • a roll-to-roll manufacturing apparatus that continuously conveys a roll-shaped film substrate 21 is shown.
  • a polysilazane is coated by applying a feeding unit 31 for feeding out the film base material 21 from a state where the film base material 21 is laminated in a roll shape, and a coating liquid containing a polysilazane compound on the film base material 21.
  • the coater 32 equipped in the coating part for forming the layer, the drying part 33 for drying the polysilazane layer formed on the film substrate 21, and the polysilazane layer by irradiating the polysilazane layer on the film substrate 21 with excimer light
  • the film base 21 is fed out from a laminating roll obtained by laminating the long film base 21 in a roll shape in the feeding section 31.
  • a coating liquid having a polysilazane compound is applied on the film substrate 21 with a desired wet film thickness while controlling the amount supplied to the coater 32 using a wet coating type coater 32 equipped in the coating unit.
  • the wet polysilazane layer 8 is formed on the film substrate 21.
  • the formed film substrate 21 having the wet polysilazane layer 8 is moved to the drying unit 33, and the polysilazane layer 8 on the film substrate 21 is removed by a dryer using drying means such as warm air and a heater. dry.
  • the film substrate 21 on which the dried polysilazane layer 8 is formed moves to the excimer light irradiation unit 34 which is the next step.
  • Excimer light irradiating section 34 for irradiating excimer light and subjecting polysilazane layer 8 to surface modification treatment includes a plurality of excimer light irradiating units U1 to U30 shown in FIG. 20 is provided. Further, a pipe (not shown) for supplying nitrogen gas and water vapor to each of the excimer light irradiation units U1 to U30 and a water vapor concentration in the excimer light irradiation unit 34 are adjusted to form nitrogen gas and a water vapor atmosphere. A gas and water vapor inlet 36 and a nitrogen gas and water vapor outlet 37 are provided. A vapor concentration measurement sensor (not shown) is provided inside the excimer light irradiation unit 34, and the water vapor concentration in the mixed gas of nitrogen gas and water vapor is controlled to a predetermined condition according to the measurement information.
  • suction wall 38 As a member for reducing the surface of the film base 21 opposite to the coating film to the atmospheric pressure. Since there is a gap between the plurality of transport rolls 20, the film base 21 side of the suction wall 38 is sucked from the suction port 39 using a vacuum pump (not shown). The surface on the opposite side can be depressurized with respect to atmospheric pressure.
  • Reference numeral 40 denotes a position for measuring the pressure during decompression.
  • the excimer light irradiation unit 34 is configured by a plurality of excimer lamps (excimer light irradiation unit 1) to increase the processing efficiency. This is a preferable configuration from the point that
  • 10 or more excimer lamps are arranged in parallel with respect to the transport direction of the film substrate.
  • a method using a small number of excimer lamps it is necessary to impart a high irradiation energy amount to the substrate in order to achieve the desired modification treatment, and the temperature of the substrate rises due to such excimer light irradiation.
  • the base material is easily damaged by heat.
  • 10 or more excimer lamps it is possible to suppress thermal damage to the substrate and perform surface modification treatment continuously at a high speed.
  • the peak illuminance on the surface of the lamp tube of the excimer lamp is preferably 50 mW / cm 2 or more, more preferably in the range of 50 to 500 mW / cm 2 , further preferably 80 mW. / Cm 2 or more, particularly preferably in the range of 80 to 200 mW / cm 2 . If the peak illuminance is 50 mW / cm 2 or more, there is no concern about a reduction in the reforming efficiency. If the peak illuminance is 500 mW / cm 2 or less, ablation (evaporation or scattering of components due to thermal destruction) may occur in the polysilazane layer.
  • the substrate is preferable because it does not damage the substrate.
  • it is necessary to reduce the number of excimer lamps or the reforming process.
  • the reforming process efficiency is sufficient. There is a problem that the life of the excimer lamp is shortened.
  • the range of 50 to 500 mW / cm 2 is preferable from the viewpoint of satisfying the above conditions.
  • the peak illuminance on the surface of the excimer lamp can be measured by placing an illuminometer (C9536 / H95535-172 manufactured by Hamamatsu Photonics) at a predetermined position below the surface of the excimer lamp. In order to obtain a desired peak illuminance, the type of excimer lamp is selected or the applied voltage is adjusted as appropriate.
  • an illuminometer C9536 / H95535-172 manufactured by Hamamatsu Photonics
  • the amount of excimer light irradiation energy on the polysilazane layer surface is preferably in the range of 200 to 20000 mJ / cm 2 , and more preferably in the range of 500 to 10000 mJ / cm 2 . If it is 200 mJ / cm 2 or more, the modification can be carried out sufficiently, and if it is 20000 mJ / cm 2 or less, it is not over-reformed and cracking and thermal deformation of the substrate can be prevented.
  • the irradiation time is preferably within a range of 0.1 second to 10 minutes, and more preferably within a range of 0.5 second to 3 minutes. .
  • an excimer lamp is used as a vacuum ultraviolet light source, and a rare gas excimer lamp is preferably used.
  • a rare gas atom such as Xe, Kr, Ar, Ne, etc. is called an inert gas because it does not form a molecule by chemically bonding.
  • 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.
  • Oxygen is required for the reaction at the time of ultraviolet light irradiation, but excimer light is absorbed by oxygen, so if oxygen is present, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of excimer light irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm.
  • the gas satisfying the irradiation atmosphere is preferably a dry inert gas, and particularly preferably a 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.
  • the polysilazane compound is irradiated with excimer light from an excimer lamp to modify a part of the polysilazane compound to silicon oxide (SiO 2 ).
  • the polysilazane applied to the formation of the polysilazane layer according to the present invention is a polymer having a silicon-nitrogen bond in the molecular structure and serving as a precursor of silicon oxynitride.
  • the polysilazane to be applied is not particularly limited. Is preferably a compound having a structure represented by the following general formula (1).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms).
  • Alkyl groups alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms), cycloalkyl groups (preferably cycloalkyl groups having 3 to 10 carbon atoms), aryl groups (preferably carbon atoms).
  • R 1 , R 2 and R 3 are aryl groups
  • silyl groups preferably silyl groups having 3 to 20 carbon atoms
  • alkylamino groups preferably 1 to 40 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms
  • An amino group or an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms).
  • R 1 , R 2 and R 3 is a hydrogen atom.
  • the alkyl group in R 1 , R 2 and R 3 is a linear or branched alkyl group.
  • an alkyl group the alkyl group applicable to a conventionally well-known polysilazane can be used.
  • the compound having a main skeleton composed of the unit represented by the general formula (1) preferably has a number average molecular weight in the range of 100 to 50,000.
  • the number average molecular weight here can be determined by measuring with a gel permeation chromatograph (GPC).
  • perhydropolysilazane (abbreviation: PHPS) in which all of R 1, R 2, and R 3 are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a gas barrier layer to be obtained.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings.
  • the molecular weight is in the range of about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • a hydrogen atom in R 1 polysilazane having an organic group in R 2 and R 3, or an organic group R 1 and R 2, those having a hydrogen atom in R 3 - (R 1 R 2 It has a cyclic structure mainly having a polymerization degree of 3 to 5 with SiNR 3 ) — as a repeating unit.
  • the polysilazane used has a main skeleton composed of units represented by the general formula (1) as described above, but the units represented by the general formula (1) may be cyclized as described above. In that case, the cyclic portion becomes a terminal group, and when such cyclization is not performed, the terminal of the main skeleton can be a group similar to R 1 , R 2 , R 3 or a hydrogen atom.
  • polysilazanes applicable to the present invention include repeating units such as [(SiH 2 ) n (NH) m ] and [(SiH 2 ) r O as described in JP-A-62-195024. (In these formulas, n, m and r are 1, 2 or 3, respectively) and a polysilazane as described in JP-A-2-84437 is reacted with a boron compound.
  • a polyborosilazane having excellent heat resistance produced by reacting a polysilazane and a metal alkoxide as described in JP-A-63-81122, JP-A-63-191832 and JP-A-2-77427.
  • Copolymer silazanes advantageous for film formation, JP-A-5-23827, JP-A-4-272020, JP-A-5-93275, JP-A-5-214268, JP-A-5-30750, JP-A-5-338524 Application to metals such as plastics and aluminum with addition or addition of a catalytic compound for promoting ceramization to polysilazane as described in the publication Possible, it may be used as well, such as low temperature curing type polysilazane more ceramics at low temperatures.
  • the polysilazane compound according to the present invention is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane compound-containing coating solution.
  • Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.
  • the polysilazane compound-containing coating solution according to the present invention can be prepared by adding the following catalyst and solvent together with the above-described polysilazane compound, if necessary.
  • a catalyst In the polysilazane-containing coating solution, a catalyst may be added in order to accelerate the reaction for converting the polysilazane compound into a silicon oxide compound.
  • a conventionally known catalyst can be used.
  • compounds described in JP-A-10-279362 can be referred to.
  • the addition amount of the catalyst with respect to the polysilazane compound is preferably 0.1 ppm or more and 5.0% or less as a mass ratio with respect to the total mass of the polysilazane compound as a solid content concentration ratio in the polysilazane compound-containing coating solution. More preferably, it is the range of 100 ppm or more and 3.0% or less.
  • solvent As the organic solvent used for the preparation of the polysilazane compound-containing coating solution, it is preferable to avoid alcohol-based or water-containing solvents that easily react with the polysilazane compound.
  • the polysilazane compound concentration in the polysilazane compound-containing coating solution varies depending on the film thickness of the target polysilazane compound-containing layer (gas barrier layer) and the pot life of the coating solution, but is generally within the range of 0.2 to 35% by mass. Preferably there is.
  • the method for applying the polysilazane compound-containing coating solution according to the present invention is preferably a wet coating method, and the wet coating method applicable to the present invention is not particularly limited and is appropriately selected from conventionally known methods. Can be used. Specific examples of coating methods include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, and gravure printing. It is done.
  • the thickness of the polysilazane compound-containing layer according to the present invention is appropriately set according to the purpose, but the thickness after drying is preferably in the range of 1 nm to 100 ⁇ m, more preferably 10 nm to 10 ⁇ m. Within the range, most preferably within the range of 10 nm to 1 ⁇ m.
  • the drying process after applying the polysilazane compound-containing coating solution on the substrate mainly removes the organic solvent, and therefore the drying conditions (temperature, treatment time) should be set appropriately according to the method of heat treatment to be applied.
  • the heat treatment temperature is preferably a high temperature from the viewpoint of rapid processing, but it is preferable to appropriately determine the temperature to be applied and the treatment time in consideration of thermal damage to the substrate that is the resin film being used. .
  • the heat treatment temperature is preferably set to 150 ° C. or less.
  • the treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the substrate is reduced. If the heat treatment temperature is 150 ° C. or lower, it is preferably set within 30 minutes.
  • the atmosphere in the drying process after coating the polysilazane compound-containing coating solution on the substrate is preferably controlled to be relatively low humidity, but the humidity in a low humidity environment changes with temperature, so the relationship between temperature and humidity
  • the preferred form is indicated by the dew point temperature.
  • the preferred dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), the more preferred dew point temperature is ⁇ 8 ° C. (temperature 25 ° C./humidity 10%) or less, and the more preferred dew point temperature is ⁇ 31 ° C. (temperature 25 ° C.). / Humidity 1%) or less.
  • the pressure in the vacuum drying can be selected in the range of normal pressure to 0.1 MPa.
  • the base material applicable to the present invention is not particularly limited as long as it is made of an organic material capable of holding a polysilazane compound-containing polysilazane layer, but is flexible from the viewpoint of imparting continuous transportability. It is preferable that it is a film base material that can be bent.
  • Examples of the material for the film base include polyacrylic acid ester, polymethacrylic acid ester, polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate (abbreviation: PBT), polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC), polyarylate, polyvinyl chloride (abbreviation: PVC), polyethylene (abbreviation: PE), polyethylene copolymer such as ethylene-cyclic olefin, polypropylene (abbreviation: PP), polystyrene (abbreviation: PS), polyamide (abbreviation) : PA), Polyetheretherketone, Polysulfone, Polyethersulfone, Polyimide, Polyetherimide, and other polymers, and heat-resistant transparent film base material based on silsesquioxane having an organic-inorganic hybrid structure (product name Si a-DEC, manufactured by Chisso Corporation), and further can
  • the thickness of the film substrate is preferably in the range of 5 to 500 ⁇ m, more preferably in the range of 10 to 250 ⁇ m, from the viewpoints of handleability and mechanical strength. Moreover, it is preferable that a glass transition temperature (Tg) is 100 degreeC or more. Moreover, it is preferable that a heat shrinkage rate is also low.
  • Tg glass transition temperature
  • An overcoat layer may be formed on the gas barrier layer according to the present invention 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.
  • the gas barrier film according to the present invention may have an anchor layer (also referred to as a smooth layer) between the base material and the gas barrier layer for the purpose of improving the adhesion between the base material and the gas barrier layer. .
  • the anchor layer can also suppress a phenomenon (bleed out) that unreacted oligomers move from the resin base material to the surface and contaminate the contact surface.
  • the anchor layer is preferably smooth in order to form a gas barrier layer thereon, and the surface roughness Ra value is preferably in the range of 0.3 to 3 nm, more preferably 0. It is in the range of 5 to 1.5 nm. If the surface roughness Ra value is 0.3 nm or more, the surface has an appropriate smoothness, and can maintain the smoothness when forming a gas barrier layer by the roller transportability and the surface modification treatment method of the present invention. . On the other hand, when the thickness is 3 nm or less, it is possible to prevent a minute defect from being generated in the gas barrier layer when forming the gas barrier layer, and to obtain a high level of gas barrier properties and adhesion.
  • thermosetting resin and an active energy ray curable resin can be cited because smoothness is required, but an active energy ray curable resin is preferable because it is easy to mold.
  • curable resins can be used singly or in combination of two or more.
  • the curable resin may be a commercially available product or a synthetic product.
  • the active energy ray-curable material examples include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene
  • examples thereof include compositions containing polyfunctional acrylate monomers such as glycol acrylate and glycerol methacrylate.
  • curable bifunctional acrylate NK ester from Shin-Nakamura Chemical Co., Ltd.
  • A-DCP tricyclodecane dimethanol diacrylate
  • UV curable organic / inorganic hybrid hard coating material from OPSR (registered by JSR Corporation) Trademark) series (compounds obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) and the like can be used.
  • the thickness of the anchor layer is preferably in the range of 0.3 to 10 ⁇ m, more preferably in the range of 0.5 to 5 ⁇ m from the viewpoint of adjusting curl.
  • a bleed-out preventing layer can be formed on the substrate before the polysilazane layer is formed on the substrate.
  • the bleed-out prevention layer suppresses a phenomenon in which, when a base material having an anchor layer (smooth layer) is heated, unreacted oligomers are transferred from the base material to the surface and contaminate the contact surface.
  • a base material having an anchor layer smooth layer
  • the bleed-out prevention layer may basically have the same configuration as the anchor layer described above as long as it has this function.
  • the curable resin constituting the anchor layer can be used in the same manner. Furthermore, a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, a unitary unsaturated organic compound having one polymerizable unsaturated group in the molecule, or the like can be added. Moreover, you may contain a mat agent as an additive. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 ⁇ m are preferable.
  • the bleed-out prevention layer is blended with other components as necessary, and is prepared as a coating solution using a diluting solvent as necessary, and the coating solution is applied to the surface of the film substrate 21 by a conventionally known coating method. Then, it can be produced by irradiating with ultraviolet rays or ionizing radiation and curing.
  • the thickness of the bleed-out preventing layer is preferably in the range of 1 to 10 ⁇ m, more preferably 2 to 2 from the viewpoint of preventing the curling of the substrate when the bleed-out preventing layer is provided only on one side of the substrate.
  • the range is 7 ⁇ m.
  • a dry gas barrier layer may be provided in addition to the gas barrier layer formed by the surface modification treatment method of the present invention.
  • the gas barrier property can be further improved by a synergistic effect by repairing fine defects of the dry gas barrier layer by a uniform film by coating. I can expect.
  • a film containing an oxide or nitride, nitride oxide, or carbide containing one or more metal atoms selected from Zr as a main component can be used.
  • Silicon oxide, silicon nitride oxide, silicon nitride, aluminum oxide, oxidation Silicon aluminum, silicon aluminum nitride oxide, ZTO, ITO, and ZnO are preferably used.
  • These films may contain a certain proportion of carbon, or may be gradient films having a composition change in the film thickness direction.
  • the dry gas barrier layer can be produced by physical vapor deposition (eg, vacuum vapor deposition, ion plating, sputtering) or chemical vapor deposition (eg, PECVD, Cat-CVD, atmospheric pressure plasma, ALD) ) Can be used.
  • physical vapor deposition eg, vacuum vapor deposition, ion plating, sputtering
  • chemical vapor deposition eg, PECVD, Cat-CVD, atmospheric pressure plasma, ALD
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Corporation is used. After coating with a die coater so as to be 4 ⁇ m, after drying at 80 ° C. for 3 minutes as a drying condition, 1.0 J / cm 2 as a curing condition using a high-pressure mercury lamp in an air atmosphere. Curing was performed to form an anchor layer. At this time, the maximum cross-sectional height Rt (p), which is the surface roughness, was 16 nm.
  • the surface roughness Rt (p) is calculated from an uneven cross-sectional curve continuously measured by a detector having a stylus having a minimum tip radius using an AFM (Atomic Force Microscope). The measurement was performed a number of times within a section having a measurement distance of 30 ⁇ m with a stylus having a very small tip radius, and the average roughness regarding the amplitude of fine irregularities was obtained.
  • a polysilazane layer (8) was formed by applying and drying a coating liquid containing a polysilazane compound on the anchor layer surface of the PEN film provided with the anchor layer and the bleed-out prevention layer according to the following method. .
  • ⁇ Preparation of polysilazane compound-containing coating solution 20% by mass of perhydropolysilazane containing 5% by mass of an amine catalyst and 20% by mass dibutyl ether solution of uncatalyzed perhydropolysilazane (Aquamica (registered trademark) NN120-20 manufactured by AZ Electronic Materials Co., Ltd.)
  • a dibutyl ether solution (Aquamica (registered trademark) NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) is mixed and used to adjust the amine catalyst to 1% by mass in solid content, and further diluted with dibutyl ether.
  • a dibutyl ether solution containing 5% by mass of perhydropolysilazane was prepared, and this was used as a polysilazane compound-containing coating solution.
  • the prepared polysilazane compound-containing coating solution is lined on the anchor layer surface of the PEN film using a die coater equipped in the coating section (32).
  • the drying part (33) shown in FIG. 2 is dried at a drying temperature of 50 ° C. for 1 minute at a dew point of 10 ° C., and then at a drying temperature of 80 ° C.
  • the polysilazane layer (8) having a thickness of 150 nm after drying was formed at a dew point of 5 ° C. for 2 minutes.
  • the film base material (21) having the polysilazane layer (8) formed through the coating part (32) and the drying part (33) is transported to the excimer light irradiation part (34) and subjected to surface modification treatment by excimer light irradiation. Went.
  • Excimer light irradiation uses a xenon excimer lamp (wavelength: 172 nm, peak illuminance: 120 mW / cm 2 ) manufactured by MD Excimer as the excimer lamp 3, and the film substrate (21) transport direction as shown in FIG.
  • 30 excimer lamps U1 to U30 were arranged.
  • the installation position of the excimer lamp was adjusted so that the shortest distance (h) between the excimer lamp tube surface and the surface of the substrate being conveyed was 3 mm.
  • the peak illuminance was measured at a position 3 mm from the lamp tube surface of the excimer lamp (3) using an illuminometer (C9536 / H95535-172 manufactured by Hamamatsu Photonics).
  • the excimer lamp holder (2) supplying a N 2 gas and water vapor, N 2 towards the flanks of the excimer lamp width hand the film base surface and the injection density control water vapor (see FIG. 1B. ).
  • the oxygen concentration at the time of excimer light irradiation is such that nitrogen gas and water vapor are also supplied to the enclosure surrounding the entire excimer lamp, so that the oxygen concentration between the excimer lamp tube surface and the film substrate becomes 0.1% or less. Adjustments were made as follows.
  • the water vapor concentration is 30 total of Zentol digital dew point meters (XDT series) manufactured by Mitsubishi Chemical Analytech Co., Ltd. in the space area (S) of each excimer lamp, and the excimer lamp (3) and film base While constantly monitoring the water vapor concentration in the space region (S) between the materials (21), the average water vapor concentration was controlled to be 151 ppm (dew point -39 ° C.).
  • the polysilazane layer (8) was irradiated with excimer light and subjected to surface modification treatment to be modified into a gas barrier layer, whereby a gas barrier film 1 was produced.
  • gas barrier films 2 to 17 In the production of the gas barrier film 1, the water vapor concentration in the space region (S) between the excimer lamp (3) and the film base material (21) in the excimer light irradiation section (34), the peak illuminance of each excimer lamp (3) ( mW / cm 2 ), gas barrier film in the same manner except that the shortest distance (h) between the tube surface of the excimer lamp (3) and the surface of the film base (21) is changed to the combination shown in Table 1, respectively. 2 to 17 were produced.
  • gas barrier films 1A to 17A were used as gas barrier films at the initial production stage (immediately after the excimer lamp was turned on).
  • gas barrier films 1B to 17B were manufactured while being continuously conveyed and manufactured as excimer lamps after being irradiated for 1000 hours.
  • gas barrier films 1C to 17C were manufactured while being manufactured continuously and sampled at the time when 60000 m was produced as a gas barrier film.
  • gas barrier films 1A to 17A, gas barrier films 1B to 17B, and gas barrier films 1C to 17C produced above were evaluated for water vapor permeability (gas barrier properties) according to the following method.
  • the water vapor transmission rate was measured by the following method.
  • Vapor deposition equipment JEE-400 vacuum vapor deposition equipment manufactured by JEOL Ltd.
  • Constant temperature and humidity oven Yamato Humidic Chamber IG47M
  • Raw material Metal that reacts with moisture and corrodes: Calcium (granular)
  • Water vapor impermeable metal Aluminum ( ⁇ 3-5mm, granular)
  • a vacuum deposition apparatus vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.
  • the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the film sample.
  • the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere
  • the cell for evaluation was produced by irradiating with ultraviolet rays.
  • the obtained sample whose both surfaces are sealed with aluminum is stored in a high-temperature and high-humidity environment of 60 ° C. and 90% RH. Based on the method described in Japanese Patent Application Laid-Open No. 2005-283561, the corrosion amount of metallic calcium is introduced into the cell. The amount of moisture permeated (g / m 2 / day) was calculated.
  • ⁇ The rate of increase in the moisture content of the gas barrier film prepared after irradiating the gas barrier film prepared immediately after the lamp is lit for 1000 hours is less than 1.5 times.
  • ⁇ 1000 relative to the gas barrier film prepared immediately after the lamp is lit.
  • the rate of increase in the moisture content of the gas barrier film produced after irradiation for a period of time is 1.5 times or more and less than 5.0 times.
  • ⁇ The rate of increase in the moisture content of the gas barrier film sampled after the production of 60000 m with respect to the gas barrier film produced immediately after the lamp is lit is less than 1.5 times. ⁇ : after the production of 60000 m with respect to the gas barrier film produced immediately after the lamp is lit. The increase rate of the moisture content of the sampled gas barrier film is 1.5 times or more and less than 5.0 times. X: The moisture content of the gas barrier film sampled after preparation of 60000 m with respect to the gas barrier film prepared immediately after the lamp is turned on. The increase rate is 5.0 times or more Table 1 shows the results obtained.
  • the water vapor concentration in the region between the excimer lamp and the base material should be regulated within the range of 150 to 930 ppm when performing surface modification treatment with excimer light after continuous conveyance. Makes it possible to obtain a gas barrier film having a good gas barrier property, and further, a gas barrier film having an excellent gas barrier property even after being irradiated with an excimer lamp for a long time or after being manufactured for a long time. Can be manufactured stably.
  • the method for producing a gas barrier film of the present invention has a suitability for continuous production, can suppress a reduction in lamp illuminance and excimer lamp life of an excimer lamp, and can stably form a gas barrier layer.
  • the gas barrier film produced by these can be suitably used as a sealing film for liquid crystal display elements, solar cells, organic EL elements and the like.

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Abstract

La présente invention résout le problème de la description de : un procédé pour fabriquer un film de barrière aux gaz, ledit procédé permettant une production continue et étant capable de réduire au minimum la réduction du facteur d'illumination ou de la durée de vie d'une lampe excimère et la formation d'une couche de barrière aux gaz de façon stable ; et un procédé de modification de surface qui doit être appliqué à celui-ci. Ce procédé pour fabriquer un film de barrière aux gaz comprend : l'application d'un liquide de revêtement qui contient un composé de polysilazane sur au moins une surface d'un substrat pour former une couche de polysilazane ; et le passage du substrat pourvu de la couche de polysilazane en continu à travers une section de modification de substrat équipée de lampes excimère qui émettent un rayonnement excimère, et par conséquent l'irradiation de la couche de polysilazane avec le rayonnement excimère pour conduire une modification de surface pour modifier une couche de barrière aux gaz. Le procédé est caractérisé en ce que, pendant la modification de surface, la concentration de vapeur d'eau moyenne dans une région spatiale entre les lampes excimère et le substrat est contrôlée à 150 à 930 ppm.
PCT/JP2014/059796 2013-04-23 2014-04-03 Procédé de fabrication d'un film de barrière aux gaz et procédé de modification de surface WO2014175029A1 (fr)

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WO2011007543A1 (fr) * 2009-07-17 2011-01-20 三井化学株式会社 Stratifié et procédé pour sa production
JP2012016854A (ja) * 2010-07-07 2012-01-26 Konica Minolta Holdings Inc ガスバリア性フィルム、及び有機光電変換素子、有機エレクトロルミネッセンス素子

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JP5691309B2 (ja) * 2010-09-06 2015-04-01 コニカミノルタ株式会社 ガスバリアフィルムおよびそれを用いた電子機器デバイス
JP5552975B2 (ja) * 2010-09-07 2014-07-16 コニカミノルタ株式会社 ガスバリアフィルム及びガスバリアフィルムを有する有機電子デバイス
JP5798747B2 (ja) * 2011-01-14 2015-10-21 三井化学株式会社 積層体の製造方法
US20140106151A1 (en) * 2011-06-27 2014-04-17 Konica Minolta , Inc. Gas barrier film, manufacturing method for gas barrier film, and electronic device
JP6156366B2 (ja) * 2012-04-25 2017-07-05 コニカミノルタ株式会社 ガスバリア性フィルム、電子デバイス用基板および電子デバイス
JP6287858B2 (ja) * 2012-12-14 2018-03-07 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス

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Publication number Priority date Publication date Assignee Title
WO2011007543A1 (fr) * 2009-07-17 2011-01-20 三井化学株式会社 Stratifié et procédé pour sa production
JP2012016854A (ja) * 2010-07-07 2012-01-26 Konica Minolta Holdings Inc ガスバリア性フィルム、及び有機光電変換素子、有機エレクトロルミネッセンス素子

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