JP5861644B2 - Method for producing gas barrier film and gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film and a method for producing the same, and more specifically, a gas barrier film mainly used for display materials such as packages such as electronic devices, plastic substrates such as solar cells, organic EL elements, and liquid crystals, and the production thereof. It is about the method.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging an article that requires blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the deterioration of food, industrial goods and pharmaceuticals. In addition to the above packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates and the like.

  As a method for producing such a gas barrier film, mainly, a method of forming a gas barrier layer by a plasma CVD method (Chemical Vapor Deposition method) or a polysilazane as a main component is used. A method of applying a surface treatment after applying a coating solution, or a method of using them together is known (see, for example, Patent Documents 1 to 4).

  In the invention described in Patent Document 1, the film formation start temperature is 170 ° C. or less on the first SiN layer mainly composed of silicon nitride formed by chemical vapor deposition at a film formation start temperature of 50 ° C. or more. A method of laminating a second SiN layer mainly composed of silicon nitride formed in (1) is disclosed.

  However, the method described in Patent Document 1 requires a film thickness of 100 nm or more in order to obtain high barrier performance, and yellowing accompanying the increase in thickness is conspicuous and cannot be used for display applications.

  In the invention described in Patent Document 2, it is necessary to form a polysilazane film having a thickness of 250 nm or less by a wet method, and then to irradiate vacuum ultraviolet light. It is disclosed to achieve by a method of forming a layer by repeating two or more times.

  However, the method described in Patent Document 2 still has a problem that the flexibility is not always sufficient if the lamination is simply repeated in order to obtain a higher gas barrier property.

Moreover, in the invention described in Patent Document 3, a method of further improving the barrier performance by applying polysilazane on a gas barrier layer formed by a vacuum plasma CVD method on a resin base material and repairing the gas barrier layer by heat treatment Is disclosed. However, the function as a gas barrier layer of an organic photoelectric conversion element or the like is insufficient, and a gas barrier layer having a gas barrier property of a level that is much lower than 1 × 10 ⁻² g / m ² · day as a water vapor transmission rate. The development of was demanded. In addition, since the heat treatment of polysilazane takes 1 hour at 160 ° C., there is a difficulty that the application range is limited to a resin base material having excellent heat resistance.

  Further, the invention described in Patent Document 4 discloses a manufacturing method for forming a conductive film after applying and smoothing a polysilazane to a gas barrier layer obtained by an atmospheric pressure plasma CVD method. Although this method can achieve both high barrier properties and surface smoothness, the stress applied during bending is concentrated on the gas barrier layer, and the barrier layer is destroyed by unrelieved stress, resulting in inferior flexibility. This is the current situation.

JP 2009-31612 A JP 2009-255040 A Japanese Patent No. 3511325 JP 2008-235165 A

  This invention is made | formed in view of the said subject, The objective is to provide the gas-barrier film excellent in the high gas barrier performance, bending resistance, and the cutting processability, and its manufacturing method.

  The above object of the present invention can be achieved by the following configuration.

1. On the first barrier layer of the substrate having the first barrier layer formed by vapor deposition on at least one surface side of the substrate having a thermal expansion coefficient of 1 to 50 × 10 ⁻⁶ / ° C., polysilazane A method for producing a gas barrier film, comprising: forming a polysilazane layer by coating a containing liquid, and then forming the second barrier layer by converting the polysilazane layer into a ceramic by vacuum ultraviolet light.

2. On the first barrier layer of the substrate having the first barrier layer formed by vapor deposition on at least one surface side of the substrate having a thermal expansion coefficient of 1 to 50 × 10 ⁻⁶ / ° C., organic A method for producing a gas barrier film, comprising: applying a silica-containing liquid for forming a sol-gel coat layer composed of a film containing a hydrolyzate of a metal compound, and forming a second barrier layer after drying.

  3. 2. The method for producing a gas barrier film as described in 1 above, wherein the vacuum ultraviolet light is vacuum ultraviolet light having a wavelength component of 180 nm or less.

  4). 4. The method for producing a gas barrier film according to any one of 1 to 3, wherein the first barrier layer has a thickness of 200 to 500 nm, and the second barrier layer has a thickness of 50 to 200 nm. .

  5. 5. The method for producing a gas barrier film according to any one of 1 to 4, wherein the first barrier layer is formed by a chemical vapor deposition method and is made of silicon oxide, silicon oxynitride, or silicon nitride.

  6). 6. The method for producing a gas barrier film as described in 5 above, wherein the chemical vapor deposition method is a vacuum plasma CVD method.

  7). The gas barrier film manufactured by the manufacturing method of the gas barrier film of any one of said 1-6.

  According to the present invention, it was possible to provide a gas barrier film excellent in high gas barrier performance, bending resistance and cutting processability, and a method for producing the same.

It is a schematic diagram which shows an example of the plasma CVD apparatus which can be used by this invention. It is a schematic sectional drawing which shows an example of the layer structure of the gas barrier film of this invention.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  First, the layer structure of the gas barrier film of the present invention will be described with reference to FIG.

  In FIG. 2, the gas barrier film 11 of the present invention is formed by applying a first barrier layer 13 formed on a substrate 12 and a polysilazane-containing liquid or a silica-containing liquid for forming a sol-gel coat layer thereon. In addition, the gas barrier layer unit 15 includes the second barrier layer 14.

  After the second barrier layer 14 is formed on the first barrier layer 13, the second barrier layer 14 is subjected to a modification treatment from above using a modification treatment means L, for example, irradiation with vacuum ultraviolet rays having a wavelength component of 180 nm or less. Applied. Alternatively, the second barrier layer 14 is formed by applying a silica-containing liquid for forming a sol-gel coat layer made of a film containing a hydrolyzate of an organometallic compound on the first barrier layer 13 and drying the coating. It is formed.

  The first barrier layer 13 according to the present invention is formed by a vapor deposition method. Here, the vapor deposition method includes a chemical vapor deposition method and a physical vapor deposition method, but the chemical vapor deposition method is preferable.

  The chemical vapor deposition method according to the present invention may be an atmospheric pressure plasma CVD method, a vacuum plasma CVD method or a catalytic chemical vapor deposition method, and can be selected as appropriate. Of these, the vacuum plasma CVD method is preferable.

  Furthermore, the first barrier layer 13 according to the present invention is preferably composed of silicon oxide, silicon oxynitride, or silicon nitride.

  Hereinafter, the detail of the component of the gas barrier film of this invention is demonstrated.

《Gas barrier film》
The gas barrier film of the present invention has a gas barrier layer unit on at least one surface side of the substrate.

  The gas barrier layer unit referred to in the present invention is a first barrier layer and a silica-containing coating for forming a sol-gel coat layer by applying a polysilazane-containing liquid on the first barrier layer and performing a modification treatment. It is comprised from the 2nd barrier layer formed by apply | coating and drying a liquid. Here, the gas barrier layer unit according to the present invention can further improve the gas barrier property by constituting the gas barrier layer unit with a plurality of units. In this case, the plurality of gas barrier layer units may be the same or different. Moreover, the structure which has arrange | positioned the gas barrier layer unit on both surfaces of a base material may be sufficient. Also in this case, the gas barrier layer units formed on both surfaces of the substrate may be the same or different.

The “gas barrier property” as used in the present invention is a water vapor transmission rate (water vapor transmission rate) (60 ± 0.5 ° C., relative humidity (90 ± 2)% measured by a method in accordance with JIS K 7129-1992. When RH) is 1 × 10 ⁻³ g / (m ² · 24 h) or less, it is defined as having a water vapor barrier property, and oxygen permeability (oxygen) measured by a method according to JIS K 7126-1987 It is defined as having an oxygen barrier property when the transmittance is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1.01325 × 10 ⁵ Pa).

[First barrier layer]
The first barrier layer according to the present invention is formed by vapor deposition on at least one surface side of a base material having a thermal expansion coefficient of 1 to 50 × 10 ⁻⁶ / ° C. Here, the thickness of the first barrier layer is not particularly limited, but is preferably 150 to 600 nm, and more preferably 200 to 500 nm. If it is such a range, it will be excellent in high gas barrier performance, bending tolerance, and cutting processability.

  Here, the first barrier layer may be made of any material as will be described in detail below. For example, the first barrier layer is made of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, zirconium oxide, or the like. It is preferably composed of silicon oxide, silicon oxynitride or silicon nitride.

  Further, the method for forming the first barrier layer is not particularly limited as long as it is a vapor deposition method, and either a chemical vapor deposition method or a physical vapor deposition method may be used, but a chemical vapor deposition method is preferable. The chemical vapor deposition method is not particularly limited, and a plasma CVD method such as an atmospheric pressure plasma CVD method, a vacuum plasma CVD method, or a catalytic chemical vapor deposition method under atmospheric pressure or a pressure near atmospheric pressure can be used. Of these, the vacuum plasma CVD method is preferable. Details of the layer formation conditions of the plasma CVD method will be described later.

  The gas barrier layer obtained by vapor deposition, especially plasma CVD, is made of metal carbide, metal nitride, and metal oxide by selecting conditions such as the raw materials (also called raw materials) metal compound, decomposition gas, decomposition temperature, and input power. Further, it is preferable because a metal oxide, metal sulfide, metal halide, and a mixture thereof (metal oxynitride, metal oxyhalide, metal nitride carbide, etc.) can be separately formed.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such a raw material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  However, it is preferably a compound having a vapor pressure in a temperature range of 0 ° C to 250 ° C under atmospheric pressure, and more preferably a compound exhibiting a liquid state in a temperature range of 0 ° C to 250 ° C. This is because the pressure in the plasma film forming chamber is close to atmospheric pressure, and it is difficult to send a gas into the plasma film forming chamber unless it can be vaporized under atmospheric pressure. This is because the amount fed can be managed with high accuracy. In addition, when the heat resistance of the plastic film which forms a gas barrier layer is 270 degrees C or less, it is preferable that it is a compound which has a vapor pressure from the plastic film heat resistant temperature to 20 degrees C or less.

  Such a metal compound is not particularly limited, and examples thereof include a silicon compound, a titanium compound, a zirconium compound, an aluminum compound, a boron compound, a tin compound, and an organometallic compound.

  Among these, as silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, di Tylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, Pargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Examples of the organometallic compound include antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2, 2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermanium, tetra Methoxygermanium, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  Although the temperature (decomposition temperature) at the time of forming into a film by carrying out chemical vapor deposition of the above metal compounds as a raw material under decomposition gas is not restrict | limited, 20-250 degreeC is preferable and 80-200 degreeC is more preferable.

  In the present invention, the first barrier layer is preferably formed by chemical vapor deposition. Generally, methods for forming a functional thin film on a substrate are roughly classified into physical vapor deposition and chemical vapor deposition (chemical vapor deposition). Physical vapor deposition is performed in the vapor phase. In this method, a thin film of a target substance (for example, a carbon film) is deposited on the surface of the substance by a physical method. As these methods, a vapor deposition (resistance heating method, electron beam vapor deposition, molecular beam epitaxy) method is used. In addition, there are an ion plating method, a sputtering method, and the like. On the other hand, chemical vapor deposition (Chemical Vapor Deposition) supplies a raw material gas containing the desired thin film components onto a substrate and deposits the film by chemical reaction on the substrate surface or in the gas phase. In addition, there is a method of generating plasma or the like for the purpose of activating a chemical reaction. Thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method Although well-known CVD methods etc. are mentioned, Although it does not specifically limit, Plasma CVD method can be preferably used from a viewpoint of film forming speed or a processing area.

(Plasma CVD equipment)
A plasma CVD apparatus that can be used in the present invention will be described with reference to FIG.

  The plasma CVD apparatus 1 has a vacuum chamber 2, and a susceptor 5 is disposed on the bottom side inside the vacuum chamber 2.

  On the ceiling side inside the vacuum chamber 2, a cathode electrode 3 is disposed at a position facing the susceptor 5.

  A heat medium circulation system 6, a vacuum exhaust system 7, a gas introduction system 8, and a high-frequency power source 9 are disposed outside the vacuum chamber 2.

  A heat medium is disposed in the heat medium circulation system 6.

  The heat medium circulation system 6 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 10 having a storage device is provided.

  The heating / cooling device 10 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 5. The supplied heat medium flows inside the susceptor 5, heats or cools the susceptor 5, and returns to the heating / cooling device 10. At this time, the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 10 heats or cools the heat medium to the set temperature and supplies it to the susceptor 5. Thus, the cooling medium circulates between the susceptor and the heating / cooling device 10, and the susceptor 5 is heated or cooled by the supplied heating medium having the set temperature.

  The vacuum chamber 2 is connected to an evacuation system 7, and before the film forming process is started by the plasma CVD apparatus 1, the inside of the vacuum chamber 2 is evacuated in advance and the heat medium is heated and set from room temperature. The temperature is raised to a temperature, and a heat medium having a set temperature is supplied to the susceptor 5. The susceptor 5 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 5 is heated.

  After circulating the heat medium at the set temperature for a certain time, the substrate 12 to be formed is carried into the vacuum chamber 2 while maintaining the vacuum atmosphere in the vacuum chamber 2 and placed on the susceptor 5.

  A number of nozzles (holes) are formed on the surface of the cathode electrode 3 facing the susceptor 5.

  The cathode electrode 3 is connected to a gas introduction system 8. When CVD gas (raw material gas, decomposition gas) is introduced from the gas introduction system 8 to the cathode electrode 3, the nozzle of the cathode electrode 3 enters the vacuum chamber 2 in a vacuum atmosphere. CVD gas is ejected.

  The cathode electrode 3 is connected to a high frequency power source 9, and the susceptor 5 and the vacuum chamber 2 are connected to a ground potential.

  When a CVD gas is supplied from the gas introduction system 8 into the vacuum chamber 2, a high-frequency power source 9 is activated while supplying a heating medium having a constant temperature from the heating / cooling device 10 to the susceptor 5, and a high-frequency voltage is applied to the cathode electrode 3, Plasma of the introduced CVD gas is formed.

  When the CVD gas activated in the plasma reaches the surface of the substrate 12 on the susceptor 5, a thin film grows on the surface of the substrate 12.

  During the growth of the thin film, a heating medium having a constant temperature is supplied from the heating / cooling apparatus 10 to the susceptor 5, and the susceptor 5 is heated or cooled by the heating medium, and a thin film is formed while being maintained at a constant temperature.

  Generally, the lower limit temperature of the growth temperature when forming a thin film is determined by the film quality of the thin film, and the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the substrate 12.

  The lower limit temperature and upper limit temperature vary depending on the material of the thin film to be formed, the material of the thin film already formed, etc., but when forming a SiN film or SiON film used for a high barrier film, etc., the lower limit temperature is required to ensure the film quality. The temperature is 50 ° C., and the upper limit temperature is lower than the heat resistant temperature of the substrate.

  The correlation between the film quality of the thin film formed by the plasma CVD method of the present invention and the film formation temperature and the correlation between the damage to the film formation target (base material 12) and the film formation temperature have been determined in advance. The lower limit temperature and the upper limit temperature of the substrate 12 during the CVD process are known (the lower limit temperature of the substrate 12 during the process is 50 ° C., and the upper limit temperature is 250 ° C.).

  Furthermore, the relationship between the temperature of the heat medium supplied to the susceptor 5 and the temperature of the substrate 12 when a plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 3 is measured in advance, and the plasma CVD process The temperature of the heat medium supplied to the susceptor 5 is required in order to maintain the temperature of the base material 12 at the lower limit temperature or higher and the upper limit temperature or lower.

  The temperature is a lower limit temperature (here, 50 ° C.), the lower limit temperature is stored, and a heat medium whose temperature is controlled to be equal to or higher than the lower limit temperature is set to be supplied to the susceptor 5. The heat medium refluxed from the susceptor 5 is heated or cooled, and a heat medium having a set temperature of 50 ° C. is supplied to the susceptor 5.

  Here, a mixed gas of silane gas, ammonia gas, nitrogen gas, or hydrogen gas is supplied as the CVD gas, and the SiN film is formed on the base material 12 in a state where the substrate 12 is maintained at a temperature not lower than the lower limit temperature and not higher than the upper limit temperature. The

  Immediately after activation of the plasma CVD apparatus 1, the susceptor 5 is at room temperature, and the temperature of the heat medium returned from the susceptor 5 to the heating / cooling apparatus 10 is lower than the set temperature. Therefore, immediately after startup, the heating / cooling device 10 heats the refluxed heat medium to raise the temperature to the set temperature, and supplies it to the susceptor 5. In this case, the susceptor 5 and the base material 12 are heated and heated by the heat medium, and the base material 12 is maintained in the range of the lower limit temperature or higher and the upper limit temperature or lower.

  When a thin film is continuously formed on the plurality of base materials 12, the susceptor 5 is heated by heat flowing from the plasma. In this case, since the heat medium refluxed from the susceptor 5 to the heating / cooling device 10 is higher than the lower limit temperature (50 ° C.), the heating / cooling device 10 cools the heat medium, and the heat medium at the set temperature is transferred to the susceptor. 5 is supplied. Thereby, a thin film can be formed, maintaining the base material 12 in the range below minimum temperature and below maximum temperature.

  Thus, the heating / cooling device 10 heats the heating medium when the temperature of the refluxed heating medium is lower than the set temperature, and cools the heating medium when the temperature is higher than the set temperature. In addition, a heat medium having a set temperature is supplied to the susceptor, and as a result, the base material 12 is maintained in a temperature range between the lower limit temperature and the upper limit temperature.

  When the thin film is formed to a predetermined thickness, the substrate 12 is carried out of the vacuum chamber 2, the non-film-formed substrate 12 is carried into the vacuum chamber 2, and a heating medium having a set temperature is supplied in the same manner as described above. While forming a thin film.

[Second barrier layer of sol-gel coat layer]
The sol-gel coat layer used in the present invention is formed on the first barrier layer and is composed of a film containing a hydrolyzate of an organometallic compound, and serves as the second barrier layer of the present invention.

  In the present invention, “hydrolyzate of organometallic compound” refers to an organometallic compound or a hydrolyzate of an organometallic compound, and also includes an organometallic compound.

  Although the hydrolyzate of the organometallic compound used in the present invention is not particularly limited, for example, the following general formula:

(In the formula, A is a substituent composed of one or more carbon main chains having 1 to 10 carbon atoms (for example, a linear or branched alkyl group), M is a metal element, and R is 1 carbon atom. 10 to 10 linear or branched alkyl groups, n represents the oxidation number of the metal element, and m represents the number of substitutions (0 ≦ m <n).
It is preferable to consist of the organometallic compound shown by these, or the polymer of the said organometallic compound. The substituent of the organometallic compound represented by the above general formula may have a vinyl group, an epoxy group, an alkyl group, or an amino group. By adding one or more of these organometallic compounds, Functions, particularly water resistance and moisture resistance can be imparted.

  The metal element M represented by the above general formula is preferably silicon (Si), aluminum (Al), or titanium (Ti).

  In the present invention, the sol-gel coat layer may contain an isocyanate compound as an additive. This is because the isocyanate compound can impart moisture resistance.

  The film thickness of such a sol-gel coat layer is preferably in the range of 50 nm to 200 nm. As a result, it is possible to prevent cracks and the like from occurring during curing shrinkage due to drying during film formation of the sol-gel coat layer, and to suppress a decrease in gas barrier properties. Moreover, when the film thickness of the sol-gel coat layer is within the above range, the quick-drying property of the sol-gel coat layer can be enhanced, which is advantageous in the production process. Furthermore, if the film thickness of the gas barrier layer is within the above range, it is possible to fill defects such as pinholes and cracks in the first barrier layer. In the present invention, by including silica particles in the sol-gel coat layer, the film formability is improved. Therefore, even when the sol-gel coat layer is relatively thin, Is possible.

  As a method for forming the sol-gel coat layer, for example, a coating solution for forming a sol-gel coat layer (sol solution) is prepared from the above-described materials, and the coating solution for forming a sol-gel coat layer is applied on the gas barrier layer, A method of heating and drying can be used. In such a method, the applied coating solution for forming a sol-gel coat layer (sol solution) volatilizes the solvent and hardens (gels) by dehydration polycondensation by a sol-gel reaction to form a sol-gel coat layer. It is.

  When preparing a coating solution for forming a sol-gel coat layer, for example, colloidal silica and an aqueous alkali silicate solution are mixed, colloidal silica and an organometallic compound are mixed, or colloidal silica and an organometallic compound are hydrolyzed in advance. Can be mixed.

  In preparing the sol-gel coating layer forming coating solution, an organometallic compound or a hydrolyzate of an organometallic compound, or an alkali silicate aqueous solution, and colloidal silica are applied on the first barrier layer. It is preferable to mix immediately before. This is because colloidal silica has an action of promoting the sol-gel reaction, and if the mixture of these is stored in advance, the sol-gel reaction may proceed too much during storage.

  The method for applying the sol-gel coating layer forming coating solution is not particularly limited as long as it can be applied on the first barrier layer. For example, dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, A die coat, a screen printing method, a spray coat, a gravure offset method, a bar coat or the like can be used. Among these, for example, when applying to a film-like substrate, gravure coating, die coating, gravure offset method, and bar coating are preferably used, and gravure coating is preferably used particularly considering production efficiency and cost. It is done.

  Examples of the heat drying method include hot air drying, hot roll drying, and infrared irradiation, and are not particularly limited. Here, the heating and drying conditions are not particularly limited as long as the sol-gel coat layer is formed. For example, the heat drying temperature is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. Moreover, 1 to 300 minutes are preferable and, as for heat drying time, 5 to 150 minutes are more preferable.

(Formation of second barrier layer with polysilazane-containing coating solution)
The second barrier layer according to the present invention is formed by applying a coating liquid containing a polysilazane compound on the first barrier layer, preferably by laminating to form a polysilazane layer, and then subjecting the polysilazane layer to vacuum ultraviolet light. It is formed by ceramicizing.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll 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 coating thickness can be appropriately set according to the purpose. For example, the thickness after application of the second barrier layer is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, still more preferably about 10 nm to 1 μm, still more preferably 150 to 600 nm. Particularly preferably, it can be set to be about 50 to 200 nm. If it is such a range, it will be excellent in high gas barrier performance, bending tolerance, and cutting processability.

“Polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, SiO ₂ having a bond such as Si—N, Si—H, N—H, etc., Si ₃ N ₄ and both intermediate solid solutions SiO _x. a ceramic precursor inorganic polymer N _y or the like.

  In order not to damage the film substrate, a compound that is ceramicized at a relatively low temperature and modified to silica is preferable. For example, it is represented by the following general formula (1) described in JP-A-8-112879. A compound having a main skeleton composed of the following units is preferred.

In the general formula (1), R ¹ , R ² and R ³ each independently 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. .

In the present invention, perhydropolysilazane 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 film to be obtained.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is 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. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the above general formula (1) (for example, Japanese Patent Laid-Open No. Hei. No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (for example, see JP-A-6-122852), and alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208). Gazette), metal carboxylate-added polysilazanes obtained by reacting metal carboxylates (for example, see JP-A-6-299118), and acetylacetonate complexes obtained by reacting metal-containing acetylacetonate complexes Additional polysilazanes (eg, special Rights see JP 6-306329), fine metal particles of the metal particles added polysilazane obtained by adding (e.g., JP-see JP 7-196986), and the like. Alternatively, a commercially available polysilazane may be used.

  As the organic solvent for preparing the coating liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Therefore, specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. . Specifically, there are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing coating solution is preferably about 0.2 to 35% by mass, although it varies depending on the film thickness of the target second barrier layer and the pot life of the coating solution.

  In the polysilazane-containing coating solution, an amine or metal catalyst may be added to promote conversion to a silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

(Operation for removing organic solvent and water in second barrier layer)
The second barrier layer formed from the polysilazane-containing coating solution according to the present invention preferably has moisture removed before or during the modification treatment. Therefore, it is preferable to divide into the 1st process aiming at the removal of the organic solvent in a 2nd barrier layer, and the 2nd process aiming at the removal of the water | moisture content in the 2nd barrier layer following it. .

  In the first step, mainly the organic solvent is removed, so that the drying conditions can be appropriately determined by a method such as heat treatment, and at this time, the moisture may be removed. The heat treatment temperature is preferably a high temperature from the viewpoint of rapid processing, but it is preferable to appropriately determine the temperature and treatment time in consideration of thermal damage to the resin film substrate. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the heat treatment temperature can be set to 200 ° 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 200 ° C. or less, the treatment time can be set within 30 minutes.

  The second step is a step for removing moisture in the second barrier layer. As a method for removing moisture, a mode of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./temperature). (Humidity 1%) or less, and the maintained time is preferably set appropriately depending on the film thickness of the second barrier layer. Under the condition that the film thickness of the second barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −8 ° C. or less and the maintaining time is 5 minutes or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher, and preferably −40 ° C. or higher. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

  As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes in the first step, the dew point of the second step is 4 ° C. or less. The treatment time can be selected from 5 minutes to 120 minutes under conditions for removing moisture. The first process and the second process can be distinguished by a change in dew point, and the difference can be made by changing the dew point of the process environment by 10 ° C. or more.

  The second barrier layer according to the present invention is preferably subjected to a modification treatment while maintaining its state even after moisture is removed in the second step.

(Water content of the second barrier layer)
The moisture content of the second barrier layer according to the present invention can be measured according to the analysis method described below.

Headspace-gas chromatograph / mass spectrometry apparatus: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min), then heated to 150 ° C. at a rate of 10 ° C./min Column: DB-624 (0.25 mm × 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C, 30min
The moisture content in the second barrier layer in the present invention is defined as a value obtained by dividing the moisture content obtained by the above analysis method by the volume of the second barrier layer, and the state in which moisture is removed by the second step. Is preferably 0.1% or less, and more preferably 0.01% or less (below the detection limit).

  In the present invention, removal of moisture before or during the modification treatment is a preferable form from the viewpoint of promoting the dehydration reaction of the second barrier layer converted to silanol.

[Modification treatment of second barrier layer]
The modification treatment in the present invention refers to a conversion reaction (ceramicization) of a polysilazane compound to silicon oxide or silicon oxynitride.

  For the modification treatment in the present invention, a known method based on the conversion reaction of the second barrier layer can be selected. Formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate such as plastic.

  Therefore, in producing the gas barrier film of the present invention, from the viewpoint of adapting to a plastic substrate, a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a lower temperature is preferable.

(UV irradiation treatment)
In the present invention, treatment by ultraviolet irradiation is also preferable as one of the modification treatment methods. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. Ceramicization is promoted, and the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the method according to the present invention, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 350 nm. Use ultraviolet light.

  It is preferable that the irradiation intensity and the irradiation time be set within the range where the substrate carrying the second barrier layer to be irradiated is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. However, in the case of a film having high heat resistance such as polyimide or a substrate such as metal, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. )), UV light laser, and the like. In addition, when irradiating the generated ultraviolet rays to the second barrier layer, from the viewpoint of achieving efficiency improvement and uniform irradiation, the ultraviolet rays from the generation source are reflected by the reflector and then applied to the second barrier layer. It is desirable to guess.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a substrate (for example, a silicon wafer) having a second barrier layer on its surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known, and for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd. can be used. Moreover, when the base material which has a 2nd barrier layer on the surface is a elongate film form, it irradiates an ultraviolet-ray continuously in the drying zone equipped with the above ultraviolet-ray generation sources, conveying this. Can be made into ceramics. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate used and the second barrier layer.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm larger than the interatomic bonding force in the polysilazane compound, preferably light energy having the following wavelength components, particularly preferably light energy having a wavelength of 100 to 180 nm. Is used to form a silicon oxide film at a relatively low temperature by advancing an oxidation reaction with active oxygen or ozone while directly cutting atoms by the action of only photons called photon processes.

  As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

Since noble gas atoms such as Xe, Kr, Ar, Ne, and the like are chemically bonded and do not form molecules, they are called inert gases. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. 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.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric), the electric discharge accumulates on the surface of the dielectric and the micro discharge disappears. This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be seen 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.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge.

  Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the 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.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so that the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to discharge in the entire discharge space. Must be a thing. For this reason, an electrode in which a fine metal wire is formed in a net shape 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 the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface 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.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector, usually made of an aluminum block, is used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  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. Therefore, a very inexpensive light source can be provided.

  Since the double cylindrical lamp is processed by closing both ends of the inner and outer tubes, it is more likely to be damaged during handling and transportation than a thin tube lamp. The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. 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 is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. 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. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as polyethylene terephthalate which are considered to be easily affected by heat.

The modification treatment conditions are not limited, but, for example, when the film thickness of the second barrier layer is 50 to 1000 nm, the vacuum ultraviolet illuminance is 10 to 200 mW / cm ² , the irradiation distance is 0.1 to 10 mm, It can be selected from an oxygen concentration of 0 to 5% by volume, a dew point temperature of 10 to -50 ° C, a temperature of 25 to 200 ° C, and a treatment time of 0.1 to 150 seconds.

[Configuration of gas barrier film]
(Base material)
As the base material of the gas barrier film of the present invention, a material having a low thermal expansion coefficient or a low humidity expansion coefficient is preferably used in order to avoid deformation due to heating or moisture absorption as much as possible, and the thermal expansion coefficient is 50 × 10 ^−6. / ° C. or less and 1 × 10 ⁻⁶ / ° C. or more, preferably 20 × 10 ⁻⁶ / ° C. or less and 1.0 × 10 ⁻⁶ / ° C. or more, more preferably 15 × 10 ⁻⁶ / It is below ℃ and is above ^1.0x10-6 / ℃. These expansion coefficients can be adjusted by selecting a material and selecting a draw ratio.

  In addition to the above thermal expansion coefficient, the base film preferably has a glass transition temperature (Tg) of a resin constituting the base film of 120 ° C. or higher. When the Tg is less than 120 ° C., the base film 7 is easily softened by heat generated when the thin film layer is formed on the base film, and the base film is easily deformed by an external force applied to the base film. . In this sense, Tg is preferably higher, but in the range specifically exemplified below, it is 300 ° C. or lower. When the glass transition temperature exceeds 300 ° C., the flexibility of the base film itself is lowered and the flexibility is lost, so that continuous processing becomes difficult.

  As a synthetic resin of a material constituting a specific substrate film, as a crystalline resin, a thermoplastic resin such as polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, (PEN) or syndiotactic polystyrene As the thermosetting resin, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, fluororesin, polyether nitrile, and the like can be given as preferable resins.

  In addition, as a synthetic resin of a material constituting the base film, a non-crystalline resin is a thermoplastic resin such as polycarbonate, a modified polyphenylene ether, a polycyclohexene, or a polynorbornene resin, and a thermosetting resin is polysulfone, Polyethersulfone, polyarylate, polyamideimide, polyetherimide, thermoplastic polyimide, or the like can be mentioned as a more preferable resin. Among them, since polycarbonate has a low water absorption, the base film 7 formed using the polycarbonate has a low humidity expansion coefficient and is particularly preferable. Furthermore, acrylate type, methacrylate type, etc. can be used in the photocurable resin.

  The thermal properties required for the substrate film, particularly the behavior with respect to external force, can be specified by the deflection temperature under load, which is a more practical index, and those with a deflection temperature under load of 150 ° C. or higher are preferable. Incidentally, the deflection temperature under load of each resin is as follows: polycarbonate resin; 160 ° C., polyarylate resin; 175 ° C., polyethersulfone resin; 210 ° C., cycloolefin polymer (trade name; “Zeonor” manufactured by Nippon Zeon Co., Ltd.); Or a norbornene resin (manufactured by JSR, trade name: “ARTON”);

  Although the thickness of a base material is not restrict | limited in particular, About 5-500 micrometers is preferable, More preferably, it is 25-250 micrometers.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. It is.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate 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. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  Moreover, in the base material which concerns on this invention, you may corona-treat before forming a 1st barrier layer.

Furthermore, an anchor coat layer may be formed on the surface of the base material according to the present invention for the purpose of improving the adhesion with the first barrier layer. Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One or two or more can be used in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

(Smooth layer)
The gas barrier film of the present invention may have a smooth layer. The smooth layer flattens the rough surface of the transparent resin film substrate where protrusions and the like exist, or fills the unevenness and pinholes generated in the transparent first barrier layer with the protrusions existing on the transparent resin film substrate. Provided for flattening. Such a smooth layer is basically formed by curing a photosensitive resin.

  Examples of the photosensitive resin used for forming the smooth layer include a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, Examples thereof include resin compositions in which polyfunctional acrylate monomers such as urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with acrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  The composition of the photosensitive resin contains a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

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

  Solvents used when forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If it is smaller than 10 nm, the coating property may be impaired when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or a wireless bar in the step of coating a silicon compound described later. . Moreover, when larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

<Additives to smooth layer>
One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin. Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle size of 0.001 to 0.01 μm. The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. Addition of 20% or more improves adhesion with the gas barrier layer. On the other hand, if it exceeds 60%, the film may be bent or cracks may occur when heat treatment is performed, or the optical properties such as transparency and refractive index of the gas barrier film may be affected.

  In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  In the present invention, the thickness of the smooth layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer has a high transparency. When the film is provided only on one surface of the molecular film, curling of the smooth film can be easily suppressed.

(Bleed-out prevention layer)
In the gas barrier film of the present invention, a bleed-out prevention layer can be provided. The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film base material to the surface when the film having the smooth layer is heated and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And monounsaturated organic compounds having one polymerizable unsaturated group.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.

  In addition, as an ionizing radiation curable resin, an ionizing radiation (ultraviolet ray or electron beam) is irradiated to an ionizing radiation curable coating material in which one or more of a photopolymerizable prepolymer or a photopolymerizable monomer is mixed. Those that cure can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer as described above is prepared as a coating solution by mixing a hard coating agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can be formed by coating the film surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation. As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from 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 are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

<< Packing form of gas barrier film >>
The gas barrier film of the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the gas barrier layer was formed. In particular, when the gas barrier film of the present invention is used as a sealing material for an organic thin film device, it often becomes a defect due to dust (particles) adhering to the surface, and a protective sheet is pasted in a highly clean place. It is very effective to prevent the adhesion of dust. In addition, it is effective in preventing scratches on the gas barrier layer surface that enters during winding.

  Although it does not specifically limit as a protective sheet, The general "protection sheet" and "release sheet" of the structure which provided the weak adhesive layer on the resin substrate about 100 micrometers in thickness can be used.

<< Method for measuring characteristic values of gas barrier film >>
Each characteristic value of the gas barrier film of the present invention can be measured according to the following method.

(Measurement of water vapor transmission rate)
Various methods have been proposed for measuring the water vapor transmission rate according to the method B described in JIS K 7129 (1992). For example, the cup method, dry / wet sensor method (Lassy method), infrared sensor method (mocon method) can be mentioned as representatives, but as the gas barrier properties improve, these methods may reach the measurement limit. A method is also proposed.

<Measurement method of water vapor transmission rate other than the above>
1. Ca method A method in which metal Ca is vapor-deposited on a gas barrier film and the phenomenon in which metal Ca is corroded by moisture that has permeated through the film. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area.

2. Method proposed by MORESCO (December 8, 2009, NewsRelease)
A method of passing water vapor through a cold trap between a sample space under atmospheric pressure and a mass spectrometer in an ultra-high vacuum.

3. HTO method (US General Atomics)
A method of calculating water vapor transmission rate using tritium.

4). Method proposed by A-Star (Singapore) (International Publication No. 2005/95924)
A method of calculating a water vapor transmission rate from a change in electric resistance and a 1 / f fluctuation component contained therein using a material (for example, Ca, Mg) whose electric resistance is changed by water vapor or oxygen as a sensor.

  In the gas barrier film of the present invention, the method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, the measurement by the Ca method described above was performed as the method for measuring the water vapor transmission rate.

The water vapor permeability of the gas barrier film of the present invention is preferably as low as possible. For example, it is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² g / m ² · 24 h, and 1 × 10 ⁻⁶ to 1 × More preferably, it is 10 ⁻⁴ g / m ² · 24 h.

[Measurement of oxygen permeability]
Using an oxygen permeability measuring device (model name, “Oxytran” (registered trademark) (“OXTRAN” 2/20)) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 0% RH , Measured according to the B method (isobaric method) described in JIS K7126 (1987). In addition, each of the two test pieces was measured once, and the average value of the two measured values was used as the oxygen permeability value.

The oxygen permeability of the gas barrier film of the present invention is preferably as low as possible, but is preferably 0.01 g / m ² · 24 h · atm or less, for example, 0.001 g / m ² · 24 h · atm or less. In particular, it is more preferably less than 0.001 g / m ² · 24 h · atm (below the detection limit).

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Production of Gas Barrier Film Having First Barrier Layer >>
[Formation of first barrier layer 1] (SiN film (single layer type))
Using the vacuum plasma CVD apparatus shown in FIG. 1, a polyethylene naphthalate (PEN) film having a thermal expansion coefficient of 100 × 10 ⁻⁶ / ° C. with a hard coating on a SiN film (thickness: 125 μm, manufactured by Teijin Jupon Co., Ltd., trade name: A film was formed on Teonex). The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The source gas was introduced into the vacuum chamber at a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 50 sccm, and a hydrogen gas flow rate of 200 sccm (sccm is cm ³ / min at 133.322 Pa). A first barrier layer 1 having a film thickness of 250 nm, which is a silicon nitride thin film layer (SiN layer) containing silicon nitride as a main component by setting the film substrate temperature to 100 ° C. at the start of film formation and the gas pressure at the time of film formation to 30 Pa. Formed.

  In addition, the gas barrier film which has the 1st barrier layer 1 which changed the thermal expansion coefficient of the said base material as shown in Table 1 was also produced.

[Formation of the first barrier layer 2] (in the case of SiN film (two-layer laminated type))
Using the vacuum plasma CVD apparatus shown in FIG. 1, a polyethylene naphthalate (PEN) film (thickness: 125 μm, manufactured by Teijin DuPont, trade name: SiN film with hard coat and thermal expansion coefficient of 10 × 10 ⁻⁶ / ° C. A film was formed on Teonex). The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The source gas was introduced into the vacuum chamber at a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 50 sccm, and a hydrogen gas flow rate of 200 sccm. After the film substrate temperature was set to 100 ° C. at the start of film formation and the gas pressure at the time of film formation was set to 4 Pa to form a silicon nitride thin film layer (SiN layer) containing silicon nitride as a main component with a film thickness of 150 nm, the film substrate temperature was The second silicon nitride thin film layer (SiN layer) having a film thickness of 200 nm was continuously formed with the gas pressure set to 30 Pa, and the first barrier layer 2 having a total film thickness of 350 nm was formed.

[Formation of the first barrier layer 3] (in the case of SiON film (single layer type))
A polyethylene naphthalate (PEN) film with a thermal expansion coefficient of 10 × 10 ⁻⁶ / ° C. with a hard coat and a SiON film (thickness: 125 μm, manufactured by Teijin DuPont, trade name: vacuum plasma CVD apparatus shown in FIG. 1 A film was formed on Teonex). The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The source gas was introduced into the vacuum chamber at a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 100 sccm, and a nitrous oxide gas flow rate of 50 sccm. The first barrier layer 3 having a film thickness of 350 nm and a silicon oxynitride thin film layer (SiON layer) containing silicon nitride as a main component by setting the film substrate temperature to 100 ° C. at the start of film formation and the gas pressure at the time of film formation to 100 Pa. Formed.

[Formation of the first barrier layer 4] (in the case of SiO ₂ film (single layer type))
Using a vacuum plasma CVD apparatus shown in FIG. 1, a polyethylene naphthalate (PEN) film with a thermal expansion coefficient of 10 × 10 ⁻⁶ / ° C. with a hard coat of SiO ₂ film (thickness: 125 μm, manufactured by Teijin DuPont, trade name) : Teonex). The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. As source gases, an argon gas flow rate of 150 sccm, a silane gas flow rate of 7.5 sccm, and a nitrous oxide gas flow rate of 130 sccm were introduced into the vacuum chamber. The first barrier layer 4 having a film thickness of 350 nm is formed by setting the film substrate temperature to 100 ° C. at the start of film formation and the gas pressure at the time of film formation to 200 Pa to form a silicon oxide thin film layer (SiO ₂ layer) mainly composed of silicon nitride. Formed.

(Preparation of gas barrier film 1)
[Formation of Second Barrier Layer 1]
A 10% by mass dibutyl ether solution of perhydropolysilazane (AQUAMICA (trademark) NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) is used as a wireless bar on the first barrier layer 1 formed by the above method. Then, the coated film was coated so that the (average) film thickness after drying was 0.10 μm.

[First step: drying treatment]
The obtained coated sample was treated for 1 minute in an atmosphere of a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.

[Second step: Dehumidification treatment]
The dried sample was further held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification. The water content of the layer thus obtained was 0.01% or less (below the detection limit).

[Modification A]
The sample subjected to the dehumidification treatment was subjected to a modification treatment under the following conditions. The dew point temperature during the reforming treatment was -8 ° C.

(Modification equipment)
Apparatus: M.com Co., Ltd. excimer irradiation apparatus MODEL: MECL-M-1-200
Wavelength: 172nm
Lamp filled gas: Xe
(Reforming treatment conditions)
The sample fixed on the operation stage was subjected to a modification treatment under the following conditions to form the second barrier layer 1.

Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer irradiation time: 5 seconds The gas barrier film 1 was produced as described above.

(Coefficient of thermal expansion)
The coefficient of thermal expansion was measured by the following procedure.

  Procedure 1: A base material is cut out into length 200mm x width 10mm, and it is set as a measurement sample. Fixing jigs are attached to both ends of the measurement sample, and the length of the measurement sample exposed between the both-end fixing jigs is set to 10 mm.

  Procedure 2: A load with a tensile force of 10 N is applied to a measurement sample per 1 m width of the substrate. In the case of the measurement sample shown in Procedure 1, a load of 0.05 N is applied.

Step 3: Measure the length L ₀ of the measurement sample between the fixing jigs.

  Procedure 4: Heat to 90 to 150 ° C. at a predetermined measurement temperature (180 ° C.) at 5 ° C./min, and measure the length L between the fixing jigs of the measurement sample at the measurement temperature. .

Procedure 5: Elongation rate is calculated by the formula: (L ₀ -L) / L, and this is used as the thermal expansion coefficient of the substrate.

(Production of gas barrier films 2 to 22)
The gas barrier film 1 except that the base material and the film thickness of the first barrier layer 1 having different coefficients of thermal expansion, the film thickness of the second barrier layer, and the wavelength of the vacuum ultraviolet light are changed as shown in Table 1. In the same manner, gas barrier films 2 to 19 were obtained. Moreover, the gas barrier films 20-22 were produced like the gas barrier film 1 except having changed the 1st barrier layer 1 into the 1st barrier layers 2-4.

(Evaluation)
The obtained gas barrier films 1 to 22 were evaluated as follows, and the results are shown in Table 1.

[Evaluation of water vapor barrier properties]
According to the following measuring method, the water vapor barrier property of each gas barrier film was evaluated.

(apparatus)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
Use a vacuum evaporation system (JEOL-made vacuum evaporation system JEE-400) on the gas barrier layer surface of the sample, and mask other than the part (12mm x 12mm 9 locations) where the gas barrier film sample is to be deposited before applying the transparent conductive film. Then, metallic calcium was deposited. Thereafter, 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 sheet. After aluminum sealing, 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. In addition, in order to confirm the change in gas barrier properties before and after bending, a water vapor barrier evaluation cell was similarly prepared for the gas barrier film that was not subjected to the bending treatment.

  The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.

  In addition, in order to confirm that there is no permeation of water vapor from other than the barrier film surface, instead of the gas barrier film sample as a comparative sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm was used. The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

[Evaluation of oxygen barrier properties]
Using an oxygen permeability measuring device (model name, “Oxytran” (registered trademark) (“OXTRAN” 2/20)) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 0% RH , Measured according to the B method (isobaric method) described in JIS K7126 (1987). In addition, each of the two test pieces was measured once, and the average value of the two measured values was used as the oxygen permeability value.

[Evaluation of bending resistance]
After each gas barrier film was bent 100 times at an angle of 180 degrees so that the radius of curvature was 10 mm, the water vapor transmission rate was measured in the same manner as above, and the water vapor transmission before and after the bending treatment was measured. From the change in rate, the deterioration resistance was measured according to the following equation, and the bending resistance was evaluated according to the following criteria.

Deterioration resistance = (water vapor permeability after bending test / water vapor permeability before bending test) × 100 (%)
5: Deterioration resistance is 90% or more 4: Deterioration resistance is 80% or more and less than 90% 3: Deterioration resistance is 60% or more and less than 80% 2: Deterioration resistance is 30% or more and less than 60% 1: Deterioration resistance is less than 30% [Evaluation of cutting processability]
After cutting each gas barrier film to B5 size using a disk cutter DC-230 (CADL), each cut end was observed with a loupe, and the total number of cracks on the four sides was confirmed. Cutting suitability was evaluated.

5: No crack generation was observed 4: The number of cracks generated was 1 or more and 2 or less 3: The number of cracks generated was 3 or more and 5 or less 2: Number of cracks generated Is 6 or more and 10 or less 1: The number of occurrence of cracks is 10 or more

  It can be seen from Table 1 that the barrier produced by the production method of the present invention is excellent in water vapor transmission rate, bending resistance and cutting processability.

Example 2
[Formation of the first barrier layer 5]
Using a sputtering apparatus, a polyethylene naphthalate (PEN) film having a thermal expansion coefficient of 10 × 10 ⁻⁶ / ° C. used in the gas barrier film 12 (thickness: 125 μm, manufactured by Teijin DuPont, trade name: Teonex) An inorganic layer (aluminum oxide layer) was formed on Q65F). Aluminum was used as a target, argon was used as a discharge gas, and oxygen was used as a reaction gas. The film-forming pressure was 0.1 Pa, and the ultimate film thickness was made to have the value shown in Table 2.

Measurement of water vapor transmission rate by MOCON method of gas barrier film About the gas barrier film obtained above, using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W3 / 31), water vapor at 40 ° C./90% relative humidity. When the transmittance was measured, it was below the detection limit (0.01 g / m ² / day).

  Using the obtained gas barrier film having the first barrier layer 5, the second barrier layer is formed on the first barrier layer 5, and the film thickness is shown in Table 2 in the same manner as the gas barrier film 12. In this way, gas barrier films 23 and 24 were prepared, evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  From Table 2, it can be seen that the gas barrier film of the present invention exhibits excellent performance even when the first barrier layer is produced by sputtering.

Example 3
(Preparation of sol-gel coating solution)
To 10 g of an aqueous lithium silicate solution (Li ₂ O.nSiO ₂ , n = about 5 mol ratio) adjusted to a solid content of 10% by mass, tetraethyl orthosilicate (Si (OC ₂ H ₅ ) ₄ : abbreviated as TEOS) 8.3 g (0 .04 mol), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Chisso Siler Ace S530) 9.9 g (0.04 mol) and 0.1 N / l hydrochloric acid solution 18 g were added and stirred for 18 hours. A sol-gel coating solution was prepared.

(Preparation of colloidal silica solution)
As a colloidal silica, “Snowtex-20 (particle diameter: 10 nm to 20 nm)” manufactured by Nissan Chemical Co., Ltd. was used and prepared with isopropyl alcohol so that the solid concentration was 10% by mass to obtain a colloidal silica solution.

(Sol-gel coat layer (formation of second barrier layers 2-1 and 2-2))
A sol-gel coat solution and a colloidal silica solution were used to prepare a sol-gel coat solution: colloidal silica solution = 5: 5 (mass ratio) ratio to obtain a sol-gel coat layer forming coating solution. This sol-gel coating layer forming coating solution is used as a second barrier layer on the first barrier layer prepared by the same method as described in the preparation of the gas barrier film 12, and the dried film Bar coating was performed so that the thickness became the value shown in Table 3, and heat treatment was performed at 100 ° C. for 30 minutes to form a sol-gel coat layer, whereby gas barrier films 25 and 26 were produced. Evaluation was conducted in the same manner as in Example 1, and the results are shown in Table 3.

  From Table 3, it can be seen that the gas barrier film of the present invention exhibits excellent performance even when a sol-gel coat layer is used.

  Furthermore, this application is based on Japanese Patent Application No. 2010-258631 filed on Nov. 19, 2010, the disclosure of which is incorporated by reference in its entirety.

DESCRIPTION OF SYMBOLS 1 Plasma CVD apparatus 2 Vacuum tank 3 Cathode electrode 5 Susceptor 6 Heat medium circulation system 7 Vacuum exhaust system 8 Gas introduction system 10 Heating / cooling apparatus 11 Gas barrier film 12 Base material 13 1st barrier layer 14 2nd barrier layer 15 Barrier layer

Claims (5)

The first base material having a first barrier layer formed by vapor deposition at a thickness of 220 to 500 nm on at least one surface side of the base material having a thermal expansion coefficient of 1 to 50 × 10 ⁻⁶ / ° C. Forming a polysilazane layer on the barrier layer by forming a polysilazane layer, and then forming the second barrier layer by ceramicizing the polysilazane layer with vacuum ultraviolet light. The manufacturing method of a gas-barrier film which has a smooth layer further between 1 barrier layers.   The method for producing a gas barrier film according to claim 1, wherein the vacuum ultraviolet light is vacuum ultraviolet light having a wavelength component of 180 nm or less. Before SL is a thickness of the second barrier layer is 50 to 200 nm, a manufacturing method of the gas barrier film according to claim 1 or 2. The method for producing a gas barrier film according to any one of claims 1 to 3 , wherein the first barrier layer is formed by a chemical vapor deposition method and is made of silicon oxide, silicon oxynitride, or silicon nitride. The method for producing a gas barrier film according to claim 4 , wherein the chemical vapor deposition method is a vacuum plasma CVD method.