JPWO2013161893A1 - Method for producing laminated gas barrier resin base material - Google Patents

Abstract

The present invention provides a method for producing a laminated gas barrier resin base material having a gas barrier property by at least one of the film A and the film B on the resin base material, and having the respective films, and the film A on the resin base material. Forming step (A), laminating a resin base material having releasability on the film A, step (C) peeling the resin base material from the film A, and the film Gas barrier properties are improved by sequentially performing at least one step of applying energy to A (D) and step (E) of forming the film B on the film A.

Description

  The present invention relates to a method for producing a laminated gas barrier resin substrate. More specifically, the present invention relates to a method for producing a laminated gas barrier resin base material that can be used as a gas barrier film mainly used in display materials such as packages for electronic devices, plastic substrates such as solar cells, organic EL elements, and liquid crystal display elements. .

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or film is used to wrap articles and foods that require blocking of various gases such as water vapor and oxygen. It is widely used for packaging and the like to prevent alteration of industrial products and pharmaceuticals. In addition to packaging applications, they are used in liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and the like. In particular, liquid crystal display elements, organic EL elements, and the like are required to have high gas barrier properties (gas barrier properties) because internal penetration of water vapor or air causes deterioration in quality.

  As one of methods for meeting these demands for gas barrier properties such as high water vapor and air, a method of laminating a gas barrier layer is considered. However, when laminating the gas barrier layer, fine scratches that may occur between the gas barrier layer and the lower layer, and adhesion of foreign matters during the laminating process cause damage to the gas barrier property, This is a problem in achieving high gas barrier properties.

  In order to solve these problems, Patent Document 1 below proposes a method for preventing damage and contact of a film and reducing damage to the gas barrier layer by applying a laminate film on the gas barrier layer. However, when the laminate film is peeled off, the adhesive that is applied to the laminate film remains on the surface of the gas barrier layer, which is the lower layer, which becomes a foreign substance when laminating the subsequent gas barrier layer, which may be a problem. Are known.

  And from such a problem, in the following patent document 2, by using an adhesive film (laminate film) having an adhesive layer having a peeling force of 0.01 N / 25 mm or more and 0.06 N / 25 mm or less with respect to the gas barrier layer. , Reducing the residual adhesive.

JP 2011-167967 A JP 2011-84776 A

  However, as a result of confirmation by the present inventors, even with the conventional technique using an adhesive film (laminate film) that defines the above-described peeling force, the gas barrier property is reduced due to the remaining adhesive after the adhesive film is peeled off. As a result, it was found that countermeasures against the remaining sticky substances are not sufficient.

  Therefore, the present invention has been made in view of the above-described problems of the prior art, and the object thereof is to have a releasability in a gas barrier layer formed on a resin substrate in the formation of a laminated gas barrier resin substrate. Laminating resin material, eliminating the problem of remaining adhesive material after the resin material is peeled off, and reducing the influence of foreign matter during lamination as much as possible, and high-quality lamination with excellent gas barrier properties The object is to provide a gas barrier resin substrate.

  The above-mentioned problem according to the present invention is solved by the following means.

That is, in the method for producing a laminated gas barrier resin base material having a film A and a film B, on which a gas barrier property is exhibited by at least one of the film A and the film B on the resin base material,
Forming the film A on the resin substrate (A);
A step (B) of laminating a resin material having releasability on the film A;
A step (C) of peeling the resin material having releasability from the film A;
Applying energy to the film A (D);
Forming the film B on the film A (E);
Is a method for producing a laminated gas barrier resin substrate, which is sequentially passed at least once.

It is a figure for demonstrating the outline of the manufacturing process of one Embodiment of the laminated gas barrier resin base material of this invention. It is a figure for demonstrating the outline of the manufacturing process of one Embodiment of the laminated gas barrier resin base material of this invention. It is a figure for demonstrating the outline of the manufacturing process of another embodiment of the lamination | stacking gas-barrier resin base material of this invention. It is the schematic of an atmospheric pressure plasma processing apparatus.

  Hereinafter, modes for carrying out the present invention will be described. The production method of the present invention is a method for producing a laminated gas barrier resin base material having a film A and a film B, wherein the resin base material has a gas barrier property by at least one of the film A and the film B. The step (A) of forming the film A on the top, the step (B) of laminating a resin material having releasability on the film A, and the resin material having releasability from the surface of the film A The step (C) of peeling, the step (D) of applying energy to the film A, and the step (E) of forming the film B on the film A are sequentially performed at least once. In the case where a large number of films A or B are laminated, a laminated gas barrier resin base material can be produced by performing the above-described process a plurality of times without particular limitation. According to the present invention, a gas barrier film having high gas barrier performance and excellent continuous productivity is realized.

  Hereinafter, an outline of a preferred embodiment of the method for producing a laminated gas barrier resin substrate of the present invention will be described with reference to the drawings. However, the present invention is not limited to this embodiment. Next, the manufacturing process of the present invention includes a step (A) of forming a film A on a resin substrate, a step (B) of laminating a resin material having releasability on the film A, and a resin having releasability. The production method of the present invention will be described by dividing into a step (C) for peeling the material from the film A, a step (D) for imparting energy to the film A, and a step (E) for forming the film B on the film A. .

  1 and 3 are diagrams for explaining an outline of a method for producing a laminated gas barrier resin substrate according to an embodiment of the present invention. In FIG. 1, a film A 2 is formed on the resin base material 1 drawn out from the roll 3 through a film A forming step 5. On the film A 2, a resin material 8 having releasability is laminated for winding the film A to protect the film A. Next, after the roll 4 is conveyed or stored as necessary, as shown in FIG. 3, the resin base material 1 on which the resin material 8 having releasability is laminated is again unwound from the roll 4 and released. The resin material 8 having properties is peeled off. After the resin material 8 having releasability is peeled off, energy is applied on the film A 2 by an energy applying step 9. Next, in the film B forming step 10, the film B 11 is formed on the film A 2, and the resin base material 1 including the film A 2 and the film B 11 is wound around the roll 12.

  FIG. 2 is a view for explaining an outline of a method for producing a laminated gas barrier resin substrate according to another embodiment of the present invention. In the embodiment of FIG. 2, the film A is formed through an application process 6 and an energy application process 7 for curing. In FIG. 2, the coating liquid for the film A is applied by the film A application process 6 on the resin base material 1 drawn out from the roll 3. Next, in the energy application step 7 for curing the film A, the coating liquid for the film A is cured, and the film A2 is completed. On this film A 2, a resin material 8 having a releasability is laminated and wound on a roll 4 for protecting the film A. Next, after being transported or stored as necessary, as shown in FIG. 3, the resin base material 1 laminated with the resin material 8 having releasability is fed out again from the roll 4 and has releasability. The resin material 8 is peeled off. After the resin material 8 having releasability is peeled off, energy is applied on the film A2 by an energy applying process 9. Accordingly, in the embodiment of FIG. 2, there are at least two energy application steps. Thereafter, as shown in FIG. 3, in the film B forming step 10, the film B 11 is formed on the film A 2, and the resin base material 1 including the film A 2 and the film B 11 is wound around the roll 12. Although not shown in FIG. 3, the film B may be formed by an application process and an energy application process for curing.

(1) Step (A)
The step (A) is a method for producing a laminated gas barrier resin base material having a film A and a film B, on which a gas barrier property is exhibited by at least one or both of the film A and the film B on the resin base material. This is a step of forming a film A on top.

In the present invention, the gas barrier property means that the laminated gas barrier resin base material including the membrane A and the membrane B has a water vapor transmission rate of 0.01 g / m ² / day or less and an oxygen transmission rate of 0.01 ml / m as a whole. ² / day / atm or less. The water vapor transmission rate can be measured by a method described in JIS K 712 gB or Japanese Patent Application Laid-Open No. 2004-333127 (g / m ² / day). Similarly, the oxygen permeability can be measured by the method described in JIS K 7126B (ml / m ² / day / atm).

  In the present invention, one of the film A and the film B may exhibit the above gas barrier property, or the above gas barrier property may be achieved by combining the film A and the film B. Although the film A and the film B will be described later, they may be composed of the same material or different materials as long as the gas barrier property is exhibited. The present invention is characterized in that it has a step of applying energy after the film A is formed and a resin material having releasability is attached and peeled, and by this energy applying step, a laminated gas barrier resin is provided. It improves the final gas barrier properties of the substrate. Therefore, the manufacturing method of the present invention can be applied to the film A and the film B, as long as the film A and the film B are configured to exhibit gas barrier properties. That is, although the preferable specific example of the film | membrane A is described below, this is only an example and this invention is a manufacturing method regardless of the specific kind of film | membrane and material which show gas barrier property.

In order to have the above gas barrier properties, the film A and the film B are formed so as to have a water vapor transmission coefficient of 1 × 10 ⁻¹⁴ g · cm / (cm ² · sec · Pa) or less. It is preferable. The water vapor transmission coefficient can be measured by the following method. A membrane A and a membrane B are formed with a predetermined thickness on a known support (for example, cellulose triacetate film; thickness: 100 μm) and used as sample membranes as they are, and two primary and secondary sides separated by sandwiching the sample membrane are used. Vacuum the container. Water vapor having a relative humidity of 92% is introduced into the primary side, and the amount of water vapor that has permeated the sample film and has come out to the secondary side is measured at 250 ° C. using a vacuum gauge. This is measured over time, and a transmission curve is created by taking the secondary water vapor pressure (Pa) on the vertical axis and time (seconds) on the horizontal axis. The water vapor transmission coefficient (g · cm · cm ⁻² · sec ⁻¹ · Pa ⁻¹ ) is determined using the slope of the straight line portion of this permeation curve. Since the water vapor transmission coefficient of the support is known, the water vapor transmission coefficient can be calculated from this thickness and the thicknesses of the film A and the film B formed on the support.

  There is no restriction | limiting in particular as a formation process of the film | membrane A, A conventionally well-known thin film formation method can be used. Typically, dry coating methods such as physical vapor deposition and chemical vapor deposition, or wet coating methods such as spin coating, spray coating, plate coating, bar coating, and dip coating using a coating solution. Is mentioned.

  The dry coating method is roughly classified into a physical vapor deposition method and a chemical vapor deposition method (chemical vapor deposition method). In the physical vapor deposition method, the surface of a substance in a gas phase is subjected to a physical technique, It is a method of depositing a target substance, for example, a thin film such as a carbon film, and these methods include vapor deposition (resistance heating method, electron beam vapor deposition, molecular beam epitaxy) method, ion plating method, sputtering method, etc. is there. 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. It is a method to do. In addition, there is a method of generating plasma etc. for the purpose of activating chemical reaction, and known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. In the present invention, any of them can be advantageously used. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.

  Hereinafter, as a preferred embodiment of the present invention, a method for forming the film A using a plasma CVD method which is an example of a dry coating method will be described in detail. By forming the film A by the plasma CVD method, moisture transfer from the base material can be prevented, and a curing process (modification process by energy irradiation) at the time of forming the film B easily proceeds.

  For gas barrier layers obtained by plasma CVD, plasma CVD under atmospheric pressure or near atmospheric pressure, select conditions such as raw materials (also called raw materials), metal compounds, decomposition gas, decomposition temperature, input power, etc. Metal carbides, metal nitrides, metal oxides, metal sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxyhalides, metal nitride carbides, etc.) can be formed separately.

  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.

  Such a raw material capable of forming the film A may be in a gas, liquid, or solid state at normal temperature and pressure as long as it contains a typical or transition metal element. 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 the temperature of 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.

  A desired film A can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas. The film A formed by chemical vapor deposition is preferably a metal carbide, metal nitride, metal oxide, metal halide, metal sulfide, or a composite compound thereof from the viewpoint of permeability. Specifically, the film A is made of, for example, silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, or the like, and at least one selected from silicon oxide, silicon oxynitride, or silicon nitride in terms of gas barrier properties and transparency. It preferably has a seed, and preferably has at least one selected from silicon oxide or silicon oxynitride. The film A is preferably formed substantially or completely as a layer of an inorganic compound.

  Here, the film thickness of the film A is not particularly limited, but is preferably 1 to 1000 nm, and more preferably 50 to 800 nm. If it is such a range, it will be excellent in high gas barrier performance, bending tolerance, and cutting processability.

  Hereinafter, the plasma CVD method will be described more specifically. FIG. 4 is a schematic sectional view showing an example of a plasma CVD apparatus that can be used in the present invention. In FIG. 4, the plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. On the ceiling side inside the vacuum chamber 102, a cathode electrode 103 is disposed at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102.

  A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump that moves the heat medium, a heating device that heats the heat medium, a cooling device that cools, a temperature sensor that measures the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided.

  The heating / cooling device 160 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 105. The supplied heat medium flows inside the susceptor 105, heats or cools the susceptor 105, and returns to the heating / cooling device 160. At this time, the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 160 heats or cools the heat medium to the set temperature and supplies the heat medium to the susceptor 105. Thus, the cooling medium circulates between the susceptor and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium having the set temperature.

  The vacuum chamber 102 is connected to an evacuation system 107, and before the film formation process is started by the plasma CVD apparatus 101, the inside of the vacuum chamber 102 is evacuated in advance and the heating medium is heated to set from room temperature. The temperature is raised to a temperature, and a heat medium having a set temperature is supplied to the susceptor 105. The susceptor 105 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 105 is heated.

  After circulating the heat medium at a set temperature for a certain time, the substrate 110 to be deposited is carried into the vacuum chamber 102 and placed on the susceptor 105 while maintaining the vacuum atmosphere in the vacuum chamber 102.

  A number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105. The cathode electrode 103 is connected to a gas introduction system 108. When a CVD gas is introduced from the gas introduction system 108 to the cathode electrode 103, the CVD gas is ejected from the nozzle of the cathode electrode 103 into the vacuum chamber 102 in a vacuum atmosphere. The cathode electrode 103 is connected to a high-frequency power source 109, and the susceptor 105 and the vacuum chamber 102 are connected to the ground potential.

  When a CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102, a high-frequency power source 109 is activated while supplying a heat medium having a constant temperature from the heating / cooling device 160 to the susceptor 105, and a high-frequency voltage is applied to the cathode electrode 103, Plasma of the introduced CVD gas is formed. When the CVD gas activated in the plasma reaches the surface of the substrate 110 on the susceptor 105, a thin film grows on the surface of the substrate 110.

  During the growth of the thin film, a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and the susceptor 105 is heated or cooled by the heating medium, and a thin film is formed while being maintained at the 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 110.

  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 and the film formation temperature, and the correlation between the damage to the film formation target (substrate 110) and the film formation temperature are obtained in advance. For example, the lower limit temperature of the substrate 110 during the plasma CVD process is 50 ° C., and the upper limit temperature is 250 ° C.

  Further, when plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 103, the relationship between the temperature of the heat medium supplied to the susceptor 105 and the temperature of the substrate 110 is measured in advance, and the plasma CVD process is in progress. In addition, in order to maintain the temperature of the substrate 110 at or above the lower limit temperature and below the upper limit temperature, the temperature of the heat medium supplied to the susceptor 105 is required.

  For example, a lower limit temperature (here, 50 ° C.) is stored, and a heat medium whose temperature is controlled to a temperature equal to or higher than the lower limit temperature is set to be supplied to the susceptor 105. The heat medium refluxed from the susceptor 105 is heated or cooled, and a heat medium having a set temperature of 50 ° C. is supplied to the susceptor 105. For example, as the CVD gas, a mixed gas of silane gas, ammonia gas, nitrogen gas, or hydrogen gas is supplied, and the SiN film is formed in a state where the substrate 110 is maintained at a temperature not lower than the lower limit temperature and not higher than the upper limit temperature.

  Immediately after activation of the plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating / cooling apparatus 160 is lower than the set temperature. Therefore, immediately after the start-up, the heating / cooling device 160 heats the refluxed heat medium to raise the temperature to the set temperature and supplies it to the susceptor 105. In this case, the susceptor 105 and the substrate 110 are heated and heated by the heat medium, and the substrate 110 is maintained in a range between the lower limit temperature and the upper limit temperature.

  When a thin film is continuously formed on the plurality of substrates 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium recirculated from the susceptor 105 to the heating / cooling device 160 is higher than the lower limit temperature (50 ° C.), the heating / cooling device 160 cools the heat medium and converts the heat medium at the set temperature into the susceptor. It supplies to 105. Thereby, it is possible to form a thin film while maintaining the substrate 110 in a range between the lower limit temperature and the upper limit temperature.

  Thus, the heating / cooling device 160 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 substrate 110 is maintained in a temperature range between the lower limit temperature and the upper limit temperature.

  Once the thin film has been formed to a predetermined thickness, the substrate 110 is unloaded from the vacuum chamber 102, the undeposited substrate 110 is loaded into the vacuum chamber 102, and a heating medium having a set temperature is supplied as described above. A thin film is formed.

  As mentioned above, although an example was given about the formation method of the film | membrane A by a vacuum plasma CVD method, as a formation method of the film | membrane A, the plasma CVD method which does not require a vacuum is preferable and an atmospheric pressure plasma CVD method is further more preferable.

  The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, nitrogen gas or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon or the like is used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

<Atmospheric pressure plasma treatment with two or more electric fields of different frequencies superimposed>
Next, a preferable embodiment for the atmospheric pressure plasma treatment will be described. Specifically, the atmospheric pressure plasma treatment is one in which two or more electric fields having different frequencies are formed in the discharge space, as described in International Publication No. 2007/026545. It is preferable to use a method of forming an electric field superimposed with a high-frequency electric field.

Specifically, the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge The relationship with the starting electric field strength IV is
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is preferably 1 W / cm ² or more.

  By adopting such discharge conditions, for example, even with a discharge gas having a high discharge starting electric field strength such as nitrogen gas, the discharge can be started and a high density and stable plasma state can be maintained, and a high performance thin film can be formed. It can be carried out.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is , By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited into a plasma state.

  Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz. On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The formation of a high-frequency electric field from such two power sources is necessary for initiating the discharge of a discharge gas having a high discharge starting electric field strength by the first high-frequency electric field, and the high frequency of the second high-frequency electric field. In addition, it is possible to form a dense and high-quality thin film by increasing the plasma density due to the high power density.

  The atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to 110 kPa, and preferably 93 kPa to 104 kPa.

  Excited gas means that at least a part of the molecules in the gas move from the existing state to a higher state by obtaining energy. Excited gas molecules, radicalized gas molecules, ionized gas This includes gases containing molecules.

  The film A forms a secondary excitation gas by mixing a gas containing a raw material gas containing silicon with an excited discharge gas in a discharge space in which a high frequency electric field is generated under atmospheric pressure or a pressure in the vicinity thereof. And it is preferable that it is the method of forming an inorganic film | membrane by exposing a base material to this secondary excitation gas.

  That is, as a first step, the pressure between the counter electrodes (discharge space) is set to atmospheric pressure or a pressure near it, a discharge gas is introduced between the counter electrodes, a high frequency voltage is applied between the counter electrodes, and the discharge gas is converted into plasma. Then, the discharge gas and the raw material gas, which are in a plasma state, are mixed outside the discharge space, and the substrate is exposed to this mixed gas (secondary excitation gas) to form a film A on the substrate. To do.

  Next, a preferred embodiment of the wet coating method will be described. In the wet coating method, first, a coating solution for film A is prepared by dissolving or dispersing a material for film A such as a silicon compound described later in a solvent.

(Preparation of coating solution for film A)
First, the material for forming the film A contained in the coating liquid for forming the film A will be described. The film A is preferably a film containing an inorganic compound, and the inorganic compound material is preferably a silicon compound. The silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared. However, perhydropolysilazane is less in terms of film formation, fewer defects such as cracks, and less residual organic matter. Polysilazanes such as organopolysilazane; polysiloxanes such as silsesquioxane are preferred.

  Examples of the silicon compound that can form the film A include perhydropolysilazane, organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, and dimethyldiethoxysilane. , Methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane , Dimethyldivinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane 3,3,3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, di Acetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane , Diaryldimethoxysilane, butyldimethoxyvinylsilane, trimethyl-3-vinylthiopropylsilane, Phenyltrimethylsilane, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3- Glycidoxypropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane , 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycid Xylpropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinyl Methylphenylsilane, diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycine Sidoxypropylmethylsilane, octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenyl Lan, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1, 3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) ) Tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5 -Trimethylcyclotrisiloxane, octamethylcycloteto Siloxane, 1,3,5,7-tetra-ethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may be mentioned decamethylcyclopentasiloxane like.

  The silsesquioxanes such, Mayaterials made Q8 series of Octakis (tetramethylammonium) pentacyclo-octasiloxane-octakis (yloxide) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsesquioxane, Octa [[3 - [(3-ethyl -3-oxetanyl) methoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octaallyloxetanes sesquioxane, Octa [(3-Propylglycidylether) imethylsiloxy] silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsiloxy] octasilsesquioxane, Octakis [2- (vinyl) dimethylsiloxy] silsesquioxane Octakis (dimethylvinylsyloxy) octasilsesquioxane, Octakis [(3-hydroxypropyl) dimethylsyloxy] octasilsequioxane, Octa [(met halopropylpropyl) dimethylsilyloxy] silsesquioxane, Octakis [(3-methacryloxypropyl) dimethylsiloxyxane and hydrogenated silsesquioxides that do not contain organic groups.

In particular, an inorganic silicon compound is particularly preferable, and an inorganic silicon compound that is solid at room temperature is more preferable. Perhydropolysilazane, hydrogenated silsesquioxane and the like are more preferably used. “Polysilazane” is a polymer having a silicon-nitrogen bond, and is a ceramic precursor such as SiO ₂ , Si ₃ N ₄ composed of Si—N, Si—H, N—H, and the like, and an intermediate solid solution SiO _x N _{y of} both. It is an inorganic polymer.

  In order not to damage the resin base material, a compound (low temperature ceramicized polysilazane) which is ceramicized at a relatively low temperature and modified to silica is preferable. For example, the following general formula described in JP-A-8-112879 A compound having a main skeleton composed of the unit represented by (1) is preferred.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms). An alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms) ), A silyl group (preferably a silyl group having 3 to 20 carbon atoms), an alkylamino group (preferably 1 to 40 carbon atoms, more preferably an alkylamino group having 1 to 20 carbon atoms) or an alkoxy group (preferably Represents an alkoxy group having 1 to 30 carbon atoms. However, it is preferable that at least one of R ¹ , R ² and R ³ is a hydrogen atom.

The alkyl group in R ¹ , R ² and R ³ is a linear or branched alkyl group. Specific examples of the alkyl group having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2 -Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t-butyl-2-methylpropylene Group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, Examples include an n-pentacosyl group, an n-hexacosyl group, an n-heptacosyl group, an n-octacosyl group, and an n-triacontyl group.

  Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, and 2-pentenyl group. .

  Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

  The aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as a phenyl group, a biphenyl group, and a terphenyl group; a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, and a heptaenyl group. Group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylenyl group, pyrenyl group, Examples thereof include condensed polycyclic hydrocarbon groups such as a chrycenyl group and a naphthacenyl group.

  Examples of the silyl group having 3 to 20 carbon atoms include an alkyl / arylsilyl group, and specifically, a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group, a methyldiphenylsilyl group, a t -A butyl diphenylsilyl group etc. are mentioned.

  The alkylamino group having 1 to 40 carbon atoms is not particularly limited, and examples thereof include dimethylamino group, diethylamino group, diisopropylamino group, methyl-tert-butylamino group, dioctylamino group, didecylamino group, and dihexadecyl. An amino group, a di-2-ethylhexylamino group, a di-2-hexyldecylamino group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosyloxy group, Henecosyloxy group, docosyloxy group, tricosyloxy group, tetracosyloxy group, pentacosyloxy group, hexacosyloxy group, heptacosyloxy group, octacosyloxy group, triacontyloxy group, etc. Is mentioned.

In the present invention, the perhydropolysilazane in which all of R ¹ , R ² , and R ³ are hydrogen atoms is particularly preferable from the viewpoint of denseness as a gas barrier film to be obtained.

  The compound having a main skeleton composed of the unit represented by the general formula (1) preferably has a number average molecular weight of 100 to 50,000. The number average molecular weight can be measured by gel permeation chromatography (GPC).

  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 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.

  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 (registered trademark) NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

  Specific examples of organic solvents that can be used to prepare the coating solution for film A include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, and halogenated hydrocarbon solvents. Alternatively, 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 in accordance with characteristics such as the solubility of the material of the film A such as polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed. In the case of polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane.

  The material concentration in the coating liquid of the film A is preferably about 0.2 to 35% by mass, although it varies depending on the film thickness of the target film A and the pot life of the coating liquid.

  The coating solution is applied to a desired thickness on the resin substrate by spin coating, spray coating, plate coating, bar coating, dip coating, or the like. Next, the film A is completed by applying energy to the coating film.

(Energy application process for forming film A)
After the coating film of the film A is formed, energy can be applied to complete the film A. A preferred embodiment is a method for producing a laminated gas barrier resin base material, wherein, in the method of the present invention, the energy is selected from ultraviolet light, corona discharge, plasma discharge, and laser light. A more preferable embodiment is a method for producing a laminated gas barrier resin substrate, wherein the energy is vacuum ultraviolet light having a wavelength of 150 to 200 nm in the method of the present invention. By applying energy, it refers to a conversion reaction of the silicon compound to silicon oxide or silicon oxynitride, and specifically, an inorganic thin film having a level at which the gas barrier resin base material exhibits gas barrier properties as a whole is formed. The energy of energy irradiation is preferably any one selected from ultraviolet light, corona discharge, plasma discharge, laser, and heat, and more preferably ultraviolet light. Formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate such as plastic. Therefore, in the production of 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 rays capable of a conversion reaction at a lower temperature is preferable.

(Plasma treatment)
In the present invention, a known method can be used for the plasma treatment that can be used for forming the film A, and the above-mentioned atmospheric pressure plasma treatment and the like can be preferably used.

(Heat treatment)
A coating film containing a silicon compound can be heat-treated in combination with an excimer irradiation treatment described later.

  As the heat treatment, for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere by an external heater such as a resistance wire, an infrared region such as an IR heater, etc. Although the method using light etc. are mentioned, it does not specifically limit. Moreover, you may select suitably the method which can maintain the smoothness of the coating film containing a silicon compound.

  The temperature of the coating film during the heat treatment is preferably adjusted appropriately in the range of 50 ° C to 250 ° C, more preferably in the range of 100 ° C to 200 ° C. The heating time is preferably in the range of 1 second to 10 hours, more preferably in the range of 10 seconds to 1 hour.

(UV irradiation treatment)
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. The conversion to ceramics 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 375 nm. Use ultraviolet light.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time as long as the substrate carrying the irradiated coating film is not damaged.

Taking the case of using a plastic film as the resin 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 / The distance between the substrate and the ultraviolet irradiation lamp is set so as to be cm ^2, and irradiation can be performed for 0.1 seconds 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, it is desirable to apply the ultraviolet rays from the generation source to the coating film after reflecting the ultraviolet rays from the generation source with a reflecting plate from the viewpoint of achieving efficiency improvement and uniform irradiation.

  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, the resin base material can be processed in an ultraviolet baking furnace equipped with the ultraviolet generation 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. Further, when the resin substrate is in the form of a long film, it can be converted into ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. The time required for the 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 resin substrate used and the film A.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable energy irradiation 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, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. Preferred energy dose in the case of irradiation with vacuum ultraviolet rays for film A formation is preferably 10mJ~100J / cm ^2, more preferably 10 to 10000 mJ / cm ^2. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.

  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, Xe + 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.

(Resin base material)
The resin substrate used in the laminated gas barrier resin substrate according to the present invention is not particularly limited as long as it is a resin substrate capable of holding the above-described film A.

  Specifically, homopolymers such as ethylene, polypropylene, butene, or polyolefin (PO) resins such as copolymers or copolymers, non-quality polyolefin resins (APO) such as cyclic polyolefins, polyethylene terephthalate (PET), polyethylene Polyester resins such as 2,6 naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH), etc. Polyvinyl alcohol resin, polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin, polyvinyl Tyrate (PVB) resin, polyarylate (PAR) resin, ethylene tetrafluoride ethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), Fluorine resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA), and the like can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical reactive unsaturated compound, a resin composition comprising the acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as urethane acrylate, polyester acrylate, or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a laminate coating, as a resin base material.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX (registered trademark) and ZEONOR (registered trademark) (manufactured by Nippon Zeon Co., Ltd.), non-quality cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film Pure Ace (registered trademark) (Teijin ( Commercially available products such as Konica Katak KC4UX, KC8UX (manufactured by Konica Minolta Opto), and a polyethylene terephthalate film with a clear hard coat layer (manufactured by Kimoto Co., Ltd.) are available.

  The resin base material is preferably transparent. Since the resin base material is transparent and the film A and the film B formed on the resin base material are also transparent, it becomes possible to obtain a transparent laminated gas barrier resin base material. This is because a substrate can be used.

  Moreover, the unstretched film may be sufficient as the resin base material quoted above, and a stretched film may be sufficient as it.

  The resin substrate according to 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. In addition, 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-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or 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 substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Moreover, in the resin base material which concerns on this invention, before forming the film | membrane A, you may perform surface treatments, such as a corona treatment, a flame treatment, a plasma treatment, a glow discharge process, a roughening process, a chemical treatment.

  As the resin base material, a long product wound up in a roll shape is convenient. The thickness of the resin base material varies depending on the use of the obtained gas barrier film, so it cannot be specified unconditionally. However, when the gas barrier resin base material is used for packaging, there is no particular limitation, as a packaging material. In view of the suitability, it is preferably 3 to 400 μm, more preferably 6 to 150 μm.

(2) Step (B) and Step (C)
In the step (B), a resin material having releasability is laminated on the film A formed on the resin base as described above. By laminating a resin material having releasability, the resin base material provided with the film A can be transported, stored and the like without exposing the surface of the film A. In the step (C), the laminated resin material having releasability is peeled from the film A on the resin substrate in order to form the next film B.

  There is no particular limitation on the method for laminating a resin material having releasability on a resin substrate provided with the film A. The step (B) of laminating the resin material having releasability may be an on-line method in which the resin material is laminated continuously with the formation of the film A, or once the film A is formed, the winding shaft is temporarily After the resin base material is wound up, an off-line method in which a resin material having releasability is laminated in a separate step may be used. Further, when the laminated resin material having releasability is peeled off from the surface of the film A, an on-line method in which an energy application step (D) described later is continuously performed after peeling may be used. An off-line method may be used in which the resin substrate having the film A is once wound after the resin substrate having moldability is peeled off, and the step (D) is performed in a separate step.

  At that time, in the production method of the present invention, the resin base material having the film A laminated with the resin material having releasability is wound into a roll shape, conveyed or stored, and the resin base material is fed out from the roll. A so-called roll-to-roll manufacturing process in which the step (C) of peeling the resin material having releasability from the surface of the membrane A, the step of applying energy (D), and the step of forming the membrane B (E) are performed. It is preferable to implement. That is, after the step (B), the method further includes a step (X) of winding up the resin base material in a roll shape and a step (Y) of continuously feeding out the resin base material, and peeling off the resin material having releasability. After the step (C), it is preferable that the energy application step (D) described later is continuously performed. Therefore, in a preferred embodiment of the present invention, in the method of the present invention, after the step (B), the step (X) of winding up the resin base material in a roll shape and the step of continuously feeding out the resin base material (Y) The method for producing a laminated gas barrier resin substrate, wherein the step (C) is continuously performed.

  In general, the laminated gas barrier resin base material is manufactured as an elongated body, but it is not desirable in terms of space and conveyance to perform a long manufacturing process in one line. At the same time, if a defect occurs in a part of the line, it is preferable to divide into a plurality of lines from the viewpoint of availability and yield. For example, it is necessary to stop the entire line. In that case, it is convenient to wind up the resin base material which is a long body around a roll once, and to convey or store. Furthermore, when the surface of the film A in the middle of production is exposed when winding on a roll, the surface of the film A is damaged by foreign matter adhering to the back surface of the resin base material or the resin base material. Gas barrier properties are reduced. Therefore, it is advantageous to protect the surface of the film A once with a resin material having releasability before being wound on a roll.

  Hereinafter, preferred embodiments of the steps (B) and (C) will be described. As will be described later, the resin material having releasability is mainly composed of a base material and an adhesive layer containing an adhesive on the base material, and further has a release layer containing a release agent on the base material. . The resin material having releasability is preferably prepared in a state of being wound in a roll shape with the release layer inside. Next, the resin material having releasability is fed out from the roll, the release layer is separated to expose the adhesive layer, and the separated release layer is wound up on a take-up roll. On the other hand, the resin base material on which the film A is laminated is conveyed in the horizontal direction from the film A forming step to the position of the resin material having releasability disposed on the downstream side. Next, an adhesive layer of a resin material having releasability is bonded to the surface of the film A and laminated. A resin base material laminated with a resin material having releasability is wound up in a roll shape around a winding core attached to a winding shaft. At this time, since the resin material having releasability protects the surface of the film A, adhesion of the foreign matter adhering to the back surface of the resin base material on the back surface of the resin base material when being rolled up, and scratches during transportation Generation | occurrence | production etc. can be prevented effectively.

  Next, as shown in FIG. 3, the resin base material laminated with the resin material having releasability is fed out from the wound roll, and the resin material having releasability is peeled off, and the resin material is separated from the roll. Rolled up. The resin base material from which the resin material having releasability has been peeled is exposed again to the film A, and is conveyed to the next energy irradiation step.

(Resin material with releasability)
The resin material having releasability that can be used in the production method of the present invention is not particularly limited, and is composed of at least a resin material and an adhesive layer containing an adhesive formed on one side of the film. It is preferable to have a release layer on the surface. In the present invention, regardless of the material and forming method of the resin material having releasability, the effect of the adhesive remaining after peeling is reduced by the energy application step (D) described later. The final gas barrier property can be improved. Therefore, in a preferred embodiment, in the method of the present invention, the resin material has an adhesive layer, and in the later-described process (D), the adhesive layer remaining on the film A is removed. It is a manufacturing method. Various resin materials having releasability are widely used. For example, the present invention can be used regardless of whether it is formed by a coating method or manufactured by co-casting. The effect of improving the gas barrier property can be obtained. Hereinafter, although the preferable form of the resin material which has mold release property is demonstrated, this invention can be applied even if what kind of resin material is fundamental.

  As the pressure-sensitive adhesive, at least one selected from an acrylic pressure-sensitive adhesive, a silicon-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive can be used. Further, the adhesive strength of the adhesive is preferably 1 mN / cm or more and 2 N / cm or less, more preferably 1 mN / cm or more and 200 mN / cm or less, still more preferably 1 mN / cm or more and 80 mN / cm. It is as follows.

  If the adhesive strength of the pressure-sensitive adhesive is 1 mN / cm or more, sufficient adhesion between the resin material and the film A can be obtained, peeling during continuous conveyance does not occur, and contact with a roll or the like during conveyance Can prevent the influence on the already formed film A. If the adhesive strength is 2 N / cm or less, when the resin material is peeled off, the membrane A may be destroyed or the adhesive may remain on the membrane A without applying excessive force to the membrane A. It is preferable in terms of few points.

  The adhesive strength of the pressure-sensitive adhesive can be determined by measuring 20 minutes after the resin material is pressure-bonded to the test plate using Corning 1737 as a test plate in accordance with a measurement method based on JIS Z 0237 (2009).

  Further, the thickness of the pressure-sensitive adhesive is preferably 0.1 μm or more and 30 μm or less. If the thickness of the pressure-sensitive adhesive is 0.1 μm or more, sufficient adhesion between the resin material and the film A can be obtained, and peeling during continuous conveyance does not occur, and contact with a roll or the like during conveyance Can prevent the influence on the already formed film A. Moreover, if the thickness of the pressure-sensitive adhesive is 30 μm or less, when the resin material is peeled off, an excessive force is not applied to the film A, and the film A is destroyed or the pressure-sensitive adhesive on the film A is excessive. There is no residue.

  Moreover, it is preferable that the weight average molecular weights of the adhesive which comprises an adhesion layer are 400,000 or more and 1.4 million or less. If the weight average molecular weight is 400,000 or more, the adhesive strength is not excessive, and if it is 1.4 million or less, sufficient adhesive strength can be obtained. If the weight average molecular weight is within the above range, it is possible to prevent the adhesive from remaining on the gas barrier layer, and particularly when the film A is formed by the plasma treatment method, heat and energy are applied. When the molecular weight is in an appropriate range, it is possible to prevent the adhesive material from being transferred or peeled off.

  Next, each constituent material of the resin material having releasability will be described.

  The base material used for the resin material having releasability is not particularly limited, but is a polyolefin film such as a polyethylene film or a polypropylene film; a polyester film such as polyethylene terephthalate or polybutylene terephthalate; a hexamethylene adipamide; Polyamide film; halogen-containing film such as polyvinyl chloride, polyvinylidene chloride, and polyfluoroethylene; plastic film such as polyvinyl acetate such as polyvinyl acetate, polyvinyl alcohol, and ethylene acetate pinyl copolymer and its derivative film, Is preferable because fine dust is not generated. In the present invention, a polyethylene terephthalate film is preferably used from the viewpoints of heat resistance and availability.

  The thickness of the substrate is not particularly limited, but those having a thickness of 10 μm to 300 μm are used. Preferably it is a thing of 25 micrometers-150 micrometers. When the thickness is less than 10 μm, the film is thin, so that it is difficult to handle. When the thickness exceeds 300 μm, the film becomes hard and the transportability and the adhesion to the roll are deteriorated.

  The type of the adhesive is not particularly limited, and for example, an acrylic adhesive, a rubber adhesive, a urethane adhesive, a silicon adhesive, an ultraviolet curable adhesive, a polyolefin adhesive, an ethylene vinyl acetate copolymer (EVA) ) -Based pressure-sensitive adhesives, etc., and preferably at least one selected from acrylic pressure-sensitive adhesives, silicon-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives.

  As the acrylic pressure-sensitive adhesive, for example, a homopolymer of (meth) acrylic acid ester or a copolymer with another copolymerizable monomer is used. Furthermore, examples of monomers or copolymerizable monomers constituting these copolymers include alkyl esters of (meth) acrylic acid (for example, methyl esters, ethyl esters, butyl esters, 2-ethylhexyl esters, octyl esters, isoforms). Nonyl esters, etc.), hydroxyalkyl esters of (meth) acrylic acid (eg, hydroxyethyl ester, hydroxybutyl ester, hydroxyhexyl ester), (meth) acrylic acid glycidyl ester, (meth) acrylic acid, itaconic acid, maleic anhydride , (Meth) acrylic acid amide, (meth) acrylic acid N-hydroxymethylamide, (meth) acrylic acid alkylaminoalkyl ester (for example, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate) Over preparative etc.), acetic pinyl, styrene, and acrylonitrile. As the monomer of the main component, an alkyl acrylate ester having a homopolymer glass transition point of 500 ° C. or lower is usually used.

  As the curing agent for the acrylic pressure-sensitive adhesive, for example, an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used. As the isocyanate curing agent, an aromatic type such as toluylene diisocyanate (TDI) can be preferably used for the purpose of obtaining a stable adhesive force even after long-term storage and obtaining a harder adhesive layer. Furthermore, the pressure-sensitive adhesive may contain, for example, a stabilizer, an ultraviolet absorber, a flame retardant, and an antistatic agent as additives.

  Also, in order to impart re-peelability or to keep the adhesive strength low and stable, low surface energy such as organic resin such as wax, silicon, fluorine, etc. is used to such an extent that these components do not migrate to the counterpart substrate. You may add the component which has. For example, in an organic resin such as wax, a higher fatty acid ester or a low molecular weight phthalate ester may be used.

  Examples of the rubber-based pressure-sensitive adhesive include polyisobutylene rubber, butyl rubber and a mixture thereof, or these rubber-based pressure-sensitive adhesives such as apinic acid rosin ester, terpene / phenol copolymer, terpene / indene copolymer, etc. Those containing a tackifier are used.

  Examples of the rubber-based adhesive base polymer include natural rubber, isoprene-based rubber, styrene-tadiene rubber, recycled rubber, polyisobutylene rubber, styrene-isoprene styrene rubber, styrene butadiene styrene rubber, and the like. It is done.

  Among them, the block rubber-based pressure-sensitive adhesive is a block copolymer represented by a general formula A-B-A or a block copolymer represented by a general formula A-B (where A is a styrene-based polymer block, B Is a butadiene polymer block, an isoprene polymer block, or an olefin polymer block obtained by hydrogenating them, and is mainly composed of a styrene-based thermoplastic elastomer), and is mainly composed of a tackifier resin, a softener and the like. Composition.

  In the block rubber adhesive, the styrene polymer block A preferably has an average molecular weight of about 4,000 to 120,000, and more preferably about 10,000 to 60,000. The glass transition temperature is preferably 150 ° C. or higher. Further, the butadiene polymer block, the isoprene polymer block, or the olefin polymer block B obtained by hydrogenation thereof, preferably has an average molecular weight of about 30,000 to 400,000, and more preferably 60,000 to 200, About 000 is more preferable. The glass transition temperature is preferably -150 ° C or lower. A preferable mass ratio of the A component and the B component is A / B = 5/95 to 50/50, and more preferably A / B = 10/90 to 30/70. When the value of A / B exceeds 50/50, the rubber elasticity of the polymer becomes small at room temperature, and the tackiness is hardly expressed. When it is less than 5/95, the styrene domain becomes sparse, and the cohesive force is insufficient. In addition, the adhesive force cannot be obtained, and the adhesive layer is broken at the time of peeling.

  Furthermore, by adding a polyolefin-based resin to the pressure-sensitive adhesive, it is possible to improve the releasability from the release paper or release film. Examples of the polyolefin resin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene α-olefin copolymer, propylene α-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene -Vinyl acetate copolymer, ethylene methyl methacrylate copolymer, ethylene n-butyl acrylate copolymer, and mixtures thereof.

  The polyolefin resin preferably has a low molecular weight, and specifically, the low molecular weight extracted by boiling boiling with n-pentane is preferably less than 1.0% by mass. This is because if the low molecular weight component exceeds 1.0% by mass, the low molecular weight component adversely affects the adhesive properties and decreases the adhesive force in accordance with changes in temperature and changes over time.

  Moreover, the affinity with the white back surface in which the coating film which has polyvinyl alcohol as a main component was provided can further be reduced by adding silicone oil to the said adhesive. This silicone oil is a high molecular compound with a polyalkoxysiloxane chain in the main chain, which increases the hydrophobicity of the adhesive layer and further bleeds to the adhesive interface, ie, the adhesive layer surface. There is a function that makes it difficult for a phenomenon to occur.

  A cross-linking agent is added to the rubber-based pressure-sensitive adhesive to cross-link to form a pressure-sensitive adhesive layer.

  As the crosslinking agent, for example, sulfur, a vulcanization aid, and a vulcanization accelerator (typically, dibutylthiocarbamate zinc, etc.) are used for crosslinking of the natural rubber-based pressure-sensitive adhesive. Polyisocyanates are used as a cross-linking agent capable of cross-linking an adhesive made from natural rubber and carboxylic acid copolymerized polyisoprene at room temperature. Polyalkylphenol resins are used as a crosslinking agent in which a crosslinking agent such as butyl rubber and natural rubber has heat resistance and non-fouling characteristics. There are organic peroxides such as benzoyl peroxide and dicumyl peroxide in the crosslinking of pressure-sensitive adhesives made from butadiene rubber, styrene-butadiene rubber and natural rubber, and non-fouling pressure-sensitive adhesives can be obtained. Polyfunctional methacrylic esters are used as a crosslinking aid. There is also the formation of pressure-sensitive adhesives by crosslinking such as ultraviolet crosslinking and electron beam crosslinking.

  Silicone adhesives include addition reaction curable silicone adhesives and condensation polymerization curable silicone adhesives. In the present invention, addition reaction curable adhesives are preferably used.

As the composition of the addition reaction curable silicone pressure-sensitive adhesive composition, those listed below are preferably used.
(A) Polydiorganosiloxane having two or more alkenyl groups in one molecule (B) Polyorganosiloxane containing SiH groups (C) Control agent (D) Platinum catalyst (E) Conductive fine particles where (A ) Component is a polydiorganosiloxane having two or more alkenyl groups in one molecule, and examples of such alkenyl group-containing polydiorganosiloxane include those represented by the following general formula (1).

General formula (1)
_{R (3-a) X a} SiO- (RXSiO) m - (R 2 SiO) n - (RXSiO) p -R (3-a) X a SiO
In the general formula (1), R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is an organic group containing an alkenyl group. a is an integer of 0 to 3, preferably 1, and m is 0 or more, but when a = 0, m is 2 or more, and m and n each satisfy 100 ≦ m + n ≦ 20,000. And p is 2 or more.

  R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group or a tolyl group. An aryl group such as, for example, is mentioned, and a methyl group and a phenyl group are particularly preferable.

  X is an alkenyl group-containing organic group, preferably having 2 to 10 carbon atoms, specifically pinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclohexenylethyl group. Group, pinyloxypropyl group, and the like, among which vinyl group and hexenyl group are particularly preferable.

  The polydiorganosiloxane may be in the form of oil or raw rubber, and the viscosity of the component (A) is preferably 100 mPa · s or more, particularly 1,000 mPa · s or more at 250 ° C. The upper limit is not particularly limited, but is preferably selected so that the degree of polymerization is 20,000 or less because of easy mixing with other components. Moreover, (A) component may be used individually by 1 type, and may use 2 or more types together.

  The polyorganosiloxane containing SiH groups as the component (B) is a crosslinking agent, and is an organohydropolysiloxane having at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule. , Branched, annular, etc. can be used.

  (B) As a component, although the compound represented by following General formula (2) can be mentioned, it is not limited to these.

General formula (2)
_{^{H b R 1 (3-b}} ) SiO- (HR 1 SiO) x - (HR 1 SiO) y -SiR 1 (3-b) H
In the general formula (2), R ¹ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond having 1 to 6 carbon atoms. b is an integer of 0 to 3, and x and y are integers, respectively, and indicate the number at which the viscosity of this organohydropolysiloxane at 250 ° C. is 1 to 5,000 mPa · s.

  The viscosity of this organohydropolysiloxane at 250 ° C. is preferably 1 to 5,000 mPa · s, particularly preferably 5 to 1000 mPa · s, and may be a mixture of two or more.

  Cross-linking by addition reaction occurs between the component (A) and the component (B) of the cross-linking agent, and the amount of the adhesive layer after curing is determined by the proportion of the cross-linking component. (A) It is preferable to mix | blend so that the molar ratio of the SiH group in (B) component with respect to the alkenyl group in (A) component may be in the range of 0.5-20, especially 0.8-15. If it is 0.5 or more, the crosslinking density is maintained, and a holding force can be obtained accordingly. On the other hand, if it is 20 or less, adhesive force and tack can be obtained.

  In addition, in order to improve the heat resistance such as heat resistance and solvent resistance such as suppression of solvent penetration, the proportion of the cross-linking component in the composition may be increased. There may be effects such as reduced flexibility. From such a point, the blending mass ratio of the component (A) / (B) may be 20/80 to 80/20, and is particularly preferably 45/55 to 70/30. If the blending ratio of component (A) is 20/80 or more, sufficient adhesive properties such as adhesive strength and tack can be obtained, and if it is 80/20 or less, sufficient heat resistance is obtained.

  Component (C) is an addition reaction control agent, so that when a silicone pressure-sensitive adhesive composition is prepared and applied to a substrate, the treatment liquid does not thicken or gel before heat curing. It is to be added.

  Specific examples of the component (C) include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl. Cyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethyl Siloxycyclohexane, pis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetrapinylcyclotetrasiloxane, 1,1,3 Examples include 3-tetramethyl-1,3-divinyldisiloxane.

  The amount of component (C) is preferably in the range of 0 to 5.0 parts by weight, particularly 0.05 to 2.0 parts by weight, based on a total of 100 parts by weight of components (A) and (B). Is preferred. If it exceeds 5.0 parts by mass, curability may be lowered.

  Component (D) is a platinum catalyst, containing chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and containing chloroplatinic acid and a vinyl group A reaction product with siloxane can be used.

  Component (D) is preferably added in an amount of 1 to 5,000 ppm, particularly preferably 5 to 2,000 ppm in terms of platinum relative to the total amount of components (A) and (B). If it is 1 ppm or more, sufficient curability is obtained, the crosslinking density is high, and the holding power can be maintained.

  The shape of the conductive fine particles of component (E) is not particularly limited, such as a spherical shape, a dendritic shape, or a needle shape. The particle size is not particularly limited, but it is preferable that the maximum particle size does not exceed 1.5 times the coating thickness of the pressure-sensitive adhesive. Therefore, the floating from the adherend tends to occur starting from this portion.

  Various additives may be added to the pressure-sensitive adhesive layer. For example, a crosslinking agent, a catalyst, a plasticizer, an antioxidant, a colorant, an antistatic agent, a filler, a tackifier, a surfactant and the like may be added.

  As a method of coating the adhesive layer on the substrate, it is performed by a roll coater, blade coater, bar coater, air knife coater, gravure coater, reverse coater, die coater, lip coater, spray coater, comma coater, etc. An adhesive layer is formed through smoothing, drying, heating, electron beam exposure processes such as ultraviolet rays, and the like.

  The material used as the release layer is preferably a plastic film that does not generate dust. The plastic film used for the release layer according to the present invention is not particularly limited, but is a polyolefin film such as polyethylene film or polypropylene film; a polyester film such as polyethylene terephthalate or polybutylene terephthalate; a polyamide such as hexamethylene adipamide. Film-containing films: Halogen-containing films such as polyvinyl chloride, polyvinylidene chloride, and polyfluoroethylene; Vinyl acetate such as polyvinyl acetate, polyvinyl alcohol, and ethylene acetate pinyl copolymer, and derivative films thereof are used. A polyester film is preferable, for example, polyethylene terephthalate. It is because it has moderate elasticity. The plastic film used for the release layer may be one to which a release agent is applied. Specific examples of the coating solution for performing the mold release treatment include solvent-free 636, 919, 920, 921, 924, and emulsion type 929 among DEHESIVE (registered trademark) series manufactured by Asahi Kasei Wacker Silicon Co., Ltd. 430, 440, 39005, 39006, solvent type 940, 942, 952, 953, 811 and the like are silicon for release paper manufactured by GE Toshiba Silicon Corporation: TPR6500, TPR6501, UV9300, UV9315, XS56A2775, XS56-A2982, TPR6600, TPR6605, TPR6604, TPR6705, TPR6722, TPR6721, TPR6702, XS56-B3884, XS56-A8012, XS56-B2654, TPR6700, TPR6701, TPR6707, T R6710, TPR6712, XS56-A3969, XS56-A3075, YSR3022 and the like.

(3) Process (D)
In the step (D), as described above, after the resin material having releasability is peeled off, energy is applied to the exposed film A. The inventors of the present invention have found that the gas barrier property of the finally obtained laminated gas barrier resin base material is improved by applying energy to the surface of the film A as compared with the prior art.

  Although the mechanism by which the gas barrier property of the resin base material is improved by applying energy is not clear, the adhesive of the resin material having releasability and the adhering foreign matter that have remained on the film A in the past have disappeared by applying energy. Is considered to have contributed. This is because such a residue of the pressure-sensitive adhesive is considered to be a foreign substance and reduce the gas barrier property of the final laminated gas barrier resin base material. The disappearance of the adhesive layer remaining on the film A can be confirmed by, for example, visual observation of the surface of the film A, microscopic observation, and other various analysis methods capable of comparing the surface state of the film A before and after energy application.

  The present invention can basically be applied to any resin material and pressure-sensitive adhesive having any releasing property, and an effect of improving the gas barrier property can be obtained. Further, after laminating a resin material having releasability and winding it up in a roll shape, the energy application step (D) is also performed when stored for about 1 to 20 hours, typically overnight. As a result, the influence of the residue can be reduced, and the effect of improving the gas barrier property can be obtained. Further, it is conceivable that the physical property of the surface of the film A is affected by the application of energy, such as improving the smoothness of the surface of the film A and contributing to the adhesion with the film B. A laminated gas barrier resin base material can be obtained.

  The energy to be applied is preferably one selected from ultraviolet light, corona discharge, plasma discharge, and laser light. Of these, it is preferable to use the same energy as that used for forming the film A from the viewpoint of simplicity of equipment and cost. As with the formation of the film A, the energy to be applied is particularly preferably vacuum ultraviolet light having a wavelength of 150 to 200 nm. In addition, in the step (D), when the same method as the energy application for forming the film A is used, the energy application is not less than 1% and less than 100% of the energy application amount used for forming the film A. More preferably, it may be 1 to 20%, more preferably 5 to 15%, and the effect of improving the gas barrier property can be obtained with this amount of energy applied. Such weaker energy application than the formation of the film A not only removes the residue of the adhesive, but also has some effect on the surface of the film A, resulting in a gas barrier property of the final laminated gas barrier resin base material. It is possible that they are contributing. The specific energy application amount varies depending on the composition of the film A and the energy source, and can be appropriately selected according to them.

For the ultraviolet light irradiation, the same method as that described in the formation step (B) of the film A can be adopted except for the energy irradiation amount. Energy irradiation amount in the case of the ultraviolet light irradiation is preferably less than 1 or more 360 J / cm ^2, more preferably from 10 to 100J / cm ^2. In the case of vacuum ultraviolet light irradiation (excimer irradiation), it is preferably 1 or more and less than 10,000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² .

Also for the plasma irradiation, the same method as that described in the formation step (B) of the film A can be adopted except for the energy irradiation amount. Among the plasma irradiations, the irradiation amount particularly in the case of atmospheric pressure plasma irradiation is preferably 1 or more and less than 200 J / cm ² , more preferably 5 to 50 J / cm ² .

There is no restriction | limiting in particular about corona irradiation, A corona discharge process can be performed to the film | membrane A using a conventionally well-known corona discharge processing apparatus (for example, Kasuga Denki Co., Ltd. make). The output is preferably 10 mW · min / m ² or more, more preferably 10 to 200 W · min / m ² .

There is no restriction | limiting in particular about laser beam irradiation, For example, energy irradiation can be performed using an excimer laser (wavelength (lambda) = 248nm). As the output of the lamp ^{400W~30kW, 100mW / cm 2 ~100kW /} cm 2 as illuminance, as the irradiation energy amount is preferably 10~5000mJ / cm ^2, and more preferably 100 to 2000 mJ / cm ^2.

  If the amount of energy irradiation is within the above range, the desired effect of improving the gas barrier property can be obtained, and the problem of the film A due to excessive energy irradiation does not occur.

  In the present invention, it is preferable to apply energy immediately after the film A is continuously conveyed after the resin material having releasability is peeled off.

(5) Process (E)
In the step (E), as described above, the resin material having releasability is peeled from the surface of the film A and given energy, and then the film B is formed on the surface of the film A.

  The film B exhibits the gas barrier property of the laminated gas barrier resin base material of the present invention together with the film A. As the material and forming method of the film B, the same material and method as those of the above-described film A can be employed, and thus description thereof is omitted here. The film B may be made of the same material as the film A, or may be different. When the film A and the film B are composed of the same material, the film having the same performance is composed of a plurality of thin layers, so that there is an advantage that cracks are not easily generated in each layer. When the film A and the film B are made of different materials, the respective layers can have different functions, and the characteristics of the entire laminated gas barrier resin base material can be improved according to the application. In the present invention, the laminated gas barrier resin substrate may be composed of a multilayer film including two or more layers including the film A and the film B. In the case of such a multilayer film, the layer on which the resin material having releasability is laminated for transportation and storage is the film A, and the layer formed after peeling off the resin material having releasability As long as it is the film B, the layers other than those may have any configuration. For example, after forming the film A and the film B, a film C (a film made of a material different from the film A and the film B) may be appropriately formed, or after forming the film C or the like on the resin substrate, A film A and a film B may be formed on the film C. That is, the film formed on the resin base material can form various films in addition to the film A and the film B. Further, when two or more combinations (units) of the film A and the film B are laminated (two or more units are laminated), the gas barrier property of the entire laminated gas barrier resin base material is further improved. Moreover, when manufacturing such a multilayer film, the process of (A)-(E) of this invention may be repeated twice or more.

  As a film thickness of the film | membrane B, 1-1000 nm is preferable and 50-800 nm is still more preferable. If it is this range, gas barrier performance will fully be exhibited and the malfunction that a film | membrane cracks can also be avoided.

  A laminated gas barrier resin base material is produced by the above steps (A) to (E).

(6) Other Steps The laminated gas barrier resin base material produced in the present invention may have a layer other than the film A and the film B that bear gas barrier properties, and may further include a step therefor. Good. For example, an anchor coat layer may be formed on the surface of the resin base material for the purpose of improving the adhesion with the film A. In order to flatten the rough surface of the resin base material surface and fill in irregularities and pinholes, A smooth layer may be provided between the resin base material and the film A. When a smooth layer is provided, unreacted oligomers migrate from the resin base material to the surface and contaminate the contact surface. In order to suppress this phenomenon, a bleed-out layer may be provided on the surface opposite to the surface of the resin base material having the smooth layer.

  Examples of the 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. These may be used alone or in combination of one or more.

  Examples of the photopolymerizable monomer forming the smooth layer include a photopolymerizable monomer composition containing an acrylate compound having a radical reactive unsaturated compound, and a photopolymerizable monomer containing an acrylate compound and a mercapto compound having a thiol group. Examples thereof include a photopolymerizable monomer composition in which a polyfunctional acrylate monomer such as a composition, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate is dissolved. The bleed-out prevention layer may basically have the same configuration as the smooth layer.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to a following example.

(Preparation of sample 1)
[Example 1]
Membrane A on a transparent resin substrate with a hard coat layer (polyethylene terephthalate (PET) film with double-sided clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd., PET thickness 125 μm, length 50 m, CHC thickness 6 μm) under the following conditions The film A was laminated with a resin material A (Sanitec (registered trademark) PAC3-60, ethylene vinyl acetate copolymer (EVA), adhesive strength 0.13 N / 25 mm) manufactured by Sanei Kaken Co., Ltd.) and wound into a roll. . The wound roll was stored overnight in a desiccator. Thereafter, the resin base material was continuously drawn out from the roll, and while the resin A was peeled off, the surface of the film A was irradiated with energy, and further the film B was formed to prepare a sample 1. Hereinafter, detailed conditions of Example 1 will be described.

(Formation of film A)
(Application)
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica (registered trademark) NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and 20% of perhydropolysilazane containing 5% by mass of an amine catalyst in solid content. A mass% dibutyl ether solution (Aquamica (registered trademark) NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed and used to adjust the amine catalyst to 1% by mass as a solid content, and then further with dibutyl ether. By diluting, a polysilazane compound-containing coating solution was prepared as a dibutyl ether solution. This solution was further diluted with dibutyl ether to adjust the concentration of perhydropolysilazane to 10% by mass and applied using a die coater, followed by drying at 80 ° C. for 3 minutes, and after drying, containing a perhydropolysilazane having a film thickness of 150 nm. A layer was formed. At this time, the polysilazane-containing layer is not completely solidified.

(Vacuum ultraviolet light irradiation)
Subsequent to the formation of the polysilazane layer, vacuum ultraviolet light irradiation (excimer irradiation) was continuously performed using a vacuum ultraviolet light irradiation device. The excimer lamp used was a xenon excimer irradiation apparatus MODEL: MEUTH-1-400 (wavelength: 172 nm) manufactured by MD Excimer, and the resin substrate was irradiated with VUV light by excimer emission. The irradiation device was provided with a flow meter, a thermometer, and the like, and an excimer lamp was provided in the vacuum ultraviolet irradiation chamber. A film A was formed by irradiation with vacuum ultraviolet light using this excimer irradiation apparatus. The energy (vacuum ultraviolet light) irradiation amount at the time of forming the film A was 2100 mJ / cm ² .

(Energy irradiation treatment)
Excimer irradiation treatment was performed in the same manner as the formation of the film A except that the energy irradiation amount was changed on the surface of the film A while peeling the resin material A. The energy (vacuum ultraviolet light) irradiation amount was 210 mJ / cm ² , which was 10% of the energy irradiation amount for forming the film A.

(Film B: Polysiloxane coating (application))
<Preparation of polysiloxane compound-containing coating solution>
An amine compound was appropriately added to a polysiloxane-containing solution (Glaska HPC7003 manufactured by JSR Corporation), and if necessary, diluted with butanol to obtain a coating solution (polysiloxane concentration of 10% by mass).

(Formation of polysiloxane layer)
On the film | membrane A, after apply | coating the said coating liquid using a die-coater, it dried at 120 degreeC for 10 minutes, and formed the polysiloxane containing layer with a film thickness of 600 nm after drying.

(Vacuum ultraviolet light irradiation treatment)
After the polysiloxane layer coating film was formed as described above, the vacuum ultraviolet light irradiation treatment was performed on the polysiloxane layer by the same method as the vacuum ultraviolet light irradiation treatment for the polysilazane layer of the film A. In this way, a laminated gas barrier resin base material was completed.

(Example 2)
In the manufacturing method of the laminated gas barrier resin substrate of Example 1, a gas barrier film was manufactured by the same manufacturing method except that the energy irradiation after the resin material A peeling was performed by atmospheric pressure plasma.

(Atmospheric pressure plasma treatment)
The sample was plasma treated under the following conditions. The substrate holding temperature during film formation was 120 ° C.

  The treatment was performed using a roll electrode type discharge treatment apparatus. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film transport direction, and gas and electric power are supplied to each electrode part, and processing is appropriately performed so that the coated surface is irradiated with plasma for 20 seconds as follows. went.

  In addition, the dielectric material which coat | covers each said electrode of a plasma discharge processing apparatus used what coat | covered the 1-mm-thick alumina by single-sided by the ceramic spraying process for both opposing electrodes.

  The electrode gap after coating was set to 0.5 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used. The energy irradiation amount was 120 J or less.

Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 100 kHz, 6 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ²
Plasma processing time: 20 seconds

(Example 3)
In the manufacturing method of the laminated gas barrier resin base material of Example 1, a gas barrier film was manufactured by the same manufacturing method except that the energy irradiation after peeling of the resin material A was performed by ultraviolet irradiation. The energy irradiation amount was 360 J or less.

(UV irradiation treatment)
The sample was subjected to ultraviolet irradiation treatment under the following conditions.

<Ultraviolet irradiation device>
Apparatus: Ushio Electric Co., Ltd., UV irradiation apparatus Model UVH-0252C
<Ultraviolet irradiation treatment conditions>
The sample fixed on the operation stage was subjected to ultraviolet irradiation treatment under the following conditions.

Ultraviolet light intensity: 2000 mW / cm ² (365 nm)
Distance between sample and light source: 30 mm
Stage heating temperature: 100 ° C
Oxygen concentration in the irradiation device: 5%
Ultraviolet light irradiation time: 180 seconds

Example 4
In the method for producing a gas barrier film of Example 1, except that the resin material A is changed to the resin material B (Proserve ASR 38ASR, manufactured by PANAC, antistatic layer-containing adhesive, adhesive strength 0.04 N / 25 mm, antistatic adhesive layer) Produced a gas barrier film by the same production method.

(Comparative Example 1)
As Comparative Example 1, a gas barrier film was produced by the same production method except that the resin material A was not used and the energy irradiation treatment was not performed in the production of Example 1.

(Comparative Example 2)
As Comparative Example 2, a gas barrier film was produced by the same production method except that the energy irradiation treatment after peeling off the resin material A was not performed in the production of Example 1.

(Comparative Example 3)
As Comparative Example 3, in the production of Example 1, the gas barrier film was produced by the same production method except that the resin material A was changed to the resin material B and the energy irradiation treatment after peeling the resin material B was not performed. did.

(Evaluation of sample 1)
(Evaluation 1: Evaluation of water vapor barrier properties)
In evaluating the water vapor barrier property, the following apparatuses and materials were used.

<Device used>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
<Evaluation materials>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
<Preparation of water vapor barrier property sample>
Using a vacuum deposition apparatus (JEE-400), metallic calcium was deposited in a size of 12 mm × 12 mm through a mask on the protective layer surface of the produced water vapor barrier film (Sample Nos. 1 to 30).

  Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A sample for water vapor barrier property evaluation was prepared by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.

Then, using a constant temperature and humidity oven, the obtained sample for evaluation was stored at 85 ° C. and 90% RH under high temperature and high humidity for 20 hours, 40 hours, and 60 hours, respectively. The area where metal calcium corroded relative to the area was calculated in%, and the water vapor barrier property was evaluated according to the following criteria. The evaluation results thus obtained are shown in Table 1 below.
(Double-circle): The area which metal calcium corroded is less than 0.5%.
A: The area where metallic calcium corroded is 0.5% or more and less than 1.0%.
(Triangle | delta): The area which metal calcium corroded is 1.0% or more and less than 5.0%.
X: The area which metal calcium corroded is 5.0% or more.

(Evaluation 2: Evaluation of film surface quality)
As a differential interference microscope, Nikon Corporation Eclipse E600 and microscope digital camera DXM1200F are used, the resin material is laminated on the film A formed on the resin base material, and the release surface of the resin base material after being peeled off, Observation in the range of 30 × 30 mm was performed at a magnification of 400 times in the reflection mode. At the time of observation, foreign substances, scratches, and residue of the gas barrier resin base material were evaluated according to the following criteria, and the film surface quality was evaluated according to the following criteria. The evaluation results thus obtained are shown in Table 1 below.
O: No foreign matters or scratches of 1 μm or more were observed, and foreign materials, scratches, or residue of 1 μm or less were hardly observed (foreign matters of 1 μm or less: less than 5).
Δ: No foreign matters or scratches of 1 μm or more were observed, but there were slight foreign materials, scratches or residue remaining of 1 μm or less (1 μm or less of foreign materials: 5 or more).
X: Foreign matters and scratches of 1 μm or more were confirmed, and many foreign matters, scratches and residue remaining of 1 μm or less were confirmed.

(Evaluation 3: Evaluation of adhesion)
The adhesion was examined by a cross-cut peeling method based on JIS (Japanese Industrial Standards) K5600-5-6 (ISO 2409). The evaluation results thus obtained are shown in Table 1 below.
○: not peeled ×: even a part was peeled off.

(Example 5)
In the method for producing a gas barrier film of Example 1, a laminated gas barrier resin base material was produced by the same production method except that the membrane A was formed using atmospheric pressure plasma.

(Film A)
A transparent resin substrate (Kimoto with a hard coat layer) is formed by an atmospheric pressure plasma method using an atmospheric pressure plasma film forming apparatus (described in FIG. 3 of JP-A-2008-56967, roll-to-roll atmospheric pressure plasma CVD apparatus). Polyethylene terephthalate (PET) film with clear hard coat layer (CHC) manufactured by the company, the hard coat layer is composed of a resin mainly composed of an acrylic resin, the thickness of PET is 125 μm, and the thickness of CHC is 6 μm. A silicon oxide film A (100 nm) was formed under the formation conditions.

(Mixed gas composition)
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
(Deposition conditions)
<First electrode side>
Power supply type: HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency: 100kHz
Output density: 10 W / cm ²
Electrode temperature: 120 ° C
<Second electrode side>
Power supply type: Pearl Industry 13.56MHz CF-5000-13M
Frequency: 13.56MHz
Output density: 10 W / cm ²
Electrode temperature: 90 ° C
(Film B)
Membrane B was produced in the same manner as Example 1.

(Energy irradiation treatment)
Excimer irradiation treatment after peeling off the resin material A was performed in the same manner as in Example 1.

(Example 6)
In the method for producing a gas barrier film of Example 5, a laminated gas barrier resin base material was produced by the same production method except that the film A was formed using vacuum plasma.

(Vacuum plasma deposition)
Film A was formed using a vacuum plasma CVD apparatus. At this time, the high frequency power source used was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The raw material gas was introduced into the vacuum chamber under conditions of 7.5 sccm with silane gas as flow rate, 100 sccm with ammonia gas as flow rate, and 50 sccm with nitrous oxide gas as flow rate, and then the film substrate temperature was set to 100 ° C. at the start of film formation. Then, the gas pressure at the time of film formation was set to 100 Pa, and a film A mainly composed of silicon oxynitride was formed to a thickness of 200 nm to obtain a laminated gas barrier resin base material.

(Example 7)
In the method for producing a laminated gas barrier resin substrate of Example 5, a laminated gas barrier resin substrate was produced by the same production method except that the film A was formed by sputtering.

(Sputter deposition)
A resin base material was set in a vacuum chamber of a sputtering apparatus, and was evacuated to a level of 10 ⁻⁴ Pa. Argon was introduced as a discharge gas at a partial pressure of 0.5 Pa. When the atmospheric pressure was stabilized, discharge was started, plasma was generated on the Si ₃ N ₄ target, and a sputtering process was started. When the process was stable, the shutter was opened and formation of a silicon oxide layer on the film was started. When the 5 nm film was deposited, the shutter was closed to complete the film formation.

(Comparative Example 4)
In the manufacturing method of Example 5, it manufactured with the same manufacturing method except not having performed the energy irradiation process after peeling the resin material A. FIG.

(Evaluation of sample 1)
About the laminated gas barrier resin base materials of Examples 5 to 7 and Comparative Example 4 obtained as described above, in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 3, water vapor barrier properties, film surface quality, Adhesion was evaluated. The evaluation results are shown in Table 2 below.

(Preparation of sample 2)
<< Production of organic electronic devices (organic EL elements) >>
The gas barrier resin base materials obtained in Examples 5 to 7 and Comparative Example 4 were each used as a display substrate for organic EL, on which a transparent electrode constituting an anode electrode, a hole transport layer having hole transportability, A light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a back electrode to be a cathode were laminated.

<Formation of first electrode layer>
Transparent electrode: ITO 150nm
Hole transport layer: m-MTDATXA 40 nm
Light emitting layer:
Light emitting layer A: CDBP, Ir-15 (3%) 25 nm
Intermediate layer 1: L-98 3 nm
Light emitting layer B: CDBP, Ir-16 (8%) 10 nm
Hole blocking layer: L-98 10 nm
Electron transport layer: Alq3 35 nm
Cathode buffer layer: lithium fluoride 0.5 nm
Cathode: Aluminum 110nm
Further, an organic EL element (OLED) adhered, bonded and sealed using a glass can for sealing is formed on each of these layers through a UV (thermal) curable epoxy sealing adhesive material (ThreeBond 3124C). did. 50 times magnified photographs were taken after storage for 50 hours at 60 ° C. and 90% RH, respectively.

(Evaluation 4: Evaluation of organic EL element)
The organic EL device (sample 2) obtained using the laminated gas barrier resin base materials of Examples 5 to 7 and Comparative Example 3 as described above was stored at 60 ° C. and 90% RH for 50 hours, and was in a state before storage. And compared.

(Spot evaluation method)
A current of 1 mA / cm ² was applied to the sample to emit light, and a part of the panel was magnified with a 100 × microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200), and photographing was performed. The photographed image was cut out in a 2 mm square and visually observed to examine the state of black spots (DS). As a result, the OLED element produced by the method of the present invention generated less DS. DS is generated when the gas barrier property of the laminated gas barrier resin base material is lowered and the element is deteriorated by oxygen or water vapor. The evaluation results are shown in Table 3 below.

  The present application is based on Japanese Patent Application No. 2012-99083 filed on April 24, 2012 and Japanese Patent Application No. 2013-13763 filed on January 28, 2013. That disclosure is incorporated by reference in its entirety.

1 resin base material,
2 membrane A,
3, 4, 12 rolls,
5 Film A deposition process,
6 Coating process of film A,
7, 9 Energy application process,
8 resin material having releasability,
10 Film B forming step,
11 Membrane B
101 plasma CVD apparatus,
102 vacuum chamber,
103 cathode electrode,
105 susceptors,
106 heat medium circulation system,
107 vacuum exhaust system,
108 gas introduction system,
109 high frequency power supply,
110 substrates,
160 Heating and cooling device

Claims (5)

In the method for producing a laminated gas barrier resin base material having a film A and a film B, on which a gas barrier property is exhibited by at least one of the film A and the film B on the resin base material,
Forming the film A on the resin substrate (A);
A step (B) of laminating a resin material having releasability on the film A;
A step (C) of peeling the resin material having releasability from the film A;
Applying energy to the film A (D);
Forming the film B on the film A (E);
The method for producing a laminated gas barrier resin base material, wherein at least once is passed in order.   The method according to claim 1, wherein the energy is one selected from ultraviolet light, corona discharge, plasma discharge, and laser light.   The method according to claim 1, wherein the energy is vacuum ultraviolet light having a wavelength of 150 to 200 nm. After the step (B), the method further includes a step (X) of winding the resin base material into a roll and a step (Y) of continuously feeding the resin base material,
The method according to any one of claims 1 to 3, wherein the step (C) is continuously performed.   The method according to claim 1, wherein the resin material has an adhesive layer, and the adhesive layer remaining on the film A is removed in the step (D).