JP5729127B2 - Method for producing gas barrier film - Google Patents

Description

The present invention relates to a method for producing a gas barrier film, and more particularly to a method for producing a gas barrier film by applying a solution containing a silicon compound to a substrate.

A coating liquid containing a silicon compound has a property of reacting with moisture in the air to be polymerized or fixed. In particular, a solution containing polysilazane has the property of causing a chemical reaction to become polymerized or solidified even with a small amount of moisture, and clogging occurs even if a filter for removing the altered silicon compound (polysilazane) is provided. It becomes easier and a decrease in work efficiency may be a problem due to filter replacement. Thus, studies have been made to deal with the peculiar defects of silicon compound-containing solutions. For example, when applying a coating liquid containing polysilazane, a technique is known in which the coating liquid container and the coating liquid supply system are purged with an inert gas to prevent alteration of the coating liquid (for example, see Patent Document 1). However, it has been found that there is the following problem when a polysilazane film is formed by applying a coating liquid containing polysilazane by the technique described in Patent Document 1.
(1) A new solid substance adheres to the gas-liquid interface (coating liquid separation area of the coater) between the coating liquid and the atmosphere of the coating liquid discharge section of the coater, and a coating streak failure occurs. (2) A foreign matter adheres to a part that defines the coating width of the coater, and a desired coating width cannot be obtained. (3) Foreign matter defects are observed in the coating film of the coated sample after film formation.

  As a method for preventing the above problems in coating using polysilazane, there is a description that the inner wall and piping of the container are made of fluororesin or coated with fluororesin (for example, see Patent Document 2). However, a liquid feeding means such as a pump or a coating device such as a coater is not coated with fluororesin or fluororesin, and the same problem as in Patent Document 1 occurs.

  Under such circumstances, when a coating solution containing a silicon compound is applied onto a substrate to form a silicon compound film, there is no application failure and stable coating can be obtained, resulting in a high-quality silicon-containing coating. It is desired to develop a coating method that can be applied.

Japanese Patent Laid-Open No. 9-19658 JP 2005-236050 A

  The object of the present invention is to prevent the coating solution containing a silicon compound from adhering to and adhering to the liquid contact portion with which the coating solution comes into contact due to the reaction with a small amount of moisture. An object of the present invention is to provide a method for producing a laminate that can be sustained and enables highly accurate and highly stable coating.

  As a result of intensive studies, coating with a silicon compound (polysilazane) maintains the anti-adhesion effect by coating the wetted parts of the manufacturing equipment with a diamond-like carbon (DLC) film, which is highly accurate and stable. It came to provide the manufacturing method of the laminated body which enables coating with high property. In particular, by coating the DLC film on the coating liquid discharge part of the coating apparatus that is exposed to the atmosphere, it is possible to obtain a method for manufacturing a laminate that enables highly accurate and highly stable coating.

  That is, the present invention is achieved by the following means.

1. In a method for producing a gas barrier film in which a coating liquid containing polysilazane is applied to a base material to form a silicon-containing film on the base material, the wetted part is exposed to the atmosphere, and the coating liquid contacts A method for producing a gas barrier film , comprising using a coating apparatus having a member coated with a diamond-like carbon (DLC) film at least a part of a liquid contact portion.

  According to the present invention, in the coating using a silicon compound, it is possible to prevent adhesion and adhesion to the wetted part of the production apparatus due to the reaction of the silicon compound, and to maintain the effect of preventing such adhesion to the wetted part. It was possible to perform coating with high accuracy, high coating quality, durability and stability, and it became possible to obtain a laminate having a silicon-containing film with high characteristics.

It is a layout view of a manufacturing apparatus used in the method for manufacturing a laminate according to the present invention. It is the schematic shown about the application | coating using an extrusion coater.

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

  The silicon compound used in the present invention is a compound that is modified by reaction with water and converted into silicon oxide, nitrogen oxide, silicon nitride, or the like, and is particularly limited as long as a coating solution containing the silicon compound can be prepared. Of these, polysilazane compounds, polysiloxane and the like are preferable.

  Examples of the silicon compound according to the present invention include perhydropolysilazane, silsesquioxane, tetramethylsilane, methyltrimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetramethoxysilane, hexamethyldisiloxane, and hexamethyl. Disilazane, trimethoxyvinylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, 3-aminopropyltrimethoxysilane, diacetoxymethylvinylsilane, aryloxy Dimethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetraacetoxysilane, 1,3-divinyl-1,1,3,3-tetramethyl Disiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 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, octamethylcyclotetrasiloxane, 1,3,5, Examples thereof include 7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

  The silsesquioxane, Mayaterials made Q8 series of Octakis (tetramethylammonium) pentacyclo-octasiloxane-octakis (yloxide) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsesquioxane, Octa [[3 - [(3-ethyl-3 -Oxyethyl) methoxy] propyl] dimethylsiloxy] octasilsesquioxane and the like, and hydrogenated silsesquioxanes that do not contain organic groups.

  Among the silicon compounds, inorganic silicon compounds are preferable, and silicon compounds that are solid at room temperature are particularly preferable, and perhydropolysilazane, hydrogenated silsesquioxane, and the like are more preferably used.

  Among these, polysilazanes are particularly preferable because they are modified by low-temperature firing to form a dense film having a high gas barrier property.

  If the molecular weight of polysilazane is too low, the yield at the time of baking will become low and it is not practical. On the other hand, if the molecular weight is too high, the stability of the solution is low and a healthy film cannot be obtained. For these reasons, the molecular weight of the polysilazane used is a number average molecular weight and the lower limit is 100, preferably 500. The upper limit is 50,000, preferably 10,000.

  In order to apply a silicon compound such as polysilazane, a silicon compound is dissolved in a solvent to prepare a coating composition. Solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon hydrocarbon solvents, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, aliphatic ethers, and alicyclic ethers. Etc., ethers such as straight chain hydrocarbons, and alkoxysilanes can be used. When these solvents are used, for example, in the case of polysilazane, two or more kinds of solvents can be mixed in order to adjust the solubility of polysilazane and the evaporation rate of the solvent.

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

  The amount (ratio) of the solvent used is selected so as to improve workability depending on the coating method employed, and varies depending on the average molecular weight, molecular weight distribution, and structure of the silicon compound to be used, and can be freely mixed as appropriate. Preferably, it can mix in 1-50 mass% in solid content concentration.

  In addition, an appropriate filler and / or extender can be added to the coating composition containing a silicon compound as necessary. Examples of the filler include fine oxides of oxide inorganic substances such as silica, alumina, zirconia and mica, or non-oxide inorganic substances such as silicon carbide and silicon nitride. Depending on the application, metal powders such as aluminum, zinc and copper can be added.

  These fillers may be used in various shapes such as needles (including whiskers), granules, scales, etc., alone or in combination. The size of the filler particles is preferably smaller than the film thickness applicable at one time. Moreover, the addition amount of a filler is the range of 0.05-10 mass parts with respect to 1 mass part of silicon compounds, and the especially preferable addition amount is the range of 0.2-3 mass parts. Furthermore, in the coating composition, various pigments, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, surface modifiers, plasticizers, drying accelerators, if necessary, An anti-flow agent, etc. may be added.

  The base material used in the method for producing a laminate according to the present invention includes various plastic materials, such as polyethersulfone (PES), polycarbonate (PC), polyarylate (PAr), polymethyl methacrylate (PMMA). ), Polyethylene terephthalate (PET), polypropylene (PP), cellulose acetate (TAC), and the like.

  The laminated body according to the present invention forms a silicon compound film by applying it to at least one surface of the base material as described above. As the application method, methods commonly used for coating on a substrate, that is, roll coating, dip coating, spray coating, web coating (gravure, die, kiss, flexo, kiss maker bar), etc. are used. It is done. Subsequent to the coating step, the solvent of the silicon compound coating film is removed by passing through a drying temperature zone corresponding to the heat resistant temperature of the film. For example, in the case of a film having a polysilazane coating film, the solvent removal step is performed at a temperature zone of 60 ° C. to 350 ° C., preferably 70 ° C. to 250 ° C. for 0.01 to 20 minutes, preferably 0 It is preferably carried out while being conveyed so as to exist for 05 to 10 minutes. The dry atmosphere may be either in oxygen or air. A polysilazane coating film in which Si—O, Si—N, Si—H, and N—H bonds exist is formed by drying treatment in the above temperature range.

  In the above coating step, by using the production method of the present invention, the solid material formed by the reaction of the silicon compound with water does not adhere to the wetted part of the member in direct contact with the coating liquid, and is highly accurate. This makes it possible to apply highly stable coatings. By coating the DLC film on the coating liquid discharge part of the coating apparatus that is exposed to the atmosphere in particular, these adhesion prevention effects can be maintained, and highly accurate and highly stable coating can be performed.

  The liquid contact part in the present invention refers to a part where the solution (coating liquid) containing the silicon compound of the present invention contacts the manufacturing apparatus in the manufacturing apparatus used in the present invention.

  Diamond-like carbon (hereinafter, simply referred to as DLC) coating can be performed by disassembling the surface in contact with the coating liquid of each component constituting the apparatus used in the manufacturing method of the present invention, if necessary, and coating the liquid contact surface. Good.

  The DLC coating that can be preferably used in the present invention can be formed by, for example, an ionized vapor deposition method. That is, a hydrocarbon gas such as benzene is introduced into a vacuum chamber, and this gas is converted into plasma by direct current arc discharge to generate hydrocarbon ions. It is possible to form an amorphous film of diamond-like carbon (DLC) by colliding with a liquid contact portion of a member having a portion.

  For example, there are NANOCOAT-1000 and NANOCOAT-4000 (manufactured by Nanotech Co., Ltd.) as DLC film forming apparatuses, and uniform coating can be applied to the surface of complicated shapes by an apparatus equipped with a substrate rotation mechanism.

  Since the DLC film has an amorphous structure, it does not have a crystal grain boundary and has a smooth surface as compared with a crystalline material. The film forming temperature of the DLC coating is preferably about 200 ° C. or less. The thickness of the DLC coating is preferably in the range of 0.005 to 50 μm. More preferably, it is 0.02-20 micrometers. Forms excellent films such as high hardness, low coefficient of friction, high wear resistance, and high chemical stability.

  When the thickness is 0.005 μm or less, the merit (reduction in the coefficient of static friction) of coating the DLC coating becomes small. When the thickness of the DLC coating increases, the DLC coating may be peeled off.

  For the measurement of the film thickness, a non-contact film thickness measuring apparatus using a spectral interference method is used. The thin film sample is irradiated with white light, and the reflection spectrum from the interface between the surface and the substrate is analyzed by a curve fitting method or FFT (Fast Fourier Transform) to measure the film thickness.

  Instead of the ionized vapor deposition method, a high-frequency plasma CVD method, or a physical vapor deposition method (PVD method) such as an arc ion plating method or a sputtering method can be used. When using the PVD method, graphite is used as a target.

  Next, the apparatus used for the manufacturing method of the laminated body which concerns on this invention is demonstrated using FIG.

  FIG. 1 is a diagram showing an example of a production apparatus for producing a laminate according to the present invention.

  As a flow of the apparatus, a coating liquid containing a silicon compound is prepared in the solution tank 1. The liquid is preferably prepared in an inert gas atmosphere in order to suppress deterioration of the silicon compound raw material.

  The solution tank 1 containing the coating liquid preferably contains an inert gas G. The prepared liquid is adjusted in flow rate by a liquid feed pump 3, sent to the die coater 5 via the liquid feed pipe 4, and applied to the base material with the coating liquid discharged from the die coater 5. Get the body.

  Next, each part of the manufacturing apparatus according to the present invention for manufacturing a laminate will be described.

  The solution tank 1 is a hermetically sealed tank (material is a stainless steel tank and DLC is coated on the liquid contact part), and may be of a type provided with a load cell for liquid amount management. The valve 2 (the wetted part is coated with DLC on stainless steel) serves to open and close the flow of the coating liquid. The liquid feed pump 3 (the wetted part is coated with DLC on stainless steel) is not particularly limited to the type.

  For piping 4 (stainless steel piping is coated with DLC), each part is connected. Further, the joints for connecting the pipes are also DLC coated. The die coater 5 (the wetted part is coated with DLC on stainless steel) is a part that applies a coating solution to a substrate. When DLC is coated on stainless steel, it can be coated entirely or partially. The base material before application | coating is unwound from the unwinder 6, and the base material apply | coated with the winder 7 is wound up. In the middle, the solvent contained in the coating solution is dried in the drying zone 8.

  In the die coater 5, since a gas-liquid interface between the coating liquid and the atmosphere is formed in the coating liquid discharge part (coating liquid separation area of the coater), solids are likely to adhere and coating streak failure is likely to occur. It is preferable to apply a DLC coating. As a result, it is possible to solve the problem that a foreign matter is difficult to adhere to a portion that defines the coating width of the coater and a desired coating width cannot be obtained.

  There is no particular limitation on the coating method, and any appropriate method can be selected. As the die coater, for example, an extrusion-type extrusion coater that is an extrusion method or a curtain-type coating head is used. And a slide type coating coater and the like are not particularly limited.

  The following description will be made using an extrusion coater as an example of a die coater.

  FIG. 2 is a schematic view showing application by an extrusion coater. FIG. 2A is a schematic perspective view of coating using an extrusion coater. FIG. 2B is a schematic cross-sectional view along AA ′ in FIG. FIG.2 (c) is a schematic enlarged view of the part shown by P of FIG.2 (b).

  In the figure, reference numeral 502 denotes a coating apparatus. As the coating device 502, an extrusion coater 502a is used. Reference numeral 502a1 denotes a supply pipe to the extrusion coater 502a of a silicon compound film forming coating solution containing a silicon compound. 502a2 indicates a slit of the extrusion coater 502a, and 502a3 indicates a discharge port at the tip of the slit 502a2. 502a4 indicates a lip portion on the downstream side, and 502a41 indicates an edge portion. 502a5 indicates an upstream lip portion, and 502a51 indicates an edge portion. The polysilazane film forming coating solution 8 ′ supplied from the supply pipe 502 a 1 is discharged from the discharge port 502 a 3 through the slit 502 a 2 and applied onto the substrate 301. At this time, if the coating is performed for a long time, the silicon compound film-forming coating liquid adheres to the portion of the extrusion coater 502a indicated by Q in FIG. To do. A specific part of the extrusion coater 502a indicated by Q where solids are particularly likely to adhere is a separation region of the coating liquid for forming a polysilazane film on the upstream lip 502a5 (in the vicinity of the edge 502a51 and the edge 502a51). And a separation region of the coating solution for forming a silicon compound film on the downstream lip 502a4 (in the vicinity of the edge 502a41 and the edge 502a41). The separation region of the silicon compound film forming coating solution refers to a region where the silicon compound film forming coating solution is separated from the lip portion.

  Therefore, it is necessary to perform DLC coating of the die coater not only in the die coater slit but also on the outer surface portion in contact with the coating solution. Of the outer surface, it is sufficient that the portion represented by Q is at least DLC coated. However, since coating only on that portion requires man-hours, the coater surface region including the portion represented by Q, The entire coater surface area may be coated.

  If the DLC film forming apparatus equipped with the substrate rotating mechanism is used, it is possible to coat the surface of a complicated shape, for example, the inside of the slit, etc., and also disassemble the die coater to the inside of the slit. Can be coated. Accordingly, the outer surface of the die coater (including the lip portion and the edge portion), the inside of the supply pipe to the coater 502a with which the coating liquid for forming the silicon compound film inside the extrusion coater comes into contact, the slit 502a2, the discharge port 502a3, etc. DLC coating is applied to the whole.

  As a result of DLC coating on the die coater, foreign matter is less likely to adhere to both ends in the width direction of the discharge port, which is the part that defines the coating width of the coater, and the desired coating width cannot be obtained. This will not happen.

  As described above, the extrusion coater has been described as an example of the die coater, but is not limited to the extrusion coater.

  When manufacturing a laminated body by applying a coating solution containing a silicon compound to a base material, a manufacturing apparatus in which a wetted part in contact with the coating solution is coated with a diamond-like carbon (DLC) film is used. In addition, it prevents streaks due to the generation of solids due to the reaction of silicon compounds with moisture and prevents the solids from adhering to the wetted parts where the coating solution comes into contact. Enables high-performance coating.

  The silicon-containing film obtained by the method for producing a laminate of the present invention has no defects and has good characteristics as a film.

  When a polysilazane compound is used as the silicon compound, the coating film of the silicon compound is modified by a known method to form silicon oxide (nitride) as a silicon-containing film. For the modification of the polysilazane compound, generally, treatment at a high temperature of 450 ° C. or higher is preferable, and adaptation is difficult when the substrate is made of a resin or in a flexible substrate such as plastic.

  Therefore, in the production of the laminate of the present invention, a method using plasma, ozone, ultraviolet rays, particularly vacuum ultraviolet rays, which can be converted at a lower temperature, is preferable.

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

  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. Moreover, when irradiating the generated ultraviolet rays to the barrier layer, it is desirable to apply the ultraviolet rays from the generation source to the polysilazane coating layer after reflecting the ultraviolet rays from the generation source with a reflecting plate from the viewpoint of improving efficiency and achieving uniform irradiation.

  The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and layer used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable reforming treatment method (method for causing a conversion reaction) 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 having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms only to photons called photon processes. By this action, a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.

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

  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.

  A laminate having a silicon oxide (nitride) film obtained by applying a coating device having a member coated with a diamond-like carbon (DLC) film according to the present invention and obtained by modifying a silicon compound, Forms a film with few defects, excellent barrier properties, film attachment, and durability. In addition, since the coater head is not easily scratched, the characteristics can be maintained for a long time, and there is little fluctuation in characteristics for each lot.

  As described above, a laminate formed by applying a coating solution containing a silicon compound on a base material and converted into a silicon oxide (nitride) or the like by a modification treatment includes, for example, a stress relaxation layer, a hard coat layer, and the like. Other layers may be used, for example, as a gas barrier film, etc., and can be used as a sealing member for packaging applications, liquid crystal display elements, solar cells, organic electroluminescence (EL), etc. It is. The hard coat film can be used as a protective film for displays, touch panels, residential windows, show windows, vehicle windows, vehicle windshields, game machines, eyeglass lenses, and the like.

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

Example 1
(Support)
As a thermoplastic resin support, a 50 μm-thick polyester film (Teijin DuPont Films Co., Ltd., Tetoron HPE) with easy adhesion on both sides was used as a substrate.

(Formation of bleed-out prevention layer)
On one side of the support, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied and applied with a die coater so that the film thickness after drying was 4 μm. After drying for 3 minutes, curing was performed in air using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a bleed-out prevention layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the opposite surface of the support, and after applying with a die coater so that the film thickness after drying is 4 μm, drying conditions; After drying at 80 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 1.0 J / cm ² curing was performed to form a smooth layer.

  The maximum cross-sectional height Rt (p) at this time was 16 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

(Preparation of silicon compound-containing coating solution A)
Polysilazane: NAX120-20 300g
(Manufactured by AZ Electronic Materials)
Polysilazane: NN120-20 200g
(Manufactured by AZ Electronic Materials)
Dibutyl ether (manufactured by AZ Electronic Materials) 1500g
The above additives were sequentially mixed to obtain a silicon compound-containing coating solution A.

Experimental Example 1 (present invention)
<Evaluation of coating property and adhesion of coating solution A>
A laminate was produced using the coating liquid A using the production apparatus of FIG. On the transparent resin substrate formed up to the smooth layer, after coating continuously for 1000 m at a coating speed of 2.0 m / min so that the (average) film thickness after drying becomes 0.15 μm, 30 ° C. for 1 minute / 50. Drying was performed at 1 ° C./80° C. for 1 minute. The applicability and adhesion at that time were visually evaluated. The results are shown in Table 1.

  The DLC coating uses an ionization vapor deposition method as a DLC film forming apparatus. In the manufacturing apparatus of FIG. 1, the material of the solution tank 1 is a wetted part of a stainless steel tank, a wetted part of a valve 2, and a feed pump 3 Moreover, DLC coating was performed on the stainless steel pipe 4 and used. Further, the stainless die coater 5 was disassembled and DLC coating was applied to the inside of the slit. The thickness of the coating was about 1 μm.

<Durability evaluation>
Durability (adhesion suppression effect persistence) was evaluated by the following method. Bonstar # 0000 made by Nippon Steel Wool Co., Ltd. is cut into a 15 mm square and placed on the die wetted part (lip part). Then, a load of 1 kg was applied, and the surface of the die was rubbed 20 times in the direction perpendicular to the fiber direction of steel wool at intervals of 3 to 4 cm. Thereafter, the coating solution A was applied continuously for 1000 m at a coating speed of 2.0 m / min so that the (average) film thickness after drying was 0.15 μm. The results are shown in Table 1 together with the contact angles of water before and after friction.

Experimental example 2 (comparison)
In the manufacturing apparatus of FIG. 1, a manufacturing apparatus having the same configuration is used except that the wetted part is changed to fluorine coating (Teflon (registered trademark) coating (PTFE: thickness 1 μm)) instead of DLC coating. Thus, the applicability, adhesion and durability were evaluated. The results are shown in Table 1.

Experimental Example 3 (Comparison)
In the manufacturing apparatus of FIG. 1, the applicability and adhesion were evaluated in the same manner as in Experimental Example 1 using a manufacturing apparatus having the same configuration except that the wetted part was changed to stainless steel (not coated). . The results are shown in Table 1.

Above,
(Applicability)
1: Time streak generation within 250 m after start of coating 2: Time streak generation within 250 to 500 m after start of coating 3: Time streak generation within 500 to 750 m after start of coating 4: No time streak generation (adhesiveness)
Teflon (registered trademark) spatula (As One Co., Ltd.) for solid matter adhered to the wetted part of the die (lip part) after the continuous application of 1000 m (and in the durability evaluation, after further application of 1000 m) The company product number 7-629-01) was used to see if it was easy to remove and peel.

    ○: Easily removed.

(Can be removed and removed immediately by rubbing once or twice with a Teflon (registered trademark) spatula)
(Triangle | delta): If it took time, it was able to remove.

(Can be removed by rubbing with Teflon (registered trademark) spatula for 20-30 minutes while applying solvent (dibutyl ether))
X: It was difficult to remove over time.

(Cannot be removed by rubbing with a Teflon (registered trademark) spatula for 1 hour or more while applying a solvent (dibutyl ether))
(Example 2)
(Preparation of coating solution B containing silicon compound)
Polymer liquid of photo-curing resin: JSR Z7535 (manufactured by JSR Corporation) 1000 g
Silane coupling agent: KBM-903 (manufactured by Shin-Etsu Silicone) 100g
The above additives were sequentially mixed to obtain a silicon compound-containing coating solution B.

Experimental Example 4 (present invention)
Except for using the coating liquid B, the coating property, adhesion property, and durability were evaluated in the same manner as in Experimental Example 1. The results are shown in Table 2.

Experimental Example 5 (Comparative Example)
The applicability, adhesion and durability were evaluated in the same manner as in Experimental Example 2 except that the coating liquid B was used. The results are shown in Table 2.

Experimental Example 6 (Comparative Example)
The applicability, adhesion and durability were evaluated in the same manner as in Experimental Example 3 except that the coating liquid B was used. The results are shown in Table 2.

  From the above results, the DLC coating is applied to the wetted part where the coating solution comes into contact with the laminate manufacturing apparatus that manufactures the laminate by applying the silicon compound coating solution to the base material. It can be seen that the durability and durability are greatly improved.

(Example 3)
Experimental Example 7 (present invention)
About the coating sample used for evaluation of the coating property after friction in the durability evaluation of Experimental Example 1, 50m portion, 500m portion, and 950m portion were collected from the top of the coating, and surface treatment was performed by the method described below.

(VUV light irradiation)
About 3 widths x 3 lengths = 9 points of the sampling part at each m, using a stage movable xenon excimer irradiation device MODEL: MECL-M-1-200 (wavelength 172 nm) manufactured by MD Excimer, The sample was fixed so that the irradiation distance of the sample was 3 mm, and the sample was reciprocated at a moving speed of 10 mm / sec while maintaining the sample temperature at 100 ° C., for a total of 5 reciprocations. After irradiation, a sample was taken out.

(Adjustment of oxygen concentration)
The oxygen concentration at the time of VUV light irradiation is determined by measuring the flow rate of nitrogen gas and oxygen gas introduced into the VUV light irradiation chamber with a flow meter, and the oxygen concentration depends on the nitrogen gas / oxygen gas flow rate ratio of the gas introduced into the chamber. It adjusted so that it might be in the range of 0.9% to 1.1%.

<Evaluation of water vapor transmission rate>
The following measurement methods were used for evaluation.

(apparatus)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
<Production of water vapor barrier property evaluation cell>
Using a vacuum vapor deposition apparatus (JEOL-made vacuum vapor deposition apparatus JEE-400), the part other than the part (12 mm x 12 mm 9 places) to be vapor-deposited of the film sample irradiated with VUV light was masked, and metal calcium was vapor-deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

  The obtained sample with both sides sealed is stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in Japanese Patent Application Laid-Open No. 2005-283561, the amount of moisture permeated into the cell from the corrosion amount of metallic calcium Was calculated and evaluated by the average value of each measurement location (9 locations of 50 m portions, 9 locations of 500 m portions, 9 locations of 950 m portions).

4: 5 × 10 ⁻⁴ g / m ² / day or more, less than 5 × 10 ⁻³ g / m ² / day 3: 5 × 10 ⁻³ g / m ² / day or more, 5 × 10 ⁻² g / m Less than ² / day 2: 5 × 10 ⁻² g / m ² / day or more, less than 5 × 10 ⁻¹ g / m ² / day 1: 5 × 10 ⁻¹ g / m ² / day or more The results are shown in Table 3. Show.

Experimental Example 8 (Comparison)
The water vapor transmission rate was evaluated in the same manner as in Experimental Example 7 except that it was changed to the coating sample used for the coating property evaluation after friction in the durability evaluation performed in Experimental Example 2 instead of Experimental Example 1. The results are shown in Table 3.

Experimental Example 9 (Comparison)
The water vapor transmission rate was evaluated in the same manner as in Experimental Example 7 except that instead of Experimental Example 1, the sample was changed to a coating sample used for evaluation of coating properties after friction in durability evaluation performed in Experimental Example 3. The results are shown in Table 3.

  From the above results, a film obtained by applying a DLC coating to a wetted part where the coating solution comes into contact with a laminate manufacturing apparatus for manufacturing a laminate by applying a silicon compound coating solution to a substrate. It can be seen that the water vapor transmission rate is greatly improved.

DESCRIPTION OF SYMBOLS 1 Solution tank 2 Valve | bulb 3 Liquid feed pump 4 Piping 5 Die coater 6 Unwinder 7 Winder 8 Drying zone G Inert gas 301 Base material 502 Coating apparatus 502a Extrusion coater

Claims (1)

In a method for producing a gas barrier film in which a coating liquid containing polysilazane is applied to a base material to form a silicon-containing film on the base material, the wetted part is exposed to the atmosphere, and the coating liquid contacts A method for producing a gas barrier film , comprising using a coating apparatus having a member coated with a diamond-like carbon (DLC) film at least a part of a liquid contact portion.

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