JP2014213221A - Method of manufacturing functional film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of continuously manufacturing a functional film by a roll-to-roll method, which includes surface regeneration means of a base material for thin film transfer, and is excellent in smoothness, various functionalities, and foreign matter failure resistance.SOLUTION: A method of manufacturing a functional film includes: conveying means which continuously conveys an endless heat-resistant base material; thin film forming means which forms a thin film by applying and drying a coating liquid for forming a thin film on the heat-resistant base material; transfer means which transfers the formed thin film on a surface of the continuously conveyed plastic film base material; and cleaning means which cleans the surface of the heat-resistant base material after transferring the thin film to regenerate the surface.

Description

  The present invention relates to a method for producing a functional film for transferring a functional thin film onto a plastic film, and to a method for producing a functional film provided with a means for cleaning a heat-resistant substrate surface for thin film transfer. More specifically, the surface property regeneration means for a heat-resistant substrate that can be used repeatedly when continuously producing a gas barrier film, etc., which has been transferred to a plastic film, with a gas barrier thin film that requires surface uniformity. The present invention relates to a method for producing a functional film.

  At present, functional films having various functions are widely known. The functional film is a film in which a constituent layer (functional layer) that expresses various functions is provided on a flexible plastic film, such as a gas barrier film, an antireflection film, an antiglare film, and a heat ray. Examples include a blocking film, a transparent conductive film, a moisture-proof film, an ultraviolet deterioration preventing film, a diffusion film, a weather resistant film, and an antibacterial film.

  A gas barrier film, which is an example of a functional film, generally has a thin film containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide, that is, a gas barrier layer, formed on the surface of a substrate or film made of a thermoplastic resin. It is a thing. Such a gas barrier film has a function of blocking various gases such as water vapor and oxygen, and is widely used for packaging of articles and packaging for preventing deterioration of food, industrial supplies, pharmaceuticals, and the like. . In addition to the above packaging applications, they are used as electronic device materials such as liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) substrates and the like.

  A gas barrier film using a plastic film as a base material is superior in flexibility (flexibility) compared with a case where a glass substrate is used as a base material, and is suitable for production in a roll system. Use of a simple gas barrier film is advantageous in terms of weight reduction and handleability of the electronic device.

  As a method for producing such a gas barrier film, mainly on a substrate such as a plastic film by a thermal evaporation method, a plasma CVD method (Chemical Vapor Deposition method), a sputtering method or the like. In addition, a method of forming a gas barrier layer is known (see, for example, Patent Document 1).

  However, thermal vapor deposition, plasma CVD (chemical vapor deposition), sputtering, etc. require large-scale equipment, and roll-to-roll due to restrictions on the equipment used. -There is a limitation in continuous production by the roll method, and there is a problem in terms of economy and productivity, and a method for producing a gas barrier film having high gas barrier properties at high speed has been demanded.

  On the other hand, as a method of forming a barrier layer other than vapor deposition, for example, JP-A-8-269690 discloses a coating solution containing perhydropolysilazane (hereinafter also referred to as PHPS) or organic polysilazane in a polyester film. A method is disclosed in which an inorganic polymer layer made of silicon oxide or the like is formed by applying and curing and polymerizing PHPS or organic polysilazane by plasma treatment. However, the inorganic polymer layer in the method disclosed in JP-A-8-269690 is used as an intermediate layer between the base material and the metal vapor deposition layer. It is a layer for imparting stability and is less effective as a gas barrier layer.

  Also, a layer forming step for forming a polysilazane layer made of a compound derived from polysilazane on a plastic film surface by a coating method under atmospheric pressure, and the polysilazane layer formed in the layer forming step is chemically changed to be ceramicized. There is disclosed a method for producing a silica-coated plastic film, characterized by comprising a ceramization step for converting into a siliceous layer and a discharge treatment step for subjecting the siliceous layer to gas discharge treatment (for example, (See Patent Document 2).

  However, even in the method described in the cited document 2, it takes a long processing time to form a good silica-coated film on a plastic film, which has a problem in production capacity.

JP 2011-116124 A JP 2000-246830 A

  The present invention has been made in view of the above problems, and its solution is a continuous functional film manufacturing method using a roll-to-roll method, and a surface regeneration means for a substrate for thin film transfer It is providing the manufacturing method of the functional film which has and was excellent in smoothness, various functionality, and a foreign material failure tolerance.

  As a result of intensive studies in view of the above-mentioned problems, the present inventor has carried a transport means for continuously transporting an endless heat-resistant substrate, and a thin film that forms a thin film by applying and drying a thin film-forming coating solution on the heat-resistant substrate. Forming means, transfer means for transferring the formed thin film to the surface of the plastic film substrate to be continuously conveyed, and cleaning means for cleaning the heat-resistant substrate surface after transferring the thin film to regenerate the surface. It has been found that the method for producing a functional film can provide a method for producing a functional film having high productivity and excellent smoothness, gas barrier properties, and foreign matter failure resistance.

  That is, the said subject of this invention is solved by the following means.

  1. Conveying means for continuously conveying an endless heat-resistant substrate, thin film forming means for forming a thin film by applying and drying a coating solution for forming a thin film on the heat-resistant substrate, and the thin film formed on the surface of a plastic film substrate that is continuously conveyed A method for producing a functional film, comprising: a transfer means for transferring the film; and a cleaning means for cleaning the surface of the heat-resistant substrate after transferring the thin film to regenerate the surface.

  2. The surface roughness Rpv1 (nm) of the heat resistant substrate before the surface property regeneration treatment and the surface roughness of the heat resistant substrate after the surface property regeneration treatment is performed 100 times on the surface of the heat resistant substrate by the cleaning means. 2. The method for producing a functional film according to item 1, wherein a difference (Rpv2−Rpv1) from Rpv2 (nm) is within a range of ± 50 (nm).

  3. Between the thin film forming means and the transfer means, there is provided a heat baking means for heat baking the heat resistant substrate having the thin film at a temperature of 300 ° C. or higher and below the heat resistant temperature of the heat resistant substrate. The method for producing a functional film according to item 1 or 2.

  4). The functionality according to any one of claims 1 to 3, further comprising a release layer coating means for providing a release layer on the heat-resistant substrate before the thin film forming means. A method for producing a film.

  By the above means of the present invention, a roll-to-roll method is a continuous functional film manufacturing method comprising a surface regeneration means for a thin film transfer base material, smoothness, various functionalities and foreign matter failure The manufacturing method of the functional film excellent in tolerance can be provided.

Schematic process drawing showing an example of a surface regeneration method for a substrate for thin film transfer applied to the method for producing a functional film of the present invention Schematic process drawing showing another example of the surface regeneration method of the substrate for thin film transfer applied to the method for producing the functional film of the present invention Schematic showing an example of a method for cleaning the surface of a heat-resistant substrate applicable to cleaning means Schematic showing another example of a method for cleaning a heat-resistant substrate surface applicable to a cleaning means

The method for producing a functional film of the present invention comprises a conveying means for continuously conveying an endless heat-resistant substrate, a thin-film forming means for forming a thin film by applying and drying a coating solution for forming a thin film on the heat-resistant substrate, and continuous conveyance. A transfer means for transferring the formed thin film to the surface of the plastic film substrate, and a cleaning means for cleaning the surface of the heat-resistant substrate after transferring the thin film to regenerate the surface. This feature is a technical feature common to the inventions according to claims 1 to 4.

  As an embodiment of the present invention, from the viewpoint that the effects of the present invention can be further manifested, the surface roughness Rpv1 (nm) of the heat-resistant substrate before the surface property regeneration treatment and the heat-resistant substrate by the cleaning means are used. The difference (Rpv2−Rpv1) from the surface roughness Rpv2 (nm) of the heat-resistant substrate after the surface property regeneration treatment is performed 100 times on the surface is within a range of ± 50 (nm). And it is preferable from a viewpoint which can form the thin film excellent in smoothness stably.

  The method further includes a thermal baking means for baking the heat resistant substrate having the thin film at a temperature of 300 ° C. or higher and below the heat resistant temperature of the heat resistant substrate between the thin film forming means and the transfer means. It is preferable from the viewpoint that a dense inorganic film or the like can be stably formed.

  Further, before the thin film forming means, a release layer applying means for providing a release layer is provided on the heat resistant substrate, and a coating film formed on the heat resistant substrate is provided by providing the release layer. From the viewpoint of being able to stably transfer to the surface of the plastic film substrate that is continuously conveyed in the transfer step.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in the following description is used with the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Method for Producing Functional Film of the Present Invention >>
The method for producing a functional film of the present invention comprises a conveying means for continuously conveying an endless heat-resistant substrate, a thin-film forming means for forming a thin film by applying and drying a coating solution for forming a thin film on the heat-resistant substrate, and continuous conveyance. A transfer means for transferring the formed thin film to the surface of the plastic film substrate, and a cleaning means for cleaning the surface of the heat-resistant substrate after transferring the thin film to regenerate the surface.

《Main steps constituting the production process of functional film》
In this invention, as a manufacturing process of a functional film, it is a process applicable to manufacture of a gas barrier film etc., for example, and it is preferable to be comprised from each process shown below.

1) A coating process in which a thin film is formed by applying and drying a coating solution for forming a thin film on a heat-resistant substrate that is continuously conveyed,
2) Adhesion process for adhering the surface of the heat-resistant substrate having the thin film and the plastic film surface;
3) a transfer process for transferring the thin film to the plastic film surface;
4) A cleaning process for cleaning the surface of the heat-resistant substrate after transferring the thin film to regenerate the surface.
It is mainly composed.

  That is, the method for producing a functional film of the present invention is characterized by having at least the steps 1) to 4).

Furthermore, in the method for producing the functional film of the present invention, if necessary,
5) A drying process for drying the formed thin film,
6) The fired thin film is fired to form an inorganic layer, for example,
7) An adhesive layer forming step of providing an adhesive layer on the plastic film before the adhesion step;
8) A thin film is formed by applying and drying a coating solution for forming a thin film on a heat resistant substrate 1) A release layer forming step for forming a release layer on the heat resistant substrate before the coating step,
Can be provided as needed.

  Moreover, in the surface regeneration process of a heat-resistant base material, an endless heat-resistant base material that is continuously transported and a roll-shaped film that is continuously transported as a plastic film are used to perform steps 1) to 8). By performing the roll method (online method), high productivity can be realized.

《Representative flow of functional film manufacturing process》
The details of the method for producing a functional film provided with a cleaning means for cleaning and regenerating the surface of the heat-resistant substrate of the present invention will be described below with reference to the drawings.

  FIG. 1 is a schematic process diagram showing an example of a method for producing a functional film provided with a cleaning means for cleaning and regenerating the surface of the heat-resistant substrate of the present invention. It is process drawing applicable to preparation of the gas barrier film which forms.

  FIG. 1 shows a process of applying a thin film forming coating solution onto an endless heat-resistant substrate that is continuously conveyed to form a thin film, a transfer process of transferring the formed thin film to the surface of the plastic film substrate, and a post-transfer It is the figure which showed the basic composition which has the washing | cleaning process which wash | cleans the heat-resistant base-material surface.

  Specifically, as shown in FIG. 1, the heat-resistant substrate S that is an endless belt is continuously held at a predetermined conveyance speed (m / min) using the driving roller 11 while being held by a plurality of support rollers SR. Is being transported. Next, in the thin film forming process, which is the process A, the thin film forming coating solution stored in the storage tank 6 is supplied to the coater C2 at a predetermined flow rate, and the thin film 7 on the heat-resistant substrate S being continuously conveyed, For example, a precursor layer or the like for forming the inorganic layer is formed. Next, the formed thin film 7 is dried using warm air or the like in the drying apparatus 4 of the drying process which is the process B.

  Next, in the thermal firing step which is Step C, the thin film 7 formed using the thermal firing apparatus 8 is subjected to heat treatment, and the thin film 7 is modified into a functional layer 9 (for example, an inorganic layer or a gas barrier layer). The formed inorganic layer is cooled to room temperature using the cooling device 10 in Step D.

  Next, in the transfer process which is the process E, the heat-resistant substrate S having the converted functional layer 9 and the plastic film F which is continuously transported on the other transport line, the driving roller 11 and the back roller 12 at the point P. The functional layer 9 formed on the heat-resistant substrate S, for example, the gas barrier layer, is transferred to the plastic film F by being in close contact with the roller pair and separated instantaneously. A barrier film is produced.

  On the other hand, on the surface of the heat-resistant substrate S to which the functional layer 9 has been transferred, the residue of the functional layer 9 remaining at the time of transfer and a part of the release layer to be described later are attached. When the coating liquid for forming a thin film is applied with A, it becomes impossible to form a uniform coating film due to the adhered residue, etc., and as a result, the moisture barrier property as a gas barrier layer is reduced, and an electronic device is used. It causes light emission failure (generation of dark spots) due to the influence of humidity and the like when applied.

  In the present invention, in order to solve such a problem, before applying the thin film forming coating liquid to the surface of the heat-resistant substrate S to which the functional layer 9 has been transferred, the surface is free of dirt and foreign matter. It has the washing | cleaning process which is the process W, It is characterized by the above-mentioned.

  Although the specific example of the washing | cleaning means applicable to a washing | cleaning process is mentioned later, for example, as shown in FIG. 1, the washing | cleaning liquid 2 is stored in the washing | cleaning container 1, for example, a water retaining member is provided on the surface of a roller-shaped metal core. For example, the cleaning roller 3 having a sponge or the like is used to clean the surface of the heat-resistant substrate S to remove foreign matters or the like. Moreover, when using water etc. at the washing | cleaning process, you may provide the drying process which has the drying apparatus 4 as the process F before the process A which apply | coats the coating liquid for thin film formation.

  Next, FIG. 2 shows another example of the method for regenerating the surface property of the thin film transfer base material in which other steps are provided with respect to FIG.

  In addition to FIG. 1 described above, a release layer coating step (step G) for providing a release layer may be provided on the heat-resistant substrate S before applying the thin film forming coating solution in step A. it can. In Step G, the release layer forming coating solution stored in the storage tank 5 is supplied to the coater C1 at a predetermined flow rate, and the release layer 17 is formed on the heat-resistant substrate S that is continuously conveyed, Next, the thin film 7 is formed on the release layer 17 in Step A.

  Further, in the other continuous conveyance line of the plastic film F (lower right in the drawing), the plastic film F is unloaded from the long stacking roll 13 from the original winding portion, and on the plastic film F in the process H. Then, the adhesive layer coating solution stored in the storage tank 14 is supplied from the coater C3 to form an adhesive layer, and then dried by the drying device 4 provided in the process J.

  Next, in step E, the heat-resistant substrate S having the functional layer 9 and the plastic film F on which the adhesive layer is formed are nipped between the functional layer 9 surface and the adhesive layer surface at the point P by the driving roller 11 and the back roller 12. Then, the functional layer 9 formed on the heat resistant substrate S, for example, the gas barrier layer, is transferred to the plastic film F by being brought into close contact with each other and being immediately separated. Next, since the plastic film F to which the functional layer 9 has been transferred is attached with transfer debris and a release layer in the same manner as the surface of the heat-resistant substrate S after transfer, after cleaning the surface in the cleaning step H, It dries as needed and winds up as a lamination | stacking roll 16 in a winding-up part. As a cleaning method applied in the cleaning process, the same means as that applied in the process W which is the above-described cleaning process can be used.

《Constituent elements of functional film production method》
Next, details of each process and its components applied to the method for producing a functional film provided with a cleaning means for cleaning and regenerating the surface of the heat-resistant substrate will be described.

[Heat resistant substrate]
In the present invention, the heat-resistant substrate preferably has a belt-like shape that can be continuously conveyed without end.

  The heat-resistant substrate in the present invention is not particularly limited as long as it does not cause a significant change in physical properties after being heated to a high temperature, but is preferably a metal, for example, nickel, stainless steel (SUS), carbon Steel, titanium alloy and the like can be mentioned, but stainless steel is preferably used because it has durability against chemicals and oxidation, and has physical strength and heat resistance up to 500 ° C. The types of stainless steel include austenitic stainless steel (chromium nickel), martensitic stainless steel (chromium), ferritic stainless steel (chromium), duplex stainless steel (chromium nickel), and precipitation hardened stainless steel (chromium nickel). System). The thickness is preferably in the range of 0.05 to 2.0 mm from the viewpoint of durability and flexibility.

[Process W: Cleaning process of heat-resistant substrate surface]
Process W is a cleaning process for removing foreign matter and dust adhering to the surface of the heat-resistant substrate S after transfer.

  The cleaning means applicable to the present invention is not particularly limited as long as the surface smoothness of the surface of the heat resistant substrate S can be maintained in the initial state even after the cleaning process is repeated.

  Examples of cleaning methods include wet cleaning methods such as cleaning with acidic, neutral, alkaline water or organic solvents, ultrasonic cleaning, and physical processing such as flame processing, discharge processing, plasma discharge processing, and UV / ozone processing. A washing method is preferably used. In addition, it is possible to apply a method in which a member such as metal fiber, brush, rubber or the like is brought into contact with the surface to remove dirt on the surface by friction to regenerate the surface of the heat-resistant substrate.

  If the cleaning strength is weak, the dirt on the heat-resistant substrate S cannot be completely removed, and the roughness of the surface of the heat-resistant substrate S increases after repeated cleaning, and is a thin film formed in the subsequent process. The surface properties of the will gradually deteriorate. On the other hand, when the strength of the cleaning is excessively strong, the transferability of the thin film may be deteriorated by making it smaller than the initial surface roughness of the heat-resistant substrate S, and it becomes difficult to perform uniform thin film transfer. . Alternatively, the surface of the heat-resistant substrate is washed and worn unevenly, so that the surface roughness is increased, which also causes deterioration of the uniformity and smoothness of the thin film.

  As the regeneration method by washing treatment of the heat-resistant substrate in the present invention, the surface roughness Rpv1 (nm) of the heat-resistant substrate S before the surface regeneration treatment and the surface against the surface of the heat-resistant substrate S by washing means (process W). It is preferable to maintain the difference (Rpv2−Rpv1) from the surface roughness Rpv2 (nm) of the heat-resistant substrate S after performing the property regeneration treatment 100 times within a range of ± 50 (nm). It is.

  In the thermal baking step (step C) and the subsequent transfer step (step E) according to the present invention, for example, the thin film 7 is modified into a gas barrier layer in the thermal baking step, and the gas barrier layer is transferred onto the plastic film F. Later, dirt (foreign matter, transfer residue, etc.) tends to remain on the heat-resistant substrate surface after transfer, and it is difficult to remove. Therefore, a sufficient cleaning process is necessary. However, if the surface property (roughness) of the base material changes, it is difficult to maintain a good transfer process, and the gas barrier property of the gas barrier layer formed after the transfer also fluctuates. Stabilization cannot be achieved. Moreover, as above-mentioned, when washing | cleaning is too weak, stain | pollution | contamination will remain and smoothness will fall. On the other hand, if the cleaning is too strong, the surface of the substrate will be damaged and unevenness will occur, resulting in a loss of smoothness, or if the cleaning method dissolves the surface of the substrate, the smoothness will be too high and stable. Transferability may be impaired.

  That is, if the rate of change of the heat-resistant substrate surface Rpv after continuous regeneration is −50% or less, the transferability of the gas barrier layer from the heat-resistant substrate S can be maintained, the occurrence of transfer defects can be suppressed, and the gas barrier layer The generation of pinholes can be reduced, and gas permeation (gas purge) therefrom can be prevented. On the other hand, when the substrate surface Rpv change rate is + 50% or less, the surface roughness after transfer from the heat-resistant substrate of the gas barrier layer can be prevented from becoming excessively large, and the organic electroluminescence layer is laminated The occurrence of dark spots can be prevented.

  As cleaning methods applicable to the present invention, the following various cleaning methods can be used without limitation.

  The cleaning referred to in the present invention is a treatment for removing particles and foreign matters adhering to the surface of the heat-resistant substrate after transfer, and the cleaning methods are roughly classified into the following three methods.

  The first method is a method called a dry cleaning method (dry cleaning method), and examples include a plasma cleaning method, an ion beam cleaning method, a UV ozone cleaning method, a UV excimer irradiation method, and a laser cleaning method.

  The second method is a method called a wet cleaning method (wet cleaning method), in which a heat-resistant substrate is immersed in a liquid and then cleaned using, for example, jet cleaning, bubbling cleaning, ultrasonic cleaning, running water cleaning, or the like. It is.

  The third method is a physical peeling method in which a physical force (for example, impact force of an object) is directly applied to the surface of the heat-resistant substrate for cleaning. For example, scrub cleaning, shower cleaning (for example, , High pressure spray cleaning, ultrasonic shower cleaning, two-fluid nozzle cleaning), ice blast cleaning (for example, micro ice jet, dry ice scrub cleaning) and the like. Since these physical peeling methods directly act on foreign matters such as particles adhering to the surface of the heat-resistant substrate, their detergency (foreign matter removal rate) is extremely high and the processing time is short. doing.

  Next, scrub cleaning which is one of physical peeling methods applicable to the present invention will be described. Scrub cleaning refers to physical cleaning in which a foreign material on the surface of a heat-resistant substrate is mechanically removed and cleaned using a friction material such as a sponge or a brush.

  Specifically, a method of using a scrub roller in which a sponge member or a brush member is mounted on the entire surface of a roller-shaped cylindrical body (for example, made of metal or plastic) or a disk-shaped member, and a gas barrier There is a method of cleaning the surface of the gas barrier layer using a scrub pad having a brush or sponge attached to the contact surface with the layer and rotating the scrub pad. Other scrub cleaning methods include, for example, Japanese Patent No. 4554367, International Patent Publication No. 2009/031401, Japanese Patent Application Laid-Open No. 2009-117765, Japanese Patent Application Publication No. 2010-286632, Japanese Patent Application Publication No. 2011-018668, Japanese Patent Application No. 2011-040653. Reference can be made to the methods described in Japanese Laid-Open Patent Publication No. 2011-066386.

  FIG. 3 is a schematic view showing an example of scrub cleaning which is one of physical peeling methods applicable to the present invention.

  In FIG. 3, a scrub member 19 (for example, sponge, brush, etc.) is provided on the entire circumference of the metal core 18 with respect to the surface of the heat-resistant substrate S after the transfer of the gas barrier layer, and is opposite to the transport direction. A cleaning roller (scrub roller) 3 rotating in the direction is brought into contact. At this time, the cleaning roller 3 is immersed in the cleaning container 1 holding the cleaning liquid 2 and, for example, while constantly supplying the cleaning liquid 2 to the scrub member 19 of the cleaning roller, the surface of the heat-resistant substrate S is cleaned and foreign matter is removed. Remove G etc.

  Other physical peeling methods applicable to the present invention include shower cleaning (for example, high pressure spray cleaning, ultrasonic shower cleaning, two-fluid nozzle cleaning) and ice blast cleaning (for example, micro ice jet cleaning). it can.

  The high-pressure spray cleaning is a method in which high-pressure water, a cleaning agent, or the like is sprayed on the surface of the gas barrier layer in a jet state using a spray mechanism such as a nozzle. Ultrasonic shower cleaning is a method in which a liquid used for cleaning is introduced into a container containing an ultrasonic vibration element and applied to the surface of the gas barrier layer as a shower liquid in a state where ultrasonic vibration is applied to the liquid. . The two-fluid nozzle cleaning method is a method in which two kinds of fluids, for example, water and air, a cleaning agent and air, and the like are associated at a nozzle portion and jetted in a jet state.

  As an example of ice blast cleaning, a micro ice jet method using a gas mixed with ice particles can be given. In the micro ice jet method, only compressed air and water are used, and the compressed air is subjected to adiabatic expansion when it is accelerated to supersonic speed at the expansion portion and supersonic at the expansion portion, and the temperature is lowered. The water droplets supplied at this time are accelerated and cooled to become fine ice particles and supercooled droplets, and are supplied to the surface of the gas barrier layer at supersonic speed for cleaning. Instead of the gas mixed with ice particles, a gas mixed with dry ice particles can also be used.

  FIG. 4 is a schematic diagram showing a two-fluid nozzle cleaning method as another example of the scrub cleaning method which is a physical peeling cleaning method as the cleaning means according to the present invention.

  In FIG. 4, the heat-resistant substrate S after the transfer of the gas barrier layer is cleaned by the two-fluid nozzle cleaning device 107 from the diagonally lower part in the transport direction while transporting in the left direction A of the paper. In the two-fluid nozzle cleaning device 107, for example, water is stored in one tank 108A, compressed air is stored in the other tank 108B, and two liquids of water and compressed air are simultaneously supplied to the injection nozzle unit 109. In this state, the two liquids are mixed to form a shower 110, which is supplied to the surface of the heat-resistant substrate S at a high speed, and the foreign matter G adhering to the surface is removed and washed.

  The above-described cleaning method can be similarly applied to the process H for cleaning the transferred plastic film surface shown in FIG.

(Process G: Release layer forming process)
Next, the release layer forming coating stored in the stock tank 5 on the heat-resistant substrate S that has been cleaned while transporting the heat-resistant substrate 1 whose surface has been cleaned in the above-described step W through the driving roller 11. The liquid is supplied and applied to the coater C1 at a predetermined flow rate to form the release layer 17.

  In addition, you may provide the drying process for drying the apply | coated release layer 17 after the process G as needed.

  The material constituting the release layer according to the present invention is not particularly limited as long as it is a material that can be dissolved and applied in water or an organic solvent, and has durability at the firing temperature and release properties. Although it can be used, organic, inorganic low molecular weight substances, oligomers, polymers or mixtures thereof are preferred.

  Examples of organic materials include cellulose resins such as methyl cellulose, ethyl cellulose, and cellulose acetate, polyvinyl acetal resins, polyvinyl butyral resins, polyvinyl alcohol, and polyvinyl pyrrolidone. Examples of inorganic materials include polysiloxane resins, titanium oligomers, and silica sols.

  Further, polyvinyl pyrrolidones (including vinyl pyrrolidone polymers) can also be used as a release agent. Examples of polyvinylpyrrolidones include polyvinylpyrrolidone (Mw about 40,000), polyvinylpyrrolidone (Mw about 9,000), polyvinylpyrrolidone (Mw about 16,000), vinylpyrrolidone-vinyl acetate copolymer (copolymerization mole). Ratio = 7: 3, Mw about 4,000), vinylpyrrolidone-methyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw about 1,000), vinylpyrrolidone-ethyl acrylate copolymer (copolymerization mole) Ratio = 7: 3, Mw about 25,000), vinylpyrrolidone-butyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw about 7,000), vinylpyrrolidone-2-ethylhexyl acrylate copolymer (copolymer) Polymerization molar ratio = 7: 3, Mw about 18,000), vinylpyrrolidone-styrene copolymer (copolymerization molar ratio) 1: can be mentioned 3, Mw about 20,000), and the like.

  Examples of the polyvinyl pyrrolidone include a polyvinyl pyrrolidone single polymer. Moreover, as a polyvinyl pyrrolidone, a thing with a viscosity average molecular weight of 5000-50000 is preferable. Moreover, as polyvinyl pyrrolidone, a commercial item can also be used and specifically, PSFK15 and PVPK30 by BASF Japan are mentioned.

  In the present invention, the release layer coating solution is prepared by dissolving the polyvinylpyrrolidone in an appropriate solvent, for example, an organic solvent such as water or alcohol.

  The coater C1 used in the process G is not particularly limited as long as it is a wet coater. For example, a blade coater, knife coater, impregnation coater, die coater, slot die coater, roller coater, gravure coater, bar coater, comma Examples of the coating device include a coater, an extrusion type coater, a slide type coater, and an inkjet head.

  Moreover, there is no restriction | limiting in particular as application | coating temperature of a mold release layer, It can carry out by selecting an optimal temperature suitably.

  In the present invention, the layer thickness of the release layer is not particularly limited, but the layer thickness after drying shown below is in the range of about 0.2 to 10 μm, preferably 0.5 to 5.0 μm. More preferably, it is in the range of 1.0 to 3.0 μm.

(Process A: Thin film application process)
Next, in step A, the thin film 7 is formed on the release layer 17 formed above.

  Hereinafter, the formation of an inorganic layer forming precursor layer used to form a gas barrier layer (inorganic layer) as a functional layer will be described below as an example of a thin film according to the present invention.

  In the thin film forming process which is the process A, the thin film 7 is applied to the coater C2 at a predetermined flow rate with the thin film forming coating solution stored in the stock tank 6, and the thin film 7 is continuously conveyed on the heat resistant substrate S. A layer forming precursor layer or the like is formed.

  The inorganic layer forming precursor contained in the inorganic layer forming precursor layer that is the thin film 7 is a material that is converted into the inorganic layer 9 by heat treatment in the thermal baking step (step C) as the next step. Can be mentioned.

<Inorganic layer forming precursor>
Examples of the inorganic layer forming precursor applicable to the present invention include, for example, polysilazane, polysiloxane, polysilane, glass frit, glass paste, and silver having a particle size range of several nm to several μm as the SiO ₂ precursor. And metal nanopaste having conductivity including metal particles such as silver-copper. The former can be used for forming an insulating film or a gas barrier layer of oxygen or water vapor. The latter is used as a conductive film.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond in the structure, and has a bond such as Si—N, Si—H, or N—H, SiO ₂ , Si ₃ N _4, and an intermediate between them. It is a ceramic precursor inorganic polymer such as solid solution SiO _x N _y, which is a precursor of silicon oxynitride. For example, it is composed of a unit represented by the following general formula (1) described in JP-A-8-112879. A compound having a main skeleton is preferred.

General formula (1)
—Si (R ¹ ) (R ² ) —N (R ³ ) —
In the above structural formulas, R ¹ , R ^2, and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

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

  In addition, the organopolysilazane in which a part of the hydrogen atom part bonded to Si is substituted with an alkyl group or the like has improved adhesion to the release layer which is an underlayer by having an alkyl group such as a methyl group, In addition, the ceramic film made of hard and brittle polysilazane can be provided with toughness, and even when the film thickness (average film thickness) is made thicker, the occurrence of cracks can be suppressed. Accordingly, 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.

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

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.

  Therefore, as an organic solvent for preparing a coating liquid containing polysilazane, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, fats Ethers such as cyclic ethers can be used. Specifically, hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, dibutyl ether and dioxane And ethers such as tetrahydrofuran.

  These organic solvents may be selected according to the solubility of polysilazane, the evaporation rate of the solvent, and the like, and a plurality of organic solvents may be mixed.

  As the coater C2 for applying a coating solution containing an inorganic layer forming precursor such as polysilazane, the same wet coater as described in Step G can be used.

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is about 10 nm to 10 μm, preferably about 10 nm to 1 μm after drying.

(Process B: Drying process)
The wet inorganic layer forming precursor layer 7 formed on the heat resistant substrate S in the step A is dried using the drying device 4.

  Examples of the drying device 4 that can be applied in the step B include a heating device using a warm air heating method or a heater heating method (for example, a panel heater, a halogen heater, or the like).

  As a specific heating means constituting the drying apparatus 4, a heater heating method (for example, an infrared heater, a halogen heater, a panel heater or the like is installed on the upper surface or upper and lower surfaces of the heat-resistant substrate and heated by radiant heat), a heat-resistant group Examples of the transport roller that transports the material S include a method of heating using a heat roller, and a hot air heating method (for example, a method of spraying and drying temperature-controlled hot air from above and below the heat-resistant substrate S). In the present invention, the hot air heating method is preferable because temperature control can be performed with high accuracy.

(Process C: Thermal firing process)
In the process C, the inorganic layer forming precursor layer formed in the process A and the process B is subjected to a heat baking treatment to be modified into a gas barrier layer composed of an inorganic layer, for example, SiO ₂ .

In the thermal baking process which is the process C, the thermal baking apparatus 8 is used to apply high-temperature thermal energy to the inorganic layer forming precursor layer formed of, for example, polysilazane or the like, and is composed of SiO ₂ or the like. The inorganic layer 9 (gas barrier layer) is used. As the thermal baking apparatus 8, a plurality of thermal baking members are provided therein, and the inorganic layer forming precursor layer is heated and converted into the inorganic layer 9 according to a predetermined temperature history.

  The heat-fired member provided in the heat-fired apparatus 8 may be disposed on both surfaces of the heat-resistant substrate S, or may be disposed only on the surface side having the inorganic layer forming precursor layer. .

  A plurality of heat-firing members can be disposed in the heat-firing apparatus 8 and can be subjected to heat-firing treatment with a desired heating profile by setting the heating temperatures independently.

  Although there is no restriction | limiting in particular as a heat-firing temperature, It is preferable to heat-fire at 300 degrees C or more and below the heat-resistant temperature of the said heat-resistant base material.

  Moreover, it is a preferable aspect that a thermometer, for example, a non-contact type reflection thermometer, is provided in the thermal baking apparatus, and the temperature of the surface of the heat-resistant substrate during the thermal baking process is constantly monitored.

  In addition, examples of the thermal baking apparatus applicable to the thermal baking process include a roller hearth skin, a discharge plasma baking apparatus, a pulse current baking apparatus, a high-frequency baking apparatus, a near-infrared baking apparatus (NIR), and the like. A near-infrared baking apparatus (NIR) is preferable from the viewpoint of efficient thermal baking treatment. As the near-infrared baking apparatus, for example, an NIR lamp manufactured by Adphos Corporation can be used. The NIR lamp manufactured by Adfos is a lamp having a wavelength band of 800 to 1500 nm in the near infrared region and a maximum wavelength at 850 nm, and is evenly heated to the inside of the heating target (inorganic layer forming precursor layer). Therefore, when the thermal energy passes through the inorganic layer forming precursor layer uniformly at high speed, an inorganic layer in which the entire film is uniformly converted into an inorganic film can be formed. When such an NIR lamp is applied, the NIR lamp that is the heat-fired member 9 may be arranged only on one surface side having the inorganic layer forming precursor layer.

Further, in the present invention, in the thermal baking step, before applying a heat treatment to the inorganic layer forming precursor layer,
For example, pretreatment such as ultraviolet light, visible light, infrared light, ultrasonic wave, plasma discharge, corona discharge, and microwave may be performed.

(Process D: Cooling process)
Step D is a step of cooling the heat-resistant substrate heated to a high temperature in Step C, which is a previous step.

  Specifically, in the cooling device 10, cooling members are arranged on both sides with the heat-resistant substrate S interposed therebetween, and cold air or the like is blown to cool the heat-resistant substrate S having the inorganic layer 9 to near room temperature.

  In this cooling process 10 (process D), it cools to the temperature at the time of bonding with the plastic film F at the adhesion transfer process (process E) which is the next process.

  Examples of the cooling means that can be applied in the cooling device 10 include cooling with a water-cooled roller or a chill roller, cooling with cold air, and the like, but are not limited thereto.

  Moreover, it is a preferable aspect that a thermometer such as a non-contact type reflection thermometer is provided in the cooling device to constantly monitor the temperature of the heat-resistant substrate surface during the cooling process.

(Process H: Application of adhesive layer to plastic film)
<Plastic film F>
The plastic film F on the transfer side as shown in the lower right of FIG. 2 preferably contains a thermoplastic resin as a main component and has flexibility. More preferably, a base material made of a thermoplastic resin is used, and as such a base material, a plastic film or sheet is generally used, and a film or sheet made of a colorless and transparent resin is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold an adhesive layer, a gas barrier layer to be transferred, and the like, and can be appropriately selected according to the purpose of use. In the present invention, as the plastic film F, specifically, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide Resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modification Polycarbonate resin, alicyclic modified polycarbonate resin, fluorene ring modified polyester resin, film made of thermoplastic resin such as acryloyl compound, organic-inorganic hybrid structure Resistant transparent film was silsesquioxane as a basic skeleton (product name Shirupurasu, manufactured by Nippon Steel Chemical Co., Ltd.), and further, a hybrid plastic film made by laminating the above-mentioned film material 2 or more layers and the like.

  The thickness of the plastic film applied to the present invention is not particularly limited because it is appropriately selected depending on the use, but is typically in the range of 1 to 800 μm, preferably in the range of 5 to 500 μm, more Preferably it exists in the range of 10-250 micrometers, Most preferably, it exists in the range of 25-150 micrometers.

  The plastic film preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both sides of the plastic film, for example, the side on which the gas barrier layer is provided may be polished to improve smoothness.

<Applying adhesive layer>
In step H, an adhesive layer is applied on the prepared plastic film S by a wet coating method. The coating liquid for forming an adhesive layer stored in the stock tank 14 is supplied to the coater C3 at a predetermined flow rate, and an adhesive layer is formed on the plastic film F that is continuously conveyed. After applying the adhesive layer 22, a drying step (step J) as described above may be provided as necessary.

  The adhesive layer is preferably formed of a resin component, for example, a polyester resin, a urethane resin, an acrylic resin, a melamine resin, an epoxy resin, a polyamide resin, a vinyl chloride resin, and vinyl chloride acetic acid. A single resin such as a vinyl copolymer resin or a mixed resin thereof can be used.

  Among them, it is preferable to use an adhesive "MAXIVE (registered trademark)" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) for epoxy resin for gas barrier dry laminate, which contains a polyepoxy resin as a main agent and a polyamine resin as a curing agent. it can.

  The adhesive layer may consist of only one layer or may consist of a plurality of layers. The thickness of the adhesive layer is preferably in the range of 1 to 100 μm, more preferably in the range of 3 to 50 μm.

  The coater used to form the adhesive layer includes a blade coater, knife coater, impregnation coater, die coater, slot die coater, roller coater, gravure coater, bar coater, comma coater, extrusion coater, slide coater, inkjet head, etc. And the like.

  Moreover, there is no restriction | limiting in particular as application | coating temperature of an contact bonding layer, It can carry out by selecting an optimal temperature suitably in the temperature range of 20-50 degreeC.

(Process E: Adhesion / transfer process)
In the adhesion / transfer process, which is the process E, the heat-resistant substrate S having the inorganic layer 9 cooled after the thermal baking process in the cooling process of the process D, and the plastic film F provided with the adhesive layer in the process H. It is a process of adhesion and transfer.

  The close contact is made so that the inorganic layer 9 provided on the heat-resistant substrate S and the adhesive layer formed on the plastic film F face each other, and then the close contact is made at the meeting point P. For the close contact, a nip is formed using the transport roller 11 and the back roller 12, and the close contact is performed by pressurizing and transporting between the nips. Under the present circumstances, the conveyance roller 11 and the back roller 12 can also be heated as needed.

  As the transport roller 11 and the back roller 12, a rubber roller and a metal roller can be combined, or a rubber roller and a rubber roller can be combined.

  After the pressure-bonding process is performed at the meeting point P, peeling and transfer are performed. The transfer operation is not particularly limited, and an adhesive layer surface side on which the inorganic layer 9 formed on the heat resistant substrate 1 is applied to the heat resistant substrate S and the plastic film F by applying a separating force to the left and right. Transcript to.

  At this time, if the relationship between the adhesive force F1 between the heat-resistant substrate S and the inorganic layer 9 and the adhesive force F2 between the inorganic layer 9 of the adhesive layer formed on the surface of the plastic film F is F1 <F2, the relationship is stable. Can be transferred.

<< Application field of functional film (gas barrier film) >>
Applications of the gas barrier film produced according to the present invention include application to the following electronic devices and optical members.

(Electronic device)
The gas barrier film manufactured by the method for manufacturing a functional film provided with a cleaning means for cleaning and regenerating the surface of the heat-resistant substrate of the present invention is, for example, a chemical component in air (for example, oxygen, water, nitrogen oxidation) It can be preferably used for an electronic device whose performance is deteriorated by an object, sulfur oxide, ozone, etc.). Examples of the electronic device include an organic electroluminescence element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic electroluminescence element or a solar cell, and particularly preferably used for an organic electroluminescence element.

<Organic electroluminescence device>
For examples of organic electroluminescence elements to which the gas barrier film according to the present invention can be applied, for example, the contents described in detail in JP-A-2007-30387 can be referred to.

  Hereinafter, the effect of the present invention will be described using the following examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, “part” or “%” is used, but “part by mass” or “% by mass” is expressed unless otherwise specified. Moreover, in the following operation, unless otherwise specified, measurement of the operation and physical properties was performed in an environment of 25 ° C. and relative humidity of 50% RH.

Example 1
<Production of gas barrier film>
[Preparation of gas barrier film 1]
(Preparation of plastic film F)
As the plastic film F, a 100 μm-thick polyester film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.), which is a thermoplastic resin support and was easily bonded on both sides, was used.

(Formation of adhesive layer)
An adhesive film, Panaclean PD-R5 (adhesive layer thickness 25 μm) manufactured by Panac Co., Ltd. is uniformly bonded to one side of the plastic film F so that no air bubbles are mixed in, and a plastic film having an adhesive layer on the plastic film Was prepared (step H in FIG. 2).

(Preparation of heat-resistant substrate S)
A heat resistant substrate S having a surface roughness Rpv1 of 100 nm was prepared by buffing the surface of a stainless steel substrate (SUS304H, heat resistant temperature 500 ° C.) having a thickness of 0.2 mm. The surface roughness Rpv of the heat-resistant substrate S is calculated from an uneven cross-sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments). Then, the measurement was performed many times in a section having a measurement direction of 30 μm with a stylus having a very small tip radius, and the average roughness related to the amplitude of fine irregularities was obtained.

(Formation of release layer on heat-resistant substrate)
A 5% butanol solution of polyvinyl acetal resin (Sekisui Chemical Co., Ltd. ESREC KS-1) is applied onto a heat-resistant substrate that is continuously conveyed, and then dried at 120 ° C. for 2 minutes, whereby the film after drying. A release layer was formed on the heat-resistant substrate so as to have a thickness of 0.3 μm (step G in FIG. 2).

(Formation of inorganic layer forming precursor layer)
On the release layer thus formed, an inorganic layer forming precursor layer was formed as a thin film under the following conditions.

  A 20% by weight dibutyl ether solution of perhydroxypolysilazane (abbreviation: PHPS, AZ Electronic Materials Co., Ltd., Aquamica NN120-20) was applied so that the film thickness after drying was 0.25 μm (described in FIG. 2). Step A) and drying (Step B).

(Thermal firing treatment and cooling treatment)
A sample obtained by applying the inorganic layer forming precursor layer on the heat-resistant substrate formed in the above step A is heated from a room temperature of 25 ° C. to 300 ° C. at a rate of 50 ° C./min, and held at 300 ° C. for 2 minutes. After performing the first heat firing, the temperature is increased to 450 ° C. at a rate of 50 ° C./min, held at 450 ° C. for 2 minutes, and subjected to second heat firing to form an inorganic layer forming precursor layer as an inorganic layer ( Gas barrier layer). Thereafter, the sample temperature was lowered at a rate of 100 ° C./min and returned to room temperature (Step C and Step D described in FIG. 2).
(Transfer process)
The adhesive layer surface of the plastic film prepared above and the inorganic layer surface on the heat-resistant base material prepared through Step C and Step D are faced to each other and are adhered and pressed by the method shown in FIG. Thus, the inorganic layer formed on the heat-resistant substrate was transferred onto the adhesive layer of the plastic film. The above operation was performed 100 times while continuously transporting, and the sample produced at the 100th time was designated as the gas barrier film 1.

[Preparation of gas barrier film 2]
In the production method of the gas barrier film 1, the heat resistant substrate after the transfer of the gas barrier layer in the transfer step is performed in the same manner except that the cleaning treatment 1 is performed in the following method in the step W being the cleaning step. A gas barrier film 2 was produced.

(Cleaning process 1)
In the washing treatment 1, a horizontally long washing tank was prepared, and the washing tank was filled with alkaline blanconic (water-based cleaning agent Branson IS-III, manufactured by Branson) as a cleaning solution, kept at 50 ° C., and stirred. Subsequently, the heat-resistant substrate was continuously conveyed in the cleaning liquid over 5 minutes to perform the cleaning process 1.

[Preparation of gas barrier film 3]
A gas barrier film 3 was produced in the same manner except that the following cleaning treatment 2 was used in place of the washing treatment 1 in the method for producing the gas barrier film 2.

(Cleaning process 2)
In the washing process 2, a horizontally long washing tank is prepared, a Bransonic ultrasonic cleaner DHA-1000-6J (manufactured by Branson) is arranged in the washing tank, and ultrasonic waves are oscillated in a pure water bath at 30 ° C. However, the heat-resistant substrate was continuously conveyed in the pure water bath for 10 minutes to perform the cleaning treatment 2.

[Preparation of gas barrier film 4]
A gas barrier film 3 was produced in the same manner as in the production method of the gas barrier film 2 except that the following washing treatment 3 was used instead of the washing treatment 1.

(Cleaning process 3)
In the washing treatment 3, the pure water bath in the washing treatment 2 is changed to the alkaline blanconic (water-based detergent Branson IS-III, manufactured by Branson) bath used in the washing treatment 1, and heated to 50 ° C. The heat-resistant substrate was continuously conveyed in the cleaning bath over 1 minute while oscillating ultrasonic waves, and cleaning treatment 3 was performed.

[Preparation of gas barrier film 5]
A gas barrier film 4 was produced in the same manner as in the production method of the gas barrier film 2 except that the following washing treatment 4 was used instead of the washing treatment 1.

(Cleaning process 4)
In the method described in the example of Japanese Patent Application Laid-Open No. 2006-20002, cleaning with a rotating brush was referred to as cleaning processing 4.

[Preparation of gas barrier film 6]
A gas barrier film 5 was produced in the same manner except that the following cleaning treatment 5 was used in place of the cleaning treatment 1 in the method for producing the gas barrier film 2.

(Cleaning process 5)
In the washing treatment 5, a horizontally long washing tank was prepared, and the washing tank was filled with a mixed solvent of n-butanol / cyclohexanone = 1/1, kept at 50 ° C., and stirred. Subsequently, the heat-resistant substrate was continuously conveyed in this cleaning liquid over 3 minutes, and cleaning treatment 5 was performed.

[Preparation of gas barrier film 7]
In the method for producing the gas barrier film 2, a gas barrier film 7 was produced in the same manner except that the following washing treatment 6 was used instead of the washing treatment 1.

(Cleaning process 6)
Using a plasma cleaner PXA-100 manufactured by Samco Corporation, Ar plasma was irradiated for 3 minutes in total using a plasma cleaner PXA-100 manufactured by Samco Corporation.

[Production of gas barrier film 8]
A gas barrier film 8 was produced in the same manner as in the production method for the gas barrier film 2 except that the following washing treatment 7 was used instead of the washing treatment 1.

(Cleaning process 7)
A UV ozone cleaning means was applied for 5 minutes on a heat-resistant substrate that was continuously conveyed using UV ozone cleaner UV-300HC manufactured by Samco Corporation.

[Preparation of gas barrier films 9-12]
In the production of the gas barrier film 4, the gas barrier films 9 to 12 are produced in the same manner except that the second thermal firing temperature in the thermal firing treatment (step C) is changed from 400 ° C. to the temperature shown in Table 1. did.

<< Evaluation of surface regeneration method >>
[Measurement of surface roughness Rpv of heat-resistant substrate S]
(Measurement of surface roughness Rpv1 of heat-resistant substrate before surface regeneration treatment)
As described above, the surface was buffed and the surface roughness Rpv1 of the heat-resistant substrate before the surface property regeneration treatment was set to 100 nm. As described above, the surface roughness Rpv1 is calculated from an uneven cross-sectional curve continuously measured with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments). The measurement was performed a number of times in a section having a measurement direction of 30 μm with a stylus having a radius of the tip, and the average roughness regarding the amplitude of fine irregularities was obtained.

  In the production of the gas barrier films 1 to 12, the surface roughness Rpv1 is 100 nm.

(Measurement of the surface roughness Rpv2 of the heat-resistant substrate after 100 times of surface property regeneration treatment)
In the production of the gas barrier films 1 to 12, the process G, the process A to the process E, the process W, and the process F are defined as one cycle, and after performing this up to 100 cycles, The surface roughness Rpv was measured in the same manner as described above, and this was defined as the surface roughness Rpv2.

  Subsequently, the difference (Rpv2-Rpv1 (100 nm)) between the measured surface roughness Rpv2 and the surface roughness Rpv1 (100 nm) was determined.

<< Evaluation of gas barrier film >>
[Evaluation of surface smoothness]
In the preparation of the gas barrier films 1 to 12, the process G, the process A to the process E, the process W and the process F are defined as one cycle, and the surface roughness is measured for the gas barrier film sampled after performing this up to 100 cycles. The maximum cross-sectional height Rpv represented is calculated from the cross-sectional curve of the unevenness measured continuously with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments). The measurement was performed a number of times in a section having a measurement direction of 30 μm with a stylus having a radius of the tip, and the average roughness regarding the amplitude of fine irregularities was obtained. Subsequently, the surface smoothness was evaluated according to the criteria shown below. The evaluation ranks of the gas barrier films 1 to 13 sampled in the first cycle were all “5”.

5: Maximum cross-section height Rpv is less than 20 nm 4: Maximum cross-section height Rpv is 20 nm or more and less than 50 nm 3: Maximum cross-section height Rpv is 50 nm or more and less than 100 nm 2: Maximum cross-section height Rpv is 100 nm or more and less than 200 nm 1: Maximum cross-sectional height Rpv is 200 nm or more [Evaluation of gas barrier properties (water vapor permeability)]
In the production of the gas barrier films 1 to 12, the process G, the process A to the process E, the process W, and the process F are defined as one cycle, and the gas barrier film sampled after performing this up to 100 cycles is manufactured by MOCON, Using a MOCON water vapor transmission rate measuring device PERMATRAN-W, the water vapor transmission rate at 39 ° C. and 90% RH was measured. Next, gas barrier properties were evaluated according to the criteria shown below. The gas barrier properties of the gas barrier films 1 to 12 sampled in the first cycle were all rank 5.

5: water vapor permeability is less than 0.05g ^/ m 2 · day 4: Water vapor transmission rate, 0.05g ^/ m 2 · day or more and less than 0.10g ^/ m 2 · day 3: water vapor permeability The rate is 0.10 g / m ² · day or more and less than 1.00 g / m ² · day 2: The water vapor transmission rate is 1.00 g / m ² · day or more and less than 5.00 g / m ² · day 1: The water vapor transmission rate is 5.00 g / m ² · day or more. The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, transfer and production using the heat-resistant substrate regenerated by the method for producing a functional film provided with a cleaning means for washing and regenerating the surface of the heat-resistant substrate of the present invention It can be seen that the obtained gas barrier film maintains the initial performance even after continuous production of high surface smoothness and gas barrier properties with good repeatability.

Example 2
<< Preparation of gas barrier films 13-19 >>
In the production of the gas barrier film 4 described in Example 1, the temperature of the alkali cleaning bath in the cleaning treatment 3 was appropriately changed in the range of 20 to 70 ° C., and the cleaning time was in the range of 10 seconds to 10 minutes. Gas barrier films 13 to 19 were produced in the same manner except that the surface roughness Rpv2 of the heat-resistant substrate and the change width of the surface roughness Rpv were adjusted to the values shown in Table 2. The surface roughness Rpv was measured in the same manner as described in Example 1.

<< Evaluation of gas barrier film and organic EL element >>
[Evaluation of gas barrier film]
In the same manner as in the method described in Example 1, the surface smoothness and gas barrier property (water vapor permeability) of the gas barrier film were evaluated.

[Evaluation of organic EL elements]
According to the following method, after producing an organic EL element using each gas barrier film, the following evaluation was performed.

(Production of organic EL element)
<Formation of transparent conductive film>
As the plasma discharge device, an electrode having a parallel plate type is used, and each gas barrier film after performing the surface property regeneration treatment prepared 100 times is placed between the electrodes, and a mixed gas is introduced into the discharge space. A transparent conductive film was formed. In addition, as a ground (ground) electrode, a 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried. An electrode was used which was cured by ultraviolet irradiation and sealed, and the dielectric surface thus coated was polished, smoothed and processed to have an Rmax of 5 μm. Further, as the application electrode, an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used. A plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space. Moreover, as a power source used for plasma generation, a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and 5 W / cm ² of power was supplied at a frequency of 13.56 MHz.

  Then, a mixed gas having the following composition is caused to flow between the electrodes to form a plasma state, each gas barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film is formed to a thickness of 100 nm on the gas barrier layer. Then, a transparent conductive film was formed.

Discharge gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
<Formation of organic functional layer>
The gas barrier films 13 to 19 on which the obtained transparent conductive film was formed were cut into a size of 100 mm × 80 mm to form a gas barrier film substrate, which was patterned and then the gas barrier film substrate provided with this ITO transparent electrode Was ultrasonically washed with isopropyl alcohol and dried with dry nitrogen gas. This gas barrier film substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus. Meanwhile, 200 mg of α-NPD is put into a molybdenum resistance heating boat, and 200 mg of CBP as a host compound is put into another resistance heating boat made of molybdenum. 200 mg of Bathocuproin (BCP) is put into a resistance heating boat made of molybdenum, 100 mg of Ir-1 is put into another resistance heating boat made of molybdenum, and 200 mg of Alq ₃ is put into another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus. It was.

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and the gas barrier film substrate was positioned at the center at a deposition rate of 0.1 nm / second. As described above, vapor deposition was performed in an area of 80 mm × 60 mm to provide a hole transport layer.

  Next, the heating boat containing CBP and Ir-1 was energized and heated, and co-evaporated on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively, to form a light emitting layer. Provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Further, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a hole blocking layer having a thickness of 10 nm.

Further, the heating boat containing Alq ₃ is further heated by energization, and is deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element samples 13-19 using the gas barrier films 13-19 were produced, respectively.

<Sealing of organic EL element sample>
In an environment purged with nitrogen gas (inert gas), the cathode deposition surface of the organic EL element samples 13 to 19 and an aluminum foil having a thickness of 100 μm face each other, and an epoxy adhesive manufactured by Nagase ChemteX Corporation. Then, the four sides of the gas barrier film substrate end were bonded with a width of 10 mm, respectively, and sealed to prepare organic EL elements 13 to 19.

(Evaluation of organic EL element: Evaluation of dark spot resistance)
The produced organic EL devices 13 to 19 were energized in an environment of 25 ° C. and 40% RH, and the occurrence of dark spots and light emission unevenness were visually observed from 0 hour to 100 hours. Resistance (dark spot resistance) evaluation was performed.

5: At the start of light emission, no dark spot or luminance unevenness is observed. Further, even after energization for 100 hours continuously, the non-light-emitting area is less than 0.1% of the total light-emitting area, and all the generated dark spots have a size (0.1 mm or less) that cannot be easily observed visually. Slight dark spots are observed at the start, but all the generated dark spots are of a size (0.1 mm or less) that cannot be easily observed visually, and no occurrence of luminance unevenness is observed. The non-light emitting region was 0.1% or more and less than 0.5% of the total light emitting area after 100 hours of continuous energization, and the generated dark spot maintained a size (0.1 mm or less) that could not be easily observed visually.

  3: When the energization was started, luminance unevenness that could be visually discerned was not observed, and all the generated dark spots had a size (0.1 mm or less) that could not be easily observed by visual inspection. After 100 hours of continuous energization, the non-light emitting region was 0.5% or more and less than 1.0% of the total light emitting area.

2: At the start of energization, the occurrence of visually uneven brightness and dark spots were observed, and after 60 hours of continuous energization, the total non-light emitting area of the dark spots was 10% or more of the initial total light emitting area. 1: Energization At the start, non-light-emitting areas with dark spots and uneven brightness that can be visually recognized were observed exceeding 1.0% of the total light-emitting area, and the non-light-emitting areas exceeded 30% of the total light-emitting area within 30 hours Table 2 shows the evaluation results obtained by the above.

  As is clear from the results shown in Table 2, an organic material provided with a gas barrier film produced by applying a method for producing a functional film provided with a cleaning means for cleaning and regenerating the surface of the heat-resistant substrate of the present invention. Among EL elements, the difference between the surface roughness Rpv1 (nm) and the surface roughness Rpv2 (nm) (Rpv2−Rpv1) is within the range of ± 50 (nm) by a heat resistant substrate using a cleaning method. It turns out that the organic EL element provided with the manufactured gas barrier film is more excellent in the dark spot tolerance of the organic EL element.

Example 3
<< Preparation of conductive films 13-19 >>
In the production of the gas barrier films 13 to 19 described in Example 2, a high-conductivity silver nanoparticle paste (MDot-SLP, manufactured by Mitsuboshi Belting Co., Ltd.) was used instead of perhydroxypolysilazane which is a material for forming the gas barrier layer. Conductive films 13 to 19 were produced in the same manner except that coating was performed on the release layer by a printing method to form a conductive layer having a thickness of 3.0 μm.

<< Evaluation of conductive film: Evaluation of surface smoothness >>
Surface roughness R (1) of a conductive film prepared using a heat-resistant base material that has not been subjected to surface regeneration treatment, and a conductive film produced using a heat-resistant base material that has been subjected to surface property regeneration treatment 100 times The surface roughness R (100) was measured, the surface roughness change rate (%) was determined according to the following formula, and the surface smoothness was evaluated according to the following criteria.

Surface roughness change rate (%) = [R (100) -R (1)] / R (1)
5: Surface roughness change rate is less than 1.0% 4: Surface roughness change rate is 1.0% or more and less than 3.0% 3: Surface roughness change rate is 3.0 % Or more and less than 10.0% 2: The surface roughness change rate is 10.0% or more and less than 50.0% 1: The surface roughness change rate is 50.0% or more. The surface roughness is calculated from an uneven cross-sectional curve continuously measured with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments), and the surface roughness is measured with a minimum tip radius. The measurement was performed many times in a section having a measuring direction of 30 μm with a needle, and the average roughness regarding the amplitude of fine irregularities was obtained.

  The results obtained as described above are shown in Table 3.

  As is apparent from the results shown in Table 3, the surface of the conductive film produced by applying the method for producing a functional film provided with a cleaning means for cleaning and regenerating the surface of the heat-resistant substrate of the present invention A conductive film made of a heat-resistant substrate using a cleaning method in which the difference (Rpv2-Rpv1) between the roughness Rpv1 (nm) and the surface roughness Rpv2 (nm) is within a range of ± 50 (nm) is It can be seen that the surface roughness change rate is small, and even when continuously manufactured, it is possible to manufacture a conductive film having high repeatability and high uniformity.

DESCRIPTION OF SYMBOLS 1 Cleaning container 2 Cleaning liquid 3 Cleaning roller 4 Drying device 5, 6, 14 Storage tank 7 Thin film 8 Thermal baking device 9 Functional layer 10 Cooling device 11 Driving roller 12 Back roller 13, 16 Lamination roll C1-C3 Coater F Plastic film S Heat resistance Base material

Claims (4)

  Conveying means for continuously conveying an endless heat-resistant substrate, thin film forming means for forming a thin film by applying and drying a coating solution for forming a thin film on the heat-resistant substrate, and the thin film formed on the surface of a plastic film substrate that is continuously conveyed A method for producing a functional film, comprising: a transfer means for transferring the film; and a cleaning means for cleaning the surface of the heat-resistant substrate after transferring the thin film to regenerate the surface.   The surface roughness Rpv1 (nm) of the heat resistant substrate before the surface property regeneration treatment and the surface roughness of the heat resistant substrate after the surface property regeneration treatment is performed 100 times on the surface of the heat resistant substrate by the cleaning means. The method for producing a functional film according to claim 1, wherein a difference (Rpv2-Rpv1) from Rpv2 (nm) is within a range of ± 50 (nm).   Between the thin film forming means and the transfer means, there is provided a heat baking means for heat baking the heat resistant substrate having the thin film at a temperature of 300 ° C. or higher and below the heat resistant temperature of the heat resistant substrate. The manufacturing method of the functional film of Claim 1 or Claim 2.   The functionality according to any one of claims 1 to 3, further comprising a release layer coating means for providing a release layer on the heat-resistant substrate before the thin film forming means. A method for producing a film.

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