WO2014175023A1

WO2014175023A1 - Functional film manufacturing method

Info

Publication number: WO2014175023A1
Application number: PCT/JP2014/059737
Authority: WO
Inventors: 健治属; 和喜田地
Original assignee: コニカミノルタ株式会社
Priority date: 2013-04-23
Filing date: 2014-04-02
Publication date: 2014-10-30
Also published as: JP2016128211A

Abstract

The present invention addresses the problem of providing a functional film manufacturing method capable of manufacturing a functional film having excellent functionality (for example, a gas barrier property), transparency, and planarity with excellent economic efficiency and production stability and high productivity by a simple method without requiring a large-scale facility. This functional film manufacturing method is a method for manufacturing a functional film through an application step for applying an inorganic layer forming precursor onto a heat-resistant substrate to form an inorganic layer forming precursor layer, a heat burning step for heat-burning the formed inorganic layer forming precursor layer to form an inorganic layer, a cooling step for cooling the formed inorganic layer, a close attachment step for closely attaching a surface having the inorganic layer of the heat-resistance substrate and a plastic film surface to each other, and a transfer step for transferring the inorganic layer to the plastic film surface after the close attachment, the method being characterized in that the transfer step is performed before the temperature of the heat-resistant substrate drops to 40°C after the cooling step.

Description

Method for producing functional film

The present invention relates to a method for producing a functional film excellent in production efficiency.

Currently, functional films with various functions are widely known. A 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 anti-reflection film, and the like. Examples include a dazzling film, a heat ray 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.

An example of a functional film, a gas barrier film with a metal oxide thin film such as aluminum oxide, magnesium oxide, or silicon oxide formed on the surface of a plastic substrate or plastic film, blocks various gases such as water vapor and oxygen. It is widely used as a packaging application for necessary articles and a packaging application for preventing deterioration due to water vapor, oxygen, etc. of foods, industrial products and pharmaceuticals.

In addition to the above packaging applications, it is also used as an electronic device material such as a liquid crystal display element, a solar cell, and an organic electroluminescence (hereinafter abbreviated as organic EL) substrate.

Hereinafter, a gas barrier film will be described as a representative example of a functional film.

As the gas barrier layer constituting the gas barrier film, generally, a method of forming a silica vapor deposition film using a vacuum vapor deposition apparatus or the like is known. In this vacuum vapor deposition, a large vacuum apparatus or the like is used. In addition, due to restrictions on the equipment to be used, the suitability for continuous production by the roll-to-roll method was poor, and there was a problem in terms of economy and productivity.

As a method for forming a barrier layer other than the above vapor deposition method, for example, JP-A-8-269690 discloses a coating solution containing perhydropolysilazane (hereinafter also referred to as PHPS) or organic polysilazane on a polyester film. A method is disclosed in which PHPS or organic polysilazane is cured and polymerized by plasma treatment to form an inorganic polymer layer made of silicon oxide or the like. However, the inorganic polymer layer formed by the method disclosed in Japanese Patent Application Laid-Open No. 8-269690 is a layer disposed between the base material and the metal vapor deposition layer, and the adhesion between the metal vapor deposition layer and the base material. In addition, it is a layer for imparting chemical stability to the base material, and its effect as a gas barrier layer is low.

Also disclosed is a method for converting a thin film (0.05 to 5 μm) containing PHPS or organic polysilazane as a main component into a dense glass-like layer having transparency and a high barrier property to gas ( For example, see Patent Document 1.) The conversion method described in Patent Document 1 is adapted to the substrate used by irradiation with vacuum ultraviolet light (hereinafter also referred to as VUV) having a wavelength of 230 nm or less and UV light having a wavelength of less than 300 nm. Although a method for performing a treatment time as short as possible (0.1 to 10 minutes) in a temperature range as low as possible is disclosed, in the method disclosed herein, the gas barrier property of the obtained gas barrier layer is as follows: It is insufficient.

On the other hand, the flexible thin film plastic film applied to various electronic devices does not have sufficient gas barrier properties as described above, and when the gas barrier properties are imparted to the plastic film, the gas barrier properties as described above. However, because the plastic film itself has low heat resistance, the gas barrier layer formation is limited by the maximum temperature of the process, and must be kept low. This is a major obstacle in forming the layer. As a result, an electronic device having high reliability using a plastic film has not been realized.

For the above problem, a method is disclosed in which a solution containing, for example, polysilazane or a siloxane polymer is applied on a heat resistant substrate (for example, a glass substrate), an inorganic layer is formed by baking treatment, and then transferred onto a plastic film. (For example, see Patent Document 2). However, in the method described in Patent Document 2, the man-hours for peeling off the formed inorganic layer and the man-hours for adhering to the other substrate are many, the process is complicated, and the production suitability, particularly continuous production. This is a very poor method. In addition, since the conditions in the peeling step and the adhesion step are not strictly controlled, it is difficult to stably form the gas barrier layer.

Therefore, development of a method for producing a functional film having excellent gas barrier properties, transparency and flatness, and having high productivity and production capacity (production speed) is eagerly desired.

Special table 2009-503157 Japanese Patent No. 4974452

The present invention has been made in view of the above problems, and its solution is a functional film excellent in functionality (for example, gas barrier properties), transparency and flatness, without requiring a large facility, It is an easy method to provide a method for producing a functional film that is excellent in economic efficiency and production stability and can be produced at a high production capacity (production speed).

As a result of intensive studies in view of the above problems, the present inventor applied an inorganic layer forming precursor on a heat-resistant substrate to form an inorganic layer forming precursor layer, and then thermally baked the inorganic layer forming precursor layer In the process of cooling the inorganic layer after forming the inorganic layer, the function is achieved by closely contacting and transferring the formed inorganic layer to the plastic film surface under the condition that the temperature of the heat-resistant substrate is equal to or higher than a specific temperature. A functional film, which is characterized by producing a film, is a functional film excellent in functionality (for example, gas barrier properties), transparency and flatness, without requiring large equipment, and simple. It has been found that the method can provide a method for producing a functional film that is excellent in economic efficiency and production stability and can be produced at a high production capacity (production speed).

That is, the above-mentioned problem of the present invention is solved by the following means.

1. A coating step of coating the inorganic layer forming precursor on the heat-resistant substrate to form an inorganic forming precursor layer;
A thermal firing step of thermally firing the formed inorganic layer forming precursor layer to form an inorganic layer;
A cooling step for cooling the formed inorganic layer;
An adhesion process for closely adhering the surface of the heat-resistant substrate having the inorganic layer and the plastic film surface;
A transfer step of transferring the inorganic layer to the plastic film surface after being adhered,
A functional film manufacturing method for manufacturing a functional film via
The method for producing a functional film, wherein the transfer step is performed until the temperature of the heat-resistant substrate is lowered to 40 ° C. after the cooling step.

2. 2. The method for producing a functional film as set forth in claim 1, wherein a maximum temperature reached in the thermal baking step is in a temperature range of 200 to 600 ° C.

3. Having a release layer forming step of forming a release layer on the heat resistant substrate before the coating step of applying the inorganic layer forming precursor on the heat resistant substrate to form the inorganic layer forming precursor layer; A method for producing a functional film according to

item

1 or 2, characterized in that:

4. The method for producing a functional film according to any one of claims 1 to 3, further comprising a film cleaning step of cleaning the transferred inorganic layer surface after the transfer step.

5. The heat-resistant base material is an endless heat-resistant base material that is continuously conveyed, and the coating process, the thermal baking process, the cooling process, the adhesion process, and the transfer process are online processes that are performed by continuously conveying the endless heat-resistant base material. The method for producing a functional film according to any one of Items 1 to 4, wherein the method is characterized.

6. 6. The method for producing a functional film according to claim 5, further comprising a washing step of washing the surface of the endless heat-resistant substrate that is continuously conveyed before the coating step.

7. The method for producing a functional film according to any one of claims 1 to 6, wherein the functional film is a gas barrier film.

By the above means of the present invention, a functional film excellent in functionality (for example, gas barrier property) and transparency is not required for large equipment, and is excellent in economic efficiency and production stability by a simple method, and A method for producing a functional film that can be produced at a high production capacity (production speed) can be provided.

The technical reason why the intended effect of the present invention can be obtained by the configuration defined in the present invention has not been clarified in all the details of the mechanism, but is presumed as follows.

In the method described in Patent Document 2, there are many peeling steps of the formed inorganic layer and adhesion steps to other substrates, and the transfer step of the inorganic layer is complicated, and production suitability, particularly continuous production. The method was extremely poor in suitability. In the present invention, an inorganic layer can be transferred and formed on a plastic film by a simple process flow. In particular, using an endless heat-resistant substrate that is continuously conveyed, it is continuously roll-to-roll. It is optimal as a method for producing a functional film, and the functional film can be produced with extremely high productivity and production efficiency by simple equipment.

Also, after the inorganic layer forming precursor layer is changed to the inorganic layer in the thermal firing process, the transfer is performed within a specific temperature condition range during the cooling process in the process of transferring onto the plastic film in the cooling process of the inorganic layer. As a result, the adhesiveness between the inorganic layer and the plastic film can be increased as compared with the method of transferring the inorganic layer to room temperature and transferring it after cooling or transferring it by reheating after cooling. This is because by transferring at a stage where the temperature is high to a certain degree, the surface activity of the inorganic layer can be in close contact with the plastic film, and softening at the temperature at the close contact with the plastic film. It is estimated that the followability with the heat-resistant base material is improved and the transfer can be stably performed.

Process flow figure which shows an example of the manufacturing process by the single wafer system which is an example of the manufacturing method of the functional film of this invention Graph showing an example of temperature history pattern in each manufacturing process The process flow figure which shows an example of the on-line manufacturing process by the roll-to-roll system which is an example of the manufacturing method of the functional film of this invention

In the method for producing a functional film of the present invention, an inorganic layer forming precursor is applied on a heat resistant substrate to form an inorganic layer forming precursor layer, and then the inorganic layer forming precursor layer is thermally baked to form an inorganic layer. After the formation, in the process of cooling the inorganic layer, a functional film is produced by closely adhering and transferring the formed inorganic layer to the plastic film surface under the condition that the temperature of the heat-resistant substrate is a specific temperature or higher. It is characterized by. This feature is a technical feature common to the inventions according to claims 1 to 7.

As an embodiment of the present invention, from the standpoint that the effects of the present invention can be further manifested, the highest attainable temperature in the thermal firing step is within a temperature range of 200 to 600 ° C. Is preferable from the viewpoint that can be stably formed.

In addition, a release layer forming step of forming a release layer on the heat resistant substrate is performed before the coating step of applying the inorganic layer forming precursor on the heat resistant substrate to form the inorganic layer forming precursor layer. It is preferable from the viewpoint that the inorganic layer can be stably transferred to the plastic film surface side when the formed inorganic layer is transferred in close contact with the plastic film surface.

In addition, after the transfer step, having a film cleaning step for cleaning the surface of the transferred inorganic layer provides a higher quality functional film by removing the release layer remaining on the inorganic layer. From the viewpoint of being able to do so.

In addition, from the viewpoint that the productivity and production efficiency, which are the effects of the present invention, can be further exhibited, the heat-resistant substrate is an endless heat-resistant substrate that is continuously conveyed, and the coating process, the heat-firing process, and the cooling In a more preferred embodiment, the process and the transfer process are online processes in which the endless heat-resistant substrate is continuously conveyed.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the following description, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<< Method for producing functional film >>
In the present invention, as the production process of the functional film, mainly,
(1) A coating step of coating an inorganic layer forming precursor on a heat resistant substrate to form an inorganic layer forming precursor layer,
(2) a thermal firing step of thermally firing the formed inorganic layer forming precursor layer to form an inorganic layer;
(3) a cooling step for cooling the formed inorganic layer;
(4) Adhering step between the surface of the heat-resistant substrate having the inorganic layer and the plastic film surface;
(5) a transfer step of transferring the inorganic layer to the plastic film surface;
The technical feature is that (3) the temperature at which the inorganic layer and the plastic film surface are adhered and transferred in the (4) adhesion step and (5) transfer step after the cooling step. In the cooling step, the heat-resistant substrate is cooled and the temperature is lowered to 40 ° C.

Furthermore, as a manufacturing process constituting the method for manufacturing the functional film of the present invention,
(6) before the adhesion step, an adhesive layer application step of forming an adhesive layer on the plastic film;
(7) Applying an inorganic layer forming precursor on a heat resistant substrate to form an inorganic layer forming precursor layer (1) Forming a release layer that forms a release layer on the heat resistant substrate before the coating step Process,
Can be provided as needed.

Also, it is possible to use a plastic film in which an adhesive layer is previously formed in a separate line.

In the method for producing a functional film of the present invention, the above steps (1) to (7) may be carried out by a batch method (also referred to as a single wafer method or an offline method). Using the endless heat-resistant substrate that is continuously transported as a film and the roll film that is long and continuously transported as a plastic film, the above steps (1) to (7) are performed in a roll-to-roll system (also referred to as an online system). The method of performing is preferable from the viewpoint of realizing high productivity.

《Outline of manufacturing process of functional film》
First, the overall outline of the method for producing the functional film of the present invention by the single wafer method will be described with reference to the drawings. However, the present invention is not limited to the production methods exemplified here.

FIG. 1 shows a single-wafer manufacturing process flow as an example of a method for manufacturing a functional film of the present invention.

In process route 1, which is a process for forming an inorganic layer, the surface of the heat-resistant substrate 1 is subjected to plasma cleaning 2 or the like in step A to clean the surface of the heat-resistant substrate 1. Next, the release layer 3 is formed on the heat-resistant substrate 1 washed in the process B while the heat-resistant substrate 1 is conveyed by the conveyance roller DR using the coater C1. Next, the formed release layer 3 in the wet state is dried in step C using the drying device 4 while blowing warm air 6 from the heating means 5. Next, in Step D, a coating liquid for forming an inorganic layer forming precursor layer is applied on the dried release layer 3 using the coater C2, thereby forming the inorganic layer forming precursor layer 7. The formed heat-resistant substrate 1 inorganic layer forming precursor layer 7 is dried with warm air 6 in the drying step of Step E having the same configuration as Step C. Next, the heat-resistant substrate 1 having the dried inorganic layer forming precursor layer 7 is transferred to the thermal firing step which is Step F, and is heated and heated to a predetermined temperature by the thermal firing member 9 using the thermal firing apparatus 8. Then, the inorganic layer forming precursor layer 7 is subjected to a heat baking treatment to be converted into the inorganic layer 10. The heat-resistant base material 1 converted into the inorganic layer 10 by the heat baking treatment is transferred to the cooling step which is the step G, and the cooling member 12 incorporated in the cooling device 11 is blown with the cold air 13 to start cooling.

On the other hand, in process route 2, in process H. A plastic film 21 constituting a functional film is prepared, and in Step I, an adhesive layer 22 is applied to the surface of the plastic film 21 with a coater C3, and drying is performed in the same manner as in Step C as necessary.

Alternatively, the plastic film 21 with the adhesive layer 22 having the adhesive layer 22 already formed on another line may be used.

Next, in the cooling step of Step G, the temperature (T ₂ ) until the heat-resistant substrate 1 having the inorganic layer 10 is cooled from the heat firing temperature and the temperature of the heat-resistant substrate 1 decreases to reach 40 ° C. Thus, the inorganic layer 10 and the adhesive layer 22 provided on the plastic film 21 produced in the process route 2 are bonded in the process J. Subsequently, in the crimping process of the process K, it crimps | bonds using the nip roller 14 grade | etc., And the adhesive layer 22, the inorganic layer 10, and the release layer 3 are comprised on the heat-resistant base material 1 and the plastic film 21 by the process M. The functional film unit 15 is separated.

洗浄 The separated functional film unit 15 is subjected to a cleaning process on the film surface in Step N to remove an unnecessary release layer, thereby producing the functional film unit 15.

《Functional film manufacturing process flow》
Next, details of each step shown in FIG. 1 will be described.

[Process route 1]
(Process A: Heat-resistant substrate surface cleaning process)
In step A shown in FIG. 1, the surface of the heat-resistant substrate 1 on which the inorganic layer is formed is subjected to a cleaning process.

As the heat resistant substrate 1 applicable to the present invention, a metal substrate excellent in heat resistance is preferable, and for example, nickel, stainless steel (SUS), carbon steel, titanium alloy and the like can be used.

The thickness of the heat-resistant substrate is preferably configured within a range of 0.3 to 2.0 mm.

As the cleaning treatment means 2 for the surface of the heat-resistant substrate 1, known cleaning means such as a plasma cleaning method and a dry ice cleaning method can be applied.

For example, atmospheric pressure plasma is suitably used as a cleaning treatment condition by the plasma cleaning apparatus. Examples of the cleaning conditions include conditions in which a cleaning surface modification treatment is performed using a nitrogen gas containing 1 to 20% by volume of oxygen, a frequency of 100 kHz to 150 MHz, a voltage of 10 V to 10 kV, and an irradiation distance of 5 to 20 mm. As the plasma cleaning apparatus, for example, an atmospheric pressure plasma surface treatment apparatus AP Plasma manufactured by E-square Co., Ltd. using a dielectric barrier discharge downstream type plasma head can be mentioned.

(Process B: Application process of release layer forming coating solution)
Next, while transporting the heat-resistant substrate 1 whose surface has been cleaned in the above step A with the transport roller DR, a release layer forming coating solution is applied onto the heat-resistant substrate 1 using the coater C1, and the wet state A release layer 3A is formed.

The material constituting the release layer 3 according to the present invention is not particularly limited as long as it is a material having a release function, but polyvinyl pyrrolidones (including vinyl pyrrolidone polymers) are preferably used. 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 polyvinyl pyrrolidone include a polyvinyl pyrrolidone single polymer. The polyvinyl pyrrolidone preferably has a viscosity average molecular weight of 5000 to 50000. 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 polyvinyl pyrrolidone is dissolved in an appropriate solvent, for example, an organic solvent such as water or alcohol to prepare a release layer forming coating solution.

The coater C1 used in the step B 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.

Further, the temperature at the time of application of the release layer forming coating liquid is not particularly limited, and can be carried out by appropriately selecting an optimum temperature.

In the present invention, the layer thickness of the release layer 3 is not particularly limited, but the layer thickness after the process C (drying process-1) shown below is within a range of about 0.2 to 10 μm. Yes, preferably in the range of 0.5 to 5.0 μm, more preferably in the range of 1.0 to 3.0 μm.

(Process C: Drying process-1)
The wet release layer 3 </ b> A formed on the heat-resistant substrate 1 in the step B is dried using the drying device 4 to form the release layer 3.

Examples of the drying apparatus 4 that can be applied in the process C include a heating apparatus such as a warm air heating method or a heater heating method (for example, a panel heater, a halogen heater, or the like).

The heating means 5 constituting the specific drying apparatus 4 includes a heater heating method (for example, a method in which infrared heaters, halogen heaters, panel heaters and the like are installed above and below the heat-resistant substrate 1 and heated by radiant heat), a heat-resistant group As a transport roller (not shown) for transporting the material 1, a method of heating using a heat roller, a hot air heating method (for example, temperature-controlled hot air is blown from the top and bottom of the heat-resistant substrate 1, and a release layer In the present invention, the hot air heating method is preferable because temperature control can be performed with high accuracy.

1 shows an example of the hot air heating method. In Step C of FIG. 1, the heat-resistant substrate 1 on which the wet release layer 3 </ b> A is formed in Step B is transferred to the drying device 4 by the transport roller DR. The drying device 4 is provided with heating means 5 on the upper part (the release layer 3 surface side) and the lower part (the back surface side of the heat resistant base material 1) of the heat resistant base material 1, respectively. Is sprayed to dry the release layer 3.

(Process D: Coating process of coating solution for forming inorganic layer forming precursor layer)
Next, in Step D, a coating liquid for forming the inorganic layer forming precursor layer is applied on the release layer 3.

In FIG. 1, a coating liquid for forming an inorganic layer forming precursor layer using a coater C2 is applied on the release layer 3 of the heat-resistant substrate 1 conveyed by a conveyance roller (not shown) or the like from the process C. Thus, the wet inorganic layer forming precursor layer 7A is formed.

The inorganic layer forming precursor contained in the inorganic layer forming precursor layer 7 (7A) is a material that is converted into an inorganic layer by heat treatment in the subsequent heat firing step (step F). Materials 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 the like as the SiO ₂ precursor.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond in the structure, and has SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and an intermediate between them. a polymer made of ceramic precursor inorganic polymer such as a solid solution SiO _x N _y as a precursor of silicon oxide nitride, for example, a unit represented by the following general formula described in JP-a-8-112879 (1) 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 preferred from the viewpoint of the denseness as the gas barrier layer to be obtained.

In addition, organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an alkyl group such as a methyl group, thereby improving the adhesiveness with the release layer 3 which is an underlayer. 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. The number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), 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 polysilazanes obtained by reacting glycidol (see, for example, JP-A-6-122852), and alcohol-added polysilazanes obtained by reacting with alcohol (see, for example, JP-A-6-6 240208), obtained by reacting a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (see, for example, JP-A-6-299118), and an acetylacetonate complex containing a metal. Acetylacetonate complex-added polysilazane ( In example, JP-A 6-306329 JP reference.), Fine metal particles of the metal particles added polysilazane obtained by adding (e.g., JP-A-7-196986 JP reference.), And the like.

In the polysilazane-containing coating solution, amines or metal catalysts can 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 Co., Ltd.

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.

(Polysiloxane with terminal Si-H)
An example of a polysiloxane having a methyl group as an organic group and terminated with Si—H is represented by the following general formula (2). The organic group may be other than a methyl group, for example, a phenyl group, or may be different such that each organic group is mixed.

(Polysiloxane with terminal Si-OH)
An example of a polysiloxane having a methyl group as an organic group and terminated with Si—OH is represented by the following general formula (3). The organic group may be other than a methyl group, for example, a phenyl group, or may be different such that each organic group is mixed.

(Polysiloxane with Si-H in the side chain)
An example of a polysiloxane having a methyl group as an organic group and Si—H in the side chain is represented by the following general formula (4). The organic group may be other than a methyl group, for example, a phenyl group, or may be different such that each organic group is mixed.

In the above general formula (4), when m + n = 100, n is in the range of 1 to 100, preferably 30 to 100, and more preferably 50 to 100.

Examples of the glass frit and glass paste include powder glass manufactured by AGC Electronics (for example, trade names: ASF series, SK-231-300, KF 9173, LS-5-300M, etc.) and glass paste (AP series, etc.). And the like.

In addition to the above polymer compounds, organic compounds containing the following metal elements can be exemplified.

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

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

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

Examples of aluminum compounds include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyldialuminum tri-s-butoxide. Can be mentioned.

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 the step B can be used.

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

(Process E: Drying process-2)
The wet inorganic layer forming precursor layer 7 </ b> A formed on the heat-resistant substrate 1 in the step C is dried using the drying device 4 to form the inorganic layer forming precursor layer 7.

As the drying apparatus 4 applicable in the process E, the same apparatus as the drying apparatus 4 described in the above-mentioned process C can be exemplified.

(Process F: Thermal firing process)
In the process F, the inorganic layer forming precursor layer 7 formed in the process E is subjected to a heat baking treatment to be modified into a gas barrier layer composed of the inorganic layer 10, for example, SiO ₂ .

In the thermal baking process which is the process F, the thermal baking apparatus 8 is used to apply high-temperature thermal energy to the inorganic layer forming precursor layer 7 formed of, for example, polysilazane or the like, and is composed of SiO ₂ or the like. The inorganic layer 10 is formed. As the thermal baking apparatus 8, a plurality of thermal baking members 9 are provided therein, and the inorganic layer forming precursor layer 7 is heated and converted into the inorganic layer 10 according to a preset temperature history.

As shown in FIG. 1, the plurality of heat-fired members 9 may be disposed on both surfaces of the heat-resistant substrate 1 or may be disposed only on the surface side having the inorganic layer forming precursor layer 7. Also good.

The heating temperature by the plurality of heat-fired members 9 can be controlled independently, and each heat-fired member 9 is set to an optimum heating temperature so as to have a heating profile as shown in FIG. .

The thermal firing temperature is not particularly limited, but the highest temperature is preferably in the temperature range of 200 to 500 ° C.

Although not shown in FIG. 1, the thermal baking apparatus is equipped with a thermometer, for example, a non-contact type reflection thermometer, and constantly monitors the temperature of the heat-resistant substrate surface during the thermal baking process. Is a preferred embodiment.

Specific examples of the baking apparatus 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 processing. As the near-infrared baking apparatus, for example, an NIR lamp manufactured by Adphos Corporation can be used. The NIR lamp made by Adphos is a lamp having a wavelength range of 800 to 1500 nm in the near infrared region and a maximum wavelength at 850 nm, and evenly to the inside of the heating object (inorganic layer forming precursor layer 7). Since the heat rays reach, the inorganic layer 10 in which the entire film is uniformly converted into the inorganic film can be formed by allowing the heat energy to pass through the inorganic layer forming precursor layer 7 uniformly at high speed. When such an NIR lamp is applied, the NIR lamp that is the thermal firing member 9 may be arranged only on one surface side having the inorganic layer forming precursor layer 7.

In the present invention, before the inorganic layer forming precursor layer 7 is subjected to heat treatment in the thermal baking step, for example, before ultraviolet rays, visible rays, infrared rays, ultrasonic waves, plasma discharges, corona discharges, microwaves, etc. Processing may be performed.

(Process G: Cooling process)
The process G is a process of cooling the heat-resistant substrate 1 heated to a high temperature in the process F, which is a previous process.

Specifically, as shown in FIG. 1, in the cooling device 11, a cooling member 12 is disposed on both sides of the heat-resistant substrate 1, and a cold air 13 or the like is blown to the heat-resistant group having the inorganic layer 10. The material 1 is cooled to a predetermined temperature.

In this cooling process (process G), it cools to the temperature at the time of bonding with the plastic film 21 mentioned later at the bonding process (process J) which is a next process. In this invention, bonding is performed at the temperature of 40 degreeC or more of the temperature of a heat-resistant base material. More specifically, the bonding temperature is preferably in the range of 60 to 200 ° C, more preferably in the range of 100 to 150 ° C.

The cooling means that can be applied in the cooling step includes a cooling method using a water cooling roller or a chill roller, a cooling method using cold air, and the like, but is not limited thereto.

Although not shown in FIG. 1, the cooling device is equipped with a thermometer, for example, a non-contact type reflection thermometer, and the temperature of the heat-resistant substrate surface during the cooling process can be constantly monitored. This is a preferred embodiment.

[Process route 2]
(Process H: Preparation of plastic film)
The plastic film 21 on the transfer side is preferably a transparent transparent plastic film. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose Acetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetates such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, Syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyester Imide, polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (manufactured by JSR) or Appel (Mitsui) And cycloolefin-based resins.

(Process I: Adhesive layer application process)
Step I is a step of applying an adhesive layer 22 on the prepared plastic film 21 by a wet coating method. After applying the adhesive layer 22, a drying step as described in the above-described step C may be provided as necessary.

The adhesive layer 22 is preferably formed of a resin component, for example, polyester resin, urethane resin, acrylic resin, melamine resin, epoxy resin, polyamide resin, vinyl chloride resin, and vinyl chloride. A single resin such as a vinyl acetate 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 22 may be composed of only one layer or may be composed of a plurality of layers. The thickness of the adhesive layer 22 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 a wet coating apparatus.

In addition, the application temperature of the adhesive layer is not particularly limited, and an optimum temperature condition can be appropriately selected within a temperature range of 20 to 50 ° C.

[Process route 3]
(Process J: Pasting process)
In the bonding step, which is the step J, the heat-resistant substrate 1 having the inorganic layer 10 cooled after the thermal baking treatment in the cooling step of the step G, and the plastic film 21 provided with the adhesive layer 22 in the step I. It is a process of bonding.

Bonding is performed after arranging the inorganic layer 10 provided on the heat-resistant substrate 1 and the adhesive layer 22 formed on the plastic film 21 to face each other.

In the present invention, as described above, the temperature at which the two are bonded is performed under a temperature condition in which the temperature of the heat-resistant substrate 1 is 40 ° C. or higher. More specifically, as described above, the bonding temperature is preferably in the range of 60 to 200 ° C., and more preferably in the range of 100 to 150 ° C.

In this invention, the adhesiveness of an inorganic layer and a plastic film can be made high by bonding the heat resistant base material 1 and the plastic film 21 on the temperature conditions whose temperature of the heat resistant base material 1 is 40 degreeC or more. I guess. This is because adhesion and transfer at a certain high temperature level allow the inorganic layer 10 to be in close contact with the plastic film 21 with extremely high surface activity, and the plastic film 21 is softened at the temperature at the time of adhesion. By doing so, the followability with the heat-resistant substrate 1 is improved, it is possible to suppress defects such as wrinkles and unevenness at the time of transfer, and it is assumed that transfer can be performed stably.

Although the same effect as described above can be obtained by the method of reheating after cooling, since the reheating process is provided, the production line from the formation of the inorganic layer to the transfer becomes longer, and there is an opportunity for foreign matters to adhere to the surface of the inorganic layer 10. Increase. If such foreign matter adheres to the surface of the inorganic layer, the inorganic layer 10 is crushed by the attached foreign matter during transfer, resulting in a point failure, which is not a preferable method. The method is extremely excellent in obtaining a high-quality functional film.

(Process K: Crimping process)
In order to completely bond the unit A composed of the heat-resistant substrate 1 having the inorganic layer 10 simply bonded in the process J and the plastic film 21 having the adhesive layer 22, a pressure-bonding process is performed.

As a method of performing the pressure-bonding treatment, the unit A produced as described above is pressure-conveyed between the nips using the nip

rollers

14 and 14 ′ and is pressure-bonded. At this time, the nip rollers 14 and 14 'can be heated as necessary.

As the nip rollers 14 and 14 ', a rubber roller and a metal roller can be combined, or a rubber roller and a rubber roller can be combined.

(Process M: peeling process)
The unit A subjected to the pressure-bonding process in the process K is peeled off. There is no restriction | limiting in particular as peeling operation, A force is applied to the upper and lower sides of the unit A, and from the unit A, from the heat-resistant base material 1, the plastic film 21, the adhesive layer 22, the inorganic layer 10, and the release layer 3 (part). Separated into gas barrier film laminates to be constructed.

(Process N: Film surface cleaning process)
Next, in order to remove the release layer 3 adhering to the surface of the gas barrier film laminate composed of the peeled plastic film 21 / adhesive layer 22 / inorganic layer 10 / release layer 3 (part). The film surface cleaning process is performed to produce a gas barrier film unit 15 which is an example of a functional film.

As the film surface cleaning treatment, for example, an atmospheric pressure plasma surface treatment apparatus AP Plasma manufactured by E Square Co., Ltd. using the above-described dielectric barrier discharge downstream type plasma head can be mentioned.

In addition, as other surface cleaning methods, the following methods can be exemplified.

The first method is a method called a dry cleaning method (dry cleaning method). In addition to the plasma cleaning method described above, an ion beam cleaning method, a UV ozone cleaning method, a UV excimer irradiation method, a laser cleaning method, and the like can be given. .

The second method is a method called a wet cleaning method (wet cleaning method). After immersing a substrate having a gas barrier layer in a liquid, for example, jet cleaning, bubbling cleaning, ultrasonic cleaning, running water cleaning, or the like is used. This is a method of cleaning. Although this wet cleaning method exhibits a certain level of detergency, it requires a drying step after that, and thus has a problem that the processing time becomes long.

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 gas barrier layer 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 gas barrier layer, they have the feature that their cleaning power (foreign matter removal rate) is extremely high and the processing time is short. is doing.

<< Temperature pattern of process in the production of functional film >>
FIG. 2 shows a typical temperature history pattern in the functional film manufacturing process described above.

FIG. 2 mainly shows a temperature history pattern of the heat-resistant substrate 1 from the process B (release layer application process) to the process J (bonding process).

In step B, which is a step of forming the release layer 3A in a wet state, the heat-resistant substrate 1 has the same temperature as the release layer forming coating solution. Next, in step C (drying step 1), the heat-resistant substrate 1 is heated to a higher temperature by the heat drying step. Next, in Step D, the coating liquid for forming the inorganic layer forming precursor layer is applied, but the coating may be performed as it is at the temperature of Step C, which is the previous step, or after cooling once after Step C, the inorganic layer is formed. You may apply | coat the coating liquid which forms a layer formation precursor layer. Next, after performing a drying process again in the process E, a heat baking process is performed as the process F. In step F, examples of the temperature rising pattern up to a desired thermal firing temperature include a method of increasing the temperature at a constant temperature increase rate and a method of increasing the temperature stepwise in block units. At this time, it is preferable that the maximum temperature T _max in the process F is in a temperature range of 200 to 600 ° C. The time T for maintaining the maximum temperature T _max can be set as appropriate.

Note that, if necessary, the step E (drying step) may be omitted, and after applying the coating liquid for forming the inorganic layer forming precursor layer in the step D, the thermal baking treatment may be directly performed in the step F. good.

When the thermal baking process is completed in the process F, a cooling process is performed in the process G. In the present invention, the process is not performed until room temperature (T ₁ ) and the heat-resistant substrate 1 is still heated, that is, under the temperature condition of 40 ° C. (T ₂ ) or more as the heat-resistant substrate 1. Perform the bonding process.

《Online manufacturing method of functional film》
In FIG. 1, an example of a method for producing a functional film by a single-wafer method is shown. However, in the present invention, from the viewpoint of realizing higher productivity (production speed), as shown in FIG. 3. An on-line manufacturing method based on a roll-to-roll method is more preferable.

FIG. 3 is a process flow diagram showing an example of an on-line manufacturing process using a roll-to-roll method, which is an example of a method for manufacturing a functional film of the present invention.

Note that each device shown in FIG. 3 has the same configuration as that of each device described in FIG. 1, and description thereof is omitted here, and only the feature points of the process flow are described.

In the process route 1 for forming the inorganic layer 10 on the heat-resistant substrate 1, an endless heat-resistant substrate 1 (hereinafter also referred to as an endless belt 1A), for example, a stainless steel casting belt, is held by the support roller SR and supported. While a part of the roller SR functions as a driving roller, it is conveyed endlessly. In step A, after the endless belt 1 is cleaned, the back surface of the endless belt is not supported by the support roller SR in step B. Therefore, the release layer coating solution is supplied by the coater C1 to release the wet state. After forming the mold layer 3 </ b> A, drying is performed by the drying device 4 in Step C to form the release layer 3. Next, in Step D, the coating liquid for forming the inorganic layer forming precursor layer 7A was supplied onto the release layer 3 from the coater C2, and then dried in Step E to form the inorganic layer forming precursor layer 7. Thereafter, a thermal baking treatment is performed in Step F to modify the inorganic layer forming precursor layer 7 to the inorganic layer 10. Next, in step G, the endless belt 1 heated at a high temperature is cooled, and the temperature of the endless belt 1 is monitored with a surface thermometer installed at the exit of the step G, but the temperature of the endless belt 1 is 40 ° C. or higher. Then, it is unloaded from the cooling device 11.

On the other hand, in the process route 2, the plastic film 21 is unloaded from the long laminating roller at the original unwinding part (unwinder part) UW, and the adhesive layer coating solution is applied onto the plastic film 21 from the coater C3 in the process I. , And the adhesive layer 22 is formed, followed by drying with the drying device 4.

Next, the inorganic layer surface on the heat-resistant substrate 1 produced in the process G of the process route 1 and controlled to a temperature of 40 ° C. or higher, and the adhesive layer surface on the plastic film 21 produced in the process route 2 are combined in the process route 3. After bonding in step J, niping and pressing with support roller SR and back roller BR in step K, 1 unit of heat-resistant substrate and 21 units of plastic film are separated from each other in step M, whereby a heat-resistant substrate is obtained. The inorganic layer and the release layer formed on 1 are transferred onto the adhesive layer of the plastic film 21. In the above process, the processes J, K and M are performed almost simultaneously.

Next, in Step N, the release layer residue adhering to the outermost surface of the plastic film 21 is removed by a film surface cleaning process. Furthermore, after application of other functional layers in the process P, for example, formation of a protective layer and the like, and drying in the process Q as necessary, the film is wound by a winding part (winder part) W. In addition, you may perform the process P which forms another functional layer in another line.

<< Embodiment of the manufacturing method of a functional film >>
The functional film of the present invention can be manufactured by the following embodiment, but the present invention is not limited to the manufacturing method exemplified here.

The specific method will be described by taking the roll-to-roll method on-line manufacturing method shown in FIG. 3 as an example.

Step A: Cleaning the surface of the heat-resistant substrate On the surface of the stainless steel casting belt that is continuously transporting the heat-resistant substrate 1, as a plasma cleaning device 2, an atmospheric pressure plasma surface treatment device AP Plasma manufactured by E-Square Co., Ltd. The surface was cleaned by plasma irradiation.

Step B and Step C: Mold Release Layer Formation and Drying Next, using a slot die coater (corresponding to C1) on the stainless steel casting belt continuously conveyed in Step B, polyvinyl pyrrolidone (PVP) as a release agent. ) Was applied to a dry film thickness of 1.5 μm and dried in Step C to form a release layer 3.

Step D and Step E: Application and Drying of Inorganic Layer Forming Precursor Layer In Step D, perhydropolysilazane (PHPS) is used as polysilazane as a coating liquid for forming the inorganic layer forming precursor layer 7 on the release layer 3. The film was applied using a slot die coater (corresponding to C2) under the condition that the film thickness after drying was 50 nm, and then dried in Step E.

Step F: Thermal Firing Step Next, in Step F, an NIR lamp manufactured by Adphos is used as the thermal firing device 8 and heated at 280 ° C. for 1 minute, and then heated at 500 ° C. for 3 minutes as the maximum temperature (T _max ). Then, the inorganic layer forming precursor layer 7 was modified to form the inorganic layer 10.

Step G: Cooling Step Next, in the cooling step, cold air was blown from both sides of the casting belt to cool the heat-resistant substrate 1 to 120 ° C.

Step I: Formation of Adhesive Layer Separately, in Process Route 2, a polyethylene terephthalate (PET) film having a thickness of 100 μm as a plastic film 21 and an adhesive for gas barrier dry laminate epoxy resin as an adhesive “MAXIVE (registered trademark)” “Mitsubishi Gas Chemical Co., Ltd.” was applied at a thickness of 10 μm and dried to form an adhesive layer 22.

Steps J, K, M: Pasting and Separation Next, the cooling step was passed, and the casting belt having a substrate temperature of 120 ° C. and the PET film were pasted with the inorganic layer and the adhesive layer facing each other. Subsequently, both base materials were separated and the release layer 3 and the inorganic layer 10 on the heat-resistant base material 1 were transferred onto the PET film.

Step N: Film cleaning step Next, the surface of the transferred PET film is subjected to a plasma cleaning treatment for 1 minute using an atmospheric plasma surface treatment apparatus AP Plasma manufactured by E-Square Co., Ltd., and remains on the surface. The release agent (polyvinyl pyrrolidone) was removed, and the gas barrier film unit 15 was produced.

<Characteristic evaluation of gas barrier film unit>
About the produced gas barrier film unit, according to the following method, gas barrier property, transparency, and planarity are evaluated, and the obtained result is shown.

[Evaluation of gas barrier properties (evaluation of water vapor barrier properties)]
About the produced gas barrier film unit, the water vapor | steam barrier property was evaluated in accordance with the following method.

(Water vapor barrier property evaluation sample preparation device)
Vapor deposition equipment: JEE-400 vacuum vapor deposition equipment 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)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was deposited in a size of 12 mm × 12 mm through the mask on the inorganic layer forming surface of the produced gas barrier film unit. At this time, the deposited film thickness was set to 80 nm.

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

The obtained sample was stored under high temperature and high humidity of 60 ° C. and 90% RH, and the state of metallic calcium corroding with respect to the storage time was observed. Observation is performed every hour for up to 6 hours, every 3 hours for up to 24 hours, every 6 hours for up to 48 hours thereafter, and every 12 hours thereafter, a 12 mm x 12 mm metal The area where metallic calcium corroded relative to the calcium deposition area was calculated in%. The time when the area where the metal calcium corrodes becomes 1% is obtained by interpolating from the observation result by a straight line, and the metal calcium vapor deposition area, the amount of water vapor corroding the metal calcium for the area of 1%, and the time required for it. From the relationship, the water vapor transmission rate of each gas barrier film unit was calculated.

As a result of the above measurement, the water vapor permeability of the produced gas barrier film unit was 2.0 × 10 ⁻⁴ g / (m ² · 24 h).

(Evaluation of transparency)
With respect to the produced gas barrier film unit, the visible light transmittance was measured using a spectrophotometer V-570 (manufactured by JASCO Corporation). As a result, the transmittance at 590 nm was 92%.

(Evaluation of flatness)
The gas barrier film unit produced above was cut into a size of 00 mm × 100 mm, stored for 24 hours in an environment of 40 ° C. and 90% RH, and then stored for 2 hours in an environment of 40 ° C. and 10% RH. A test was conducted. Next, the gas barrier film unit was moved to an environment of 23 ° C. and 55% RH, placed on a flat quartz plate, and the average value of the height of lifting from the quartz plate surface at the four corners was measured. As a result of evaluating the flatness of the gas barrier film unit, the evaluation rank was “◯”.

A: The average value of the average lift height at the four corners is less than 1.0 mm. O: The average value of the average lift height at the four corners is 1.0 mm or more and less than 2.0 mm. The average value of the average lift height is 2.0 mm or more and less than 5.0 mm, but it is a quality that is practically acceptable. X: The average value of the average lift height of the four corners is 5.0 mm or more As described above, the functional film (gas barrier film unit) produced by the method for producing a functional film of the present invention has gas barrier properties (water vapor barrier properties), transparency and flatness. It was confirmed that it was excellent in performance.

The method for producing a functional film of the present invention is a functional film excellent in functionality (for example, gas barrier properties), transparency and flatness, without requiring large equipment, in a simple manner, economically and It has excellent production stability and can be produced at a high production capacity (production speed), and the functional film obtained thereby can be used for packaging products that require the blocking of various gases such as water vapor and oxygen, and for foods. It can be suitably used as a packaging application for preventing alteration of industrial articles and pharmaceuticals, and as an electronic device material such as a liquid crystal display element, a solar cell, and an organic electroluminescence substrate.

DESCRIPTION OF SYMBOLS 1 Heat-resistant base material 1A Endless belt 2 Plasma cleaning 3A Wet release layer 3 Release layer 4 Drying device 5 Heating means 6 Hot air 7A Wet inorganic layer formation precursor layer 7 Inorganic layer formation precursor layer 8 Thermal firing Device 9 Heat-fired member 10 Inorganic layer 11 Cooling device 12 Cooling member 13 Cold air 14, 14 'Nip roller 15 Gas barrier film unit 21 Plastic film 22 Adhesive layer C1, C2, C3, C4 Coater BR Back roller DRU Dancer roller unit SR Support Roller UW Unwinder W Winder

Claims

On the heat-resistant substrate, an application step of applying an inorganic layer forming precursor to form an inorganic layer forming precursor layer,
A thermal firing step of thermally firing the formed inorganic layer forming precursor layer to form an inorganic layer;
A cooling step for cooling the formed inorganic layer;
An adhesion process for closely adhering the surface of the heat-resistant substrate having the inorganic layer and the plastic film surface;
A transfer step of transferring the inorganic layer to the plastic film surface after being adhered,
A functional film manufacturing method for manufacturing a functional film via
The method for producing a functional film, wherein the transfer step is performed until the temperature of the heat-resistant substrate is lowered to 40 ° C. after the cooling step.
2. The method for producing a functional film according to claim 1, wherein the highest ultimate temperature of the heat resistant substrate having the inorganic layer forming precursor layer in the thermal baking step is within a temperature range of 200 to 600 ° C. .
Having a release layer forming step of forming a release layer on the heat resistant substrate before the coating step of applying the inorganic layer forming precursor on the heat resistant substrate to form the inorganic layer forming precursor layer; The method for producing a functional film according to claim 1 or 2, wherein:
The method for producing a functional film according to any one of claims 1 to 3, further comprising a film cleaning step of cleaning the transferred inorganic layer surface after the transfer step.
The heat-resistant base material is an endless heat-resistant base material that is continuously conveyed, and the coating process, the thermal baking process, the cooling process, the adhesion process, and the transfer process are online processes that are performed by continuously conveying the endless heat-resistant base material. The manufacturing method of the functional film as described in any one of Claim 1 to 4 characterized by the above-mentioned.
6. The method for producing a functional film according to claim 5, further comprising a washing step of washing the surface of the endless heat-resistant substrate that is continuously conveyed before the coating step.
The method for producing a functional film according to any one of claims 1 to 6, wherein the functional film is a gas barrier film.