JP6428633B2 - Film forming apparatus and film forming method - Google Patents

Description

  The present invention relates to a film forming apparatus and a film forming method used for forming a functional layer on a flexible resin substrate by a roll-to-roll method, and more specifically, it is possible to oxidize with oxygen plasma under reduced pressure. As a chemical deposition method for forming a film on a flexible resin substrate, a plasma CVD method (Chemical Vapor Deposition) is used to form a functional layer having excellent film formation stability, gas barrier properties, and film surface uniformity. The present invention relates to an apparatus and a film forming method.

  At present, functional films having various functions are widely known. A functional film is a film in which a functional layer, which is a constituent layer having various functions, is provided on a flexible resin substrate. For example, a gas barrier film, an antireflection film, an antiglare film, etc. Examples thereof include a heat-resistant film, a heat ray shielding film, a transparent conductive film, a moisture-proof film, an ultraviolet deterioration preventing film, a light diffusion film, a weather resistant film, and an antibacterial film.

  An example of a functional film is a gas barrier film in which a thin film (gas barrier layer) of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a film-like resin substrate. It is widely used as a harmful gas barrier film used to block gases that affect various qualities such as, and a packaging film for preventing deterioration of foods, industrial products, pharmaceuticals, and the like.

  In addition to the above packaging applications, it is mainly used as a sealing member for electronic device materials such as liquid crystal display elements, solar cells, and organic electroluminescence (hereinafter abbreviated as organic EL) substrates.

  Hereinafter, a method for producing a gas barrier film will be described as a representative example of the functional film.

  As a method of forming a gas barrier layer constituting a gas barrier film, a method of forming a silica vapor deposition film using a vacuum vapor deposition apparatus or the like is generally known. This vacuum vapor deposition is a large vacuum. The apparatus is required, and further, continuous production by the roll-to-roll method is difficult due to restrictions on the equipment configuration to be used, and there are problems in terms of economy and productivity.

  As a method for forming a gas barrier layer by a method other than the above vacuum vapor deposition method, for example, in JP-A-8-269690, a coating liquid containing perhydropolysilazane or organic polysilazane is applied to a polyester film, and plasma is applied. A method of forming a polymer layer composed of silicon oxide or the like by polymerizing and curing perhydropolysilazane or organic polysilazane by treatment is disclosed. However, the polymer layer formed by the method disclosed in Japanese Patent Application Laid-Open No. 8-269690 functions as an intermediate layer between the base material and the metal vapor deposition layer. This is a layer for imparting chemical stability of the material, and its function as a gas barrier layer is low.

In view of the above problems, Patent Document 1 forms a gas barrier layer of 1 × 10 ⁻⁴ g / m ² · day level by a roll-to-roll method using a plasma CVD apparatus equipped with opposing roller electrodes. A manufacturing method is disclosed. The gas barrier film produced by the method described in Patent Document 1 is characterized by applying a CVD method in which a large number of carbon atoms can be arranged around the substrate, and has adhesion and flexibility with the substrate. However, in electronic device applications such as organic EL elements used in harsh outdoor environments of high temperature and high humidity, the obtained gas barrier properties, adhesion, and flexibility are insufficient. It turned out to be.

  Furthermore, in a method of forming a gas barrier layer while continuously transporting a resin base material in a roll-to-roll system as disclosed in Patent Document 1, from a state in which a long resin film is laminated in a roll shape, When the resin base material is fed out (hereinafter referred to as an unwinder part or UW part), peeling electrification occurs when the laminated resin base material is fed out, and the charged electric charge causes the resin base material. Alternatively, the formed functional layer may be damaged.

  In order to solve such problems, attempts have been made in recent years to form a conductive antistatic layer on one side of a resin substrate. By forming the antistatic layer on the resin substrate, the electric charge generated by the peeling of the UW part is removed, but a functional layer, for example, a gas barrier layer is formed on the resin substrate having the antistatic layer. When the plasma CVD process is applied to the electrode, the plasma intensity in the discharge space formed between the opposing roller electrodes decreases, becomes nonuniform, or the plasma intensity is biased, and the thin film to be formed, for example, the nonuniformity of the gas barrier layer, In the method described in Document 1, the element distribution profile in the functional layer, for example, the carbon atom distribution varies from the designed conditions, has a predetermined element distribution, and has adhesion and flexibility with a resin substrate. It has been found that there is a problem that it is impossible to obtain a functional film excellent in.

  Therefore, in the thin film formation method of forming a functional layer on a resin substrate stably and under a desired configuration condition by a plasma CVD method using a resin film having an antistatic layer on at least the back surface, Development of a method capable of satisfying both a function of preventing the peeling charge by the provided resin film and a function of suppressing a decrease in plasma intensity associated with insulation of a guide roller that holds and transports the resin film is eagerly desired.

WO2012 / 046767

  The present invention has been made in view of the above problems, and a solution to the problem is to form a functional layer on a flexible resin substrate by a roll-to-roll method using a plasma CVD method. To provide a film forming apparatus and a film forming method for forming a functional layer having excellent stability, gas barrier properties, and film surface defect resistance.

  As a result of diligent investigation in view of the above problems, the present inventors have found that a functional layer is formed by a plasma CVD treatment method on a flexible resin substrate having an antistatic layer by a roll-to-roll method. However, at least one of the four guide rollers positioned at the closest distance on the upstream side and the downstream side in the conveyance direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing unit. Function that is excellent in film formation stability, gas barrier property, and film surface defect resistance by using an electrically insulating roller and using a conductive roller as the guide roller located at the closest distance to the unwinder or winder unit The present inventors have found that a conductive layer can be formed, and have reached the present invention.

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

1. A film forming apparatus that forms a functional layer on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers in a roll-to-roll system under reduced pressure,
At least an unwinder portion for feeding out a flexible resin base material laminated in a roll shape;
A plasma CVD processing unit comprising a pair of opposed roller electrodes and forming a functional layer on the flexible resin substrate in a discharge space formed between the roller electrodes;
It has a winder part that winds up a flexible resin base material on which a functional layer is formed,
The flexible resin base material that is continuously conveyed has an antistatic layer on the surface (B surface) opposite to the surface (A surface) on which the functional layer is formed,
All of the four guide rollers located at the closest distance on the upstream side and the downstream side in the conveyance direction of the flexible resin base material are electrically connected to the pair of roller electrodes constituting the plasma CVD processing unit. It is composed of insulating rollers with insulating properties ,
The relative unwinder unit or the winder unit, a guide roller which is located closest, electrically deposition apparatus characterized in that it is made of a conductive roller having conductivity.

2 . The insulating roller, the film forming apparatus according to paragraph 1, characterized in that the rollers provided with the ceramic bearings rubber-coated roller or core.

3 . The film forming apparatus according to item 1 or 2 , wherein the conductive roller is a metal roller.

4 . Said flexible resin substrate has a clear hard coat layer on the surface A side, one on the clear hard coat layer, the first term and forming the functional layer to the third term The film forming apparatus according to claim 1.

5 . The film deposition apparatus according to any one of Items 1 to 4 , wherein a gas barrier layer is formed as the functional layer on the flexible resin base material.

6 . A film forming method in which a functional layer is formed by a plasma CVD processing method having a plasma CVD processing section on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers in a roll-to-roll system under reduced pressure. There,
The flexible resin base material has an antistatic layer on the surface (B surface) opposite to the surface (A surface) forming the functional layer,
The plasma CVD processing unit forms a plasma discharge space by applying a voltage between a pair of opposed roller electrodes, and forms a functional layer on the flexible resin substrate in the plasma discharge space,
All of the four guide rollers located at the closest distance on the upstream side and the downstream side in the conveyance direction of the flexible resin base material are electrically connected to the pair of roller electrodes constituting the plasma CVD processing unit. to constitute an insulating roller having an insulating property, to form the functional layer in the plasma CVD processing unit,
Electrically conducting the guide roller located at the closest distance to the unwinder part that feeds out the flexible resin base material laminated in a roll shape or the winder part that winds up the flexible resin base material on which the functional layer is formed. film how to characterized in that it constitutes a conductive roller having a resistance.

7 . 7. The film forming method according to claim 6 , wherein a rubber-coated roller or a roller having a ceramic bearing in the core is used as the insulating roller.

8 . The film forming method according to claim 6 or 7 , wherein a metal roller is used as the conductive roller.

9 . It said flexible resin substrate has a clear hard coat layer on the surface A side, to the clear hard coat layer, from Section 6 to paragraph 8, characterized in that to form the functional layer The film-forming method as described in any one of these.

1 0 . 10. The film forming method according to any one of items 6 to 9 , wherein a gas barrier layer is formed as the functional layer.

  By the above-mentioned means of the present invention, a method of forming a functional layer on a flexible resin substrate by a roll-to-roll method using a plasma CVD method, which is excellent in film formation stability, gas barrier properties and film surface uniformity. A film forming apparatus and a film forming method for forming the functional layer can be provided.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  When a plasma treatment is performed on a flexible resin substrate having an antistatic layer in the method of forming a functional layer, a flow of electric charges that reaches the ground through the antistatic layer and the guide roller is generated although it is weak, As a result, it is presumed that a phenomenon occurs in which the plasma intensity during the plasma treatment decreases. On the other hand, by insulating the guide roller closest to the plasma processing section, the phenomenon that the plasma intensity during the plasma processing is reduced can be suppressed, and a flexible resin base material having no antistatic layer It is possible to form a functional layer under the same plasma intensity conditions.

  On the contrary, in the unwinder part, the effect of removing the electric charge generated in the flexible resin base material by peeling is established by arranging a conductive guide roller. When an insulating roller subjected to such an insulating process is applied, the charge removing effect is lost, and the problem of peeling electrification occurs again. Thus, the unwinder section and the guide roller closest to the winder section have the greatest influence on the state of peeling charging.

  In addition, with respect to the pair of roller electrodes constituting the plasma CVD processing unit, four guide rollers and an unwinder unit located at the closest distances on the upstream side and the downstream side in the conveyance direction of the flexible resin base material, respectively. For the guide rollers other than the guide roller located at the closest distance to the winder unit, the material to be employed can be freely selected to some extent in view of the plasma intensity and the state of peeling charging.

Schematic diagram showing an example of the configuration of a film forming apparatus of the present invention that forms a functional layer on a flexible resin substrate that is continuously conveyed The schematic diagram which shows an example of the other structure of the film-forming apparatus of this invention which forms a functional layer on the flexible resin base material which carries continuously The schematic diagram which shows an example of the other structure of the film-forming apparatus of this invention which forms a functional layer on the flexible resin base material which carries continuously Sectional drawing which shows an example of a structure of the flexible resin base material used for the film-forming method, and the gas-barrier film formed Sectional drawing which shows another example of the structure of the flexible resin base material used for the film-forming method, and the gas-barrier film formed

The film forming apparatus of the present invention is a film forming apparatus that forms a functional layer on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers in a roll-to-roll manner under reduced pressure. An unwinder unit for feeding out a flexible resin base material laminated in a roll shape and a pair of roller electrodes facing each other, functioning on the flexible resin base material in a discharge space formed between the roller electrodes The structure having a plasma CVD processing part for forming a functional layer and a winder part for winding up the flexible resin base material on which the functional layer is formed, and the flexible resin base material to be continuously conveyed is provided with an antistatic layer on the back side. All of the four guide rollers located at the nearest distance on the upstream side and the downstream side in the transport direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing unit. Electrically disconnected It is composed of an insulative roller having a property, and the guide roller located at the closest distance to the unwinder part or the winder part is composed of a conductive roller having electrical conductivity. To do. This feature is a technical feature common to or corresponding to the inventions according to the following embodiments .

  In addition, the insulating roller is a rubber-coated roller or a roller having a ceramic bearing in the core, or the conductive roller is a metal roller, from the viewpoint that the object effect of the present invention can be further expressed. preferable.

  Moreover, it is preferable that a conductive roller is a metal roller at the point which can express the more excellent conductive effect.

  In addition, the flexible resin base material has a clear hard coat layer on the A surface side, and the formation of the functional layer on the clear hard coat layer can be carried before the functional layer is formed. This is preferable from the viewpoint of preventing damage such as scratches on the surface of the flexible resin substrate.

  In addition, forming a gas barrier layer as the functional layer on the flexible resin base material is not affected by charging or the like, and can precisely design a desired element profile; and It is preferable from the viewpoint that a gas barrier film excellent in gas barrier properties can be obtained.

In addition, the film forming method of the present invention is based on a plasma CVD processing method having a plasma CVD processing section on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers in a roll-to-roll manner under reduced pressure. A film forming method for forming a functional layer, wherein the flexible resin substrate has an antistatic layer on a surface (B surface) opposite to a surface (A surface) on which the functional layer is formed. The plasma CVD processing section forms a plasma discharge space by applying a voltage between a pair of opposed roller electrodes, and forms a functional layer on the flexible resin substrate in the plasma discharge space. All of the four guide rollers located at the closest distance on the upstream side and the downstream side in the transport direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing unit are electrically connected. Insulative insulation Guide roller located at the closest distance to the unwinder part that is composed of a flexible roller and feeds out a flexible resin base material laminated in a roll shape, or the winder part that winds up the flexible resin base material on which a functional layer is formed Is constituted by a conductive roller having electrical conductivity.

  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.

<Film deposition system>
[Overall configuration of deposition system]
First, the overall configuration of the film forming apparatus of the present invention will be described.

As described above, the film forming apparatus according to the present invention uses a plasma CVD processing unit on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers under a reduced pressure by a roll-to-roll method. It is a device that forms a thin functional layer.
(1) An unwinder unit for feeding out a flexible resin base material laminated in a roll shape;
(2) a plasma CVD processing unit comprising a pair of opposed roller electrodes and forming a functional layer on the flexible resin substrate in a discharge space formed between the roller electrodes;
(3) It is the structure which has a winder part which winds up the flexible resin base material which formed the functional layer,
The flexible resin substrate that is continuously conveyed has an antistatic layer on the surface opposite to the surface (A surface) on which the functional layer is formed (hereinafter referred to as the back surface side), and has a plasma CVD processing section. All four guide rollers located at the closest distance on the upstream side and the downstream side in the conveyance direction of the flexible resin base material with respect to the pair of roller electrodes that constitute the electrical insulation. The guide roller located in the nearest distance with respect to an unwinder part or the said winder part is comprised with a conductive roller electrically provided with electroconductivity.

The four guide rollers positioned at the closest distance on the upstream side and the downstream side in the transport direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing unit referred to in the present invention are described later. 1 to 3, the upstream side and the downstream side in the transport direction in the transport path of the flexible resin substrate unit 2 with respect to the film formation roller 31 and the film formation roller 32 constituting the plasma CVD processing unit P. The four guide rollers 21 to 24 located at the closest distance on the side are all characterized by being composed of electrically insulating rollers that are all electrically insulating. And

  Moreover, as shown in FIGS. 1 to 3 to be described later, the guide roller located at the closest distance to the unwinder section or the winder section referred to in the present invention is an unwinder section (UW section) or a winder section ( The guide roller closest to the distance in the transport path of the flexible resin base unit unit 2 is defined as “the guide roller located at the closest distance” and is shown in FIGS. The guide roller 12 and the guide roller 70 correspond. In the configuration of the film forming apparatus of the present invention, one guide roller is located at the closest distance to the unwinder part (UW part) or one guide roller is located at the closest distance to the winder part (W part). is there.

(Film forming apparatus illustrated in FIG. 1)
FIG. 1 shows an outline of a configuration and a process flow of a film forming apparatus of the present invention for forming a functional layer on a flexible resin substrate that is continuously conveyed.

A film forming apparatus 1 shown in FIG. 1 has a plasma CVD processing unit P, and continuously rolls a flexible resin substrate unit 2 in a roll-to-roll manner from an unwinder unit (UW unit) to a winder unit (W unit). A functional layer is formed on the flexible resin base unit 2 while being conveyed. Flexible resin substrate unit 2 referred to herein is a flexible surface side of the resin substrate 101 has a clear hard coat layer 102 (A ₁ side shown in FIG. 4A described below), back side (described later Fig. a structure having an antistatic layer on the B ₁ side) shown in 4A.

  The film forming method of the present invention is a method of forming a functional layer on a flexible resin substrate by plasma CVD treatment under reduced pressure. A film forming apparatus 1 illustrated in FIG. 80. A vacuum pump 82 which is a vacuum exhaust means is connected to the vacuum chamber 80 via an exhaust port 81, and the pressure in the vacuum chamber 80 can be appropriately adjusted by the vacuum pump 82 and the film forming gas supply pipe 41. It is possible. Note that the vacuum pump 82 can evacuate the inside of the vacuum chamber 80 to a vacuum state or a low pressure state according to vacuum. The low pressure state means that the pressure in the vacuum chamber 80 is in the range of 0.01 to 20 Pa.

In FIG. 1, the roll laminated body 11 which laminated | stacked the flexible resin base unit 2 in roll shape is arrange | positioned at an unwinder part (UW part), and the flexible resin base unit 2 longer than a UW part. To pay out. At this time, the flexible resin substrate unit unit 2, as shown in FIG. 4A described below, the configuration on the back side of the flexible resin substrate 101 _(first surface B) has an antistatic layer 103 was characterized further configured to have a clear hard coat layer 102 on the surface side (a ₁ side) is preferable. The flexible resin substrate unit 2, the back side having an antistatic layer 103 _(first surface B) is continuously conveyed in a state in contact with the conductive guide rollers 12.

Next, for example, a gas barrier layer 104 is continuously formed as a functional layer on the surface side (A ₁ surface) of the flexible resin base unit 2 in the plasma CVD processing unit P, as shown in FIG. 4B. A gas barrier film G having such a structure is produced.

  In FIG. 1, the plasma CVD processing region is composed of at least film forming rollers 31 and 32, a film forming gas supply pipe 41, and a plasma generating power source 51. Further, the plasma CVD processing part P referred to in the present invention includes film forming rollers 31 and 32 which are a pair of opposed roller electrodes, and a discharge space is formed between the roller electrodes. This is a region on which a functional layer is formed, and is a region indicated by a broken line in FIG.

  In the plasma CVD processing section P having such a configuration, the pair of film forming rollers (the film forming roller 31 and the film forming roller 32) function as a pair of counter electrodes. It is connected to the. By supplying electric power to the pair of film forming rollers (film forming roller 31 and film forming roller 32) from the power source 51 for generating plasma, a discharge space is formed in the space between the film forming roller 31 and the film forming roller 32. Thus, plasma is generated in the discharge space between the film forming roller 31 and the film forming roller 32. In this way, in the plasma CVD processing part P, since the film forming roller 31 and the film forming roller 32 are used as electrodes, each roller may be configured using a material that can be used as an electrode. Good. Moreover, in such a plasma CVD processing part P, it is preferable to arrange | position a pair of film-forming roller (the film-forming roller 31 and the film-forming roller 32) substantially parallel on the same axis. Thus, by arranging a pair of film forming rollers (film forming roller 31 and film forming roller 32) in parallel, the film forming rate can be doubled and a functional layer having the same structure can be formed.

(Film forming apparatus provided with the magnetic field generator shown in FIG. 2)
FIG. 2 is a schematic diagram showing an example of a configuration of a film forming apparatus to which the film forming apparatus of the present invention for forming a functional layer on the flexible resin base unit 2 that is continuously conveyed can be applied.

  The plasma CVD processing unit P shown in FIG. 2 is different from the plasma CVD processing unit P shown in FIG. 1 described above even if each film forming roller rotates inside the film forming roller 31 and the film forming roller 32. The magnetic field generator 61 and the magnetic field generator 62 fixed so as not to rotate are provided. By setting it as such a structure, the content profile of the component atom in the functional layer to form can be adjusted arbitrarily. The other configuration of the film forming apparatus 1 is the same as the configuration shown in FIG.

(Structure of deposition system)
In the film forming apparatus 1 of the present invention, as the film forming roller 31 and the film forming roller 32, conventionally known rollers configured using materials that can be used as electrodes can be appropriately selected and used. As the film-forming roller 31 and the film-forming roller 32, it is preferable to use rollers having the same diameter from the viewpoint of efficiently and stably forming a thin film (functional layer). In addition, the diameters of the film forming roller 31 and the film forming roller 32 are preferably in the range of 100 to 1000 mmφ, particularly in the range of 100 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter is 100 mmφ or more, the plasma discharge space does not become too small, so there is no reduction in productivity, and it is possible to avoid the total amount of heat of the plasma discharge from being applied to the flexible resin base material in a short time. This is preferable from the viewpoint of making the stress difficult to increase. On the other hand, if the diameter is 1000 mmφ or less, it is preferable because the conditions for forming a precise functional layer (for example, a gas barrier layer) can be maintained in terms of device design including uniformity of the plasma discharge space.

  In the present invention, as a guide roller disposed in the plasma CVD processing section P having such a configuration, the upstream side in the conveyance direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing section. One of the features is that at least one of the four guide rollers located at the closest distance on the downstream side is composed of an insulating roller having electrical insulation. 1 and 2, at least one of the guide rollers 21 to 24 is an insulating roller.

  In the present invention, further, four guides positioned at the closest distances on the upstream side and the downstream side in the conveyance direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing unit P, respectively. It is preferable that all of the rollers are constituted by insulating rollers having electrical insulation. That is, it is preferable that all of the guide rollers 21 to 24 shown in FIG. 1 and FIG. 2 are configured by insulating rollers having insulating properties.

  In addition, as shown in FIG. 3, with respect to a pair of roller electrode which comprises the plasma CVD process part P, the four guide rollers 21-24 located in the nearest distance and the unwinder part or the winder part are the closest. With respect to the guide rollers 25 and 26 arranged at their respective intermediate positions other than the guide rollers 12 and 70 located at a distance, the constituent materials and electrical characteristics (conductivity) are examined in view of the plasma intensity and the state of peeling charging. Alternatively, the insulating property can be changed as appropriate.

  In addition, as the film forming gas supply pipe 41 constituting the plasma CVD processing region, a material capable of supplying or discharging the functional gas for forming the functional layer to the discharge space at a predetermined speed is appropriately used. Can be used. Furthermore, as the plasma generating power source 51, a conventionally known power source for a plasma generating apparatus can be used. Such a power source 51 for generating plasma supplies power to the film forming roller 31 and the film forming roller 32 connected thereto, and makes it possible to use these as counter electrodes for discharge. As such a plasma generation power source 51, an AC power source capable of alternately reversing the polarities of a pair of film forming rollers is used because the plasma CVD processing method can be performed more efficiently. It is preferable to do. In addition, since such a plasma generating power source 51 can perform the plasma CVD method more efficiently, the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. A power source that can be in the range of ~ 500 kHz is more preferable. Moreover, as the magnetic field generator 61 and the magnetic field generator 62, a well-known magnetic field generator can be used suitably.

  As described above, in the plasma CVD processing section P, the gas barrier film G (for example, having the configuration shown in FIG. 4B) in which a functional layer, for example, a gas barrier layer is formed, is a winder section ( W part), it is wound up in a roll shape to form a roll laminate 71. At this time, from the viewpoint of preventing charge from being brought into the roll laminate 71 due to charging or the like, it is a preferable aspect that at least the guide roller 70 in front of the W portion is formed of a conductive roller.

  A functional layer, for example, a gas barrier layer is formed on a flexible resin substrate unit by using the film forming apparatus of the present invention having a configuration in which a conductive roller and an insulating roller are arranged at specific positions. Thus, a functional layer excellent in film formation stability, gas barrier property and film surface uniformity can be formed.

〔guide roller〕
In the film forming apparatus of the present invention, four guides positioned at the closest distances on the upstream side and the downstream side in the transport direction of the flexible resin base material with respect to the pair of roller electrodes constituting the plasma CVD processing unit. At least one of the rollers is composed of an electrically insulating roller, and the guide roller located at the closest distance to the unwinder or winder is electrically conductive. It is characterized by comprising a sex roller.

In the present invention, “conductive” means that the volume resistivity at 25 ° C. is less than 1 × 10 ⁻⁴ Ω · cm, and “insulating” means that the volume resistivity at 25 ° C. It means a range of 1 × 10 ¹⁰ Ω · cm or more.

(Insulating roller)
The insulating roller applicable to the present invention is not particularly limited as long as it is composed of an electrically insulating material and has a volume resistivity in the range specified above, but preferably Can include a rubber roller or a roller having a ceramic bearing in the axial center.

  As a rubber roller applicable to the present invention, the entire roller may be composed of a rubber material. However, from the viewpoint of the strength and handleability of the roller, the shaft center portion is composed of a metal core, and the shaft center. It is preferable that the surface of the part is covered with a rubber material.

Examples of the rubber material covering the surface of the metal core include, for example, natural rubber (NR, 1 × 10 ¹⁰ to 1 × 10 ¹⁵ ), isoprene rubber (IR, 1 × 10 ¹⁰ to 1 × 10 ¹⁵ ), butadiene rubber ( BR, 1 × 10 ¹⁴ to 1 × 10 ¹⁵ ), styrene butadiene rubber (SBR, 1 × 10 ¹⁰ to 1 × 10 ¹⁵ ), butyl rubber (IIR, 1 × 10 ¹⁶ to 1 × 10 ¹⁸ ), nitrile rubber (NBR, 1 × 10 ¹⁰ ), ethylene propylene rubber (EPM, EP, EPDM, 1 × 10 ¹² to 1 × 10 ¹⁵ ), chloroprene rubber (CR, 1 × 10 ¹⁰ to 1 × 10 ¹² ), urethane rubber (PUR, U, 1 × 10 ¹⁰ to 1 × 10 ¹² ), silicone rubber (Si, VMQ, SR, 1 × 10 ¹¹ to 1 × 10 ¹⁵ ), fluoro rubber (FKM, FPM, 1 × 10 ¹⁵ to 1 × 10) ¹⁸ ), ethylene / vinyl acetate rubber (EVA, 1 × 10 ¹² to 1 × 10 ¹⁴ ), polysulfide rubber (T, 1 × 10 ¹⁵ ) and the like. The alphabetic characters in parentheses represent abbreviations, and the numerical values represent volume resistivity (Ω · cm).

  Moreover, as a metal core metal which comprises an axial center part, metals and alloys, such as aluminum, stainless steel (SUS), iron, copper, a true casting, can be mentioned, for example.

On the other hand, as a ceramic material constituting the ceramic bearing provided in the shaft center portion, as a fine ceramic, alumina (> 1 × 10 ¹⁴ ), zirconia (> 1 × 10 ¹² ), silicon nitride (> 1 × 10 ¹⁴ ), Examples include aluminum nitride (> 1 × 10 ¹⁴ ), cordierite (1 × 10 ¹³ ), mullite (1 × 10 ¹⁴ ), steatite (1 × 10 ¹⁴ ), sialon (> 1 × 10 ¹⁵ ), and the like. Of these, zirconia ceramics and silicon nitride ceramics are preferable. The numerical value in parentheses is the volume resistivity (Ω · cm).

  The specific structure of the ceramic bearing is that the inner and outer rings and the bearing are made of silicon nitride, the holder is made of PTFE (fluororesin), the inner and outer rings and the bearing are made of zirconia, and the holder Are made of PTFE (fluororesin), inner and outer rings and bearings are made of zirconia, and the holder is made of SUS304.

(Conductive roller)
The conductive roller applicable to the present invention is not particularly limited as long as it is a roller made of an electrically conductive material, but a typical roller includes a metal roller.

The material of the metal roller is not particularly limited as long as it has electrical conductivity and good mechanical strength and thermal conductivity. For example, tungsten (5.5 × 10 ⁻⁶ ), molybdenum (5.7) × ^{10 -6),} tantalum ^{(12.4 × 10 -6), SUS310S} (90 × 10 -6), SUH446 (60 × 10 -6), SUS316 (74 × 10 -6), SUS304 (71 × 10 - ⁶ ), iron (19.5 × 10 ⁻⁶ ), aluminum (2.7 × 10 ⁻⁶ ), copper (1.7 × 10 ⁻⁶ ), etc., but aluminum or general-purpose stainless steel Is preferable from the viewpoint of cost, and aluminum, SUS304, and SUS316 are particularly preferable. The numerical value in parentheses is the volume resistivity (Ω · cm).

[Method for depositing functional layer by plasma CVD processing section]
Using the film-forming apparatus of the present invention configured by the plasma CVD processing unit P provided with the insulating roller, the conductive roller, and the counter electrode described with reference to FIG. 1 and FIG. By appropriately adjusting the power of the electrode drum of the plasma generator, the strength of the magnetic field generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the conveyance speed of the flexible resin substrate, A functional film in which a functional layer according to the present invention, for example, a gas barrier layer is formed on a substrate can be produced.

  The functional film that can be manufactured by the film forming apparatus of the present invention includes a gas barrier film having a gas barrier layer, an insulating film having an insulating layer, and a refractive index difference with respect to the substrate. Examples include a reflective film in which a plurality of thin films having the same structure are laminated. Among them, when the gas barrier layer has many film defects, gas such as water and oxygen penetrates through the film defects, and the gas barrier performance is remarkably deteriorated, so that a thin film with few film defects can be formed. The film forming apparatus is suitable for producing a gas barrier film.

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

  FIG. 4B shows a schematic configuration of a gas barrier film produced by the film forming method of the present invention.

As shown in FIG. 4B, a gas barrier film G according to the present invention is characterized by having an antistatic layer 103 on the back surface side _(first surface B) of the resin substrate 101, the surface side (A ₁ side) It has a clear hard coat layer 102 and a gas barrier layer 104 on the clear hard coat layer 102.

  Using the plasma CVD processing portion P shown in FIG. 1 or the plasma CVD processing portion P of a method of applying a magnetic field to the discharge space shown in FIG. 2, while supplying a film forming gas (such as a source gas) into the vacuum chamber, By forming a plasma discharge space between the pair of film forming rollers (the film forming roller 31 and the film forming roller 32), the film forming gas (raw material gas, etc.) is decomposed by the plasma, and the flexibility on the film forming roller 31 is obtained. The gas barrier layer according to the present invention is formed on the surface of the flexible resin substrate unit 2 and on the surface of the flexible resin substrate unit 2 on the film forming roller 32 by the plasma CVD method. In such film formation, the flexible resin base unit 2 is conveyed by the delivery roller 11, the film formation roller 31 and the like, respectively, so that a roll-to-roll continuous film formation process is performed. A gas barrier layer can be continuously formed on the surface of the flexible resin substrate unit 2.

In the present invention, as described above, each of the pair of roller electrodes constituting the plasma CVD processing portion P is located at the nearest distance on the upstream side and the downstream side in the transport direction of the flexible resin base material 4 By configuring all of the two guide rollers with electrically insulating rollers, the plasma discharge in the plasma CVD processing part P can be stabilized and a functional layer having a desired element profile can be formed. it can. In addition, by configuring the guide roller located at the closest distance to the unwinder part or the winder part with a conductive roller having electrical conductivity, when the flexible resin base unit is extended, By reducing the charge amount of the flexible resin base material, damage due to peeling charging can be reduced.

[Production method of gas barrier film]
Next, as a representative example of the functional film produced by the film forming apparatus of the present invention, constituent materials and formation conditions will be described in more detail with respect to a gas barrier film.

(Flexible resin base material)
Examples of the flexible resin base material (hereinafter also simply referred to as a resin base material) applicable to the present invention include methacrylic acid ester, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), and polycarbonate. (Abbreviation: PC), polyarylate, polystyrene (abbreviation: PS), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, and other resin films, and two or more layers of the above resins A laminated film formed by laminating can be mentioned. In terms of cost and availability, a film made of each resin such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC) is preferably used.

  The thickness of the resin substrate is preferably in the range of 5 to 500 μm, more preferably in the range of 25 to 250 μm.

  Moreover, it is preferable that the resin base material which concerns on this invention is transparent. If the resin base material is transparent and the layer formed on the resin base material is also transparent, it becomes a transparent gas barrier film. Therefore, it should be used as a transparent substrate for electronic devices (for example, organic EL). Is also possible.

(Formation of gas barrier layer)
In the film forming method using the film forming apparatus of the present invention, as shown in FIG. 4B, it is preferable to form the gas barrier layer 104 as a functional layer on the flexible resin base unit 2. Such a configuration is preferable from the viewpoint that the effects of the present invention can be exhibited.

The gas barrier layer as used in the field of this invention is a layer which has gas barrier property. Specifically, the gas barrier layer has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2%) measured by a method according to JIS-K-7129-1992, 0.01 g / (m It is preferable that the gas barrier property is ² · 24 hours or less. Moreover, the oxygen permeability measured by the method based on JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 1 × 10 ^{− It} preferably has a gas barrier property of ⁵ g / (m ² · 24 hours) or less.

  As a constituent material of the gas barrier layer formed by the film forming method of the present invention, for example, inorganic silicon compounds such as silicon oxide, silicon oxynitride, silicon dioxide, silicon nitride, and organic silicon compounds can be used.

  In particular, the gas barrier layer is preferably formed by oxidizing or nitriding a gas obtained by vaporizing an organosilicon compound with a plasma CVD apparatus.

<Raw gas>
In the formation of the gas barrier layer according to the present invention, it is preferable to use an organosilicon compound containing at least silicon as the source gas constituting the film forming gas.

  Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl. Examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer. Moreover, these organosilicon compounds can be used individually or in combination of 2 or more types.

  The film forming gas preferably contains oxygen gas as a reaction gas in addition to the source gas. The oxygen gas is a gas used to react with the raw material gas to form an inorganic compound such as an oxide.

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber 80 as shown in FIG. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

  When such a film forming gas contains a raw material gas containing an organosilicon compound containing silicon and an oxygen gas, the ratio of the raw material gas to the oxygen gas is such that the raw material gas and the oxygen gas are completely reacted. It is preferable that the oxygen gas ratio is not excessively higher than the theoretically required oxygen gas ratio. If the ratio of oxygen gas is excessive, it is difficult to obtain the target gas barrier layer in the present invention. Therefore, in order to obtain the desired performance as a barrier film, it is preferable that the total amount of the organosilicon compound in the film forming gas is less than the theoretical oxygen amount necessary for complete oxidation.

(Degree of vacuum)
Although the pressure (degree of vacuum) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set in the range of 0.5 Pa-100 Pa.

(Deposition with a pair of opposed roller electrodes)
In the film-forming method using the plasma CVD processing part provided with the film-forming rollers 31 and 32 comprised by a pair of counter electrode as shown in FIGS. 1-3, between the film-forming roller 31 and the film-forming roller 32 In order to discharge, the power applied to the electrode drum connected to the plasma generating power source 51 (installed in the film forming roller 31 and the film forming roller 32 in FIGS. 1, 2 and 3) is: Although it can adjust suitably according to the kind of raw material gas, the pressure in a vacuum chamber, etc. and it cannot generally say, it is preferable to set it as the range of 0.1-10 kW. When the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range, so that the surface temperature of the resin base material during film formation increases. Further, it is possible to prevent thermal deformation of the resin base material, performance deterioration due to heat, and generation of wrinkles during film formation. In addition, damage to the film forming roller due to melting of the resin base material by heat and generation of a large current discharge between the bare film forming rollers can be prevented.

  Although the conveyance speed (line speed) of the resin base material 2 can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min. More preferably, it is in the range of 0.5 to 20 m / min. When the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.

  As a film forming apparatus according to the present invention, a magnetic field is generated in a film forming roller 31 and a film forming roller 32 as shown in FIG. The configuration in which the device 61 and the magnetic field generation device 62 are respectively provided is preferable from the viewpoint that the element profile in the gas barrier layer to be formed can be precisely controlled.

  When forming a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms using a counter-roller electrode type plasma CVD processing unit equipped with a magnetic field generator as shown in FIG. 2, the gas barrier layer As for, it is preferable to form by the film-forming method which satisfy | fills the conditions of the element profile as described in following (1)-(4).

  (1) Carbon whose carbon atom ratio in the gas barrier layer continuously changes in correspondence with the distance from the surface within the distance range from the surface of the gas barrier layer to 89% of the layer thickness in the layer thickness direction. Element profile.

  (2) The maximum value of the carbon atom ratio of the gas barrier layer is less than 20 at% within the distance range from the surface of the gas barrier layer to 89% of the layer thickness in the layer thickness direction.

  (3) The carbon atom ratio of the gas barrier layer is within a distance range of 90 to 95% of the layer thickness from the surface of the gas barrier layer in the layer thickness direction (a range of 5 to 10% from the surface adjacent to the resin substrate) In), increase continuously.

  (4) The maximum value of the carbon atom ratio of the gas barrier layer is within a distance range of 90 to 95% of the layer thickness from the surface of the gas barrier layer in the layer thickness direction (5 to 5 from the surface adjacent to the resin substrate). In the range of 10%), it must be 20 at% or more.

  About a specific control method etc., it can carry out according to the method as described in WO2012 / 046767A1, for example.

[Other component layers]
(Antistatic layer)
As shown in FIGS. 4A and 4B, the antistatic layer 103 according to the present invention has a back surface side (B ₁ surface side, B ₂ surface side) of the resin base material 101, that is, conductive guide rollers 12 and guide rollers. 70 is provided on the side in contact with 70.

  The antistatic layer 103 has a function of preventing the film surface from being charged when the resin base material 101 is fed out from the laminated roll-shaped laminate 11.

  As a technique for imparting antistatic ability to the antistatic layer, there is a method of imparting conductivity to the antistatic layer and reducing the electric resistance value of the antistatic layer.

  For example, as an antistatic technique, a method in which a conductive filler which is a conductive substance is dispersed and contained in an antistatic layer, a method using a conductive polymer, a method in which a metal compound is dispersed or coated on a surface, an organic sulfonic acid And an internal addition method using an anionic compound such as organic phosphoric acid, a method using a surface active type low molecular weight antistatic agent such as polyoxyethylene alkylamine, polyoxyethylene alkenylamine, and glycerin fatty acid ester, carbon There is a method of dispersing conductive fine particles such as black. In particular, it is preferable to use a method in which conductive fillers, which are conductive substances, are dispersed and contained.

  In addition, regarding the electrical resistance value of an antistatic layer, when the resistance in a coating film is divided roughly, it can be divided into particle internal resistance and contact resistance. The internal resistance of particles is affected by the doping amount of different metals, the amount of oxygen defects, and crystallinity. The contact resistance is affected by the particle diameter and shape, the dispersibility of the fine particles in the paint, and the conductivity of the binder resin. Since a film having a relatively high conductivity is considered to have a larger influence of contact resistance than internal resistance of the particle, it is important to form a conductive path by controlling the particle state.

  The antistatic layer preferably has an antistatic property by containing a conductive filler. Examples of the conductive filler contained in the antistatic layer include conductive inorganic fine particles, and among them, metal fine particles, conductive inorganic oxide fine particles, and the like are preferably used. In particular, conductive inorganic oxide fine particles can be preferably used. Examples of the metal fine particles include fine particles of gold, silver, palladium, ruthenium, rhodium, osmium, iridium, tin, antimony, indium and the like. Examples of the inorganic oxide fine particles include fine particles of indium antimony pentoxide, tin oxide, zinc oxide, ITO (indium tin oxide), ATO (antimony tin oxide), phosphorus-doped oxide, and the like. Among these, inorganic double oxide fine particles such as phosphorus-doped oxide are preferable because of their high conductivity and weather resistance.

  When dispersing the conductive filler in the antistatic layer, it is preferable that the primary particle diameter of the conductive filler is in the range of 1 to 100 nm, particularly 1 to 50 nm in order not to lower the transparency of the antistatic layer. It is preferable to be within the range. In order to ensure conductivity, the particles must be close to each other to some extent, so that the particle diameter is preferably 1 nm or more. If the particle diameter is 100 nm or less, a decrease in light transmittance can be suppressed without excessively reflecting light.

  As the conductive inorganic oxide fine particles, commercially available fine particles can also be used. Specifically, Cellax series (manufactured by Nissan Chemical Industries, Ltd.), P-30, P-32, P-35, P -45, P-120, P-130 (manufactured by JGC Catalysts & Chemicals Co., Ltd.), T-1, S-1, S-2000, EP SP2 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) and the like can be used. .

  In the antistatic layer, an organic binder or an inorganic binder can be used as a binder for holding the conductive filler.

  As the organic binder, a resin can be used, and examples thereof include acrylic resins, cycloolefin resins, and polycarbonate resins. Furthermore, as an organic binder, a hard coat can be used as a binder, and an ultraviolet curable polyfunctional acrylic resin, urethane acrylate, epoxy acrylate, oxetane resin, polyfunctional oxetane resin, and the like can be used. Examples of the inorganic binder include inorganic oxide binders (may be inorganic oxide binders using a sol-gel method) and tetrafunctional inorganic binders.

  Preferable examples of the inorganic oxide binder include silicon dioxide, titanium oxide, aluminum oxide, strontium oxide and the like. Particularly preferred is silicon dioxide.

  Preferred examples of the tetrafunctional inorganic binder include polysilazane (for example, trade name: Aquamica (manufactured by AZ Electronics)), a siloxane compound (for example, Colcoat P (manufactured by Colcoat, Inc.)), alkyl silicate, and metal alcoholate. FJ803 (manufactured by GRANDEX), alumina sol (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like can be used. Further, as a tetrafunctional inorganic binder, a sol-gel solution containing tetraethoxysilane as a main raw material and added with a catalyst may be used.

  Furthermore, examples of materials having both organic and inorganic properties include polyorganosiloxane and polysilazane. These materials can be said to be organic binders and inorganic binders. A mixture of an inorganic binder and an organic binder may be used as the binder for the antistatic layer, but the total amount of the binder is preferably an inorganic binder.

  When the binder is an inorganic binder, when used outdoors, it is desirable because it has weather resistance against ultraviolet rays and can maintain high antistatic properties over a long period of time. In addition, since the outermost layer contains a metalloxane skeleton, if the binder of the antistatic layer is an inorganic binder, the adhesion between the antistatic layer and the outermost layer is improved, preventing problems such as a decrease in reflective performance due to peeling between layers. This is preferable because it is possible. Furthermore, the inorganic binder is more likely to crack than the organic binder, but by providing the outermost layer as the upper layer of the antistatic layer, the effect of preventing cracking, chipping prevention and chipping scattering is obtained, and the inorganic binder is easily cracked. Even binders can be used without problems.

  This antistatic layer can be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, or a die coating method.

  In addition, it is preferable that the layer thickness of an antistatic layer exists in the range of 100 nm-1 micrometer. If the film thickness of the antistatic layer is 100 nm or more, the planarity can be maintained without the conductive filler being lifted from the antistatic layer. Moreover, if the film thickness of the antistatic layer is 1 μm or less, the light transmittance is not deteriorated.

  The antistatic layer preferably contains a conductive filler (conductive inorganic fine particles) in the range of 75 to 95% by mass with respect to the total mass of the antistatic layer. If the content of the conductive filler is 75% by mass or more, the conductivity can be ensured, and if the content of the conductive filler is 95% or less, desired light transmittance can be maintained.

(Clear hard coat layer)
As shown in FIG. 4A and FIG. 4B, the clear hard coat layer 102 according to the present invention is formed on the surface side (A ₁ surface side or A1 side of the resin base material 101 before forming the gas barrier layer by the film forming method of the present invention. It provided a _2-surface side).

  Examples of the curable resin applicable to the formation of the clear hard coat layer according to the present invention include a thermosetting resin and an active energy ray curable resin. However, since the thin film can be easily formed, the active energy ray curable resin is used. Can be preferably used.

<Thermosetting resin>
The thermosetting resin applicable to the present invention is not particularly limited, and various heats such as an epoxy resin, a cyanate ester resin, a phenol resin, a bismaleimide-triazine resin, a polyimide resin, an acrylic resin, and a vinylbenzyl resin can be used. A curable resin is mentioned.

<Active energy ray-curable resin>
The active energy ray-curable resin that can be suitably used in the present invention refers to a resin having a property of being cured through a crosslinking reaction or the like by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used. The active energy ray curable resin is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. A resin layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable flag resin, but an ultraviolet curable resin that is cured by ultraviolet irradiation is preferable.

<UV curable resin>
The ultraviolet curable resin suitable for forming the clear hard coat layer according to the present invention will be described below.

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

<Various additives>
Further, the clear hard coat layer may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.

  These clear hard coat layers can be coated by a known wet coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an inkjet method using a clear hard coat layer forming coating solution. it can.

  The coating amount of the hard coat layer coating solution is suitably in the range of 0.1 to 40 μm as a wet film thickness, and preferably in the range of 0.5 to 30 μm. Moreover, as a layer thickness, the inside of the range of 0.1-30 micrometers is suitable, Preferably it exists in the range of 1-10 micrometers.

<Curing method of clear hard coat layer>
After forming a clear hard coat layer on a resin base material that has been subjected to vacuum ultraviolet irradiation treatment on the surface, the clear hard coat layer is irradiated with active energy rays, preferably ultraviolet rays, to finally form a clear hard coat layer. Harden.

[Other functional layers]
In the gas barrier film according to the present invention, in addition to the above-described constituent layers, functional layers can be provided as necessary.

<Overcoat layer>
An overcoat layer may be formed on the gas barrier layer according to the present invention for the purpose of further improving the flexibility. The material used for forming the overcoat layer is preferably an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group. Can be used. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. Preferably, the overcoat layer is formed by applying a light irradiation treatment or heat treatment to the layer applied from the organic resin composition coating solution to be cured.

<Application field of gas barrier film>
The gas barrier film produced by the film forming method of the present invention is preferably provided as a film for electronic devices.

  Examples of the electronic device include an organic electroluminescence panel (organic EL panel), an organic electroluminescence element (organic EL element), an organic photoelectric conversion element, and a liquid crystal display element.

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

<< Preparation of flexible resin base unit >>
[Preparation of flexible resin base unit 1: with antistatic layer]
(Preparation of flexible resin base material)
As the flexible resin base material 101, a transparent biaxially stretched polyethylene terephthalate (PET) film KEL86W (manufactured by Teijin DuPont Films, length 100 m, width 0.35 m, thickness 125 μm, hereinafter abbreviated as PET film) Prepared.

The surface of this PET film was subjected to corona treatment using a corona discharge device AGI-080 (manufactured by Kasuga Denki Co., Ltd.). During the corona treatment, the gap between the discharge electrode of the corona discharge device and the surface of the film was set to 1 mm, and the treatment output was 600 mW / cm ² , and a corona discharge was performed for 10 seconds.

(Formation of clear hard coat layer)
Then, on the surface side of the PET film _{(A 1} side according to FIG. 4A), according to the following method, to form a clear hard coat layer 102.

While continuously transporting the PET film, on the surface side (A ₁ side), an ultraviolet curable resin-containing coating liquid (purple UV-1700B, manufactured by Nippon Synthetic Chemical Co., Ltd.) mainly composed of polyurethane acrylate and acrylate ester, Using a wet coater, coating was performed so that the film thickness after drying was 4 μm, and then drying was performed at 80 ° C. for 3 minutes. The dried coating film was cured by irradiation with actinic rays of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere to form a clear hard coat layer 102 and laminated in a roll shape.

(Formation of antistatic layer)
Then, to the surface to form a clear hard coat layer 102 of PET film on the opposite side (B ₁ side according to FIG. 4A), according to the following method to form an antistatic layer.

<Preparation of coating solution for forming antistatic layer>
14 parts of a siloxane-based material Colcoat P (manufactured by Colcoat) as an inorganic binder, 85 parts of a phosphorus-doped tin oxide Cellux CX-S501M (manufactured by Nissan Chemical Industries) as an inorganic double oxide, and BYK3550 (BIC Chemie) as a leveling agent 1 part of Japan) was mixed with stirring to prepare a coating solution for forming an antistatic layer.
An antistatic layer is formed using this antistatic coating solution.

<Applying an antistatic layer>
The clear hard coat layer 102 and the formed surface opposite surfaces of the PET film _(first surface B), the antistatic layer coating solution prepared above, using a wet coater, a dry film thickness of 300nm Then, the antistatic layer 103 was formed by drying at 80 ° C. for 10 seconds to produce the flexible resin substrate unit 1.

[Fabrication of flexible resin base unit 2: no antistatic layer]
In the production of the flexible resin substrate unit 1, the clear hard coat layer 102 is formed on both surfaces of the flexible resin substrate 101 without forming the antistatic layer on the back surface (B ₁ surface). A flexible resin base unit 2 was produced.

[Fabrication of flexible resin base unit 3: no hard coat layer]
In the preparation of the flexible resin substrate unit 1, except that was not the formation of the hard coat layer on the surface side (A ₁ side) in the same manner, to prepare a flexible resin substrate unit 3.

<< Production of gas barrier film >>
[Preparation of gas barrier film 1]
The film formation roller 31 and the film formation roller 32 shown in FIG. 2 are provided with a plasma CVD processing unit P in which a magnetic field generation device 61 and a magnetic field generation device 62 are respectively provided. A gas barrier layer was formed using a film forming apparatus to produce a gas barrier film 1.

  Specific production conditions are as follows.

And the Roll laminate 11 of the flexible resin substrate unit 1 having the antistatic layer of length 100m prepared above on the back side _(one side B) in the unwinder unit (UW portion).

  Next, the flexible resin base unit 1 was unwound from the roll laminate 11 and transported at a transport speed of 10 m / min.

Next, a 300 nm thick silicon oxycarbide SiOC film is formed on the clear hard coat layer (A ₁ side) of the flexible resin base unit 1 under the following film formation conditions by the plasma CVD processing unit P as a gas barrier. It formed continuously as a layer and obtained the gas-barrier film 1 which consists of a structure of FIG. 4B.

  The film forming conditions for producing the gas barrier film 1 are as follows.

(Deposition conditions)
Source gas 1: hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O)
Supply amount of raw material gas 1: 50 sccm (Standard Cubic Centimeter per Minute)
Source gas 2: Oxygen (O ₂ ) gas Supply amount of source gas 2: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Power applied by the power supply: 1.5 kW
Power supply frequency: 80 kHz
(Configuration of guide roller: Fig. 2)
Conductive guide rollers 12 and 70: metal roller made of SUS304 having a roller diameter of φ130 mm (volume resistivity: 71 × 10 ⁻⁶ Ω · cm)
Insulating guide rollers 21, 22, 23, and 24: made of aluminum (A5052) having a core metal of φ80 mm, and a styrene butadiene rubber (abbreviation: SBR, volume resistivity: 1 × 10 ¹² Ω ·) having a thickness of 10 mm on the surface thereof cm) roller coated with φ100 mm [Preparation of gas barrier film 2]
In the production of the gas barrier film 1, the gas barrier film 2 was produced in the same manner except that the guide rollers 21, 22, 23 and 24 were changed to insulating guide rollers provided with the following ceramic bearings.

Insulating guide rollers 21, 22, 23 and 24: The axial center part is made of a ceramic bearing made of silicon nitride (volume resistivity:> 1 × 10 ¹⁴ Ω · cm), and the outer peripheral part is made of PTFE (fluororesin). Constructing roller [Production of gas barrier film 3]
In the production of the gas barrier film 1, the thickness of each styrene butadiene rubber (abbreviation: SBR) of the insulating guide rollers 21, 22, 23, and 24 is changed to 25 mm, and the same is performed except that the rollers are changed to φ130 mm. Thus, a gas barrier film 3 was produced.

[Preparation of gas barrier film 4]
In producing the gas barrier film 1, the rubber material of the insulating guide rollers 21, 22, 23 and 24 is replaced with styrene butadiene rubber (abbreviation: SBR), and nitrile rubber (abbreviation: NBR, volume resistivity: 1). A gas barrier film 4 was produced in the same manner except that × 10 ¹⁰ Ω · cm) was used.

[Preparation of gas barrier film 5]
In the production of the gas barrier film 1, the rubber material of the insulating guide rollers 21, 22, 23 and 24 is replaced with styrene butadiene rubber, natural rubber (abbreviation: NR, volume resistivity: 1 × 10 ¹² Ω · The gas barrier film 5 was produced in the same manner except that cm) was used.

[Preparation of gas barrier film 6]
In the production of the gas barrier film 1, the conductive guide rollers 12 and 70 were replaced with SUS304 metal rollers, and SUS316 metal rollers (volume resistivity: 74 × 10 ⁻⁶ Ω · cm) were used. Except for the above, a gas barrier film 6 was produced in the same manner.

[Preparation of gas barrier film 7]
In the production of the gas barrier film 1, the conductive guide rollers 12 and 70 are replaced with SUS304 metal rollers, and aluminum metal rollers (volume resistivity: 2.7 × 10 ⁻⁶ Ω · cm) are used. A gas barrier film 7 was produced in the same manner except that it was used.

[Preparation of gas barrier film 8]
In the production of the gas barrier film 1, the gas barrier film 8 is the same except that the insulating guide rollers 21, 22, 23 and 24 are changed to insulating guide rollers having ceramic bearings having the following configuration. Was made.

Insulating guide rollers 21, 22, 23 and 24: The axial center part is composed of zirconia (volume resistivity:> 1 × 10 ¹² Ω · cm) ceramic bearing, and the outer peripheral part is composed of PTFE (fluororesin) Roller [Production of gas barrier film 9]
In the production of the gas barrier film 1, the gas barrier film 9 is the same except that the insulating guide rollers 21, 22, 23, and 24 are changed to insulating guide rollers each having a ceramic bearing having the following configuration. Was made.

Insulating guide rollers 21, 22, 23 and 24: Rollers whose axis is composed of zirconia (volume resistivity:> 1 × 10 ¹² Ω · cm) ceramic bearing and whose outer periphery is composed of SUS304 [Production of Gas Barrier Film 10]
In the production of the gas barrier film 1, the flexible resin base unit 1 is changed to the flexible resin base unit 2 having no antistatic layer, and all the guide rollers have a roller diameter of A gas barrier film 10 was produced in the same manner except that the metal roller was made of SUS304 having a diameter of 130 mm (volume resistivity: 71 × 10 ⁻⁶ Ω · cm).

[Preparation of gas barrier film 11]
In the production of the gas barrier film 1, all the guide rollers were changed in the same manner except that the conductive roller made of SUS304 having a roller diameter of φ130 mm (volume resistivity: 71 × 10 ⁻⁶ Ω · cm) was used. A gas barrier film 11 was produced.

[Production of gas barrier film 12]
In the production of the gas barrier film 1, all guide rollers are made of aluminum (A5052) having a core metal of φ80 mm, and a styrene butadiene rubber having a thickness of 10 mm on the surface (volume resistivity: 1 × 10 ¹² Ω · cm). A gas barrier film 12 was produced in the same manner except that it was changed to an insulative roller of φ100 mm coated with.

[Production of gas barrier film 13]
In the production of the gas barrier film 1, all the guide rollers are composed of ceramic bearings made of silicon nitride (volume resistivity:> 1 × 10 ¹⁴ Ω · cm) in the axial center and PTFE (fluororesin) in the outer periphery. The gas barrier film 13 was produced in the same manner except that the insulating roller was changed to an insulating roller.

[Production of gas barrier film 14]
In the production of the gas barrier film 12, the gas barrier film 14 was prepared in the same manner except that the thickness of the styrene butadiene rubber (volume resistivity: 1 × 10 ¹² Ω · cm) constituting the guide roller was changed to 1 mm. Produced.

[Preparation of gas barrier film 15]
In the production of the gas barrier film 2, the gas barrier film was similarly obtained except that the flexible resin base unit 3 having no hard coat layer was used instead of the flexible resin base unit 1. 15 was produced.

[Preparation of gas barrier film 16]
In the production of the gas barrier film 6, the gas barrier film was similarly obtained except that the flexible resin base unit 3 having no hard coat layer was used instead of the flexible resin base unit 1. 15 was produced.

[Preparation of gas barrier film 17]
In the production of the gas barrier film 6, the gas barrier film was similarly obtained except that the flexible resin substrate unit 2 having no antistatic layer was used instead of the flexible resin substrate unit 1. 17 was produced.

  Table 1 shows the structure of each of the gas barrier films produced above.

<Evaluation of gas barrier film>
The following evaluation was performed about the produced said gas-barrier films 1-14.

[Evaluation of plasma intensity]
The gas barrier film 10 produced using the flexible resin substrate unit 2 having no antistatic layer was measured by the following method for measuring the plasma intensity in the plasma CVD processing part P at the time of producing each gas barrier film. Assuming that the plasma intensity is 100, the relative plasma intensity of each gas barrier film was determined and the plasma intensity was evaluated according to the following criteria. As the relative plasma intensity is closer to 100, it indicates that, when the gas barrier layer is formed, there is less influence on plasma discharge due to charging of the flexible resin base material, and stable plasma discharge can be performed.

(Method of measuring plasma intensity)
Fiber multichannel spectroscope: USB2000 + (manufactured by Ocean Optics) was used, and the light emission intensity from plasma was dispersed, and a relative comparison was made on behalf of the intensity of a certain radical species. This time, the value of the H radical seen in the vicinity of 664 nm is representative, and the intensity of 664 nm of the plasma of the gas barrier film 10 using the flexible resin substrate unit 2 having no antistatic layer is set to 100, The relative values of the plasma intensity of other gas barrier films were determined, and the plasma intensity was determined according to the following criteria.

○: Relative plasma intensity is 90 or more and 100 or less Δ: Relative plasma intensity is 80 or more and less than 90 ×: Relative plasma intensity is less than 80 [Evaluation of gas barrier properties]
About each gas barrier film, the water-vapor-permeation coefficient was measured according to the Ca measuring method shown below.

(Water vapor barrier property evaluation sample preparation device)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
<raw materials>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), calcium metal was vapor-deposited in a size of 12 mm × 12 mm through a mask on the gas barrier layer forming surface of each produced gas barrier film. At this time, the deposited film thickness was set to 80 nm.

  Subsequently, 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 at a high temperature and high humidity of 60 ° C. and 90% RH, and the state in which metallic calcium was corroded 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, 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 was calculated.

  Next, the relative water vapor permeability of each gas barrier film was determined using the water vapor permeability of the gas barrier film 10 produced using the flexible resin substrate unit 2 having no antistatic layer as 100. The gas barrier properties were evaluated according to the criteria. The higher the relative water vapor transmission rate, the better the gas barrier property and the more stable the gas barrier layer can be formed. In the present invention, if the rank is Δ or more, it is determined that the quality is practically acceptable.

○: Relative water vapor transmission rate is 90 or more and 100 or less Δ: Relative water vapor transmission rate is 80 or more and less than 90 ×: Relative water vapor transmission rate is less than 80 [Evaluation of film surface defect resistance]
A 10 cm × 10 cm region of each gas barrier film produced above is observed with a magnifying glass having an optical magnification of 10 times, and is generated by peeling electrification (sparking) during film transport, and a film surface having a length of 100 μm or more The number of occurrences of cracks was measured, and film surface defect resistance was evaluated according to the following criteria.

○: The number of cracks generated due to abnormal discharge such as peeling charging is 1 or less. Δ: The number of cracks generated due to abnormal discharge such as peeling charging is 2 or more. The number of occurrences of cracks due to abnormal discharge is 11 or more, which is a quality that is practically problematic. Table 2 shows the results obtained from the above.

  As is clear from the results shown in Table 2, the gas barrier films 1 to 9, 15 and 16 of the present invention having an antistatic layer produced using a film forming apparatus constituted by a guide roller defined by the present invention are: During film formation by a plasma CVD apparatus, plasma intensity similar to that of the gas barrier films 10 and 17 that do not have an antistatic layer as a comparative example can be maintained, and film formation stability (plasma intensity stability) In addition, a gas barrier film excellent in gas barrier properties and film surface defect resistance was obtained with respect to the comparative example.

  The film forming method of the present invention is a method in which a functional layer is formed on a flexible resin base material by a roll-to-roll method using a plasma CVD method, and film forming stability, gas barrier properties, and film surface defect resistance are improved. A functional film having an excellent functional layer can be formed, and a gas barrier film that is one of the functional films produced by the film forming method of the present invention is an electronic device such as an organic electroluminescence panel, It can utilize suitably as sealing films, such as an organic electroluminescent element, an organic photoelectric conversion element, and a liquid crystal display element.

DESCRIPTION OF SYMBOLS 1 Film-forming apparatus 2 Flexible resin base material unit 11, 71 Roll laminated body 12, 70 Guide roller (electroconductive)
21, 22, 23, 24 Guide roller (insulating)
25, 26 Guide roller 31, 32 Film forming roller 41 Film forming gas supply pipe 51 Power source 61, 62 Magnetic field generator 80 Vacuum chamber 81 Exhaust port 82 Vacuum pump G Gas barrier film P Plasma CVD processing unit UW unit An Winder part W part Winder part 101 Flexible resin base material 102 Clear hard coat layer 103 Antistatic layer 104 Gas barrier layer

Claims (10)

A film forming apparatus that forms a functional layer on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers in a roll-to-roll system under reduced pressure,
At least an unwinder portion for feeding out a flexible resin base material laminated in a roll shape;
A plasma CVD processing unit comprising a pair of opposed roller electrodes and forming a functional layer on the flexible resin substrate in a discharge space formed between the roller electrodes;
It has a winder part that winds up a flexible resin base material on which a functional layer is formed,
The flexible resin base material that is continuously conveyed has an antistatic layer on the surface (B surface) opposite to the surface (A surface) on which the functional layer is formed,
All of the four guide rollers located at the closest distance on the upstream side and the downstream side in the conveyance direction of the flexible resin base material are electrically connected to the pair of roller electrodes constituting the plasma CVD processing unit. It is composed of insulating rollers with insulating properties ,
The relative unwinder unit or the winder unit, a guide roller which is located closest, electrically deposition apparatus characterized in that it is made of a conductive roller having conductivity. The film-forming apparatus according to claim 1, wherein the insulating roller is a rubber-coated roller or a roller having a ceramic bearing in a core part. The conductive roller, the film forming apparatus according to claim 1 or claim 2, characterized in that a metal roller. Any said flexible resin substrate has a clear hard coat layer on the surface A side, to the clear hard coat layer, from claim 1, characterized in that to form the functional layer to claim 3 The film forming apparatus according to claim 1. It said flexible on the resin base material film forming apparatus according to any one of claims 1, characterized in that to form a gas barrier layer as the functional layer to claim 4. A film forming method in which a functional layer is formed by a plasma CVD processing method having a plasma CVD processing section on a flexible resin substrate that is continuously conveyed while being held by a plurality of guide rollers in a roll-to-roll system under reduced pressure. There,
The flexible resin base material has an antistatic layer on the surface (B surface) opposite to the surface (A surface) forming the functional layer,
The plasma CVD processing unit forms a plasma discharge space by applying a voltage between a pair of opposed roller electrodes, and forms a functional layer on the flexible resin substrate in the plasma discharge space,
All of the four guide rollers located at the closest distance on the upstream side and the downstream side in the conveyance direction of the flexible resin base material are electrically connected to the pair of roller electrodes constituting the plasma CVD processing unit. to constitute an insulating roller having an insulating property, to form the functional layer in the plasma CVD processing unit,
Electrically conducting the guide roller located at the closest distance to the unwinder part that feeds out the flexible resin base material laminated in a roll shape or the winder part that winds up the flexible resin base material on which the functional layer is formed. film how to characterized in that it constitutes a conductive roller having a resistance. The film forming method according to claim 6 , wherein a rubber-coated roller or a roller having a ceramic bearing in a core portion is used as the insulating roller. The film forming method according to claim 6 , wherein a metal roller is used as the conductive roller. It said flexible resin substrate has a clear hard coat layer on the surface A side, to the clear hard coat layer, claims 6 to 8, characterized in that to form the functional layer The film-forming method as described in any one of these. Wherein as a functional layer, the film forming method according to any one of claims 6 to 9, characterized in that to form a gas barrier layer.

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