JP5069174B2 - Gas barrier film manufacturing apparatus and gas barrier film manufacturing method - Google Patents

Description

The present invention relates to an apparatus for manufacturing a gas barrier film and a method for manufacturing the gas barrier film , and more particularly to an apparatus for manufacturing a gas barrier film in which an inorganic film is formed on an organic film made of a specific polymer and a method for manufacturing the gas barrier film .

  Various devices such as optical devices such as gas barrier films, protective films, optical filters or antireflection films, etc. in various devices such as display devices such as optical elements, liquid crystal displays or organic EL displays, semiconductor devices, and thin film solar cells A film (functional sheet) is used.

In addition, film formation (thin film formation) by a vacuum film formation method such as sputtering or plasma CVD is used for manufacturing these functional films.
In order to perform film formation efficiently and with high productivity by the vacuum film formation method, it is preferable to perform film formation continuously on a long substrate.
As equipment for carrying out such a film forming method, a supply roll formed by winding a long substrate (web-shaped substrate) in a roll shape, and a winding roll for winding a film-formed substrate in a roll shape, A so-called roll-to-roll film forming apparatus is known. This roll-to-roll film forming apparatus inserts a long substrate from a supply roll to a take-up roll through a predetermined path that passes through a film formation chamber for forming a film on a substrate by plasma CVD. The film is continuously formed on the transported substrate in the film forming chamber while the substrate is fed out and the film-formed substrate is taken up by the take-up roll in synchronization.

In such a roll-to-roll film forming apparatus, it is not preferable that a foreign substance is present on the surface of the substrate on which the film is formed in order to manufacture a product of appropriate quality.
When transporting a long substrate, the surface of the substrate may be rubbed or damaged. Thus, it is not preferable that the surface of the substrate is damaged during transportation because the quality of the finally obtained product is deteriorated.
Therefore, various transport means have been proposed in order to prevent the substrate from being scratched during transport (see Patent Document 1).

  The film conveyance roll of patent document 1 is the structure conveyed by non-contact, without a plastic film and a roll touching directly by flowing fluids, such as air, between a conveyance roll and a plastic film. With this configuration, in Patent Document 1, it is possible to prevent scratches on the plastic film due to roll rubbing on the plastic film, biting of foreign matter, and the like.

JP 2000-86032 A

In the roll-to-roll film forming apparatus described above, a conveying means for conveying roller pairs (nip rollers) is usually arranged in order to properly convey the substrate along a predetermined path.
However, in the production of a functional film in which an inorganic film is formed by a vacuum film forming method after forming an organic film, depending on the type of organic film, a substrate such as a transport roller pair is usually used for transporting a substrate in a vacuum. If the transport means is used, the flatness of the organic film is lowered, and for example, there may be a case where a functional film having a target performance such as a sufficient gas barrier property cannot be produced.
Since this phenomenon deteriorates the surface properties of the organic film itself, no effect can be obtained even if foreign matter is removed before film formation.

In addition, although the film transport roll of Patent Document 1 can be transported in a non-contact manner, it flows fluid such as air, so there is a risk that dust in the chamber may be raised in a vacuum environment. When this dust adheres to the surface of the substrate, it becomes a defective product as a final product. Thus, there is a concern about the adverse effect on film formation due to adhesion of dust or the like.
Furthermore, since the film conveyance roll of the above-mentioned patent document 1 flows fluids, such as air, it is also difficult to maintain the vacuum degree in a vacuum chamber. For this reason, it is difficult to use the film transport roll of Patent Document 1 for transporting a substrate in a vacuum.

The object of the present invention is to solve the problems based on the above prior art, and to provide a high-quality gas barrier film having a predetermined performance for a gas barrier film having an organic film mainly composed of a polymer and an inorganic film formed thereon. it is to provide a apparatus and method for manufacturing a gas barrier film of the gas barrier film can be produced stably the gas barrier film.

In order to achieve the above object, the first aspect of the present invention includes a conveying means for conveying a substrate having an organic film formed on the surface of a long substrate in a longitudinal direction in a vacuum, and the conveying means A film forming means for depositing an inorganic film on the surface of the organic film of the substrate transported in the longitudinal direction by a vacuum film forming method, and the transport means has a roller in contact with the surface of the organic film. An apparatus for producing a gas barrier film , wherein the substrate is transported in the longitudinal direction in a contact pressure range of 10 to 200 gf / cm ^{2 where} the roller contacts the surface of the organic film. It is to provide.

In the present invention, the transport unit includes a slack portion that loosens a part of the substrate in a loop shape in a direction orthogonal to the transport direction of the substrate, on the upstream side of the roller in the transport direction. It is preferable that the surface pressure of the contact region is in the range of 10 to 200 gf / cm ² by adjusting the amount of looseness of the substrate in the slack portion.
Further, in the present invention, it further includes processing means for performing at least one of a reforming process, a degassing process, and a dust removing process on the surface of the organic film of the substrate transported by the transporting means, The processing means is preferably provided on the upstream side in the transport direction with respect to the film forming means.
Furthermore, in the present invention, it is preferable that the film forming unit forms the inorganic film while winding the substrate around a drum and transporting the substrate in the longitudinal direction.
In the transport unit, one or a plurality of rollers may be in contact with the surface of the organic film. When there are a plurality of rollers in contact with the surface of the organic film, the substrate is transported in the range of 10 to 200 gf / cm ² for the surface pressure of the contact region for each roller.

According to a second aspect of the present invention, an inorganic film is vacuum-deposited on the surface of the organic film of the substrate while conveying the substrate in which the organic film is formed on the surface of a long base in the longitudinal direction. Having a step of forming a film by a method, and transporting the substrate using a roller in contact with the surface of the organic film when transporting the substrate to form the inorganic film on the surface of the organic film of the substrate The surface pressure of the contact region where the roller and the surface of the organic film are in contact with each other is in the range of 10 to 200 gf / cm ² , and the method for producing a gas barrier film is provided.

In the present invention, for example, in the step of transporting a substrate having an organic film formed on the surface of the long substrate in the longitudinal direction, it is orthogonal to the transport direction of the substrate upstream of the roller in the transport direction. A part of the substrate is loosened in a loop shape in the direction to be conveyed, and the substrate is transported. By adjusting the amount of looseness of the substrate, the contact area has a surface pressure of 10 to 200 gf / cm ² . To do.
In the present invention, before the step of forming the inorganic film by a vacuum film forming method, at least one of a modification process, a degassing process, and a dust removing process is performed on the surface of the organic film of the substrate. It is preferable to have the process to apply.
Further, in the present invention, in the step of forming an inorganic film on the surface of the organic film of the substrate by a vacuum film forming method, the inorganic film is formed while the substrate is wound around a drum and conveyed in the longitudinal direction. It is preferable to form a film.
In the present invention, one or a plurality of rollers may be in contact with the surface of the organic film. When there are a plurality of rollers in contact with the surface of the organic film, the substrate is transported in the range of 10 to 200 gf / cm ² for the surface pressure of the contact region for each roller.

According to the present invention, an organic film having a polymer as a main component, for example, a polymer obtained by polymerizing an acrylate monomer and / or a methacrylate monomer having an ethylenically unsaturated bond as an organic film on a substrate as a main component. The gas barrier film is manufactured by forming an inorganic film on the surface of the organic film while transporting the long substrate on which the organic film is formed in a vacuum. For transporting the substrate for forming an inorganic film on the surface of the organic film of the substrate, a roller that contacts the surface of the organic film is used, and the surface pressure of the contact region where the roller and the surface of the organic film contact is set to 10. It conveys in the range of -200 gf / cm < ² >.
As a result, when the substrate on which the organic film is formed is transported (handled), the inorganic film can be formed without deteriorating the surface properties of the organic film even if it contacts the organic film. In addition, it is possible to stably produce a highly functional gas barrier film that appropriately expresses the characteristics.

Below, based on the suitable embodiment shown in an accompanying drawing, the manufacturing device of the gas barrier film and the manufacturing method of the gas barrier film of the present invention are explained in detail.
FIG. 1 is a schematic diagram showing a functional film manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a functional film manufactured by the functional film manufacturing apparatus according to the embodiment of the present invention.

A functional film manufacturing apparatus 10 (hereinafter simply referred to as a manufacturing apparatus 10) according to an embodiment of the present invention shown in FIG. 1 is an apparatus that continuously forms a film on a long substrate Z (web-shaped substrate Z). It is a roll-to-roll type device.
The manufacturing apparatus 10 uses a substrate Z (see FIG. 2) in which an organic film b is formed on a surface Bf of a long base B, and has a predetermined function on the surface Zf of the substrate Z, that is, the surface bf of the organic film b. The functional film F (refer FIG. 2), such as an optical film or a gas barrier film, is manufactured, for example.
As will be described later, the organic film b is prepared by polymerizing an acrylate monomer and / or a methacrylate monomer having an ethylenically unsaturated bond.

The manufacturing apparatus 10 basically includes a supply chamber 12 for supplying a long substrate Z, a first transfer chamber 14, a pretreatment chamber 16, a second transfer chamber 18, and an inorganic film f on the substrate Z. A film forming chamber 20 for forming the substrate, a third transfer chamber 22 for transferring the substrate Z on which the inorganic film f is formed, a winding chamber (not shown) for winding the functional film F, and a vacuum exhaust unit 24 and a control unit 26. The operation of each element in the manufacturing apparatus 10 is controlled by the control unit 26.
Further, in the manufacturing apparatus 10, a wall 15 a that partitions the supply chamber 12 and the first transfer chamber 14, a wall 15 b that partitions the first transfer chamber 14 and the pretreatment chamber 16, the pretreatment chamber 16 and the second transfer chamber 14. On the wall 15c that partitions the transfer chamber 18, the wall 15d that partitions the second transfer chamber 18 and the film forming chamber 20, and the wall 15e that partitions the second transfer chamber 18 and the third transfer chamber 22, A slit-shaped opening 15f through which the substrate Z passes is formed. The third transfer chamber 22 is also provided with a slit-shaped opening 15f for transferring the substrate Z (functional film F) to a winding chamber (not shown).

In the manufacturing apparatus 10, the supply chamber 12, the first transfer chamber 14, the pretreatment chamber 16, the second transfer chamber 18, the film forming chamber 20, the third transfer chamber 22, and a take-up chamber (not shown). The evacuation unit 24 is connected via a pipe 25. In addition, illustration of piping is abbreviate | omitted about the 3rd conveyance chamber 22 and a winding chamber (not shown).
By this evacuation unit 24, the supply chamber 12, the first transfer chamber 14, the pretreatment chamber 16, the second transfer chamber 18, the film forming chamber 20, the third transfer chamber 22, and a winding chamber (not shown). The inside of is made a predetermined vacuum.
The evacuation unit 24 evacuates the supply chamber 12, the film formation chamber 14, and the winding chamber 16 to maintain a predetermined degree of vacuum, and includes a vacuum pump such as a dry pump and a turbo molecular pump. The supply chamber 12, the film formation chamber 14, and the winding chamber 16 are each provided with a pressure sensor (not shown) for measuring the internal pressure.
Note that the supply chamber 12, the first transfer chamber 14, the pretreatment chamber 16, the second transfer chamber 18, the film forming chamber 20, the third transfer chamber 22, and the winding chamber (not shown) by the vacuum exhaust unit 24 are provided. The ultimate vacuum, that is, the ultimate pressure is not particularly limited, and a sufficient degree of vacuum (pressure) may be maintained depending on the film forming method to be performed. The evacuation unit 24 is controlled by the control unit 26.

The supply chamber 12 is a part that supplies a long substrate Z, and is provided with a rotating shaft 30 a and a guide roller 31.
The rotating shaft 30a continuously feeds the long substrate Z, and the substrate roll 30 around which the substrate Z is wound counterclockwise is attached to the rotating shaft 30a, for example.
For example, a motor (not shown) is connected to the rotary shaft 30a as a drive source. With this motor, the rotating shaft 30a is rotated in the direction r to rewind the substrate Z. In this embodiment, the rotating shaft 30a is rotated clockwise, and the substrate Z is continuously fed out from the substrate roll 30.

The guide roller 31 guides the substrate Z to the first transfer chamber 14 through a predetermined transfer path. The guide roller 31 is a known guide roller.
In the manufacturing apparatus 10 of this embodiment, the guide roller 31 may be a driving roller or a driven roller. Further, the guide roller 31 may be a roller that acts as a tension roller that adjusts the tension during conveyance of the substrate Z.

As will be described later, the first transfer chamber 14 has a surface pressure Ps in a contact region where the surface bf of the organic film b of the substrate and the pass roller 46 are in contact with each other in a range of 10 to 200 gf / cm ² (490 Pa to 19.6 kPa). A slack portion 36 is provided.
The first transfer chamber 14 includes a first transfer roller 32 and a second transfer roller 34.
The first transport roller 32 and the second transport roller 34 are arranged in parallel to face each other at a predetermined interval, and the first transport roller 32 and the second transport roller 34 are arranged on the substrate Z. It is arranged with its longitudinal direction orthogonal to the transport direction D.
The first transport roller 32 and the second transport roller 34 have a rotation axis in a direction orthogonal to the transport direction D of the substrate Z (hereinafter referred to as an axial direction) and can rotate, and the first transport roller 32. The second transport roller 34 has an axial length longer than a length in the width direction orthogonal to the longitudinal direction of the substrate Z (hereinafter referred to as the width of the substrate Z).

The substrate Z is slackened below the space h between the first transport roller 32 and the second transport roller 34, and the substrate Z is transported to the pretreatment chamber 16 through the second transport roller 34.
A slack portion 36 of the substrate Z is configured by the first transport roller 32 and the second transport roller 34.
As will be described in detail later, the surface pressure Ps in the contact region of the pass roller 46 is adjusted to a range of 10 to 200 gf / cm ² (490 Pa to 19.6 kPa) by the slack amount α of the substrate Z in the slack portion 36.
The slack amount α is a distance from the rotation shaft (not shown) of the first transport roller 32 and the second transport roller 34 to the tip of the loop.

The pretreatment chamber 16 is a place where at least one of the reforming process, the degassing process, and the dust removing process is performed on the surface bf of the organic film b of the substrate Z.
In the pretreatment chamber 16, at least one of a reforming treatment means, a degassing treatment means, and a dust removal treatment means is provided in the pretreatment section 40 so as to face the surface bf of the organic film b of the substrate Z to be transferred. It is provided as.

  The reforming processing means includes, for example, an oxygen gas supply unit and a plasma generation unit, and generates oxygen plasma above the surface bf of the organic film b of the substrate Z. The oxygen plasma causes the organic film b of the substrate Z to be generated. The surface bf of the surface is modified.

The degassing processing means includes, for example, a heating unit that heats the surface bf of the organic film b of the substrate Z to a predetermined temperature, and performs the degassing process by this heating unit.
By this degassing treatment, a solvent such as MEK (methyl ethyl ketone), moisture, oxygen, nitrogen, etc. attached to the inside of the substrate Z or the inside of the organic film b, or the surface Zf of the substrate Z or the surface Bf of the organic film b, etc. Release from Z and organic film b.

The dust removal processing means includes, for example, a removal roller that removes dirt such as dust, dust, and dust adhering to the surface bf of the organic film b of the substrate Z, and rotates the removal roller while transporting the substrate Z. Thus, dirt such as dust, dust, and dust on the surface bf of the organic film b of the substrate Z is removed.
As the dust removal processing means, an ionizer (electrostatic discharger) may also be used. This ionizer may remove static electricity on the surface bf of the organic film b of the substrate Z, and suppress the adhesion of foreign matters such as dust and dirt to the surface bf of the organic film b of the substrate Z.
As an ionizer, the thing of a corona discharge system and an ion production | generation system can be used, for example.

The second transfer chamber 18 includes a first guide roller 42, a second guide roller 44, and a pass roller 46.
The first guide roller 42 and the second guide roller 44 are arranged in parallel so that the longitudinal direction of the first guide roller 42 and the second guide roller 44 are opposed to each other at a predetermined interval with respect to the transport direction D of the substrate Z. Yes.
One pass roller 46 is provided below the space H between the first guide roller 42 and the second guide roller 44. The pass roller 46 is arranged with its longitudinal direction parallel to the longitudinal directions of the first guide roller 42 and the second guide roller 44.

The first guide roller 42, the pass roller 46, and the second guide roller 44 have a rotation axis in a direction (axial direction) orthogonal to the transport direction D of the substrate Z and can rotate, and the guide roller 50 The length in the axial direction is longer than the width of the substrate Z.
The first guide roller 42, the second guide roller 44, and the pass roller 46 have the same configuration as the guide roller 31 provided in the supply chamber 12 except for the configuration described above, and thus detailed description thereof is omitted. .

By the first guide roller 42, the pass roller 46 and the second guide roller 44, the substrate Z on which the surface bf of the organic film b has been pretreated in the pretreatment chamber 16 is transferred to the film formation chamber 20.
The first guide roller 42 and the second guide roller 44 convey the substrate Z while being in contact with the back surface Zb of the substrate Z.

In the state where the substrate Z is wound around the surface (circumferential surface) 46a of the pass roller 46 with the surface bf of the organic film b facing, the surface 46a of the pass roller 46 and the surface bf of the organic film b are in contact with each other. In this state, the substrate Z is transported in the transport direction D.
In the present embodiment, the first guide roller 42 has a surface pressure Ps of 10 to 200 gf / cm ² (490 Pa to 19.6 kPa) in a contact region where the surface bf of the organic film b of the substrate contacts the pass roller 46. Then, the substrate Z transferred from the pretreatment chamber 16 by the pass roller 46 and the second guide roller 44 is transferred to the film forming chamber 20.
In the present invention, the number of pass rollers 46 that contact the surface bf of the organic film b is not limited to one, and there may be a plurality of pass rollers 46 that contact the surface bf of the organic film b.
Thus, when there are a plurality of pass rollers 46 in contact with the surface bf of the organic film b, it is necessary to transport the substrate Z with the surface pressure Ps in the contact area of 10 to 200 gf / cm ² for each pass roller 46. .

In the present invention, the reason why the surface pressure Ps in the contact region is 10 to 200 gf / cm ² (490 Pa to 19.6 kPa) will be described in detail later.
The surface pressure Ps (10 to 200 gf / cm ² (490 Pa to 19.6 kPa)) defined in the present invention is adjusted by the slack amount α of the substrate Z in the slack portion 36.
In the present embodiment, the surface pressure Ps of the pass roller 46 is measured, and the relationship between the amount of slack α of the substrate Z in the slack portion 36 and the surface pressure Ps of the pass roller 46 is obtained in advance, and the surface pressure Ps during transport of the substrate Z is obtained. Is conveyed while maintaining a predetermined amount of the slack amount α so that the value falls within the above range.
Furthermore, when there are a plurality of pass rollers 46 that contact the surface bf of the organic film b, the relationship between the slack amount α of the substrate Z in the slack portion 36 and the surface pressure Ps of each pass roller 46 is obtained in advance. When Z is conveyed, the sheet is conveyed while maintaining a predetermined amount of the slack amount α so that the surface pressure Ps in the contact area of each pass roller 46 is in the above range.

Further, there is a correlation between the tension T acting in the direction opposite to the conveyance direction D in the conveyance path and the surface pressure Ps of the pass roller 46. There is also a correlation between the tension T and the amount of slack α of the substrate Z at the slack portion 36. That is, there is a correlation between the tension T and the own weight W of the substrate Z. Therefore, the tension T can be changed by changing the slack amount α. From this, the surface pressure Ps of the pass roller 46 can be adjusted by changing the amount of slack α of the substrate Z by the slack portion 36.
Therefore, the relationship between the tension T and the surface pressure Ps of the pass roller 46 and the relationship between the slack amount α of the substrate Z and the tension T in the slack portion 36 are obtained in advance, and the surface pressure Ps is within the above range when the substrate Z is transported. The slack amount α is conveyed while maintaining a predetermined amount so that the tension T is generated.
Even in this case, when there are a plurality of pass rollers 46 that contact the surface bf of the organic film b, the relationship between the tension T and the surface pressure Ps of each pass roller 46 and the amount of slack α of the substrate Z in the slack portion 36. The relationship with the tension T is obtained in advance, and when the substrate Z is transported, it is transported while maintaining a predetermined amount of the slack amount α so that the tension T in which the surface pressure Ps of each pass roller 46 falls within the above range is generated. .

  The film forming chamber 20 continuously transfers the substrate Z on the surface bf of the organic film b (surface Zf of the substrate Z) formed on the surface Bf of the base B, among the vacuum film forming methods, for example, plasma. This is a portion where the inorganic film f is formed by the CVD method. In the film forming chamber 20, a drum 48 and a film forming unit 50 are provided.

The drum 48 has, for example, a cylindrical shape, has a rotation axis A, and can rotate in the rotation direction ω with respect to the rotation axis A. The drum 48 is arranged with its longitudinal direction in a direction orthogonal to the transport direction D and parallel to the longitudinal direction of the second guide roller 44. The length of the drum 48 in the axial direction is longer than the width of the substrate Z, and the drum 48 is grounded (not shown).
In the present embodiment, the drum 48 is wound around the surface 48a (circumferential surface) and rotated in the rotation direction ω, thereby holding the substrate Z at a predetermined film formation position and in the transport direction. The substrate Z is transported to D.

  The rotation shaft 30a, the guide roller 31, the first conveyance roller 32, the second conveyance roller 34, the slack portion 36, the first guide roller 40, the pass roller 46, and the second guide roller 44 are used to convey the present invention. Means are configured.

In order to adjust the temperature, the drum 48 may be provided with, for example, a heater (not shown) and a temperature sensor (not shown) for measuring the temperature of the drum 48 at the center of the drum 48. Furthermore, a pipe (not shown) for circulating the refrigerant and a pump (not shown) for circulating the refrigerant may be provided inside the drum 48. The piping, the refrigerant, and the pump constitute a cooling means.
The heater, pump, and temperature sensor are connected to a temperature adjustment unit (not shown). The temperature adjusting unit is connected to the control unit 26, and the temperature of the drum 48 is adjusted by the control unit 26 via the temperature adjusting unit, and the temperature of the drum 48 is maintained at a predetermined temperature. A temperature adjusting means is constituted by a heater (not shown), a cooling means (not shown), a temperature sensor (not shown), and a temperature adjusting unit (not shown).
The drum 48 is heated to an appropriate temperature by the temperature adjusting means according to the composition of the inorganic film f to be formed. Thereby, it is possible to obtain an inorganic film f with even better quality.

The film forming unit 50 was formed on the surface Zf of the substrate Z while the substrate Z was transported in the transport direction D while the substrate Z was wound around the drum 48 and the drum 48 was rotated in the rotational direction ω. An inorganic film f is formed on the organic film b.
The film forming unit 50 forms a film by, for example, a plasma CVD method among vacuum film forming methods. As this plasma CVD method, for example, a capacitively coupled plasma CVD method (CCP-CVD method) is used.
The film forming unit 50 includes film forming electrodes 52 a to 52 d, a high frequency power supply 54, and a source gas supply unit 56. The control unit 26 controls the high frequency power supply 54 and the source gas supply unit 56 of the film forming unit 50.

  In the film forming unit 50, a plurality of film forming electrodes 52a to 52d are provided. Each of the film forming electrodes 52a to 52d is formed of, for example, a flat plate-like electrode plate having a rectangular shape in plan view, and a plurality of holes (not shown) are formed at equal intervals on a wide surface. This is called an electrode. Each of the film forming electrodes 52a to 52d is electrically connected, for example, at an end portion in the longitudinal direction. The position where each of the film forming electrodes 52a to 52d is conducted is not particularly limited as long as the conduction is maintained.

  Each of the film forming electrodes 52a to 52d has a longitudinal direction parallel to the rotation axis A of the drum 48 and a wide surface facing the surface 48a of the drum 48, with a predetermined gap S from the surface 48a of the drum 48, The drums 48 are arranged in contact with each other along the rotational direction ω so as to surround the surface 48 a of the drum 48. For example, each of the film forming electrodes 52 a to 52 d is matched with a tangential line on the concentric circle of the surface 48 a of the drum 48.

Each film-forming electrode 52a to 52d is connected to a high-frequency power supply 54, and the high-frequency power supply 54 applies a high-frequency voltage to each film-forming electrode 52a to 52d of each film-forming electrode 52a to 52d. The high frequency power supply 54 can change the applied high frequency power (RF power).
Moreover, you may connect each film-forming electrode 52a-52d and the high frequency power supply 54 via the matching box for taking an impedance matching as needed.
In the present embodiment, the gaps S between the film forming electrodes 52a to 52d and the surface 48a of the drum 48 are the same. Even if the gaps vary in the gaps S, for example, they are within 20%. It is preferable.

The source gas supply unit 56 supplies, for example, a source gas for forming the inorganic film f into the gap S through a plurality of holes of the film forming electrodes 52 a to 52 d via the pipe 58. A gap S between the surface 48a of the drum 48 and each of the film forming electrodes 52a to 52d becomes a plasma generation space.
In this embodiment, as the raw material gas, for example, when an SiO ₂ film is formed as the inorganic film f, TEOS gas and oxygen gas as the active species gas are used. Further, when a silicon nitride film is formed as the inorganic film f, SiH ₄ gas, NH ₃ gas, and N ₂ gas are used.

As the source gas supply unit 56, various gas introduction means used in a CCP-CVD apparatus or the like can be used.
In the source gas supply unit 56, various gases used in the CCP-CVD method, such as not only the source gas but also inert gas such as argon gas or nitrogen gas, and active species gas such as oxygen gas, etc. May be supplied to the gap S together with the raw material gas. As described above, when a plurality of types of gases are introduced, the gases may be mixed in the same pipe and supplied to the gap S through the plurality of holes of the film forming electrodes 52a to 52d. You may supply to the clearance gap S through several holes of each film-forming electrode 52a-52d from piping.
Further, the types or introduction amounts of the source gas or other inert gas and active species gas may be appropriately selected / set according to the type of film to be formed, the target film formation rate, or the like.

  As the high-frequency power source 54, a known high-frequency power source used for film formation by plasma CVD can be used. Further, the high-frequency power supply 54 is not particularly limited in the maximum output and the like, and may be appropriately selected / set according to the film to be formed or the film formation rate.

The third transfer chamber 22 is a part for transferring the functional film F produced in the film forming chamber 20 to a take-up chamber (not shown). In the third transfer chamber 22, a guide roller 60 is provided. Is provided.
The guide roller 60 guides the substrate Z (functional film F) transported from the film forming chamber 20 to a winding roll (not shown) in the winding chamber through a predetermined transport path. The guide roller 60 has the same configuration as that of the guide roller 31 in the previous supply chamber 12. Like the guide roller 31 in the supply chamber 12, the guide roller 60 may be a drive roller or a driven roller. The guide roller 31 may be a roller that acts as a tension roller.

The manufacturing apparatus 10 of the present embodiment winds the substrate Z made of the base B on which the organic film b is formed in a roll shape, and loads the roll into the manufacturing apparatus 10 that forms the inorganic film f to form the organic film. The functional film F is manufactured by forming an inorganic film f on the surface b of b.
Note that the organic film b and the inorganic film f may be continuously formed while the substrate B is conveyed as long as the surface bf of the organic film b is not in contact with outside the pressure range.

Next, a method for forming the organic film b constituting the substrate Z of this embodiment will be described.
FIG. 3 is a schematic diagram showing an organic film production apparatus for a substrate used in the functional film production apparatus of the embodiment of the present invention.

In the substrate Z used in the functional film F manufacturing apparatus 10 of the present embodiment, for example, the organic film b is formed on the surface of the base B by an organic film forming apparatus 70 as shown in FIG.
The organic film forming apparatus 70 is an apparatus for forming an organic film b on the surface of the base B by applying / drying a paint containing a monomer (monomer mixture) to be the organic film b to the base B and polymerizing the monomer. It is.
The organic film forming apparatus 70 includes a coating unit 72, a drying unit 74, a UV irradiation device 76, a rotating shaft 78, and a winding shaft 80.
In the organic film forming apparatus 70, the coating film 72 is formed by applying a coating material containing a monomer prepared in advance onto the substrate B, drying, and polymerizing the coating film.
In the present invention, when the organic film b is formed by photopolymerization such as photopolymerization such as UV irradiation or visible light irradiation, the paint containing the monomer preferably contains a photopolymerization initiator. This will be explained later.

  The organic film forming apparatus 70 forms an organic film b by roll-to-roll, and is loaded on a rotating shaft 78 as a substrate roll 82 around which a base B is wound, while being conveyed in the longitudinal direction. The organic film b is formed, and the substrate Z on which the organic film b is formed is wound around the winding shaft 80 as the substrate roll 30.

  The organic film forming apparatus 70 sends out the substrate B from a substrate roll 82 formed by winding a long substrate B (film raw fabric) into a roll, and forms an organic film b while conveying the substrate B in the longitudinal direction. This is an apparatus for performing film formation by so-called roll-to-roll, in which the substrate Z on which the film b is formed is wound in a roll shape.

In the organic film forming apparatus 70, the long base B is loaded on the rotating shaft 78 as the substrate roll 82 as described above.
When the substrate roll 82 is loaded on the rotating shaft 78, the base body B passes from the substrate roll 82 through the lower part of the coating means 72, the drying means 74, and the UV irradiation device 76 and reaches the take-up shaft 80. The route is carried. In the organic film forming apparatus 70, the feeding of the base B from the substrate roll 82 and the winding of the substrate Z on the winding shaft 80 are performed in synchronization, and the long base B is moved in the longitudinal direction along a predetermined transport path. The substrate Z is formed by continuously forming the organic film b on the substrate B.

  In the organic film forming apparatus 70, the base B sent out from the substrate roll 82 is first transported to the coating means 72. The coating means 72 is for applying a paint containing a monomer to be the organic film b prepared in advance on the surface of the base B. As will be described later, all the usual liquid application methods can be used for applying the paint.

  There is no particular limitation on the coating method including a monomer that becomes the organic film b prepared in advance on the surface bf of the substrate B by the coating means 72, and there is no particular limitation. Dip coating method, air knife coating method, curtain coating method, roller coating method Any known method such as a wire bar coating method, a gravure coating method, a slide coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294 may be used.

Next, the substrate B is conveyed to the drying means 74.
The drying means 74 dries the paint applied by the applying means 72. There is no particular limitation on the method of drying the paint, and the paint can be dried before reaching the UV irradiation device 76 according to the conveyance speed of the substrate B, such as heat drying with a heater, heat drying with warm air, or the like. Any known drying means can be used.

Next, the substrate B is conveyed to the UV irradiation device 76.
The UV irradiation device 76 polymerizes the monomer by irradiating the coating material applied by the applying means 72 and dried by the drying means 74 with UV light (ultraviolet rays) as in the previous example, thereby forming the organic film b. To do.
The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more.

In the organic film forming apparatus 70, the monomer is polymerized by irradiating UV light to form the organic film b.
Thus, when performing photopolymerization, it is preferable that the coating material apply | coated by the application means 72 contains a photoinitiator (it is preferable to use a photoinitiator together).
Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc. commercially available from Ciba Specialty Chemicals as photopolymerization initiators. ), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, etc.) commercially available from Sartomer Similarly, oligomer type Ezacure KIP series and the like can be mentioned.

The polymerization method of the monomer is not limited to the ultraviolet irradiation in the illustrated example, and heat polymerization, light (visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination of these (including ultraviolet irradiation) is also preferably used.
When performing heat polymerization, the substrate B needs to have appropriate heat resistance. In this case, at least the glass transition temperature (Tg) of the substrate B needs to be higher than the heating temperature.

Here, acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air.
Accordingly, in the present invention, when these are used as the organic film b, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization.
When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. In addition, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

  In the present invention, the polymerization rate of the monomer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. The polymerization rate here means the ratio of the reacted polymerizable groups among all polymerizable groups in the monomer mixture (for example, acrylate or methacrylate, acryloyl group and methacryloyl group).

In the present embodiment, the method for forming the organic film b is not limited to the coating method as described above, and a vacuum film forming method can also be suitably used.
Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable. Of these, the flash vapor deposition methods described in US Pat. Nos. 4,842,893, 4,954,371, and 5,034,461 are particularly preferable. The flash vapor deposition method is particularly useful because it has an effect of reducing dissolved oxygen in the monomer and can increase the polymerization rate.
In the present invention, a polymer may be applied by a solution, or a hybrid coating method containing an inorganic substance as disclosed in JP-A Nos. 2000-323273 and 2004-25732 may be used. Alternatively, a polymer layer may be formed by polymerizing a polymer precursor (for example, a monomer) after film formation. Furthermore, the organic film b can also be formed by applying and curing a commercially available polymerizable adhesive.

In the present embodiment, the organic film b formed as described above is preferably smooth and has a high film hardness. The smoothness of the organic film b is preferably 10 nm or less, and more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm square.
It is preferable that the film hardness of the organic film b has a certain hardness. The preferable hardness is preferably 100 N / mm ² or more, more preferably 200 N / mm ² or more as the indentation hardness when measured by the nanoindentation method. The pencil hardness is preferably HB or higher, more preferably H or higher.
The film thickness of the organic film b is not particularly limited, but if it is too thin, it is difficult to obtain film thickness uniformity, and if it is too thick, cracks are generated due to external force and the barrier performance is lowered. From this viewpoint, the thickness of the organic film b is preferably 10 nm to 2 μm, and more preferably 100 nm to 1 μm.

The organic film b is not limited to a single layer, and two or more layers may be formed.
In this case, each organic film may have the same composition or a different composition. Further, when two or more organic films are formed, it is preferable that each organic film is within the above-described preferable range.

  As shown in FIG. 1, a substrate roll 30 wound with a substrate Z made of a base B on which an organic film b is formed, produced by an organic film forming apparatus 70, has a rotating shaft 30 a in a supply chamber 12 of the manufacturing apparatus 10. Is loaded.

  In the present invention, the substrate B on which the organic film b is formed (the substrate Z of the functional film F) is not particularly limited, and various resins such as PET film and PEN film, and various metals such as an aluminum sheet. Various substrates used for various functional films such as a gas barrier film, an optical film, and a protective film, as long as an organic film b and an inorganic film f can be formed by vacuum film formation, such as a sheet. (Base film) are all available. Further, the base B may have a surface on which various films such as a protective film or an adhesive film are formed.

Hereinafter, the organic film b formed on the surface bf of the substrate B in the substrate Z will be described.
Specifically, the organic film b is made of polyester, acrylic resin, methacrylic resin (hereinafter, acrylic resin and methacrylic resin are also referred to as acrylate polymer), methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, Polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetheretherketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modification It is a layer of a thermoplastic resin such as polycarbonate, fluorene ring-modified polyester, acryloyl compound, or polysiloxane or other organic silicon compound.
The organic film b may be made of a single material or a mixture. Two or more organic films may be stacked. In this case, each layer may have the same composition or a different composition. Further, as disclosed in US Patent Publication No. 2004-46497, a layer in which the interface with the inorganic film is not clear and the composition continuously changes in the film thickness direction may be used.

In the present invention, preferred monomers that can be used for forming the organic film b include acrylates and methacrylates, and commercially available adhesives. That is, in the present invention, the organic film b is preferably composed mainly of a polymer obtained by polymerizing an acrylate monomer and / or a methacrylate monomer having an ethylenically unsaturated bond. In particular, when an acrylate monomer and / or a methacrylate monomer are used for forming the organic film b for the purpose of avoiding inconvenience in a vacuum, which will be described later, those having a molecular weight of 700 or less, especially 150 to 600 are used. It is preferable to use it.
Examples of the commercially available adhesive include Ezonec series made by Daizonichimomori, XNR-5000 series made by Nagase ChemteX, and 3000 series made by ThreeBond.
Preferable examples of acrylate and methacrylate include, for example, compounds described in US Pat. Nos. 6,083,628 and 6,214,422. Some of these are exemplified below.

  Other examples include the following compounds.

In the present invention, a particularly preferable organic film b is a polymer having a structural unit represented by the following general formula (I) having a structural unit in which m is 2 and a structural unit in which m is 3 or more. Polymer) as a main component.
Formula (I)
(Z-COO) _m -L
[In general formula (I), Z is represented by the following (a) or (b), R ¹ and R ² in the above structure each independently represent a hydrogen atom or a methyl group, and * represents general formula (I ) Represents a position bonded to a carbonyl group, and L represents an m-valent linking group. The m Zs may be the same as or different from each other, but at least one Z is represented by the following (a). ]

The organic film b is, in particular, a polymer having a structural unit in which m is 2 and a structural unit in which m is 3, a polymer having a structural unit in which m is 2 and a structural unit in which m is 4 or more, The film is preferably a film containing as a main component any one of a polymer having a structural unit in which m is 2, a structural unit in which m is 3, and a structural unit in which m is 4 or more.
Or you may have two or more of these polymers, and may become the main component of the organic film b collectively.

L is an m-valent linking group. In the present invention, the carbon number of L is not particularly limited, but is preferably 3 to 18, more preferably 4 to 17, further preferably 5 to 16, and particularly preferably 6 to 15.
When m is 2, L is a divalent linking group. Examples of such divalent linking groups include alkylene groups (for example, 1,3-propylene group, 2,2-dimethyl-1,3-propylene group, 2-butyl-2-ethyl-1,3-propylene). Group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, 1,16-hexadecylene group, etc.), ether group, imino group, carbonyl group, and a plurality of these divalent groups. Examples include divalent residues bonded in series (for example, polyethyleneoxy group, polypropyleneoxy group, propionyloxyethylene group, butyroyloxypropylene group, caproyloxyethylene group, caproyloxybutylene group). Among these, an alkylene group is preferable.

L may have a substituent.
Examples of the substituent that can substitute L include an alkyl group (for example, a methyl group, an ethyl group, and a butyl group), an aryl group (for example, a phenyl group), and an amino group (for example, an amino group, methylamino). Group, dimethylamino group, diethylamino group, etc.), alkoxy group (for example, methoxy group, ethoxy group, butoxy group, 2-ethylhexyloxy group, etc.), acyl group (for example, acetyl group, benzoyl group, formyl group, pivaloyl group) Etc.), alkoxycarbonyl groups (eg methoxycarbonyl group, ethoxycarbonyl group etc.), hydroxy groups, halogen atoms (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group and the like. As the substituent, a group having no oxygen-containing functional group is preferable for the reason described later, and particularly an alkyl group.
That is, when m is 2, L is most preferably an alkylene group having no oxygen-containing functional group. By employing such a group, when the present invention is used for the production of a gas barrier film, the water vapor permeability of the obtained gas barrier film can be further reduced.

When m is 3, L represents a trivalent linking group. Examples of such a trivalent linking group include a trivalent residue obtained by removing one hydrogen atom from the above divalent linking group, or an arbitrary hydrogen atom from the above divalent linking group. And a trivalent residue obtained by substituting an alkylene group, an ether group, a carbonyl group, and a divalent group in which these are connected in series. Among these, a trivalent residue containing no oxygen-containing functional group obtained by removing one arbitrary hydrogen atom from an alkylene group is preferable. When this invention is utilized for manufacture of a gas barrier film among functional films, it becomes possible to make the water vapor permeability of the obtained gas barrier film lower.
When m is 4 or more, L represents a tetravalent or higher linking group. Examples of such tetravalent or higher valent linking groups are also given. Preferred examples are also given. In particular, a tetravalent residue which does not contain an oxygen-containing functional group and is obtained by removing two arbitrary hydrogen atoms from an alkylene group is preferable. By adopting such a group, when the present invention is used for production of a gas barrier film among functional films, the water vapor permeability of the obtained gas barrier film can be further reduced.

  In the present invention, when the polymer that forms the organic film b is a polymer including a structural unit in which m is 2 and m is 3 or more in the general formula (I), this polymer has m of 2 and / or The structural unit 3 is preferably 75 to 95% by mass, more preferably 75 to 90% by mass, and even more preferably 75 to 85% by mass.

When the polymer that forms the organic film b is a polymer that includes a structural unit in which m is 2 and a structural unit in which m is 3 in the general formula (I), the polymer has a structural unit in which m is 2 in the range of 60 to 80 mass. % Is preferable, and 65 to 75% by mass is more preferable. On the other hand, the structural unit in which m is 3 is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.
By setting it as such a range, coexistence of film | membrane hardness and a polymerization rate is exhibited more effectively, and it is preferable.

  In addition, when the polymer forming the organic film b is a polymer having a structural unit in which m is 2 and a structural unit in which m is 4 or more in the general formula (I), this polymer has m of 4 The above structural unit is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass. Further, m is preferably 4.

  Furthermore, when the polymer that forms the organic film b is a polymer that includes a structural unit in which m is 2 in the general formula (I), a structural unit in which m is 3, and a structural unit in which m is 4 or more, The polymer preferably contains 75 to 95% by mass, more preferably 75 to 90% by mass, and 75 to 85% by mass in total of the structural unit where m is 2 and the structural unit where m is 3. Is more preferable. The structural unit having m of 4 or more is preferably 5 to 25% by mass, more preferably 10 to 25% by mass, and further preferably 15 to 25% by mass.

The polymer that is the main component of the organic film b may have a structural unit not represented by the general formula (I).
For example, you may have a structural unit formed when an acrylate monomer and a methacrylate monomer are copolymerized. In the polymer, the structural unit not represented by the general formula (I) is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

As described above, the organic film b is a film mainly composed of a polymer having a structural unit represented by the general formula (I). The “main component” referred to here is represented by the general formula (I). It means that the polymer having the structural unit represented is 80% by mass or more of the total weight of the organic film. In particular, in the organic film b, the polymer is preferably 90% by mass or more.
Although there is no limitation in particular in the polymer which does not have the structural unit represented by general formula (I) which can be contained in the organic film b, As an example, polyester, a methacrylic acid-maleic acid copolymer, polystyrene, Transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetherketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, Examples include alicyclic modified polycarbonate, fluorene ring modified polyester, and the like.

一般式（II）において、Ｒ^３は水素原子またはメチル基を表し、Ｌはｎ価の連結基を表す。ｎが２以上の場合、それぞれのＲ^３は同一であってもよいし、異なっていてもよい。 Such a polymer, which is the main component of the organic film b, is obtained by polymerizing a mixture (monomer mixture) containing a monomer having n of 2 in the following general formula (II) and a monomer having n of 3 or more. Can be polymerized.
Formula (II)

In the general formula (II), R ³ represents a hydrogen atom or a methyl group, and L represents an n-valent linking group. When n is 2 or more, each R ³ may be the same or different.

That is, in other words, in the particularly preferable method for producing the functional film F of the present invention, the surface Bf of the substrate B contains a monomer having n of 2 in the general formula (II) and a monomer having n of 3 or more. Then, an inorganic film f is formed on the surface bf of the organic film b by a vacuum film forming method using a material in which the organic film b is formed by polymerizing the monomer mixture. When the substrate Z is transported, the contact pressure Ps of the contact area between the surface 46a of the pass roller 46 and the surface bf of the organic film b in contact with the organic film b in vacuum is 10 to 200 gf / cm ² (490 Pa to 19.6 kPa). It is a manufacturing method of the functional film F conveyed by.

Specific examples and preferred ranges of L are the same as the specific examples and preferred ranges of L in the aforementioned general formula (I).
In addition, the preferable range of the content of the monomer in which n is 2 and the monomer in which n is 3 or more (a monomer in which n is 3 or a monomer in which n is 4 or more) in the monomer mixture is In the formula (I), the preferred range of the content of the structural unit where n is 2 and the structural unit where n is 3 or more (the structural unit where n is 3 and the structural unit where n is 4 or more) is the same.

In the present invention, in particular, by polymerizing a monomer mixture containing a monomer in which n is 2 and a monomer in which n is 3, or a monomer in which n is 2 and a monomer in which n is 4 or more The organic film b is formed by polymerizing the monomer mixture contained, or by polymerizing the monomer mixture containing the monomer having n = 2, the monomer n = 3, and the monomer n = 4 or more. A membrane is preferred.
Alternatively, the organic film b may be formed by polymerization using a plurality of these monomer mixtures.

  Specific examples of the monomer in which n in the general formula (II) is 2 or 3 are shown below, but the monomer in which n is 2 or 3 that can be used in the present invention is not limited thereto.

As the monomer in which n in the general formula (II) is 4 or more, a monomer in which n is 4 to 6 is preferably used, and a monomer in which n is 4 is particularly preferable. Specific examples include monomers having a pentaerythritol skeleton and a dipentaerythritol skeleton.
Specific examples of the monomer in which n in the general formula (II) is 4 or more are shown below, but the 4 or more monomers that can be used in the present invention are not limited thereto.

  In the general formula (II), a monomer in which n is 2 and a monomer in which n is 3 or more (a monomer in which n is 3 and a monomer in which n is 4 or more) are each included in the monomer mixture only in one type. Or 2 or more types may be contained.

As described above, in the present invention, it is possible to produce a functional film F having better characteristics when the organic film b is harder.
In order to increase the hardness of the organic film b, the following method is exemplified.
(1) Increase the monomer polymerization rate (2) Use a polyfunctional monomer (3) Do not use a highly flexible oxygen-containing functional group as a linking group for the monomer.
The polymerization rate and the number of functional groups are in a trade-off relationship, and the degree of polymerization decreases as the number of functional groups increases. According to the study by the present inventors, as a result of studying the formulation for increasing the number of functional groups of the monomer and increasing the degree of polymerization, the monomer mixing ratio as described above is preferable.

In order to form the organic film b having good hardness, it is preferable that the mixing ratio of the monomer components is in the following range.
For example, when only a monomer having n of 2 and a monomer having n of 3 is used as the monomer component represented by the general formula (II) in the monomer mixture, the mixing ratio of the monomer having n of 2 is 60. It is preferable that it is -80 mass%, and it is more preferable that it is 65-75 mass%. It is preferable that the monomer whose n is 3 is 20-40 mass%, and it is more preferable that it is 25-35 mass%.

In the monomer mixture, when only the monomer having n of 2 and the monomer having n of 4 or more are used as the monomer component represented by the general formula (II), the mixing ratio of the monomer having n of 2 is used. Is preferably 75 to 95% by mass, more preferably 75 to 90% by mass, and even more preferably 75 to 85% by mass. The mixing ratio of the monomer in which n is 4 or more is preferably 5 to 25% by mass, more preferably 10 to 25% by mass, and further preferably 15 to 25% by mass.
Further, in the monomer mixture, as a monomer component represented by the general formula (II), a mixture containing only a monomer having n of 2, a monomer having n of 3, and a monomer having n of 4 or more is used. Is preferably 75 to 95% by mass, more preferably 75 to 90% by mass, and even more preferably 75 to 85% by mass in terms of the total mixing ratio of monomers in which n is 2 or 3. The mixing ratio of the monomer in which n is 4 or more is preferably 5 to 25% by mass, more preferably 10 to 25% by mass, and still more preferably 15 to 25% by mass.

In the monomer mixture that becomes the organic film b, a monomer not represented by the general formula (II) may be contained. However, these monomers are an obstacle to increasing the hardness of the organic film b described above, and therefore, the amount in the monomer mixture is preferably 20% by mass or less.
The monomer not represented by the general formula (II) is, for example, a monofunctional monomer, and is preferably a monofunctional acrylate monomer or a monofunctional methacrylate monomer. The molecular weight of the monofunctional acrylate monomer or monofunctional methacrylate monomer is not particularly limited, but those having a molecular weight of 150 to 600 are usually used. These monomers may be contained alone or in combination of two or more in the monomer mixture. Although the monofunctional monomer has an effect of increasing the polymerization rate, if the content is too large, the hardness of the organic film to be formed is impaired, so that the content is preferably 20% by mass or less as described above. A more preferable range is the same as the preferable content range of the structural unit not represented by the general formula (I).

  Although the preferable specific example of a monofunctional monomer is shown below, the monofunctional monomer which can be used by this invention is not limited to these.

The monomer mixture for forming the organic film b may contain a phosphoric acid type (meth) acrylate monomer or a (meth) acrylate monomer containing a silane coupling group in order to improve adhesion. The addition amount of these monomers is added so as to match the above-described range of the addition amount depending on the number of functional groups.
Although the preferable specific example of a phosphoric acid type monomer or a silane coupling group containing monomer is shown below, what can be used by this invention is not limited to these.

Next, the manufacturing method of the functional film by the manufacturing apparatus 10 of this embodiment is demonstrated.
In the manufacturing apparatus 10, first, the supply chamber 12, the first transfer chamber 14, the pretreatment chamber 16, the second transfer chamber 18, the film forming chamber 20, the third transfer chamber 22, the winding are performed by the vacuum exhaust unit 24. The inside of the take-up chamber (not shown) is set to a predetermined degree of vacuum.
Then, the long substrate Z is transferred from the supply chamber 12 to the first transfer chamber 14 via the guide roller 31 from the substrate roll 30 wound counterclockwise, for example.
In the manufacturing apparatus 10 of the present embodiment, the surface pressure Ps of the pass roller 46 in contact with the organic film b is set to 10 to 200 gf / cm ² (490 Pa to 19. The substrate Z is transported to the pretreatment chamber 16 and the film formation chamber 29 via the second transport roller 34 while maintaining the range of 6 kPa).

  Next, in the pretreatment chamber 16, the surface bf of the organic film b of the substrate Z is subjected to at least one of a modification process, a degassing process, and a dust removing process. Thereby, the adhesiveness etc. of the inorganic film f formed later can be improved.

Next, in the second transfer chamber 18, the substrate Z pretreated on the surface bf of the organic film b in the pretreatment chamber 16 is formed by the first guide roller 42, the pass roller 46 and the second guide roller 44. It is conveyed to the chamber 20. At this time, the surface pressure Ps in the contact area in contact with the pass roller 46 is 10 to 200 gf / cm ² (490 Pa to 19.6 kPa).
Next, the film is transferred to the film forming chamber 20, and in this film forming chamber 20, a high-frequency voltage is applied from the high-frequency power source 54 to the high-frequency power source 54 of the film forming unit 50, and from the source gas supply unit 56 through the pipe 58. A raw material gas for forming the inorganic film f in the gap S is supplied from a plurality of through holes formed on the surfaces of the film forming electrodes 52a to 52d.

  When electromagnetic waves are radiated around each of the film forming electrodes 52a to 52d, plasma localized in the vicinity of each of the film forming electrodes 52a to 52d is generated in the gap S, the source gas is excited and dissociated, and the inorganic film f To produce a reaction product. This reaction product is deposited, and a predetermined inorganic film f is formed on the surface Zf of the substrate Z, that is, the surface bf of the organic film b in the film forming chamber 20.

Then, the substrate roll 30 around which the long substrate Z is wound counterclockwise is rotated clockwise by the rotation shaft 30a by the motor so that the long substrate Z is continuously fed out, and the slack portion 36 determines the predetermined length. The surface pressure Ps of the pass roller 46 in contact with the organic film b is maintained in the range of 10 to 200 gf / cm ² (490 Pa to 19.6 kPa) while maintaining the slack amount α of the organic film b on the surface Zf of the substrate Z. Then, the inorganic film f is continuously formed by the film forming unit 50 by rotating the drum 48 at a predetermined speed while holding the substrate Z at the position where the plasma is generated by the drum 48. It is formed on the surface bf of b.

Then, the substrate Z in which the organic film b and the inorganic film f are laminated on the surface Zf is transferred to the winding chamber (not shown) through the guide roller 60 of the third transfer chamber 22, and the functional film F Is wound around a winding shaft to form a functional film roll.
As mentioned above, in the manufacturing method of the functional film F by the manufacturing apparatus 10 of this embodiment, the functional film F in which the inorganic film f was formed in the surface Zf of the board | substrate Z is manufactured.

In the manufacturing apparatus 10 of the present embodiment, the substrate Z is transported while maintaining the surface pressure Ps of the pass roller 46 in the range of 10 to 200 gf / cm ² (490 Pa to 19.6 kPa), and the inorganic film is formed in the film forming chamber 20. f is formed. Thereby, even if the unreacted monomer remaining in the organic film b is deposited on the surface bf of the organic film b in the manufacturing apparatus 10 maintained at a predetermined degree of vacuum, the deposited organic film b formed by the pass roller 46 is removed. No pressing or crimping on the surface bf occurs. For this reason, since the deposits are separated from the surface bf of the organic film b by the plasma during the transport of the substrate Z or during the formation of the inorganic film f, the flatness of the surface bf of the organic film b is not deteriorated. . Thereby, the fall of the film quality of the inorganic film f can be suppressed. From this, the functional film F finally obtained has good film quality of the organic film b and the inorganic film f, and has high quality. For example, if the functional film F is a gas barrier film, the gas barrier performance will be good. Moreover, such a high-quality functional film F is conveyed at a surface pressure Ps in a contact area with the pass roller 46 that contacts the surface bf of the organic film b at 10 to 200 gf / cm ² (490 Pa to 19.6 kPa). It can be obtained with a simple configuration. Furthermore, since the functional film F can be manufactured with a simple configuration, the functional film F can be manufactured stably.

The above effect is based on the following knowledge. Hereinafter, the knowledge of the present invention will be described.
The present inventors have intensively studied to realize a functional film such as a high-performance gas barrier film. As a result, it has been found that the performance of the functional film can be improved by having an organic film under the inorganic film that exhibits the intended function.
As a result of further investigations, the present inventors have found that the organic film b is an organic film mainly composed of a polymer obtained by polymerizing an acrylate monomer and / or a methacrylate monomer, and in particular, the general formula described in detail above. By using the organic film b mainly composed of a polymer having a structural unit represented by (1) where m is 2 and m is 3 or more, the performance of the functional film is improved. It was found that it can be improved.

The reason why the performance of the functional film can be improved by having the organic film b is not clear. However, the present inventors have speculated as follows as a result of the examination.
These organic films b are excellent in surface smoothness and surface properties. Therefore, by forming the inorganic film f on the organic film b by a vacuum film forming method, the crystallinity and crystal growth direction of the inorganic film f are improved, and it is very dense and excellent in crystallinity. A smooth inorganic film f can be formed. For this reason, the inorganic film f exhibits the desired function very suitably, and a high-quality functional film having the desired performance can be obtained.

However, as the study proceeds, the organic film b is produced by polymerizing an acrylate monomer and / or a methacrylate monomer having an ethylenically unsaturated bond, and an inorganic film f is formed on the organic film b by a vacuum film forming method. It has been found that a new problem that cannot occur in the transfer (handling) in the atmosphere occurs in the transfer (handling) in the vacuum of the substrate Z on which the organic film b is formed.
This problem is that the organic film b does not change at atmospheric pressure (under normal pressure) or in a vacuum with a low degree of vacuum (high pressure vacuum), and is transported by a pair of transport rollers (handling), or There is no problem even if the surface treatment or the like is performed while any member is in contact with the surface.
However, in a vacuum (for example, 1000 Pa or less) in which vacuum film formation is performed, unreacted monomers remaining in the organic film b are deposited on the surface bf of the organic film b in vacuum. When the precipitate comes into contact with the transporting roller or the like, the precipitate is pushed or pressed against the surface bf of the organic film b by the roller or the like, whereby the flatness of the surface bf of the organic film b is deteriorated. For this reason, when the inorganic film f is formed on the surface bf of the organic film b, the crystallinity of the inorganic film f and the growth direction of the crystals are greatly reduced. As for the inorganic film f formed on the surface bf of the organic film b, Defects such as cracks and dropouts occur. Thereby, the functional film which exhibits the target performance cannot be manufactured.
This phenomenon is caused when the organic film b is produced, and particularly when a monomer having a monofunctional group or a bifunctional group is used, the monomer is likely to precipitate, and many defects are generated. Thereby, the performance of the functional film finally formed is deteriorated, and the quality is remarkably lowered. Even when the molecular weight of the acrylate monomer and / or methacrylate monomer is 700 or less, precipitation of the monomer tends to occur.

However, the present inventor has found that when the surface pressure Ps in the contact region where the surface bf of the organic film b of the substrate Z contacts the pass roller 46 is 10 to 200 gf / cm ² (490 Pa to 19.6 kPa), the pass roller in a vacuum atmosphere. It has been found that even if the film 46 is conveyed in contact with the surface bf of the organic film b, the deterioration of the flatness of the organic film b is suppressed. If it is transported under the condition of this surface pressure Ps (10 to 200 gf / cm ² (490 Pa to 19.6 kPa)), the occurrence of defects such as cracks and missing in the inorganic film f formed on the surface bf of the organic film b is suppressed. It is possible to manufacture a functional film having a predetermined performance.

On the other hand, when the surface pressure Ps in the contact area exceeds 200 gf / cm ² (19.6 kPa), precipitates are pushed into the surface bf of the organic film b by the pass roller 46 or pressed, and the surface of the organic film b is pressed. The flatness of bf deteriorates, and defects such as cracks and missing in the inorganic film f formed on the surface bf of the organic film b occur. For this reason, the functional film which has predetermined performance cannot be manufactured.
If the contact pressure Ps in the contact area is less than 10 gf / cm ² (490 Pa), the substrate Z cannot be transferred (handled).

Here, in the present invention, when there are a plurality of pass rollers 46 that contact the surface bf of the organic film b, the surface pressure Ps in each contact region is set to 10 to 200 gf / cm ² (490 Pa to 19. If the substrate Z is transported at 6 kPa), it is possible to suppress the occurrence of defects such as cracks and disconnections in the inorganic film f formed on the surface bf of the organic film b, and to produce a functional film having a predetermined performance. be able to.
Thus, when there are a plurality of pass rollers 46, even if one of the pass rollers 46 has a surface pressure Ps in the contact area exceeding 200 gf / cm ² (19.6 kPa), the surface bf of the organic film b formed by the pass rollers 46. Deposits are pushed in or pressed, and the flatness of the surface bf of the organic film b is deteriorated, and defects such as cracks and missing in the inorganic film f formed on the surface bf of the organic film b occur. For this reason, the functional film which has predetermined performance cannot be manufactured.
Further, when there are a plurality of pass rollers 46, even if one of the pass rollers 46 has a surface pressure Ps in the contact area of less than 10 gf / cm ² (490 Pa), the substrate Z cannot be transported (handled).

In the present invention, the inorganic film f to be formed is not particularly limited, and various inorganic films corresponding to the functional film F to be manufactured can be used as long as the film can be formed by a vacuum film forming method. It is.
Further, the thickness of the inorganic film f is not particularly limited, and a necessary film thickness may be appropriately determined according to the performance required for the inorganic film f and the functional film F to be formed.

For example, when a gas barrier film (water vapor barrier film) is manufactured as the functional film F, a silicon nitride film, an aluminum oxide film, a silicon oxide film, or the like may be formed as the inorganic film f.
Moreover, when manufacturing the protective film of various devices or apparatuses, such as a display apparatus like an organic EL display and a liquid crystal display, as the functional film F, if a silicon oxide film etc. are formed as an inorganic film f Good.
Further, when an optical film such as a light reflection preventing film, a light reflection film, or various filters is manufactured as the functional film F, the inorganic film f has an inorganic film having a desired optical characteristic or a desired optical film. An inorganic film made of a material that exhibits characteristics may be formed.
In the present invention, any of the gas barrier film (water vapor barrier film), protective film and optical film formed as the functional film F is dense and cracked due to the excellent surface smoothness and surface properties of the organic film b. In addition, since the inorganic film f with very few omissions and excellent smoothness can be formed, the functional film F having desired performance can be obtained.

In the present invention, the member may be brought into contact with the surface of the substrate Z, that is, the surface of the inorganic film f (functional film F) after the film formation of the inorganic film f is completed. For this reason, although the guide roller 60 in the third transfer chamber 22 is in contact with the surface of the inorganic film f of the functional film F, there is no problem.
In the present invention, as long as it is the back surface Zb of the substrate Z (the surface on the side opposite to the surface bf on which the organic film b is formed), the member may be brought into contact regardless of whether it is in the air or in a vacuum. Furthermore, if it is in air | atmosphere, you may use the various members which contact the surface of the organic film | membrane b, such as a conveyance roller pair.

  In addition, it is conveyed from the 3rd conveyance chamber 22 to a winding chamber (not shown). The take-up chamber is provided with a guide roller and a take-up shaft, and is a part that is evacuated and maintained at a predetermined pressure by the vacuum exhaust unit 24. The functional film F conveyed to the winding chamber is guided by the guide roller and conveyed to the winding shaft, and is wound into a roll shape by the winding shaft to obtain a functional film roll. This functional film roll may be used as a final product as it is, or may be subjected to the next step if further film formation, end treatment or the like is required.

  Furthermore, the inorganic film f to be formed is not limited to a single layer, and may be a plurality of layers. When a plurality of inorganic films f are formed, each layer may be the same or different from each other.

  In the manufacturing apparatus 10 of the present embodiment, the film formation of the inorganic film f has been described by taking plasma CVD as an example, but the film formation method of the inorganic film f is not limited to plasma CVD. In the present invention, any vacuum film forming method for forming a film in a vacuum atmosphere may be used, and various vapor phase methods such as physical vapor deposition (PVD), sputtering, vapor deposition, or ion plating may be used. A film forming method can also be used.

As described above, the gas barrier film manufacturing apparatus and the gas barrier film manufacturing method of the present invention have been described in detail. However, the present invention is not limited to the above-described examples, and various improvements and modifications can be made without departing from the spirit of the present invention. Of course, changes may be made.

Hereinafter, the Example of the manufacturing apparatus of the functional film of this invention is described concretely.
In the present embodiment, in the manufacturing apparatus 10 shown in FIG. 1, the surface pressure Ps of the pass roller 46 is variously changed as shown in Table 1 below to manufacture a gas barrier film as a functional film, and handling shown in Table 1 below. The barrier performance was evaluated.
In this example, a substrate in which an acrylic resin organic film was formed on the surface of a PET film was used as the gas barrier film substrate, and an aluminum oxide film was formed as the inorganic film.
The organic film is formed by applying an acrylic resin to the surface of a PET film with a bar, followed by UV curing.

In the present embodiment, as for the surface pressure Ps, as described above, the fact that there is a correlation between the tension T acting opposite to the transport direction D and the surface pressure Ps of the pass roller 46 is used.
The relationship between the amount of slack α of the substrate Z in the slack portion 36 and the tension T is obtained in advance, and the amount of slack α in which the tension T at which the predetermined surface pressure Ps is generated is changed and adjusted.
In this example, the tension T was about 1.5 kgf / m (about 14.7 N / m), and the surface pressure was 200 gf / cm ² (19.6 kPa).

Handling was evaluated by whether or not slip occurred (whether or not slip occurred) when a substrate having an acrylic resin organic film formed on the surface of a PET film was transported (handled) by a manufacturing apparatus.
In the evaluation of handling, if the substrate slips and cannot be transferred (handled), “X” is set, and if the substrate can be transferred (handled) without slip, “○” indicates that the substrate can be transferred (handled) without slipping, and In particular, “◎” indicates that the conveyance (handling) is excellent.
In the handling column shown in Table 1 below, “-(impossible)” indicates that the substrate could not be transported.

In this example, in order to evaluate the barrier performance, the produced gas barrier film was subjected to water vapor transmission at a temperature of 40 ° C. and a relative humidity of 90% using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W3 / 31). The rate was measured.
In the evaluation of the barrier performance, 5 × 10 ⁻³ (g / m ² / day) was used as a criterion value for the measured water vapor permeability of the barrier film. In the evaluation of the barrier performance, a sample having a water vapor transmission rate smaller than the determination reference value was set as “◯”, and a sample having a water vapor transmission rate higher than the determination reference value was set as “x”.

  In the comprehensive evaluation, a case where both the handling and barrier performance evaluations were “◯” or more was “◯”, and a case where the handling or barrier performance evaluation was “×” was “×”.

As shown in Table 1 above, the substrate could not be transported at a surface pressure of 5 gf / cm ² (490 Pa). For this reason, a gas barrier film cannot be manufactured and the barrier performance is not evaluated.

10gf ^/ cm 2 (980Pa) and 200 gf ^/ cm 2 of surface pressure is in the range of the present invention (19.6 kPa) may be any evaluation of handling and barrier property, that the barrier properties to produce a high gas barrier film did it.

In contrast, the surface pressure outside the scope of the present invention is 400gf ^/ cm 2 ^(39.2kPa), in 600gf / cm 2 (58.8kPa) and 800gf ^/ cm 2 (78.4kPa), evaluation of barrier property Inferior gas barrier film having high barrier properties could not be produced.

It is a schematic diagram which shows the manufacturing apparatus of the functional film which concerns on embodiment of this invention. It is typical sectional drawing which shows the functional film manufactured with the manufacturing apparatus of the functional film which concerns on embodiment of this invention. It is a schematic diagram which shows the manufacturing apparatus of the organic film of the board | substrate used for the manufacturing apparatus of the functional film of embodiment of this invention.

Explanation of symbols

10 Functional film production equipment (production equipment)
DESCRIPTION OF SYMBOLS 12 Supply chamber 14 1st conveyance chamber 16 Pretreatment chamber 18 2nd conveyance chamber 20 Film-forming chamber 22 3rd conveyance chamber 24 Vacuum exhaust part 26 Control part 30 Substrate roll 30a, 78 Rotating shaft 31, 60 Guide roller 32 1st conveyance roller 34 2nd conveyance roller 36 Slack part 40 Pretreatment part 42 1st guide roller 44 2nd guide roller 46 Pass roller 48 Drum 50 Film-forming part 52a-52d Film-forming electrode 54 High frequency power supply 56 Source gas Supply unit 70 Organic film forming apparatus 72 Application means 74 Drying means 76 UV irradiation apparatus 80 Winding shaft B Substrate b Organic film f Inorganic film Z Substrate

Claims (8)

A conveying means for conveying a substrate in which an organic film is formed on the surface of a long substrate in a longitudinal direction in a vacuum;
A film forming means for forming an inorganic film on the surface of the organic film of the substrate transported in the longitudinal direction by the transport means by a vacuum film forming method;
The transport means includes a roller that contacts the surface of the organic film, and a surface pressure of a contact region where the roller and the surface of the organic film are in contact with each other is 10 to 200 gf / cm ^2. An apparatus for producing a gas barrier film , which is conveyed in the longitudinal direction. The transport means includes a slack portion for loosening a part of the substrate in a loop shape in a direction perpendicular to the transport direction of the substrate, the upstream side in the transport direction from the roller, and the slack of the substrate in the slack portion The apparatus for producing a gas barrier film according to claim 1, wherein the surface pressure of the contact region is adjusted to a range of 10 to 200 gf / cm ² by adjusting the amount. Furthermore, it has a processing means for performing at least one of a reforming process, a degassing process and a dust removing process on the surface of the organic film of the substrate transported by the transporting means,
The gas barrier film manufacturing apparatus according to claim 1, wherein the processing unit is provided upstream of the film forming unit in the transport direction. The gas barrier film manufacturing apparatus according to claim 1, wherein the film forming unit forms the inorganic film while winding the substrate around a drum and transporting the substrate in the longitudinal direction. A process of forming an inorganic film on the surface of the organic film of the substrate by a vacuum film-forming method while conveying a substrate having an organic film formed on the surface of a long substrate in a longitudinal direction in a vacuum. ,
When transporting the substrate to form the inorganic film on the surface of the organic film of the substrate, the substrate is transported using a roller that contacts the surface of the organic film. A method for producing a gas barrier film , wherein the surface pressure of the contact region in contact with the surface is in the range of 10 to 200 gf / cm ² . In the step of transporting the substrate having the organic film formed on the surface of the long base in the longitudinal direction, the substrate is disposed on the upstream side of the roller in the direction perpendicular to the transport direction of the substrate. 6. The surface pressure of the contact region is set to a range of 10 to 200 gf / cm ² by adjusting the amount of slackness of the substrate by transporting the substrate while partially slackening it in a loop shape. Of manufacturing a gas barrier film . The method comprising: performing at least one of a reforming process, a degassing process, and a dust removing process on the surface of the organic film of the substrate before the step of forming the inorganic film by a vacuum film forming method. A method for producing a gas barrier film according to 5 or 6. 6. In the step of forming an inorganic film on the surface of the organic film of the substrate by a vacuum film formation method, the inorganic film is formed while the substrate is wound around a drum and conveyed in the longitudinal direction. The manufacturing method of the gas barrier film of any one of -7 .

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