JP2015132007A - Method and apparatus for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate, capable of forming an atomic layer volume film having high gas barrier properties on one surface side of a base material, and an apparatus for manufacturing a laminate, capable of manufacturing the laminate.SOLUTION: A method for manufacturing a laminate comprises: the atomic layer deposition film formation step of forming an atomic layer deposition film on one surface of a base material 11 in a first processing chamber; the base material guidance step of guiding the base material 11 having the formed atomic layer deposition film into an overcoat layer formation chamber 61 (a second processing chamber) from the first processing chamber by a guide roller 27 contacted with only the outer peripheral part of the atomic layer deposition film; the overcoat layer formation step of forming an overcoat layer on one surface of the atomic layer deposition film in the overcoat layer formation chamber 61 after the base material guidance step; and the winding step of contacting one surface of the overcoat layer with the roller surface of a winding rollers 82 after forming the overcoat layer to wind a laminate 10 in a roller shape by the winding rollers 82.

Description

  The present invention relates to a laminate manufacturing method and a laminate manufacturing apparatus, and more particularly, to a laminate including an atomic layer deposition film formed on one side of a substrate, and a laminate manufacturing apparatus for manufacturing the laminate.

  Conventionally, as a method of forming a thin film on the surface of an object using a gas phase in which a substance can move at an atomic or molecular level like a gas, it is also referred to as chemical vapor deposition (CVD). And a physical vapor deposition (also referred to as PVD (Physical Vapor Deposition) method, hereinafter referred to as “PVD”) method.

  Examples of the PVD method include a vacuum deposition method and a sputtering method. The sputtering method is widely applied to display devices such as liquid crystal displays because a high-quality thin film having excellent film quality and thickness uniformity can be formed.

The CVD method is a method for growing a solid thin film by introducing a source gas into a vacuum chamber and decomposing or reacting one or more kinds of gases with thermal energy on a substrate.
At this time, in order to promote the reaction at the time of film formation or to lower the reaction temperature, there are those using plasma or a catalyst (Catalyst) reaction in combination.

Among these, the CVD method using a plasma reaction is referred to as a PECVD (plasma enhanced CVD) method. A CVD method using a catalytic reaction is called a Cat-CVD method.
When such a CVD method is used, film formation defects are reduced, and thus, for example, it is applied to a semiconductor device manufacturing process (for example, a gate insulating film forming process).

In recent years, an atomic layer deposition method (ALD (Atomic Layer Deposition) method, hereinafter referred to as “ALD method”) has attracted attention as a film formation method.
The ALD method is a method in which a surface-adsorbed substance is formed one layer at a time by a chemical reaction on the surface. The ALD method is classified into the category of the CVD method.

  A so-called CVD method (general CVD method) is a method in which a single gas or a plurality of gases are simultaneously used to react on a base slope to grow a thin film. On the other hand, the ALD method is a precursor (hereinafter referred to as “first precursor”. For example, TMA (Tri-Methyl Aluminum)) or a highly active gas called a precursor and a reactive gas (ALD method). In the following description, the precursor is referred to as a “second precursor”), and alternately used at the atomic level by adsorption on the substrate surface and subsequent chemical reaction. It is a special film formation method that grows thin films one by one.

A specific film formation method of the ALD method is performed by the following method.
First, a so-called self-limiting effect (refers to a phenomenon in which, when the surface is adsorbed on the substrate, when the surface is covered with a certain kind of gas, no further adsorption of the gas occurs). When only one layer of the precursor is adsorbed thereon, the unreacted precursor is exhausted (first step).
Next, a reactive gas is introduced into the chamber, and the precursor is oxidized or reduced to form only one layer of a thin film having a desired composition, and then the reactive gas is exhausted (second step).
In the ALD method, the first and second steps are defined as one cycle, and the cycle is repeated to grow a thin film on the substrate.

Therefore, in the ALD method, a thin film grows two-dimensionally. In addition, the ALD method is characterized in that it has fewer film-forming defects in comparison with the conventional vacuum deposition method, sputtering method, and the like, as well as the general CVD method.
For this reason, it is expected to be applied to a wide range of fields such as the packaging field for foods and pharmaceuticals and the electronic parts field.

  As one of ALD methods, there is a method of using plasma to activate the reaction in the step of decomposing the second precursor and reacting it with the first precursor adsorbed on the substrate. This method is called a plasma activated ALD (PEALD (Plasma Enhanced ALD)) method or simply a plasma ALD method.

  The technology of the ALD method itself was developed in 1974 by Finnish Dr. Proposed by Tuomo Sumtola. In general, the ALD method is used in the field of semiconductor device manufacturing (for example, a process for forming a gate insulating film) because high-quality and high-density film formation can be obtained, and ITRS (International Technology Roadmap for Semiconductors). ) Also has such a description.

The ALD method has a feature that there is no oblique effect (a phenomenon in which sputtering particles are incident on the substrate surface obliquely to cause film formation variation) compared to other film formation methods. A membrane is possible.
Therefore, the ALD method is applied to a technology related to MEMS (Micro Electro Mechanical Systems), which is a coating of lines and holes on a substrate having a high aspect ratio with a large depth to width ratio, and a coating of a three-dimensional structure. Is expected.

  However, the ALD method also has drawbacks. A drawback of the ALD method is, for example, that a special material is used, but the biggest drawback is that the film forming speed is slow. The film forming speed of the ALD method is, for example, about 1/5 to 1/10 of the film forming speed of a film forming method such as a normal vacuum deposition method or sputtering method, and is very slow.

As a substrate on which a thin film is formed using the ALD method described above, for example, a small plate-like substrate such as a wafer or a photomask, a substrate with a large area and no flexibility (for example, a glass substrate), a film, etc. There are substrates having a large area and flexibility.
In mass production facilities for forming thin films on these substrates, various substrate handling methods have been proposed and put into practical use depending on ease of handling, film formation quality, and the like.

  For example, as a film forming apparatus for forming a thin film on a wafer, a single wafer is transferred into a chamber of the film forming apparatus to form a film, and then the formed wafer and the unprocessed wafer are exchanged. Thus, there are a single-wafer type film forming apparatus that performs film forming processing again, and a batch type film forming apparatus that sets a plurality of wafers in a chamber and then performs the same film forming process on all wafers.

In addition, as a film forming apparatus for forming a thin film on a glass substrate, there is an in-line type film forming apparatus that performs film formation at the same time while sequentially transporting the glass substrate to a portion serving as a film forming source.
Furthermore, as a film forming apparatus for forming a thin film on a flexible substrate, a film is formed while the flexible substrate is unwound from a roller, and the flexible substrate is wound by another roller, so-called roll-to-roll coating formation. There is a membrane device.

In addition, not only flexible substrates, but also a web coating film forming apparatus that continuously forms films on a flexible sheet that can continuously convey a substrate to be formed, or a tray that is partially flexible, is also used for coating film formation. Included in the device.
As for the film forming method and the substrate handling method using any of the film forming apparatuses, a combination of film forming apparatuses that achieves the highest film forming speed is adopted based on the quality and ease of handling.

Patent Document 1 discloses that a light-emitting polymer is mounted on a flexible and light-transmitting plastic substrate, and an atomic layer deposition film is top-coated on the surface and side surfaces of the light-emitting polymer by the ADL method. ing.
Further, in Patent Document 1, it is possible to reduce coating defects by using the above-described method, and to reduce gas transmission by orders of magnitude at a thickness of several tens of nanometers. It is disclosed.

US Pat. No. 6,057,836 discloses a vacuum capable chamber and at least two atomic layer deposition sources within the vacuum capable chamber, each atomic layer deposition source being isolated from the rest of the vacuum capable chamber. An atomic layer deposition apparatus is disclosed that transports a substrate through a deposition source and the vacuum capable chamber (substrate transport means).
Patent Document 2 discloses that a substrate on which an atomic layer deposition film is formed is wound around a rewinding drum.

  In Patent Document 3, a first step of forming a thin-film atomic layer deposition film along the outer surface of a substrate and an in-line in a step in series with the first step are along the outer surface of the atomic deposition film. Then, an overcoat layer having a mechanical strength higher than that of the atomic deposition film is formed, and the second step of generating the laminate is laminated, and the overcoat layer formed in the second step is in contact with the rigid body. A method for manufacturing a laminate including a third step of housing a body is disclosed.

Special table 2007-516347 Special table 2007-522344 International Publication No. 2013/015417

By the way, since the atomic layer deposition film formed by the method described in Patent Document 1 is not covered with other layers, it may be easily damaged (including pinholes) by an external force. If the atomic layer deposition film is damaged by some external force, the damage may reach the substrate.
When such a flaw occurs, gas enters and exits between the atomic layer deposition film and the substrate through the flaw, so that the gas barrier property is lowered.

  In the case of manufacturing a laminate including an atomic layer deposition film that is easily damaged, in order to prevent the atomic layer deposition film from being damaged, the atomic layer deposition film and the rigid body are formed after the atomic layer deposition film is formed. It is important to avoid contact.

Referring to the configuration of the atomic layer deposition apparatus disclosed in Patent Document 2, in Patent Document 2, the atomic layer deposition film is formed so that the roller surface of the rewinding drum and the entire surface of the atomic layer deposition film are in contact with each other. It is presumed that the formed substrate is wound around a rewinding drum.
In this case, the entire surface of the atomic layer deposition film may be damaged. If the entire surface of the atomic layer deposition film is damaged, the gas barrier property of the atomic layer deposition film is deteriorated.

In the laminated body disclosed in Patent Document 3, since the overcoat layer covering the surface of the atomic layer deposition film is disposed, it is possible to solve the problem of Patent Document 2.
However, in Patent Document 3, since the overcoat film forming unit is not partitioned by the chamber (or casing) unlike the atomic layer deposited film forming unit, the overcoat deposited unit and the atomic layer deposited film deposited The atomic layer deposition film and overcoat layer are formed in an environment where gas (gas used in the overcoat film formation part and gas used in the atomic layer deposition film formation part) is easily mixed (mixed) with the part. Therefore, there is a problem that the performance of the atomic layer deposition film and the overcoat layer is deteriorated.
That is, the method for manufacturing a laminate disclosed in Patent Document 3 has a problem that the gas barrier property of the atomic layer deposition film is lowered.

  Then, this invention aims at providing the manufacturing method of the laminated body which can form an atomic layer volume film | membrane with high gas barrier property on the one surface side of a base material, and the laminated body manufacturing apparatus which manufactures this laminated body. And

  In order to solve the above problems, a method for manufacturing a laminate according to one embodiment of the present invention includes a strip-shaped base material, an atomic layer deposition film formed on one surface of the base material, and the atomic layer deposition film. An overcoat layer formed on one side of the substrate, wherein the atomic layer deposition film and the overcoat layer are formed in-line. The substrate having the atomic layer deposited film formed thereon is formed by the atomic layer deposited film forming step for forming the atomic layer deposited film on the substrate and the guide roller in contact with only the outer peripheral portion of one surface of the atomic layer deposited film. A base material guiding step for guiding from one processing chamber to a second processing chamber disposed outside the first processing chamber; and the atomic layer deposition in the second processing chamber after the base material guiding step. Overcoat layer formation to form an overcoat layer on one side of the film And after the formation of the overcoat layer, the one surface of the overcoat layer and the roller surface of the take-up roller are brought into contact with each other, and the take-up step of winding the laminate into a roller shape by the take-up roller. It is characterized by including.

  According to the present invention, the base material on which the atomic layer deposition film is formed is guided from the first processing chamber to the second processing chamber disposed outside the first processing chamber, and then the second processing chamber. Thus, by forming an overcoat layer on one surface of the atomic layer deposition film, it is possible to suppress the movement of the gas used in the second processing chamber into the first processing chamber, and in the first processing chamber. It is possible to suppress the gas to be used from moving into the second processing chamber.

  This makes it possible to suppress the formation of the atomic layer deposition film and the overcoat layer in a state where the gas used in the first processing chamber and the gas used in the second processing chamber are mixed. The performance (film quality, film characteristics, etc.) of the atomic layer deposited film and the overcoat layer can be improved. That is, an atomic layer deposition film having excellent gas barrier properties can be formed.

  Further, the atomic layer deposition is performed by guiding the base material on which the atomic layer deposition film is formed from the first processing chamber to the second processing chamber by a guide roller that contacts only the outer peripheral portion of one surface of the atomic layer deposition film. Compared with the case of transporting using a conventional guide roller that is in contact with the entire surface of the film, it is possible to suppress the occurrence of scratches on the atomic layer deposition film caused by the guide roller.

  Further, after forming the overcoat layer, one surface of the overcoat layer and the roller surface of the take-up roller are brought into contact with each other, and the laminated body is taken up into a roller shape by the take-up roller, so that the roller surface of the take-up roller becomes Since there is no direct contact with one surface of the atomic layer deposition film, it is possible to suppress the generation of scratches due to the winding roller in the atomic layer deposition film.

  In the method for manufacturing a laminate according to one embodiment of the present invention, the overcoat layer having a mechanical strength higher than that of the atomic layer deposition film may be formed in the overcoat layer forming step.

Thus, by forming an overcoat layer having a mechanical strength higher than that of the atomic layer deposition film, one surface of the overcoat layer and the roller surface of the take-up roller are brought into contact with each other, and the laminate is formed by the take-up roller. It is possible to prevent the atomic layer deposition film from being damaged when the film is wound in a roller shape.
Further, even when a rigid body other than the take-up roller (for example, another transport roller) comes into contact with the overcoat layer, damage to one surface of the atomic layer deposition film can be suppressed.

  In the method for manufacturing a laminate according to one aspect of the present invention, in the overcoat layer forming step, the atomic layer is formed such that the thickness of the overcoat layer is larger than the thickness of the atomic layer deposition film. The overcoat layer having the same mechanical strength as the deposited film may be formed.

  Thus, by forming an overcoat layer having a mechanical strength equivalent to that of the atomic layer deposition film so that the thickness is larger than the thickness of the atomic layer deposition film, one surface of the overcoat layer and the winding roller It is possible to prevent the atomic layer deposition film from being damaged when the laminate is wound into a roller shape by contacting the roller surface with the take-up roller.

  In the method for manufacturing a laminate according to one embodiment of the present invention, an undercoat layer containing an inorganic substance and / or an organic polymer is provided on one surface of the substrate before the atomic layer deposition film forming step. An undercoat layer forming step to be formed, and in the atomic layer deposition film forming step, one surface of the undercoat layer is bonded to the inorganic substance and / or the organic polymer exposed from the one surface of the undercoat layer. As described above, the atomic layer deposition film may be formed.

For example, when forming an undercoat layer containing an inorganic material, the atomic layer deposition film precursor binds to the inorganic material exposed from the surface of the undercoat layer, so that it grows in one direction of the undercoat layer. A layered atomic layer deposition film is formed.
As a result, it is difficult to form a gap through which gas passes in the thickness direction of the stacked body, so that the gas barrier property of the stacked body can be improved.

On the other hand, when an undercoat layer containing an organic polymer is formed, the organic polymer has a functional group that easily binds to the precursor of the atomic layer deposition film. Bind to each other. As a result, a two-dimensional atomic layer deposition film is formed that grows in one surface direction of the undercoat layer.
As a result, the gas barrier property of the laminate can be improved because it is difficult to form a gas that passes in the thickness direction of the laminate.

  In addition, when forming an undercoat layer containing an organic polymer and an inorganic substance, the inorganic polymer is added to the undercoat layer, so that the organic polymer and the inorganic substance combine to form an atomic layer deposition film. The adsorption density of the precursor can be further improved.

  Further, in the method for manufacturing a laminate according to one aspect of the present invention, in the base material guiding step, a pressure between the pressure in the first processing chamber and the pressure in the second processing chamber is set. The substrate may be guided to the second processing chamber via an intermediate chamber.

  For example, when the degree of vacuum between the first processing chamber and the second processing chamber is greatly different, the degree of vacuum between the first processing chamber and the second processing chamber is set to a vacuum degree. Thus, the degree of vacuum can be changed step by step.

  In the method for manufacturing a laminate according to one embodiment of the present invention, in the overcoat layer forming step, the overcoat layer may be formed by a flash vapor deposition method.

The flash vapor deposition method uses a coating material (overcoat layer material) that does not contain a solvent (in other words, generates less volatile gas).
Therefore, by forming the overcoat layer using the flash vapor deposition method, it becomes possible to further reduce the possibility that the gas in the first processing chamber and the gas in the second processing chamber are mixed. An atomic layer deposition film and an overcoat layer excellent in film quality can be formed.

  In the method for manufacturing a laminate according to one embodiment of the present invention, in the overcoat layer forming step, the overcoat layer may be formed by a vacuum evaporation method.

  In this manner, by forming the overcoat layer by a vacuum deposition method, the overcoat layer can be formed at a high speed and a thick overcoat layer can be formed.

  In the method for manufacturing a laminate according to one embodiment of the present invention, in the overcoat layer forming step, the overcoat layer may be formed by a chemical vapor deposition method.

  In this manner, by forming the overcoat layer by chemical vapor deposition, it is possible to form an overcoat layer with little damage to the atomic layer deposition film. Further, it is not necessary to increase the pressure difference between the region where the overcoat layer is formed and the outside thereof.

  In addition, the laminate manufacturing apparatus according to one embodiment of the present invention includes a belt-like base material in-line by a roll-to-roll method, the base material, and an atomic layer deposition film formed on one surface side of the base material. A laminate manufacturing apparatus for forming a laminate, the outer shape of which is cylindrical, a support member that supports the other surface located on the opposite side of the one surface of the base material by the outer surface, and an outer surface of the support member A transport unit that transports the base material in a predetermined transport direction; and is arranged on an outer surface of the support member in a state where the base material can be introduced and led out, and the atomic layer deposition film is disposed on one surface of the base material. An atomic layer deposition film forming unit including a first processing chamber for forming an overcoat layer on one surface of the atomic layer deposition film. Overcoat layer formation including second processing chamber to be formed A first guide roller that contacts only the outer peripheral portion of one surface of the atomic layer deposition film and guides the base material on which the atomic layer deposition film is formed into the second processing chamber, and the overcoat layer It has a laminated body winding part which is arranged at a subsequent stage of the forming part and winds up the laminated body in a roll shape by coming into contact with one surface of the overcoat layer constituting the laminated body.

  According to the present invention, an atomic layer deposition film forming unit including a first processing chamber for forming an atomic layer deposition film and an atomic layer deposition film disposed in a stage subsequent to the atomic layer deposition film formation unit in a predetermined transport direction. An overcoat layer forming portion including a second processing chamber for forming an overcoat layer on one surface of the first processing chamber, so that the gas used in the second processing chamber can be prevented from moving into the first processing chamber. At the same time, it is possible to suppress the movement of the gas used in the first processing chamber into the second processing chamber.

  This makes it possible to suppress the formation of the atomic layer deposition film and the overcoat layer in a state where the gas used in the first processing chamber and the gas used in the second processing chamber are mixed. The performance (film quality, film characteristics, etc.) of the atomic layer deposited film and the overcoat layer can be improved. That is, an atomic layer deposition film having excellent gas barrier properties can be formed.

In addition, since the first layer has a first guide roller that contacts only the outer peripheral portion of one surface of the atomic layer deposition film and guides the base material on which the atomic layer deposition film is formed into the second processing chamber, Compared with the case of using a conventional guide roller in contact with the entire surface, it is possible to suppress the occurrence of scratches caused by the first guide roller in the atomic layer deposition film.
Thereby, while the fall of the gas barrier property of an atomic layer deposition film can be suppressed, the fall of the adhesiveness between a base material and an atomic layer deposition film can be suppressed.

  Furthermore, the roller surface of the take-up roller is brought into contact with one surface of the atomic layer deposition film by having a laminate winding portion that winds the laminate into a roll shape by contacting with one surface of the overcoat layer constituting the laminate. Since there is no direct contact, it is possible to suppress the occurrence of scratches caused by the take-up roller on the atomic layer deposition film.

  Further, in the laminate manufacturing apparatus according to one aspect of the present invention, the base material on which the atomic layer deposition film that contacts the first guide roller is formed on a roller surface of the first guide roller. You may have a pressing roller to press.

  Thus, by having the pressing roller that presses the substrate against the roller surface of the first guide roller, the substrate on which the atomic layer deposition film is formed is firmly attached to the roller surface of the first guide roller. To prevent the base material on which the atomic layer deposition film is formed from coming off the roller surface, so that the transport direction of the base material can be changed stably.

  Further, in the laminate manufacturing apparatus according to one aspect of the present invention, the overcoat layer forming portion is disposed in the second processing chamber, and is in contact with only an outer peripheral portion of one surface of the atomic layer deposition film. The guide roller may be included.

As described above, by arranging the second guide roller in contact with only the outer peripheral portion of one surface of the atomic layer deposition film in the second processing chamber, the atomic layer deposition film is free from scratches caused by the first guide roller. Occurrence can be suppressed.
Thereby, while the fall of the gas barrier property of an atomic layer deposition film can be suppressed, the fall of the adhesiveness between a base material and an atomic layer deposition film can be suppressed.

  Moreover, in the laminated body manufacturing apparatus according to one aspect of the present invention, when the base material is transported from the first processing chamber to the second processing chamber, and the base material is transferred from the second processing chamber. You may have an intermediate chamber which passes when carrying out.

  Thus, by having an intermediate chamber that passes when the substrate is transported from the first processing chamber to the second processing chamber and when the substrate is unloaded from the second processing chamber, for example, the first chamber When the degree of vacuum between the first processing chamber and the second processing chamber differs greatly, the intermediate chamber is set to a value between the degree of vacuum in the first processing chamber and the degree of vacuum in the second processing chamber. Thus, the degree of vacuum can be changed step by step.

  Further, in the laminated body manufacturing apparatus according to one aspect of the present invention, an inorganic substance and / or an organic polymer is disposed on one surface of the base material in the predetermined transport direction and before the atomic layer deposition film forming unit. You may have an undercoat layer formation part which forms the undercoat layer containing this.

Thus, for example, an undercoat layer containing an inorganic substance is formed by having an undercoat layer forming part for forming an undercoat layer containing an inorganic substance and / or an organic polymer on one surface of the substrate. In this case, since the precursor of the atomic layer deposition film is bonded to the inorganic substance exposed from the surface of the undercoat layer, a two-dimensional atomic layer deposition film that grows in one surface direction of the undercoat layer is formed.
As a result, it is difficult to form a gap through which gas passes in the thickness direction of the stacked body, so that the gas barrier property of the stacked body can be improved.

In addition, when forming an undercoat layer containing an organic polymer, the organic polymer has a functional group that easily binds to the precursor of the atomic layer deposition film. Bind to each other. As a result, a two-dimensional atomic layer deposition film is formed that grows in one surface direction of the undercoat layer.
As a result, it becomes difficult to form a gas that passes in the thickness direction of the stacked body, so that the gas barrier property of the stacked body can be improved.

  Further, when an undercoat layer containing an organic polymer and an inorganic substance is formed, the inorganic substance is added to the undercoat layer, so that the organic polymer and the inorganic substance are combined to form an atomic layer deposition film. The adsorption density of the precursor can be further improved.

  According to the laminate manufacturing method and the laminate manufacturing apparatus of the present invention, an atomic layer volume film having a high gas barrier property can be formed on one side of a substrate.

It is sectional drawing which shows typically the laminated body manufactured by the manufacturing method of the laminated body which concerns on the 1st Embodiment of this invention. FIG. 2 is a front view showing a schematic configuration of the laminate manufacturing apparatus according to the first embodiment of the present invention. It is the figure which expanded the base material and support member which were enclosed by the area | region D shown in FIG. It is the figure which expanded the part corresponding to the area | region E among the laminated body manufacturing apparatuses shown in FIG. It is a perspective view of the guide roller shown in FIG. It is sectional drawing of the base material in which the atomic layer deposition film located between a guide roller, a pair of pressing roller, and a guide roller and a pair of pressing roller was formed. It is the figure which expanded the part corresponding to the area | region F among the laminated body manufacturing apparatuses shown in FIG. It is a flowchart for demonstrating the manufacturing method of the laminated body which concerns on the 1st Embodiment of this invention. It is a front view which shows typically schematic structure of the laminated body manufacturing apparatus which concerns on the modification of 1st Embodiment. It is sectional drawing which shows typically the laminated body manufactured by the manufacturing method of the laminated body which concerns on the 2nd Embodiment of this invention. It is a front view which shows schematic structure of the laminated body manufacturing apparatus which concerns on the 2nd Embodiment of this invention. It is a flowchart for demonstrating the manufacturing method of the laminated body which concerns on the 2nd Embodiment of this invention. It is a front view which shows schematic structure of another laminated body manufacturing apparatus. It is a front view which shows schematic structure of the laminated body manufacturing apparatus used when producing the laminated body of a comparative example.

  Embodiments to which the present invention is applied will be described below in detail with reference to the drawings. The drawings used in the following description are for explaining the configuration of the embodiment of the present invention. The sizes, thicknesses, dimensions, etc. of the respective parts shown in the drawings are the actual laminates and laminate production apparatuses. It may be different from the dimensional relationship.

(First embodiment)
<Laminated body according to the first embodiment>
FIG. 1 is a cross-sectional view schematically showing a laminate produced by the laminate production method according to the first embodiment of the present invention.

Here, before explaining the manufacturing method of the laminated body of 1st Embodiment, the structure of the laminated body 10 manufactured by the manufacturing method of the laminated body of 1st Embodiment is demonstrated.
Referring to FIG. 1, the laminated body 10 is a film-like laminated body, and includes a base material 11, an atomic layer deposition film 12, and an overcoat layer 14.

The base material 11 is a base material in the form of a strip and a film extending in a predetermined direction. The base material 11 has one surface 11a on which the atomic layer deposition film 12 is formed and another surface 11b disposed on the opposite side of the one surface 11a.
As a material of the base material 11, for example, a polymer material can be used. Examples of the polymer material include plastic materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide film (PI), polyethylene (PE), polypropylene (PP), and polystyrene (PS). it can.
In addition, the material of the base material 11 is not limited to the said material, It can select suitably considering heat resistance, an intensity | strength physical property, an electrical insulation, etc.

  The thickness of the substrate 11 is appropriately selected within a range of 12 μm or more and 200 μm or less in consideration of appropriateness as a packaging material for an electronic component such as an electroluminescence element to which the laminate 10 is applied or a precision component, for example. can do.

The atomic layer deposition film 12 is disposed so as to cover the one surface 11 a of the base material 11. The atomic layer deposition film 12 is a film formed by, for example, an ALD (Atomic Layer Deposition) method, and functions as a gas barrier layer (barrier layer).
As the atomic layer deposition film 12, for example, an inorganic oxide film such as AlO _x , TiO _x , SiO _x , ZnO _x , SnO _x , a nitride film or an oxynitride film made of these inorganic substances, or an oxide film made of other elements A nitride film, an oxynitride film, or the like can be used.
The thickness of the atomic layer deposition film 12 can be appropriately set within a range of 2 nm to 500 nm, for example.

  The overcoat layer 14 is disposed so as to cover the one surface 12 a of the atomic layer deposition film 12. The overcoat layer 14 covers the one surface 12a of the atomic layer deposition film 12, thereby suppressing direct contact between the one surface 12a of the atomic layer deposition film 12 and the rigid body, and causing damage to the atomic layer deposition film 12. Functions as a protective layer (specifically, a protective layer for suppressing a decrease in gas barrier properties of the atomic layer deposition film 12).

Thus, by arranging the overcoat layer 14 on the one surface 12a of the atomic layer deposition film 12, for example, when the laminate 10 is manufactured using the laminate manufacturing apparatus 20 shown in FIG. The laminated body 10 can be wound into a roller shape by bringing the one surface 14a of the layer 14 into contact with the roller surface of the winding roller 82.
Thereby, damage to the atomic layer deposited film due to contact with the take-up roller 82 can be suppressed.

As the overcoat layer 14, for example, a layer having a mechanical strength equal to or higher than the mechanical strength of the atomic layer deposition film 12 can be used.
In this way, by using the overcoat layer 14 having a mechanical strength equal to or higher than the mechanical strength of the atomic layer deposition film 12, damage to the atomic layer deposition film 12 due to contact with the take-up roller 82 is further increased. Can be suppressed.
In addition, even when a rigid body (for example, a transport roller) other than the take-up roller 82 comes into contact with the overcoat layer 14 and an external force is applied to the stacked body 10, the one surface 12a of the atomic layer deposition film 12 is damaged. Can be suppressed.

Further, when the overcoat layer 14 having the same mechanical strength as that of the atomic layer deposition film 12 is used, it is preferable that the thickness of the overcoat layer 14 is larger than the thickness of the atomic layer deposition film 12.
Thereby, when winding the laminated body 10 in roller shape, the effect which suppresses that the atomic layer deposition film 12 is damaged can be improved further.

As the overcoat layer 14, for example, a layer composed of an aqueous barrier coat film having a functional group having an OH group or a COOH group can be used. Further, the overcoat layer 14 may contain an inorganic substance. The water-based barrier coat film is a coat film having a barrier property, comprising a water-based organic polymer, a hydrolyzed polymer composed of an organic metal compound such as a metal alkoxide or a silane coupling agent, and a composite thereof. That means.
Examples of the water-based organic polymer include polyvinyl alcohol, polyacrylic acid, and polyethyleneimine.

The metal alkoxide which is an organometallic compound is represented by R1 (M-OR2) as a general formula. However, said R1, R2 is a C1-C8 organic group, and M is a metal atom (henceforth "the metal atom M").
As the metal atom M, for example, Si, Ti, Al, Zn or the like can be used.

Examples of R1 (Si-OR2) in which the metal atom M is Si include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraptoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and dimethyl. Examples include dimethoxysilane and dimethyldiethoxysilane.
Examples of R1 (Si—OR2) in which the metal atom M is Zr include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetraptoxyzirconium and the like.

Examples of R1 (Si-OR2) in which the metal atom M is Ti include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrapoxytitanium.
Examples of R1 (Si-OR2) in which the metal atom M is Al include tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, and tetraptoxyaluminum.

When inorganic particles are added as an inorganic substance to the overcoat layer 14, it is preferable to use, for example, an extender having a particle diameter larger than that of kaolinite, which is a kind of clay mineral.
As such an inorganic substance, for example, halloysite, calcium carbonate, anhydrous silicic acid, hydrous silicic acid, alumina or the like can be used.

  When an inorganic substance is added to the overcoat layer 14 as a layered compound, examples of the inorganic substance include artificial clay, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, sapolite. , Stevensite, montmorillonite, beidellite, kaolinite, fly bonteite and the like can be used.

  Furthermore, as an inorganic substance constituting the layered compound, for example, pyroferrite, talc, montmorillonite (overlapping with artificial clay), beidellite, nontronite, saponite, vermiculite, sericite, sea green stone, ceradonite, Kaolinite, nacrite, decaite, halosite, antigolite, chrysotile, amesite, chronite, chamosite, chlorite, alevaldite, corensite, tosudite, etc. can be used.

  As inorganic particles (spherical particles) other than extender pigments, for example, a polycrystalline compound can be used. Examples of the polycrystalline compound include metal oxides such as metal oxides such as zirconia and titania, barium titanate and strontium titanate represented by MM′OX (M, M ′,...). A metal oxide containing 2 or more types can be used.

<Laminated body manufacturing apparatus according to the first embodiment>
FIG. 2 is a front view showing a schematic configuration of the laminate manufacturing apparatus according to the first embodiment of the present invention. In FIG. 2, the same reference numerals are given to the same components as those of the laminate 10 and the laminate 10 shown in FIG. 1.
2, A is the direction of rotation of the substrate winding roller 36 (hereinafter referred to as “A direction”), B is the direction of rotation of the support member 21 (hereinafter referred to as “B direction”), and C is the dancer roller. 81 shows the rotation direction (hereinafter referred to as “C direction”).
In FIG. 2, an arrow attached to the vicinity of the base material 11 or the laminated body 10 (an arrow without the reference signs A to C) indicates a transport direction (predetermined transport direction) of the base material 11. .
Furthermore, because of space limitations, it is difficult to show the film forming portions 43 that are actually several dozen (for example, 70), and therefore, only three film forming portions 43 are shown in FIG.

Next, with reference to FIG. 2, the laminated body manufacturing apparatus 20 which concerns on 1st Embodiment used when manufacturing the laminated body 10 shown in FIG. 1 is demonstrated.
The laminated body manufacturing apparatus 20 according to the first embodiment deposits a belt-like base material 11 extending in a predetermined direction (one direction) on one surface 11a of the base material 11 by an in-line roll-to-roll method. This is an apparatus for sequentially forming the film 12 and the overcoat layer 14.
The laminate manufacturing apparatus 20 according to the first embodiment includes a support member 21, a base material transport unit 23, a plasma pretreatment unit 24, an atomic layer deposition film forming unit 26, a guide roller 27, and a pair of pressers. It has a roller 28, an intermediate chamber 29, an overcoat layer forming part 31, a roller 32, and a laminate winding part 33.

  FIG. 3 is an enlarged view of the base material and the support member surrounded by the region D shown in FIG. 3, the same components as those shown in FIGS. 1 and 2 are denoted by the same reference numerals.

Referring to FIGS. 2 and 3, the support member 21 has a cylindrical outer shape and has an outer surface 21 a that contacts the other surface 11 b of the substrate 11. The support member 21 rotates in the B direction to pass the substrate 11 supplied from the substrate winding roller 36 in the order of the plasma pretreatment unit 24, the atomic layer deposition film forming unit 26, and the guide roller 27. . The outer surface 21 a of the support member 21 functions as a guide surface for transporting the base material 11.
For example, a drum can be used as the support member 21.

The substrate transport unit 23 is disposed in front of the plasma pretreatment unit 24 so as to face the outer surface 21 a of the support member 21. The base material transport unit 23 includes a base material winding roller 36 and a base material feed roller 37.
The substrate winding roller 36 is disposed at a position separated from the support member 21 such that the roller surface faces the outer surface 21 a of the support member 21. A belt-like base material 11 extending in a predetermined direction (one direction) is wound around the roller surface of the base material winding roller 36.
The base material winding roller 36 rotates in the A direction, thereby conveying the base material 11 to the outer surface 21 a of the support member 21 via the base material feeding roller 37.

The base material feeding roller 37 is disposed between the support member 21 and the base material winding roller 36 so that the roller surface 37 a faces the outer surface 21 a of the support member 21 and the roller surface of the base material winding roller 36. Is arranged.
The base material feeding roller 37 is a roller having a smaller outer diameter than the base material winding roller 36, and is attached to the support member 21 so that the other surface 11 b of the base material 11 and the outer surface 21 a of the support member 21 are in contact with each other. The base material 11 is supplied. For this reason, the base material supply roller 37 is disposed in the vicinity of the outer surface 21 a of the support member 21.
The base material 11 supplied to the outer surface 21 a of the support member 21 is transported to the plasma pretreatment unit 24 along the outer surface 21 a of the support member 21.

Referring to FIGS. 1 and 2, the plasma pretreatment unit 24 is disposed so as to face the one surface 11 a of the substrate 11 passing between the substrate feeding roller 37 and the atomic layer deposition film forming unit 26. ing.
The plasma pretreatment unit 24 includes a processing chamber 41 that performs plasma pretreatment on the one surface 11 a of the substrate 11. The processing chamber 41 introduces the substrate 11 supplied with the substrate transport unit 23 into the processing chamber 41 (not shown) and the plasma-pretreated substrate 11 out of the processing chamber 41. And an outlet (not shown).
In the plasma pretreatment unit 24, for example, the surface 11a of the base 11 is modified by exposing the surface 11a of the base 11 to an oxygen plasma atmosphere (specifically, the functional group of the surface 11a of the base 11 is changed). Change).
The substrate 11 subjected to the plasma pretreatment is transported to the atomic layer deposition film forming unit 26 along the outer surface 21 a of the support member 21.
The plasma pretreatment conditions can be selected as appropriate according to the characteristics of the material of the substrate 11.

The atomic layer deposited film forming unit 26 includes a plurality of film forming units 43 (only three are shown for convenience of paper in the case of FIG. 2).
In the first embodiment, as an example of the atomic layer deposition film 12, the following description will be given by taking an aluminum oxide (Al ₂ O ₃ ) film as an example.

The plurality of film forming portions 43 are disposed between the plasma pretreatment portion 24 and the guide roller 27 so as to face the one surface 11 a of the base material 11.
The film forming unit 43 includes a purge chamber 45, a precursor adsorption chamber 46, and a second precursor supply nozzle 47.

In the first embodiment, the “first processing chamber” refers to a chamber including a purge chamber 45, a precursor adsorption chamber 46, and a second precursor supply nozzle 47.
Therefore, the atomic layer deposition film forming unit 26 has a plurality of first processing chambers arranged in the transport direction of the base material 11.

The purge chamber 45 accommodates a precursor adsorption chamber 46 and a second precursor supply nozzle 47 arranged in the transport direction of the substrate 11. The purge chamber 45 exposes the one surface 11 a of the base material 11 positioned before and after the precursor adsorption chamber 46 and the one surface 11 a of the base material 11 positioned before and after the second precursor supply nozzle 47. .
The purge chamber 45 has an inlet (not shown) for introducing the base material 11 into the purge chamber 45 and an outlet (not shown) for leading the base material 11 out of the purge chamber 45. And having.

The purge chamber 45 is filled with a purge gas (for example, a mixed gas obtained by mixing O ₂ gas and N ₂ gas).
In the purge chamber 45, an excess (excess) first precursor (for example, trimethylaluminum (TMA)) and a by-product that are adsorbed on the one surface 11 a of the substrate 11 by passing through the precursor adsorption chamber 46. The second precursor (for example, H ₂ O) and by-products that are excessively adsorbed on the one surface 11a of the substrate 11 by passing through the second precursor supply nozzle 47 are removed. Remove.
The “second precursor” in the present invention refers to a substance that causes the first precursor (TMA in this embodiment) to undergo an oxidation reaction.

The precursor adsorption chamber 46 is accommodated in the purge chamber 45 and is disposed in front of the second precursor supply nozzle 47.
The precursor adsorption chamber 46 includes an introduction port (not shown) for introducing the base material 11 into the precursor adsorption chamber 46 and a purge chamber 45 (in other words, outside the precursor adsorption chamber 46). And a lead-out port (not shown) for leading out the base material 11.

When trimethylaluminum (TMA) is used as the first precursor and an aluminum oxide (Al ₂ O ₃ ) film is formed as the atomic layer deposition film 12, the precursor adsorption chamber 46 contains nitrogen gas and trimethylaluminum ( (TMA) can be mixed.
In this case, the pressure in the precursor adsorption chamber 46 can be maintained at 10 to 50 Pa, for example, and the temperature of the inner wall of the precursor adsorption chamber 46 can be maintained at 70 ° C., for example.

The second precursor supply nozzle 47 is accommodated in the purge chamber 45, and is disposed downstream of the precursor adsorption chamber 46.
The second precursor supply nozzle 47 is disposed so as to face the base material 11. The second precursor supply nozzle 47 is a nozzle for supplying water to the one surface 11 a of the substrate 11.

When an aluminum oxide (Al ₂ O ₃ ) film is formed as the atomic layer deposition film 12, the atmosphere in which the nitrogen gas and water exist can be set in the second precursor supply nozzle 47.
In this case, the pressure in the second precursor supply nozzle 47 can be maintained at 10 to 50 Pa, for example, and the temperature of the inner wall of the second precursor supply nozzle 47 can be maintained at 70 ° C., for example.
In this case, in the base material 11 facing the second precursor supply nozzle 47, the trimethylaluminum (TMA) adsorbed on the one surface 11a of the base material 11 and water react to form the atomic layer deposition film 12. An atomic oxide level aluminum oxide (Al ₂ O ₃ ) layer constituting a part of the aluminum oxide (Al ₂ O ₃ ) film is formed.

Thereafter, the base material 11 in which trimethylaluminum (TMA) and water have reacted is led out from the second precursor supply nozzle 47 and conveyed into the purge chamber 45. Then, excess (excess) second precursor (in this case, H ₂ O) and by-products are removed in the purge chamber 45, so that one atomic layer level aluminum oxide (Al ₂ O ₃ ) layer is formed.
Then, the base material 11 on which the aluminum oxide (Al ₂ O ₃ ) layer is formed is led out of the purge chamber 45.

A series of processes performed in one film forming unit 43 described above is set as one cycle, and an aluminum oxide (Al ₂ O ₃ ) layer of one atomic layer level is formed, and the process of the one cycle is performed to form an atomic layer deposited film. Each of the plurality of film forming portions 43 constituting the portion 26 is performed once, so that the total thickness of the laminated aluminum oxide (Al ₂ O ₃ ) layers and the aluminum oxide (Al ₂ O ₃ ) The desired thickness of the film is substantially matched.

Therefore, the number of film forming parts 43 constituting the atomic layer deposited film forming part 26 is determined according to a desired thickness of the aluminum oxide (Al ₂ O ₃ ) film that is the atomic layer deposited film 12.
For example, on one surface 11a of the substrate 11, the thickness of the thickness (desired thickness) 10 nm aluminum oxide _(Al 2 _{O 3)} is the case of forming a film, and 1 cycle of aluminum oxide _(Al 2 _{O 3)} layer When the thickness is 0.14 to 0.15 nm, 70 cycles of treatment are required.
Therefore, in this case, the number of film forming parts 43 constituting the atomic layer deposited film forming part 26 is 70.
In the atomic layer deposition film forming unit 26, the width for forming the atomic layer deposition film 12 can be defined.

FIG. 4 is an enlarged view of a portion corresponding to the region E in the laminated body manufacturing apparatus shown in FIG. 4, the same components as those shown in FIGS. 1 and 2 are denoted by the same reference numerals.
FIG. 5 is a perspective view of the guide roller shown in FIG. In FIG. 5, the same components as those shown in FIGS. 2 and 4 are denoted by the same reference numerals.

  FIG. 6 is a cross-sectional view of a base material on which a guide roller, a pair of pressing rollers, and an atomic layer deposition film positioned between the guide roller and the pair of pressing rollers are formed. 6, the same components as those shown in FIGS. 1, 2, 4, and 5 are denoted by the same reference numerals.

2 and 4 to 6, the guide roller 27 is disposed in the vicinity of the outer surface 21 a of the support member 21 positioned between the atomic layer deposition film forming unit 26 and the intermediate chamber 29.
The guide roller 27 includes a pair (two) of guide roller main bodies 51 and a rotation shaft 52. The pair of guide roller main bodies 51 has a cylindrical shape. Each of the pair of guide roller bodies 51 has a roller surface 51a.

The pair of roller surfaces 51 a is disposed at a position where it can come into contact with the outer peripheral portion of the one surface 12 of the atomic layer deposition film 12 conveyed by the outer surface 21 a of the support member 21.
Width _W of the roller surface 51a in contact with one surface 12a of the atomic layer deposition film 12 _2, for example, can be set to a value of about 5 to 10% of the width _{W 1} of the substrate 11.

In this way, the base 11 on which the atomic layer deposition film 12 is formed in contact with only the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12 is transferred to an overcoat layer forming chamber 61 (hereinafter referred to as an overcoat layer 61). The coating layer forming chamber 61 is sometimes referred to as a “second processing chamber.”) By using the guide roller 27 for guiding the coating layer forming chamber 61 into the second processing chamber, a conventional guide roller that contacts the entire surface 12a of the atomic layer deposition film 12 is used. Compared to the case, it is possible to suppress the generation of scratches caused by the guide roller 27 in the atomic layer deposition film 12.
Thereby, while the fall of the gas barrier property of the atomic layer deposition film 12 can be suppressed, the fall of the adhesiveness between the base material 11 and the atomic layer deposition film 12 can be suppressed.

Referring to FIGS. 2 and 6, the pair (two) of pressing rollers 28 includes a pressing roller body 54 and a rotation shaft 55.
The pressing roller main body 54 has a roller surface 54 a that comes into contact with the outer peripheral portion of the other surface 11 b of the base material 11. The pressing roller body 54 is disposed at a position where the roller surface 54 a faces the roller surface 51 a of the guide roller body 51. One end of the rotating shaft 55 is connected to the pressing roller main body 54.
The pressing roller 54 configured as described above is a roller for pressing the base material 11 on which the atomic layer deposition film 12 that contacts the roller surface 51 a of the guide roller body 51 is pressed against the guide roller body 51.

  Thus, by having the pressing roller 54 that presses the base material 11 on which the atomic layer deposition film 12 that contacts the guide roller body 51 is pressed against the roller surface 51 a of the guide roller body 51, It is possible to prevent the base material 11 on which the atomic layer deposition film 12 is formed from coming off the roller surface 51a by firmly pressing the base material 11 on which the atomic layer deposition film 12 is formed against the roller surface 51a. Therefore, the conveyance direction of the base material 11 can be changed stably.

Referring to FIG. 2, the intermediate chamber 29 is disposed at a position separated from the support member 21 and the atomic layer deposition film forming unit 26. The intermediate chamber 29 has a first inlet 29-1, a second inlet 29-2, a first outlet 29-3, and a second outlet 29-4.
The first introduction port 29-1 is an introduction port for introducing the base material 11 on which the atomic layer deposition film 12 is formed from the outside of the intermediate chamber 29 into the intermediate chamber 29. The second introduction port 29-2 is an introduction port for introducing the base material 11 on which the atomic layer deposition film 12 is formed from the intermediate chamber 29 into the overcoat layer forming unit 31.

The first outlet 29-3 is an outlet for leading the base material 11 on which the overcoat layer 14 is formed in the overcoat layer forming part 31 from the overcoat layer forming part 31 into the intermediate chamber 29. is there.
The second outlet 29-4 is an outlet for leading the substrate 11 on which the overcoat layer 14 is formed by the overcoat layer forming portion 31 from the intermediate chamber 29 to the outside of the intermediate chamber 29.
The intermediate chamber 29 is used when the substrate 11 is transported from the first processing chamber to the second processing chamber, and when the substrate 11 is unloaded from the second processing chamber.

Thus, by having the intermediate chamber 29 that passes when the substrate 11 is transported from the first processing chamber to the second processing chamber and when the substrate 11 is unloaded from the second processing chamber, for example, When the degree of vacuum between the first processing chamber and the second processing chamber differs greatly, the degree of vacuum in the intermediate chamber 29 is set between the degree of vacuum in the first processing chamber and the degree of vacuum in the second processing chamber. With this value, the degree of vacuum can be changed step by step.
Specifically, the degree of vacuum in the first processing chamber (specifically, in the purge chamber 45) is 100 Pa, and the degree of vacuum in the second processing chamber (in the overcoat layer forming chamber 61) is 0.01 Pa. In this case, the degree of vacuum in the intermediate chamber 29 can be set to 1 Pa, for example.

  In addition, an intermediate chamber 29 is provided, and the base material 11 on which the atomic layer deposition film 12 is formed is transferred to the second processing chamber via the intermediate 29, whereby the gas used in the first processing chamber and the second gas are used. Mixing with the gas used in the processing chamber can be suppressed.

  The overcoat layer forming portion 31 is a portion where the overcoat layer 14 shown in FIG. 1 is formed, and includes an overcoat layer forming chamber 61 (second processing chamber), a first roller 62, and a second roller. 63, a raw material tank 65, a raw material supply pipe 66, a raw material supply pump 68, a sprayer 69, a vaporizer 72, a gas supply pipe 74, a coating nozzle 76, and a light irradiation unit 78.

The overcoat layer forming chamber 61 is disposed adjacent to the intermediate chamber 29 and is partitioned so as to expose the second inlet 29-2 and the first outlet 29-3. The overcoat layer forming chamber 61 is disposed outside the first processing chamber and at a position separated from the first processing chamber.
The overcoat layer forming chamber 61 includes a first roller 62, a second roller 63, a raw material tank 65, a raw material supply pipe 66, a raw material supply pump 68, a sprayer 69, a vaporizer 72, a gas supply pipe 74, and a coating nozzle 76. , And the light irradiation part 78 are accommodated.
The atmosphere in the overcoat layer forming chamber 61 may be, for example, an inert gas atmosphere (for example, a nitrogen atmosphere) so as not to hinder the crosslinking of the coating material.

  In this manner, the overcoat layer 14 (see FIG. 5) is disposed on the outer surface of the first processing chamber where the atomic layer deposition film 12 is formed and spaced from the first processing chamber, and on one surface 12a of the atomic layer deposition film 12. 1), the gas used in the second processing chamber can be prevented from moving into the first processing chamber, and the overcoat layer forming chamber 61 (second processing chamber) is formed. It is possible to suppress the gas used in the first processing chamber from moving into the second processing chamber.

  Thereby, it is possible to suppress the atomic layer deposition film 12 and the overcoat layer 14 from being formed in a state where the gas used in the first processing chamber and the gas used in the second processing chamber are mixed. Therefore, the performance (film quality, film characteristics, etc.) of the atomic layer deposition film 12 and the overcoat layer 14 can be improved. That is, the atomic layer deposition film 12 having excellent gas barrier properties can be formed.

  The first roller 62 is disposed in the vicinity of the second introduction port 29-2. The first roller 62 is in contact with the other surface 11b (see FIG. 1) of the base material 11 that has passed through the first and second introduction ports 29-1 and 29-2, whereby the atomic layer deposition film 12 is formed. The transport direction of the base material 11 is changed by 90 degrees, and the base material 11 is transported in the direction toward the second roller 63.

  The second roller 63 is disposed in the vicinity of the first outlet 29-3. The second roller 63 is conveyed by the first roller 62 and is in contact with the other surface 11b (see FIG. 1) of the substrate 11 on which the overcoat layer 14 is formed on the one surface 12a of the atomic layer deposition film 12. Then, the conveyance direction of the base material 11 is changed by 90 degrees, and the base material 11 is conveyed in the direction toward the first and second outlets 29-3 and 29-4.

The raw material tank 65 is connected to a sprayer 69 via a raw material supply pipe 68. The raw material tank 65 is filled with a coating material (for example, an acrylic monomer) serving as a base material of the overcoat layer 14 (see FIG. 1).
One end of the raw material supply pipe 66 is connected to the raw material tank 65, and the other end is connected to the sprayer 69.

The raw material supply pump 68 is provided in a raw material supply pipe 66 located in the vicinity of the raw material tank 65. The raw material supply pump 68 supplies the coating material filled in the raw material tank 65 to the sprayer 69 via the raw material supply pipe 66.
The sprayer 69 is connected to the other end of the raw material supply pipe 66 and the vaporizer 72. The sprayer 69 sprays the coating material supplied via the raw material supply pipe 66 to the vaporizer 72. As the sprayer 69, for example, an atomizer can be used.

The vaporizer 72 is connected to the sprayer 69 and the gas supply pipe 74. In the vaporizer 72, the coating material sprayed by the spraying device 62 is vaporized, so that the coating material is changed to a gas state. The coating material in a gaseous state is supplied to the coating nozzle 76 via the gas supply pipe 74. As the vaporizer 72, for example, an evaporator can be used.
The gas supply pipe 74 has one end connected to the vaporizer 72 and the other end connected to the coating nozzle 76. The gas supply pipe 74 supplies the coating material in a gaseous state to the coating nozzle 76. The gas supply pipe 74 is a pipe kept at a high temperature.

The coating nozzle 76 can spray a coating material in a gaseous state onto one surface 12a (see FIG. 1) of the atomic layer deposition film 12 formed on the base material 11 immediately after passing through the first roller 62. Placed in position.
The coating material that has been jetted onto the one surface 12a of the atomic layer deposition film 12 becomes a coating layer (a base material of the overcoat layer 14).

The light irradiation unit 78 is disposed at a position where light (for example, an electron beam, ultraviolet light, or the like) can be applied to the coating layer conveyed between the coating nozzle 76 and the second roller 63.
The coating layer is crosslinked by being irradiated with light (for example, an electron beam or ultraviolet rays) to form a cured overcoat layer 14. Thereby, the laminated body 10 shown in FIG. 1 is formed.

  Thereafter, the laminated body 10 that has passed through the second roller 63 is introduced into the intermediate chamber 29 via the first outlet 29-3, and then, the intermediate chamber via the second outlet 29-4. 29 is led out and is conveyed in a direction toward the roller 32.

  FIG. 7 is an enlarged view of a portion corresponding to the region F in the laminated body manufacturing apparatus shown in FIG. 7, the same components as those shown in FIGS. 2 to 4 are denoted by the same reference numerals.

2 and 7, the roller 32 has a roller surface 32 a that is disposed to face the outer surface 21 a of the support member 21 and that contacts the one surface 14 a of the overcoat layer 14 that constitutes the laminate 10. .
The roller 32 is disposed close to the support member 21 so that the laminated body 10 can be sandwiched between the roller surface 32 a and the outer surface 21 a of the support member 21.
The laminated body 10 that has passed the roller 32 is conveyed along the outer surface 21a of the support member 21 to the laminated body winding part 33 (specifically, the dancer roller 81 that constitutes the laminated body winding part 33).

Referring to FIGS. 1 and 2, the laminated body winding unit 33 includes a dancer roller 81 and a winding roller 82.
The dancer roller 81 is provided at the rear stage of the roller 32. The dancer roller 81 has a roller surface that comes into contact with one surface 14 a of the overcoat layer 14 constituting the laminate 10. The dancer roller 81 is disposed close to the support member 21 so that the laminated body 10 can be sandwiched between the roller surface of the dancer roller 81 and the outer surface 21 a of the support member 21.
The dancer roller 81 has a function of applying a predetermined tension to the laminate 10 when the laminate 10 is taken up by the take-up roller 82. The laminate 10 that has passed the dancer roller 81 is conveyed to the take-up roller 82.

The winding roller 82 is a roller having an outer diameter larger than that of the dancer roller 81. The take-up roller 82 is arranged at the rear stage of the dancer roller 81. The take-up roller 82 is a roller for taking up the sheet 10 in a roll shape. The roller surface of the take-up roller 82 is in contact with one surface 14 a of the overcoat layer 14 constituting the laminate 10.
Therefore, the roller surface of the take-up roller does not come into direct contact with one surface of the atomic layer deposition film, so that the generation of scratches on the atomic layer deposition film due to the take-up roller can be suppressed.

  According to the laminated body manufacturing apparatus of the first embodiment, the atomic layer deposition film is disposed outside the first processing chamber in which the atomic layer deposition film 12 is formed and is spaced from the first processing chamber. 12 has an overcoat layer forming chamber 61 (second processing chamber) for forming an overcoat layer 14 (see FIG. 1) on one surface 12a, so that the gas used in the second processing chamber is in the first processing chamber. It is possible to suppress the movement of the gas used in the first processing chamber and the movement of the gas used in the first processing chamber to the second processing chamber.

  Thereby, it is possible to suppress the atomic layer deposition film 12 and the overcoat layer 14 from being formed in a state where the gas used in the first processing chamber and the gas used in the second processing chamber are mixed. Therefore, the performance (film quality, film characteristics, etc.) of the atomic layer deposition film 12 and the overcoat layer 14 can be improved. That is, the atomic layer deposition film 12 having excellent gas barrier properties can be formed.

Further, a guide roller that contacts only the outer peripheral portion of one surface 12a of the atomic layer deposition film 12 and guides the base material 11 on which the atomic layer deposition film 12 is formed into the overcoat layer formation chamber 61 (second processing chamber). 27, the generation of scratches caused by the guide roller 27 in the atomic layer deposition film 12 can be suppressed as compared with the case where a conventional guide roller that contacts the entire surface 12a of the atomic layer deposition film 12 is used. Can do.
Thereby, while the fall of the gas barrier property of the atomic layer deposition film 12 can be suppressed, the fall of the adhesiveness between the base material 11 and the atomic layer deposition film 12 can be suppressed.

  Furthermore, it has the laminated body winding part 33 which winds up the laminated body 10 by roll shape by contacting with the one surface 14a of the overcoat layer 14 which comprises the laminated body 10, and comprises the laminated body winding part 33. Since the roller surfaces of the dancer roller 81 and the take-up roller 82 are not in direct contact with the one surface 12a of the atomic layer deposition film 12, the atomic layer deposition film 12 is damaged due to the dancer roller 81 and the take-up roller 82. This can be suppressed.

<The manufacturing method of the laminated body of 1st Embodiment>
FIG. 8 is a flowchart for explaining the manufacturing method of the laminated body according to the first embodiment of the present invention.
Next, with reference to FIG. 2 to FIG. 4, FIG. 7, and FIG. 8, a manufacturing method of the laminate according to the first embodiment will be described.

  When the processing of the flowchart shown in FIG. 8 is started, the base material 11 (for example, a film made of polyethylene terephthalate (PET) having a thickness of 100 μm) wound around the base material winding roller 36 by the base material transport unit 23. ) Is conveyed along the outer surface 21 a of the support member 21 in the direction toward the plasma pretreatment unit 24. At this time, the base material 11 is transported so that the other surface 11 b contacts the outer surface 21 a of the support member 21.

In STEP1, the surface 11a of the substrate 11 is subjected to plasma pretreatment. Specifically, the surface 11a of the base 11 is modified by exposing the surface 11a of the base 11 to an oxygen plasma atmosphere by the plasma pretreatment unit 24, for example.
Thereafter, the base material whose one surface 11a is modified is conveyed along the outer surface 21a of the support member 21 to the atomic layer deposition film forming unit 26, and the process proceeds to STEP2.
The conditions for the plasma pretreatment can be appropriately selected according to the characteristics of the material of the substrate 11.

In STEP 2, the atomic layer deposition film 12 having a desired thickness is formed on the one surface 11 a of the substrate 11 by the atomic layer deposition film formation unit 26 having the plurality of film formation units 43 (atomic layer deposition film formation step). ).
Specifically, in STEP 2, the following processing is performed. First, when the conveyed base material 11 reaches the first film forming portion 43, the base material 11 is introduced into a purge chamber 45 that is set to an inert gas atmosphere (for example, a nitrogen atmosphere).
In the purge chamber 45, removal of excess (excess) first precursor (for example, trimethylaluminum (TMA)) and removal of by-products adsorbed on the one surface 11a of the substrate 11 treated with STEP1 are performed. Done.

Next, the base material 11 is introduced into a precursor adsorption chamber 46 disposed in the purge chamber 45. For example, when the atmosphere in the precursor adsorption chamber 46 is an atmosphere in which nitrogen gas and trimethylaluminum (TMA) are mixed, the pressure in the precursor adsorption chamber 46 is, for example, 10 to 50 Pa. Can do. In this case, the temperature of the inner wall of the precursor adsorption chamber 46 can be maintained at 70 ° C., for example.
In this case, in the precursor adsorption chamber 46, trimethylaluminum (TMA) is adsorbed on the one surface 11a of the substrate 11 as a precursor.

  Thereafter, the base material 11 having the precursor adsorbed on one surface thereof is led out from the precursor adsorption chamber 46, and the purge chamber 45 located between the precursor adsorption chamber 46 and the second precursor supply nozzle 47. Inside, excess (excess) precursor (trimethylaluminum (TMA)) is removed.

Next, the base material 11 having the precursor adsorbed on the one surface 11 a is introduced into the second precursor supply nozzle 47.
For example, when the atmosphere in the second precursor supply nozzle 47 is an atmosphere in which nitrogen gas and water are mixed, the pressure in the second precursor supply nozzle 47 is, for example, 10 to 50 Pa. be able to. In this case, the temperature of the inner wall of the second precursor supply nozzle 47 can be maintained at 70 ° C., for example.
In this case, in the second precursor supply nozzle 47, trimethylaluminum (TMA) and water react to form a part of the aluminum oxide (Al ₂ O ₃ ) film that is the atomic layer deposition film 12. Thus, an atomic layer level aluminum oxide (Al ₂ O ₃ ) layer is formed.

Thereafter, the base material 11 in which trimethylaluminum and water have reacted is led out from the second precursor supply nozzle 47 and conveyed into the purge chamber 45. Then, excess (excess) second precursor (in this case, H ₂ O) and by-products are removed in the purge chamber 45.
Next, the base material 11 on which the aluminum oxide (Al ₂ O ₃ ) layer of one atomic layer level is formed on the one surface 11 a is led out of the purge chamber 45.

A series of processes performed in one film forming unit 43 described above is set as one cycle, and an aluminum oxide (Al ₂ O ₃ ) layer of one atomic layer level is formed, and the process of the one cycle is performed to form an atomic layer deposited film. This is performed once at each of the plurality of film forming parts 43 constituting the part 26, so that the total thickness of the stacked aluminum oxide (Al ₂ O ₃ ) layers and the atomic layer deposition film 12 are obtained. The desired thickness of the aluminum oxide (Al ₂ O ₃ ) film is substantially matched.

Specifically, for example, when an aluminum oxide film having a thickness (desired thickness) of 10 nm is formed on the one surface 11a of the base material 11, the above process is performed for 70 cycles using 70 film forming portions 43. Thus, an aluminum oxide (Al ₂ O ₃ ) film having a thickness (desired thickness) of 10 nm is formed.
When the atomic layer deposited film forming step shown in STEP 2 described above is completed, the process proceeds to STEP 3.

  In STEP 3, the base material 11 on which the atomic layer deposition film 12 is formed is passed through the intermediate chamber 29 by the guide roller 27 that contacts only the outer peripheral portion of the one surface 12 a of the atomic layer deposition film 12. Among the processing chambers, the first processing chamber arranged at the rearmost stage is guided into the overcoat layer forming chamber 61 (second processing chamber) (base material guiding step).

  Specifically, the roller surface 51a (see FIGS. 4 to 6) of the guide roller body 51 constituting the guide roller 27, and the roller surface 54a of the pair of pressing roller bodies 54 (one of the components of the pressing roller 28). (See FIGS. 2 and 4), the base material 11 on which the atomic layer deposition film 12 is formed on the one surface 11 a is a first roller 62 disposed in the overcoat layer forming chamber 61 from the outer surface 21 a of the support member 21. (In other words, the direction toward the intermediate chamber 29 and the overcoat layer forming unit 31).

  At this time, the other surface 11b of the base material 11 on which the atomic layer deposition film 12 is formed is in contact with the roller surface 54a of the pair of roller bodies 54, and the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12 is a pair of guides. It contacts the roller surface 51 a of the roller body 51.

In this way, the substrate 11 on which the atomic layer deposition film 12 is formed is transferred to the overcoat layer forming chamber 61 (second processing chamber) by the guide roller 27 that contacts only the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12. As a result, the generation of scratches caused by the guide roller 27 on the atomic layer deposition film 12 is suppressed as compared with the case where a conventional guide roller that contacts the entire surface 12a of the atomic layer deposition film 12 is used. be able to.
Thereby, while the fall of the gas barrier property of the atomic layer deposition film 12 can be suppressed, the fall of the adhesiveness between the base material 11 and the atomic layer deposition film 12 can be suppressed.

  Further, by guiding the substrate 11 on which the atomic layer deposition film 12 is formed from the first processing chamber to the second processing chamber via the intermediate chamber 29, the gas used in the first processing chamber and Since the gas used in the second processing chamber is hardly mixed, the atomic layer deposition film 12 and the overcoat layer 14 having good film quality can be formed. Thereby, it can suppress that the gas barrier property of the atomic layer deposition film 12 falls.

  Furthermore, in the base material guiding step, the base material is guided to the second processing chamber via an intermediate chamber that is set to a pressure between the pressure in the first processing chamber and the pressure in the second processing chamber. May be.

For example, when the degree of vacuum between the first processing chamber and the second processing chamber is greatly different, the degree of vacuum between the first processing chamber and the second processing chamber is set to a vacuum degree. Thus, the degree of vacuum can be changed step by step.
Specifically, the degree of vacuum in the first processing chamber (specifically, in the purge chamber 45) is 100 Pa, and the degree of vacuum in the second processing chamber (in the overcoat layer forming chamber 61) is 0.01 Pa. In this case, the degree of vacuum in the intermediate chamber 29 can be set to 1 Pa, for example.

Thereafter, the base material 11 transported into the overcoat layer forming chamber 61 is transported in the direction toward the second roller 63 by changing the transport direction by the first roller 62.
At this time, the other surface 11 b of the base material 11 on which the atomic layer deposition film 12 is formed is in contact with the roller surfaces of the first and second rollers 62 and 63. Further, the base material 11 on which the atomic layer deposition film 12 is formed is conveyed so that one surface 12 a of the atomic layer deposition film 12 faces the coating nozzle 76 and the light irradiation unit 78.
When the base material guiding process in STEP 3 is completed, the process proceeds to STEP 4.

In STEP 4, the overcoat layer 14 is formed on the one surface 12a of the atomic layer deposition film 12 in the overcoat layer forming chamber 61 (second processing chamber) maintained in an inert gas atmosphere (overcoat layer forming step). ).
Thereby, the laminated body 10 by which the base material 11, the atomic layer deposition film 12, and the overcoat layer 14 were laminated | stacked is manufactured.

  Thus, in the overcoat layer forming chamber 61 (second processing chamber) arranged outside the first processing chamber where the atomic layer deposition film 12 is formed and at a position separated from the first processing chamber. Thus, by forming the overcoat layer 14 on the one surface 12a of the atomic layer deposition film 12, the gas used in the first processing chamber and the gas used in the second processing chamber are not mixed, and the overcoat layer 14 is formed. The layer 14 and the atomic layer deposition film 12 can be formed.

  Thereby, the performance (film quality, film characteristics, etc.) of the overcoat layer 14, the atomic layer deposition film 12, and the overcoat layer 14 can be improved. That is, the atomic layer deposition film 12 having excellent gas barrier properties can be formed.

In the overcoat layer forming step, the overcoat layer 14 is formed by a flash vapor deposition method. Specifically, the overcoat layer 14 is formed by the following method.
First, a coating material (for example, an acrylic coating agent (for example, ester acrylate, ether acrylate, phenyl acrylate, urethane acrylate, epoxy acrylate, silicone acrylate, By spraying acrylic monomers or acrylic oligomers such as acetal acrylate, butadiene acrylate, melamine acrylate, or photoinitiators such as benzoin ethers, benzophenones, xanthones, acetophenone derivatives, etc.), the coating layer ( The base material of the overcoat layer 14) is formed.

Next, the overcoat layer 14 is formed by irradiating the coating layer with light (for example, electron beam light or ultraviolet light) by the light irradiation unit 78 to be crosslinked and cured.
The flash vapor deposition method is a method in which a monomer, oligomer, etc. are coated in a desired thickness in a vacuum (for example, 0.01 to 0.1 Pa in the case of electron beam light). It is possible to form an acrylic layer to be the overcoat layer 14 without generating a volatile component and with a low heat load. At this time, an acrylic monomer, an acrylic oligomer or the like that is liquid at room temperature and does not contain a solvent is used.

  Thus, the first treatment is performed by forming the overcoat layer 14 by the flash vapor deposition method using the coating material (overcoat layer material) containing no solvent (in other words, generating less volatile gas). Since the possibility of mixing the gas in the chamber and the gas in the second processing chamber is further reduced, the atomic layer deposition film 12 and the overcoat layer 14 having excellent film quality can be formed.

The thickness of the overcoat layer 14 can be set to 1 μm, for example, but is not limited thereto. The thickness of the overcoat layer 14 can be appropriately selected according to the purpose.
The thickness of the overcoat layer 14 is adjusted using the following method. When it is desired to increase the thickness of the overcoat layer 14, the amount of the coating material dropped onto the vaporizer 72 is increased. When the thickness of the overcoat layer 14 is desired to be reduced, the coating material applied to the vaporizer 72 is reduced. Reduce the amount of dripping.
The uniformity of the thickness of the overcoat layer 14 is ensured by keeping the amount of the coating material dropped per unit time constant.

In the overcoat layer forming step, an overcoat layer 14 having higher mechanical strength than the atomic layer deposition film 12 may be formed.
In this way, by forming the overcoat layer 14 having higher mechanical strength than the atomic layer deposition film 12, the one surface 14 a of the overcoat layer 14 and the roller surface of the take-up roller 82 are brought into contact with each other, and the take-up roller 82. As a result, it is possible to further prevent the atomic layer deposition film 12 from being damaged when the laminate 10 is wound into a roller shape.

  Further, even when a rigid body other than the take-up roller 82 (for example, the roller 32 and the dancer roller 81) is in contact with the overcoat layer 14, it is possible to suppress damage to the one surface 12a of the atomic layer deposition film 12.

In the overcoat layer forming step, the overcoat layer 14 having mechanical strength equivalent to that of the atomic layer deposition film 12 may be formed so that the thickness is larger than the thickness of the atomic layer deposition film 12. .
Thus, by forming the overcoat layer 14 having the same mechanical strength as that of the atomic layer deposition film 12 so that the thickness is larger than the thickness of the atomic layer deposition film 14, one surface of the overcoat layer 14 is obtained. And the roller surface of the take-up roller 82 are brought into contact with each other, and the take-up roller 82 can further prevent the atomic layer deposited film 12 from being damaged when the laminated body 10 is wound into a roller shape.

Further, even when a rigid body other than the take-up roller 82 (for example, the roller 32 and the dancer roller 81) is in contact with the overcoat layer 14, it is possible to suppress damage to the one surface 12a of the atomic layer deposition film 12.
When the overcoat layer forming step in STEP 4 is completed, the process proceeds to STEP 5.

In STEP 5, the one surface 14a of the overcoat layer 14 and the roller surface of the take-up roller 82 are brought into contact with each other, and the laminate 10 is taken up into a roller shape by the take-up roller 82 (winding step).
In this way, the surface 14a of the overcoat layer 14 is brought into contact with the roller surface of the take-up roller 82, and the take-up roller 82 winds up the laminated body 10 into a roller shape. Since there is no direct contact with the one surface 12a of the atomic layer deposition film 12, it is possible to suppress the occurrence of scratches caused by the take-up roller 82 on the atomic layer deposition film 12.

Furthermore, by forming the overcoat layer 14 that covers the one surface 12a of the atomic layer deposition film 12, there is no risk of the atomic layer deposition films 12 coming into contact with each other when wound around the take-up roller 82 (in other words, The generation of scratches due to the contact between the atomic layer deposition films 12 can be suppressed).
When the winding process in STEP 5 is finished, the process shown in FIG. 8 is finished.

  According to the manufacturing method of the laminated body of the first embodiment, the overcoat disposed outside the first processing chamber in which the atomic layer deposition film 12 is formed and at a position separated from the first processing chamber. In the layer forming chamber 61 (second processing chamber), the overcoat layer 14 is formed on the one surface 12a of the atomic layer deposition film 12 to use the gas used in the first processing chamber and the second processing chamber. The overcoat layer 14 and the atomic layer deposition film 12 can be formed without mixing with the gas to be used.

  Thereby, the performance (film quality, film characteristics, etc.) of the overcoat layer 14, the atomic layer deposition film 12, and the overcoat layer 14 can be improved. That is, the atomic layer deposition film 12 having excellent gas barrier properties can be formed.

Further, the base material 11 on which the atomic layer deposition film 12 is formed is placed in the overcoat layer forming chamber 61 (second processing chamber) by the guide roller 27 that contacts only the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12. By guiding, it is possible to suppress the occurrence of scratches caused by the guide roller 27 in the atomic layer deposition film 12 as compared with the case where a conventional guide roller that contacts the entire surface 12a of the atomic layer deposition film 12 is used. it can.
Thereby, while the fall of the gas barrier property of the atomic layer deposition film 12 can be suppressed, the fall of the adhesiveness between the base material 11 and the atomic layer deposition film 12 can be suppressed.

  Furthermore, it has the laminated body winding part 33 which winds up the laminated body 10 by roll shape by contacting with the one surface 14a of the overcoat layer 14 which comprises the laminated body 10, and comprises the laminated body winding part 33. Since the roller surfaces of the dancer roller 81 and the take-up roller 82 are not in direct contact with the one surface 12a of the atomic layer deposition film 12, the atomic layer deposition film 12 is damaged due to the dancer roller 81 and the take-up roller 82. This can be suppressed.

<Laminated body manufacturing apparatus according to a modification of the first embodiment>
FIG. 9 is a front view schematically showing a schematic configuration of the laminated body manufacturing apparatus according to the modification of the first embodiment. In FIG. 9, the same components as those of the laminate manufacturing apparatus 20 of the first embodiment shown in FIG.

  The laminated body 10 shown in FIG. 1 replaces the laminated body manufacturing apparatus 20 of 1st Embodiment shown in FIG. 2 with the laminated body manufacturing apparatus 80 which concerns on the modification of 1st Embodiment shown in FIG. It is possible to manufacture using.

Here, with reference to FIG. 9, the structure of the laminated body manufacturing apparatus 80 which concerns on the modification of 1st Embodiment is demonstrated.
The laminate manufacturing apparatus 80 is replaced with an overcoat layer forming unit 31 (an overcoat layer forming unit that forms the overcoat layer 14 by flash vapor deposition) constituting the laminate manufacturing apparatus 20 of the first embodiment. Except having the overcoat layer formation part 91 (overcoat layer formation part which forms the overcoat layer 14 with a vacuum evaporation method), it is comprised similarly to the laminated body manufacturing apparatus 20. FIG.
In the laminated body manufacturing apparatus 80, the guide roller 27 corresponds to a first guide roller, and a guide roller 85 described later corresponds to a second guide roller.

  The overcoat layer forming unit 91 includes a raw material tank 65, a raw material supply pipe 66, a raw material supply pump 68, a sprayer 69, a vaporizer 72, a gas supply pipe 74, and a coating that constitute the overcoat layer forming unit 31 described in FIG. In place of the nozzle 76 and the light irradiation unit 78, the overcoat layer forming unit 31 and the main roller 83, guide rollers 85 and 86, a roller 87, an evaporation source 89, and a heating device (not shown) are provided. It is constituted similarly.

The main roller 83 has a roller surface 83a that conveys the substrate 11 (see FIG. 4) on which the atomic layer deposition film 12 is formed on one surface 11a. The main roller 83 is disposed above the evaporation source 89 so that the roller surface 83a and the upper surface of the evaporation source 89 face each other.
When transported to a roller surface 83 a located below the main roller 83, an overcoat layer 14 (see FIG. 1) is formed on one surface 12 a of the atomic layer deposition film 12.

The guide roller 85 is disposed in the vicinity of the roller surface 83 a of the main roller 83. The guide roller 85 passes through the first roller 62 so that the other surface 11b of the substrate 11 and the roller surface 83a of the main roller 83 are in contact with each other and the substrate 11 on which the atomic layer deposition film 12 is formed. Transport.
The guide roller 85 has the same configuration as the guide roller 27. The roller surface 51 a of the guide roller main body 51 constituting the guide roller 85 is in contact with the outer peripheral portion of the one surface 12 a of the atomic layer deposition film 12.

In this way, by having the guide roller 85 that contacts only the outer peripheral portion of the one surface 12 a of the atomic layer deposition film 12 and guides the base material 11 on which the atomic layer deposition film 12 is formed to the roller surface 83 a of the main roller 83. Compared with the case where a conventional guide roller that contacts the entire surface 12a of the atomic layer deposition film 12 is used, the generation of scratches caused by the guide roller 27 on the atomic layer deposition film 12 can be suppressed.
As a result, it is possible to suppress a decrease in gas barrier properties of the atomic layer deposition film 12 and to suppress a decrease in adhesion between the substrate 11 and the atomic layer deposition film 12.

The guide roller 86 is disposed in the vicinity of the roller surface 83 a of the main roller 83. The guide roller 86 is disposed so as to face the guide roller 85 with the main roller 83 interposed therebetween.
The guide roller 86 has the same configuration as the guide roller 27. The guide roller 86 conveys the base material 11 (see FIG. 1) on which the overcoat layer 14 is formed toward the roller 87.
The guide roller 86 is a normal roller and is in contact with the outer peripheral portion of one surface 14a (see FIG. 1) of the overcoat layer 14.

  The roller 87 is disposed above the guide roller 86. The roller 87 is in contact with the other surface 11 b of the substrate 11, thereby changing the transport direction of the stacked body 10 and transporting the stacked body 10 to the second roller 63.

The evaporation source 89 is a container that stores a coating material that is a base material of the overcoat layer 14. The coating material accommodated in the evaporation source 89 is vaporized by being heated by a heating device (not shown). The vaporized coating material becomes an overcoat layer 14 by adhering to one surface 12a of the atomic layer deposition film 12 formed on the base material 11 conveyed to the roller surface 83a of the main roller 83.
As the heating device, for example, a device for heating the evaporation source 89 using an electron beam, or a refractory metal as the evaporation source 89 (in this case, functioning as a resistor) is used to energize the evaporation source 89, An apparatus for heating the coating material can be exemplified.

The laminate manufacturing apparatus 80 according to the modification of the first embodiment having the above-described configuration can obtain the same effects as those of the laminate manufacturing apparatus 20 of the first embodiment.
Moreover, when manufacturing the laminated body 10 using the said laminated body manufacturing apparatus 80, it is the same as that of the manufacturing method of the laminated body of 1st Embodiment except forming the overcoat layer 14 by a vacuum evaporation method. It can be manufactured by a technique.
The pressure in the overcoat layer forming chamber 61 can be set to 0.01 to 0.1 Pa, for example.
Thus, by forming the overcoat layer 14 by vacuum deposition, the overcoat layer 14 can be formed at a high speed, and a thick overcoat layer 14 can be formed.

(Second Embodiment)
<Laminated body according to the second embodiment>
FIG. 10 is a cross-sectional view schematically showing a laminate produced by the laminate production method according to the second embodiment of the present invention. In FIG. 10, the same components as those of the laminate 10 of the first embodiment shown in FIG.

Here, before explaining the manufacturing method of the laminated body of 2nd Embodiment, the structure of the laminated body 100 manufactured by the manufacturing method of the laminated body of 2nd Embodiment is demonstrated.
Referring to FIG. 10, the stacked body 100 is configured in the same manner as the stacked body 10 except that the stacked body 10 described in the first embodiment further includes an undercoat layer 101.

  The undercoat layer 101 is disposed on the one surface 11 a of the base material 11. The undercoat layer 101 is disposed between the base material 11 and the atomic layer deposition film 12. One surface 101 a of the undercoat layer 101 (a surface located on the opposite side of the other surface of the undercoat layer 101 that contacts the base material 11) is in contact with the atomic layer deposition film 12.

As the undercoat layer 101, for example, an inorganic substance (eg, halloysite, calcium carbonate, anhydrous silicic acid, hydrous silicic acid, alumina, etc.) and / or an organic polymer (eg, acrylic resin, urethane resin, polyimide resin, etc.) are used. An undercoat layer can be used.
Specifically, as the undercoat layer 101, for example, an acrylic coat layer, a urethane coat layer, an acrylic coat layer containing an inorganic substance, or the like can be used.
The thickness of the undercoat layer 101 can be appropriately set within a range of 0.1 to 10 μm, for example.

As described above, the undercoat is disposed between the base material 11 and the atomic layer deposition film 12, is in contact with the one surface 11 a of the base material 11 and the atomic layer deposition film 12, and contains an inorganic substance and / or an organic polymer. By having the layer 101, for example, when the undercoat layer 101 contains an inorganic substance, the precursor of the atomic layer deposition film 12 (for example, trimethylaluminum (TMA)) is exposed from the one surface 101a of the undercoat layer 101. A two-dimensional atomic layer deposition film 12 that grows in the direction of one surface of the undercoat layer 101 is formed to bond with an inorganic substance.
As a result, in the thickness direction of the laminated body 100, it is difficult to form a gap through which gas passes, so that the gas barrier property of the laminated body 100 can be improved.

In addition, when the undercoat layer 101 contains an organic polymer, the organic polymer has a functional group that easily binds to the precursor of the atomic layer deposition film 12 (for example, trimethylaluminum (TMA)). The precursors bonded to each functional group are bonded to each other. As a result, a two-dimensional atomic layer deposition film 12 growing in the direction of the one surface 101a of the undercoat layer 101 is formed.
As a result, it is difficult to form a gas that passes in the thickness direction of the stacked body 100, so that the gas barrier property of the stacked body 100 can be improved.

  Further, when the undercoat layer 101 contains an organic polymer and an inorganic substance, the addition of the inorganic substance to the undercoat layer 101 causes the organic polymer and the inorganic substance to combine to form an atomic layer deposition film. The adsorption density of the 12 precursors can be further improved.

<Laminated body manufacturing apparatus according to the second embodiment>
FIG. 11: is a front view which shows schematic structure of the laminated body manufacturing apparatus which concerns on the 2nd Embodiment of this invention. In FIG. 11, the same components as those in the laminate manufacturing apparatus 20 according to the first embodiment shown in FIG.

Next, with reference to FIG. 11, the laminated body manufacturing apparatus 110 which concerns on 2nd Embodiment used when manufacturing the laminated body 100 shown in FIG. 10 is demonstrated.
The laminated body manufacturing apparatus 110 of the second embodiment is the same as the laminated body manufacturing apparatus 20 of the first embodiment, except that it further includes an undercoat layer forming unit 111. It is comprised similarly.

The undercoat layer forming unit 111 is disposed so as to face the one surface 11 a of the base material 11 conveyed between the plasma pretreatment unit 24 and the atomic layer deposition film forming unit 26.
The undercoat layer forming unit 111 is an apparatus for forming the undercoat layer 101 containing an inorganic substance and / or an organic polymer on the one surface 11a of the substrate 11 on which the plasma pretreatment has been performed. For example, a flash vapor deposition apparatus can be used as the undercoat layer forming unit 111.
The undercoat layer forming part 111 is disposed so as to face the one surface 11a of the base material 11 passing between the base material feeding roller 37 and the atomic layer deposition film forming part 26, as well as overcoat layer formation. A processing chamber such as the chamber 61 may be provided separately.

  The laminated body manufacturing apparatus 110 having the above-described configuration has an undercoat layer 101 and a belt-like base material 11 extending in a predetermined direction (one direction) on the one surface 11a of the base material 11 by an in-line roll-to-roll method. , An atomic layer deposition film 12 and an overcoat layer 14 are sequentially formed.

  According to the laminated body manufacturing apparatus of the second embodiment, the inorganic substance and the atomic layer deposited film 12 are placed between the one surface 11a of the substrate 11 and the atomic layer deposited film 12 so as to be in contact with the substrate 11 and the atomic layer deposited film 12. When the undercoat layer 101 containing the inorganic substance and / or organic polymer is formed by having the undercoat layer forming portion 111 that forms the undercoat layer 101 containing the organic polymer, the thickness of the laminate 100 is increased. In the vertical direction, it is difficult to form a gap through which gas passes, and the gas barrier property of the laminate 100 can be improved.

<The manufacturing method of the laminated body of 2nd Embodiment>
FIG. 12 is a flowchart for explaining a method for manufacturing a laminated body according to the second embodiment of the present invention.
Next, with reference to FIGS. 10-12, the manufacturing method of the laminated body which concerns on 2nd Embodiment is demonstrated.
When the processing of the flowchart shown in FIG. 12 is started, the base material 11 (for example, a film made of polyethylene terephthalate (PET) having a thickness of 100 μm) wound around the base material winding roller 36 by the base material transport unit 23. ) Is conveyed along the outer surface 21 a of the support member 21 in the direction toward the plasma pretreatment unit 24. At this time, the base material 11 is transported so that the other surface 11 b contacts the outer surface 21 a of the support member 21.

In STEP 11, the one surface 11a of the substrate 11 is subjected to plasma pretreatment by the same method as in STEP 1 described in FIG.
Thereafter, the base material whose one surface 11a is modified is transported to the atomic layer deposition film forming unit 26 along the outer surface 21a of the support member 21, and the process proceeds to STEP12.

In STEP 12, the undercoat layer 101 is formed on the one surface 11a of the modified base material 11 (undercoat layer forming step).
Specifically, for example, an acrylic layer having a thickness of 0.1 μm is formed as the undercoat layer 101 by flash vapor deposition.
When the undercoat layer forming step shown in STEP 12 is completed, the process proceeds to STEP 13.

In STEP 13, atomic layer deposition with a desired thickness is performed on one surface 101 a of the undercoat layer 101 by the atomic layer deposition film forming unit 26 having a plurality of film forming units 43 by the same method as STEP 2 described in FIG. The film 12 is formed (atomic layer deposition film forming step).
For example, as the atomic layer deposition film 12, an aluminum oxide (Al ₂ O ₃ ) film having a thickness of 10 nm is formed.
When the atomic layer deposited film forming step shown in STEP 13 is completed, the process proceeds to STEP 14.

In STEP 14, the film disposed at the rearmost stage via the intermediate chamber 29 by the guide roller 27 that contacts only the outer peripheral portion of the one surface 12 a of the atomic layer deposition film 12 by the same method as STEP 3 described in FIG. The base material 11 on which the undercoat layer 101 and the atomic layer deposition film 12 are formed is guided from the forming unit 43 into the overcoat layer forming chamber 61 (second processing chamber) (base material guiding step).
When the degree of vacuum in the first processing chamber is 100 Pa and the degree of vacuum in the second processing chamber is 1 Pa, the degree of vacuum in the intermediate chamber 29 can be set to 10 Pa, for example.

The base material 11 transported into the overcoat layer forming chamber 61 is transported to the roller surface 83 a of the main roller 83 via the guide roller 85 with the transport direction changed by the first roller 62.
When the base material guiding process in STEP 14 is completed, the process proceeds to STEP 15.

In STEP 15, the overcoat layer 14 is formed on the one surface 12a of the atomic layer deposition film 12 in the overcoat layer forming chamber 61 (second processing chamber) maintained in an inert gas atmosphere (overcoat layer forming step). ).
Thereby, the laminated body 100 by which the base material 11, the undercoat layer 101, the atomic layer deposition film 12, and the overcoat layer 14 were laminated | stacked one by one is manufactured.
In STEP 15, the overcoat layer 14 is formed by the same method as in STEP 4 described in FIG.
When the overcoat layer forming step of STEP15 is completed, the process proceeds to STEP16.

In STEP 16, the one surface 14a of the overcoat layer 14 and the roller surface of the take-up roller 82 are brought into contact with each other, and the laminate 100 is taken up in a roller shape by the take-up roller 82 (winding step).
In STEP16, the laminated body 100 is wound up into a roller shape by the same method as STEP5 demonstrated in FIG. When the winding process of STEP 16 is finished, the process shown in FIG. 12 is finished.

According to the laminate manufacturing method of the second embodiment, the undercoat layer 101 containing an inorganic substance and / or an organic polymer is formed on the one surface 11a of the substrate 11 before the atomic layer deposition film forming step. An undercoat layer forming step to be formed, and in the atomic layer deposited film forming step, the one surface 101a of the undercoat layer 101 is bonded to an inorganic substance and / or an organic polymer exposed from the one surface 101a of the undercoat layer 101. In addition, by forming the atomic layer deposition film 12, for example, when the undercoat layer 101 containing an inorganic substance is formed, the precursor of the atomic layer deposition film 12 is exposed from the one surface 101 a of the undercoat layer 101. In order to bond to the substance, a two-dimensional atomic layer deposition film 12 growing in the direction of the one surface 101a of the undercoat layer 101 is formed.
As a result, in the thickness direction of the laminated body 100, it is difficult to form a gap through which gas passes, so that the gas barrier property of the laminated body 100 can be improved.

On the other hand, when the undercoat layer 101 containing an organic polymer is formed, the organic polymer has a functional group that easily binds to the precursor of the atomic layer deposition film 12, so that the precursor bonded to each functional group of the organic polymer. The bodies bind to each other. As a result, a two-dimensional atomic layer deposition film 12 growing in the direction of the one surface 101a of the undercoat layer 101 is formed.
As a result, it is difficult to form a gas that passes in the thickness direction of the stacked body 100, so that the gas barrier property of the stacked body 100 can be improved.

  In addition, when the undercoat layer 101 containing an organic polymer and an inorganic substance is formed, the inorganic substance is added to the undercoat layer 101, so that the organic polymer and the inorganic substance are combined to form an atomic layer. The adsorption density of the precursor of the deposited film 12 can be further improved.

  In addition, the manufacturing method of the laminated body of 2nd Embodiment can also acquire the effect similar to the manufacturing method of the laminated body of 1st Embodiment demonstrated previously.

  The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to such specific embodiments, and within the scope of the present invention described in the claims, Various modifications and changes are possible.

FIG. 13: is a front view which shows schematic structure of another laminated body manufacturing apparatus. In FIG. 13, the same components as those in the laminate manufacturing apparatus 80 according to the modification of the first embodiment shown in FIG.
As shown in FIG. 13, the laminate manufacturing apparatus 120 is configured by providing the undercoat layer forming unit 111 shown in FIG. 11 in the configuration of the laminate manufacturing apparatus 80 according to the modification of the first embodiment. May be.
The laminate manufacturing apparatus 120 configured as described above can obtain the same effects as those of the laminate manufacturing apparatus 110 of the second embodiment shown in FIG.

In the first and second embodiments, the case where the overcoat layer 14 is formed by flash vapor deposition or vacuum vapor deposition is described as an example, but by chemical vapor deposition (for example, CVD), An overcoat layer 14 may be formed.
Thus, by forming the overcoat layer 14 using the chemical vapor deposition method, the overcoat layer 14 with little damage to the atomic layer deposition film 12 can be formed. That is, the dense overcoat layer 14 with improved barrier properties can be formed.
Further, it is not necessary to increase the pressure difference between the region where the overcoat layer 14 is formed and the outside thereof.

  Examples of the present invention and comparative examples will be described below, but the present invention is not limited to the following examples.

Example 1
<Preparation of laminate of Example 1>
In Example 1, the laminate 100 shown in FIG. 10 (hereinafter, the laminate 100 of Example 1 is referred to as “laminate 100-1”) was produced using the laminate production apparatus 110 shown in FIG.
Hereinafter, with reference to FIG.10 and FIG.11, the manufacturing method of the laminated body 100-1 is demonstrated.
First, a stretched film of polyethylene terephthalate (PET) having a thickness of 100 μm wound around a base material winding roller 36 was prepared as the base material 11 (polymer film). Next, the base material transport unit 23 started transporting the base material 11.

Next, the plasma pretreatment unit 24 modified the one surface 11a of the substrate 11. At this time, as conditions for the plasma pretreatment, the atmosphere in the chamber was an atmosphere of O ₂ plasma, the power was 300 W, and the treatment time was 180 sec.
Next, the base member 11 whose one surface 11 a was modified by the support member 21 was conveyed to the undercoat layer forming unit 111.

As the undercoat layer forming part 111, a urethane acrylic coat layer having a thickness of 0.1 μm and formed from urethane acrylate was formed on the modified surface 11 a of the substrate 11 using a flash vapor deposition apparatus.
Subsequently, the base material 11 on which the undercoat layer 111 was formed was conveyed to the atomic layer deposited film forming unit 26.

Next, the base material 11 on which the undercoat layer 111 was formed was introduced into the purge chamber 45 constituting the film forming unit 43. At this time, the atmosphere in the purge chamber 45 was a mixed atmosphere of O ₂ gas and N ₂ gas. That is, a mixed gas of O ₂ gas and N ₂ gas was used as the purge gas.

Next, the base material 11 passed through the purge chamber 45 was introduced into the precursor adsorption chamber 46. At this time, the inner wall temperature of the precursor adsorption chamber 46 was maintained at 70 ° C., and the atmosphere in the precursor adsorption chamber 46 was a mixed atmosphere of N ₂ gas and trimethylaluminum (TMA). The supply time of N ₂ gas and trimethylaluminum (TMA) was 60 msec. The pressure in the precursor adsorption chamber 46 was 50 Pa.
By introducing the base material 11 into the precursor adsorption chamber 46, trimethylaluminum (TMA) as a precursor was adsorbed on one surface 111 a of the undercoat layer 111.

  Next, the base material 11 on which the precursor has been adsorbed is led out from the precursor adsorption chamber 46 and led out into the purge chamber 45, so that an excess (excess) precursor (trimethylaluminum (TMA)) and a secondary precursor are adsorbed. The product was removed. At this time, the supply time of the purge gas was 10 sec.

Next, the base material 11 on which the precursor was adsorbed was moved from the purge chamber 45 into the second precursor supply nozzle 47. At this time, the temperature of the inner wall of the second precursor supply nozzle 47 is maintained at 70 ° C., the pressure in the second precursor supply nozzle 47 is 10 to 50 Pa, and the inside of the second precursor supply nozzle 47 The atmosphere was a mixed atmosphere of N ₂ gas and H ₂ O gas. The supply time of N ₂ gas and H ₂ O gas (second precursor) was 60 msec.
By transporting the base material 11 on which the precursor has been adsorbed into the second precursor supply nozzle 47, the trimethylaluminum (TMA) adhering to the one surface 111a of the undercoat layer 111 is reacted with H ₂ O. Thus, an aluminum oxide layer (a layer constituting a part of the aluminum oxide film as the atomic layer deposition film 12) was generated. The film formation temperature of the aluminum oxide layer was 90 ° C.

Next, the base material 11 on which the aluminum oxide layer was formed was moved to the purge chamber 45 to remove trimethylaluminum (TMA) that did not contribute to the reaction. At this time, the supply time of the purge gas was 10 sec.
The thickness of the aluminum oxide layer formed in one cycle was 0.14 to 0.15 nm.
Therefore, by performing 70 cycles of film formation using 70 film forming units 43 with the above processing as one cycle, aluminum oxide (Al ₂ O ₃ ) that is the atomic layer deposition film 12 having a thickness of 10 nm is used. A film (barrier layer) was formed. The time for processing 70 cycles was 30 min.

Next, the base material 11 on which the undercoat layer 101 and the atomic layer deposition film 12 were formed was conveyed into the overcoat layer forming chamber 61 via the guide roller 27.
Subsequently, 2-hydroxy-3-phenoxypropyl acrylate: propoxylated neopentyl glycol diacrylate = 90 (% by weight) is formed on one surface 12a of the atomic layer deposition film 12 by a flash vapor deposition method using the overcoat layer forming unit 31. An uncured coating layer (base material of the overcoat layer 14) was formed, which was made of a mixture mixed at a mixing ratio of 10 (% by weight) and had a thickness of 1 μm.
At this time, the pressure in the overcoat layer forming chamber 61 was adjusted to maintain 0.05 Pa.

Subsequently, the base material 11 on which the coating layer was formed was conveyed to a position facing the light irradiation unit 78. The coating layer was cured by irradiating the coating layer with an electron beam from the light irradiation unit 29, thereby forming an acrylic coating layer (acrylic resin layer) as the overcoat layer 14 having a thickness of 1 μm.
Thus, 100 μm polyethylene terephthalate (PET) as the base material 11, 0.1 μm thick urethane acrylic coat layer as the undercoat layer 101, 10 nm thick aluminum oxide film as the atomic layer deposition film 12, A laminate 100-1 of Example 1 was produced in which the overcoat layer 14 and an acrylic coat layer having a thickness of 1 μm were sequentially laminated.

  Then, the laminated body 100-1 was conveyed to the laminated body winding part 33, and the laminated body 100-1 was wound around the roller surface of the winding roller 82 which comprises the laminated body winding part 33. FIG.

<Measurement of Water Vapor Transmission Rate (WVTR) of Laminate of Example 1>
Subsequently, in order to evaluate the gas barrier property of the laminated body 100-1 of Example 1, the laminated body 100- of Example 1 was used using MOCON Aquatran (registered trademark) which is a water vapor permeability measuring device manufactured by Modern Control. 1 water vapor transmission rate (WVTR) was measured. As measurement conditions, a temperature of 40 ° C. and a humidity of 90% RH were used.
As a result, as shown in Table 1, the water vapor transmission rate (WVTR) of the laminate 100-1 of Example 1 was 6.0 × 10 ⁻⁴ (g / m ² / day).

Table 1 shows the film type and thickness of the atomic layer deposited film (barrier layer), the type (presence / absence) of the overcoat layer, and the water vapor transmission rate (g / m ² / day) regarding Examples 1 and 2 and the comparative example. It is a table.

(Example 2)
<Preparation of the laminate of Example 2>
In Example 2, the laminate 100 shown in FIG. 10 (hereinafter, the laminate 100 of Example 2 is referred to as “laminate 100-2”) was produced using the laminate production apparatus 120 shown in FIG.
The laminated body 100-2 of Example 2 is different from Example 1 in the step of forming the overcoat layer 14, and the thickness of the aluminum oxide (Al ₂ O ₃ ) film that is the atomic layer deposition film 12 is different. except (in 5nm thickness of aluminum oxide _(Al 2 _{O 3)} film of example 2) was prepared by a procedure analogous to stack 100-1.

Therefore, only the step of forming the overcoat layer 14 will be described with reference to FIGS.
In Example 2, a silicon oxide film (SiO ₂ film) having a thickness of 200 nm was formed as the overcoat layer 14 by a vacuum vapor deposition method using the overcoat layer forming portion 91.
Specifically, a block body of SiO is accommodated in the evaporation source 89, and the block body is heated and vaporized by heating the block body with an electron beam (EB). A silicon oxide film (SiO ₂ film) was formed by vapor deposition on one surface 12a.

<Measurement of water vapor transmission rate (WVTR) of laminate of Example 2>
Subsequently, in order to evaluate the gas barrier property of the laminated body 100-2 of Example 2, the water vapor permeability (WVTR) of the laminated body 100-2 of Example 2 was measured using the water vapor permeability measuring apparatus used in Example 1. ) Was measured. The measurement conditions were the same as in Example 1.
As a result, as shown in Table 1, the water vapor transmission rate (WVTR) of the laminate 100-2 of Example 2 was 9.8 × 10 ⁻⁴ (g / m ² / day).

(Comparative example)
<Laminated body manufacturing apparatus used when manufacturing the laminated body of a comparative example>
FIG. 14: is a front view which shows schematic structure of the laminated body manufacturing apparatus used when producing the laminated body of a comparative example. In FIG. 14, the same components as those of the laminate manufacturing apparatus 20 of the first embodiment shown in FIG.

With reference to FIG. 14, the laminated body manufacturing apparatus 200 used when producing the laminated body 210 of a comparative example is demonstrated.
The laminate manufacturing apparatus 200 removes the intermediate chamber 29, the guide roller 27, the roller 32, the first roller 62, and the second roller 63 constituting the laminate manufacturing apparatus 20 of the first embodiment from the constituent elements. Instead of the overcoat layer forming part 31 constituting the laminate manufacturing apparatus 20, the overcoat layer forming part 201 is disposed in the vicinity of the outer surface 21 a of the support member 21.
The overcoat layer forming unit 201 is configured not to include the overcoat layer forming chamber 61.

<Preparation of Comparative Example Laminate>
In the comparative example, the laminated body 210 was produced using the laminated body manufacturing apparatus 210 shown in FIG.
First, in the same manner as in Example 1, 5 nm thick aluminum oxide (Al) as an atomic layer deposition film was formed on one surface of the base material (stretched film made of polyethylene terephthalate having a thickness of 100 μm) prepared in Example 1. _{A 2} O ₃ ) film was formed.

Next, 2-hydroxy-3-phenoxypropyl acrylate: propoxylated neopentyl glycol diacrylate = 90 (weight) on the upper surface of the aluminum oxide (Al ₂ O ₃ ) film by flash vapor deposition using the overcoat layer forming portion 201. %): An uncured coating layer having a thickness of 1 μm and a mixture of 10 (% by weight) was formed.

Next, the coating layer was cured by irradiating the coating layer with an electron beam from the light irradiation section 78, thereby forming an acrylic coating layer (acrylic resin) having a thickness of 1 μm as an overcoat layer.
As a result, a laminated body 210 in which a stretched film made of polyethylene terephthalate having a thickness of 100 μm, an aluminum oxide (Al ₂ O ₃ ) film having a thickness of 5 nm, and an acrylic coat layer having a thickness of 1 μm was sequentially formed. .
Thereafter, the laminate 210 was wound by the take-up roller 82 constituting the laminate take-up portion 33.

<Measurement of water vapor transmission rate (WVTR) of laminate of comparative example>
Subsequently, in order to evaluate the gas barrier property of the laminated body 210 of the comparative example, the water vapor transmission rate (WVTR) of the laminated body 210 of the comparative example was measured using the water vapor permeability measuring apparatus used in Example 1. The measurement conditions were the same as in Example 1.
As a result, as shown in Table 1, the water vapor transmission rate (WVTR) of the laminate 210 of the comparative example was 1.5 × 10 ⁻³ (g / m ² / day).

(About the measurement result of the water-vapor-permeation rate (WVTR) of the laminated body of Examples 1, 2 and a comparative example)
Referring to Table 1, as compared with the laminated body 210 of the comparative example in which the overcoat layer was formed in the film formation pressure zone equivalent to the atomic layer deposited film forming unit 26, the laminated body 100-1 of Examples 1 and 2 , 100-2, it was confirmed that the water vapor transmission rate (WVTR) improved by an order of magnitude.

  As described above, according to the present invention, by providing an overcoat layer on the surface of an ALD film formed on a polymer substrate, mechanical external force (stress) by a roll-to-roll laminate manufacturing apparatus is provided. ) Does not cause scratches or pinholes in the overcoat layer, so that the gas barrier property of the laminate can be increased. However, when forming the overcoat layer, the overcoat layer is properly formed in a single chamber By using the band, a better overcoat layer can be formed, and as a result, the WVTR can be improved.

  The present invention relates to a method for producing a laminate used for electronic components such as electroluminescence elements (EL elements), liquid crystal displays, semiconductor wafers, packaging films for pharmaceuticals and foods, packaging films for precision parts, and the like, and The present invention can be applied to a laminate manufacturing apparatus for manufacturing a laminate.

DESCRIPTION OF SYMBOLS 10,100 ... Laminated body, 11 ... Base material, 11a, 12a, 14a, 101a ... One side, 11b ... Other side, 12 ... Atomic layer deposited film, 14 ... Overcoat layer, 20, 80, 110, 120 ... Laminated body Manufacturing apparatus, 21 ... support member, 21a ... outer surface, 23 ... base material transport section, 24 ... plasma pretreatment section, 26 ... atomic layer deposition film forming section, 27, 85, 86 ... guide roller, 28 ... pressing roller, 29 ... Intermediate chamber, 29-1 ... first inlet, 29-2 ... second inlet, 29-3 ... first outlet, 29-4 ... second outlet, 31,91 ... overcoat Layer forming portion, 32, 87 ... roller, 32a, 37a, 51a, 54a, 83a ... roller surface, 33 ... laminated body winding portion, 36 ... substrate winding roller, 37 ... substrate feeding roller, 41 ... Processing chamber, 43 ... film forming section, 45 ... purge Chamber ... 46 ... Precursor adsorption chamber, 47 ... Second precursor supply nozzle, 51 ... Guide roller body, 52, 55 ... Rotating shaft, 54 ... Pressing roller body, 61 ... Overcoat layer forming chamber, 62 ... First roller 63 ... Second roller 65 ... Raw material tank 66 ... Raw material supply pipe 68 ... Raw material supply pump 69 69 Nebulizer 72 72 Vaporizer 74 74 Gas supply pipe 76 76 Coating nozzle 78 ... light irradiation unit, 81 ... dancer roller, 82 ... take-up roller, 83 ... main roller, 89 ... vapor source, 101 ... undercoat layer, 111 ... undercoat layer forming unit, _{W 1,} W 2 _... width, A , B, C ... direction, D, E, F ... area

Claims (13)

A strip-shaped base material, an atomic layer deposition film formed on one surface of the base material, and an overcoat layer formed on one surface of the atomic layer deposition film, the atomic layer deposition film and the overlayer A method for producing a laminate in which a coat layer is formed in-line,
An atomic layer deposition film forming step of forming the atomic layer deposition film on one surface of the substrate in the first processing chamber;
The base material on which the atomic layer deposition film is formed is disposed from the first processing chamber to the outside of the first processing chamber by a guide roller that contacts only the outer peripheral portion of one surface of the atomic layer deposition film. A base material guiding step for guiding the second processing chamber;
After the base material guiding step, an overcoat layer forming step of forming an overcoat layer on one surface of the atomic layer deposition film in the second processing chamber;
After forming the overcoat layer, one surface of the overcoat layer and the roller surface of the take-up roller are brought into contact with each other, and the take-up step of winding the laminate into a roller shape with the take-up roller;
The manufacturing method of the laminated body characterized by including.   The method for manufacturing a laminate according to claim 1, wherein in the overcoat layer forming step, the overcoat layer having a mechanical strength higher than that of the atomic layer deposition film is formed.   In the overcoat layer forming step, the overcoat layer having mechanical strength equivalent to that of the atomic layer deposition film is formed so that the thickness of the overcoat layer is larger than the thickness of the atomic layer deposition film. The manufacturing method of the laminated body of Claim 1 characterized by the above-mentioned. Before the atomic layer deposition film forming step, an undercoat layer forming step of forming an undercoat layer containing an inorganic substance and / or an organic polymer on one surface of the substrate,
In the atomic layer deposition film forming step, the atomic layer deposition film is formed on one surface of the undercoat layer so as to be bonded to the inorganic substance and / or the organic polymer exposed from the one surface of the undercoat layer. The manufacturing method of the laminated body of any one of Claims 1 thru | or 3 characterized by the above-mentioned.   In the base material guiding step, the base material is transferred to the second processing chamber via an intermediate chamber having a pressure between the pressure in the first processing chamber and the pressure in the second processing chamber. The method for producing a laminate according to any one of claims 1 to 4, wherein the laminate is guided to the above.   The method for manufacturing a laminate according to any one of claims 1 to 5, wherein, in the overcoat layer forming step, the overcoat layer is formed by a flash vapor deposition method.   The method for manufacturing a laminate according to any one of claims 1 to 5, wherein, in the overcoat layer forming step, the overcoat layer is formed by a vacuum deposition method.   The method for manufacturing a laminate according to any one of claims 1 to 5, wherein, in the overcoat layer forming step, the overcoat layer is formed by a chemical vapor deposition method. A laminate manufacturing apparatus for forming a laminate including an atomic layer deposition film formed on a surface side of the base material and the base material by a roll-to-roll method in a band-shaped base material,
The outer shape is a cylindrical shape, and a support member that supports the other surface located on the side opposite to the one surface of the base material by the outer surface,
A transport unit that transports the base material in a predetermined transport direction along the outer surface of the support member;
An atomic layer deposition film forming unit including a first processing chamber disposed on an outer surface of the support member and capable of forming the atomic layer deposition film on one surface of the substrate in a state where the base material can be introduced and led out; ,
An overcoat layer forming unit including a second processing chamber disposed in a subsequent stage of the atomic layer deposition film forming unit and forming an overcoat layer on one surface of the atomic layer deposition film in the predetermined transport direction;
A first guide roller that contacts only the outer peripheral portion of one surface of the atomic layer deposition film and guides the base material on which the atomic layer deposition film is formed into the second processing chamber;
A laminated body winding part that is disposed in a subsequent stage of the overcoat layer forming part and is in contact with one surface of the overcoat layer constituting the laminated body to wind the laminated body into a roll;
The laminated body manufacturing apparatus characterized by having.   The press roller according to claim 9, further comprising a pressing roller that presses the base material on which the atomic layer deposition film that contacts the first guide roller is pressed against a roller surface of the first guide roller. Laminate manufacturing equipment.   The said overcoat layer formation part is arrange | positioned in the said 2nd process chamber, and contains the 2nd guide roller which contacts only the outer peripheral part of the one surface of the said atomic layer deposition film. Laminate manufacturing equipment.   An intermediate chamber is provided which passes when the substrate is transported from the first processing chamber to the second processing chamber and when the substrate is unloaded from the second processing chamber. Item 12. The laminate manufacturing apparatus according to any one of Items 9 to 11.   An undercoat layer forming part that is disposed in the preceding stage of the atomic layer deposition film forming part in the predetermined transport direction and forms an undercoat layer containing an inorganic substance and / or an organic polymer on one surface of the substrate. The laminated body manufacturing apparatus according to any one of claims 9 to 12, characterized by comprising:

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