JP2015226996A - Method for producing laminate and laminate production device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminate capable of forming an atomic layer deposition film having high gas barrier properties on a substrate.SOLUTION: There is provided a method for producing a laminate in which an atomic layer deposition film 12 and an overcoat layer 14 are formed in line, which comprises a step in which an atomic layer deposition film 12 is formed on one surface of a substrate 11 in a first processing chamber, the substrate 11 is guided from the first processing chamber to a second processing chamber by a guide roller which contacts only with an outer peripheral part of one surface of the atomic layer deposition film 12, the overcoat layer 14 is formed on one surface of the atomic layer deposition film 12 guided into the second processing chamber, and then a laminate 10 is wound in a rolled state by a winding roller which contacts with one surface of the overcoat layer 14 in the second processing chamber.

Description

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

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 the atomic or molecular level like a gas, it is also called chemical vapor deposition (CVD). , "CVD" method) and physical vapor deposition (also referred to as PVD (Physical Vapor Deposition), 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 plasma reaction is called 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 gas having a high activity 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 for lines and holes on a substrate having a high aspect ratio with a large depth to width ratio, and a coating for 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 ALD. 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 suppress damage to the atomic layer deposition film, 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 rewind 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. Was. For this reason, there is a possibility that the performance of the atomic layer deposition film and the overcoat layer may be deteriorated.

That is, the method for manufacturing a laminate disclosed in Patent Document 3 suggests a problem that the gas barrier property of the atomic layer deposition film is deteriorated.
Therefore, the present invention provides a method for manufacturing a laminate capable of forming an atomic layer deposition film having a high gas barrier property on one surface side of a substrate, and a laminate manufacturing apparatus for manufacturing the laminate. With the goal.

  In order to solve the above problems, a method for manufacturing a laminate according to one embodiment of the present invention includes a laminate in which at least an atomic layer deposition film and an overcoat layer are laminated in this order on one surface side of a belt-like substrate. In which the atomic layer deposition film and the overcoat layer are formed in-line, wherein the atomic layer deposition film is formed on one surface of the substrate in a first processing chamber. The atomic layer deposited film is formed by a step of forming an atomic layer deposited film and a guide roller that contacts only an outer peripheral portion of one surface of the atomic layer deposited film opposite to the base. A base material guiding step for guiding the material from the first processing chamber into the second processing chamber, and an overcoat layer is formed on one surface of the atomic layer deposition film guided into the second processing chamber Overcoat layer forming step, and the overcoat layer After forming the layer, in the second processing chamber, the surface of the overcoat layer opposite to the atomic layer deposition film is brought into contact with the roller surface of the winding roller, and the stacking layer is rotated by the winding roller. And a winding step of winding the body into a roller shape.

  In addition, the laminate manufacturing apparatus according to one embodiment of the present invention includes an in-line roll-to-roll method for a strip-shaped base material, and the atomic layer deposition film formed on one surface side of the base material. A laminated body manufacturing apparatus for forming a laminated body, wherein a support member that supports the other surface opposite to one surface of the base material by an outer surface formed of a cylindrical surface, and along the outer surface of the support member A transport unit that transports the base material in a set transport direction; and the base material is disposed on an outer surface of the support member in a state where the base material can be introduced into and led out from the first processing chamber. An atomic layer deposition film forming portion for forming the atomic layer deposition film on one surface of the substrate; and the atomic layer in a second processing chamber disposed downstream of the atomic layer deposition film formation portion in the transport direction. Overcoat that forms an overcoat layer on one side of the deposited film 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; The laminated body that is disposed downstream of the overcoat layer forming portion and winds the laminated body in a roll shape by contacting with one surface of the overcoat layer constituting the laminated body in a second processing chamber And a winding part.

  According to the laminated body manufacturing method and the laminated body manufacturing apparatus of the present invention, an atomic layer deposited film having a high gas barrier property can be formed on one surface 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 A 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 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.

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 the other 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 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 one surface 12 a of the atomic layer deposition film 12. The overcoat layer 14 covers the one surface 12 a of the atomic layer deposition film 12, thereby suppressing direct contact between the one surface 12 a of the atomic layer deposition film 12 and the rigid body, and scratching the atomic layer deposition film 12. It functions as a protective layer (specifically, a protective layer for suppressing a decrease in gas barrier properties of the atomic layer deposition film 12) for suppressing the occurrence of.

In this way, by arranging the overcoat layer 14 on the one surface 12a of the atomic layer deposition film 12, for example, when the stacked body 10 is manufactured using the stacked body manufacturing apparatus 20 shown in FIG. The one side 14a of the overcoat layer 14 and the roller surface of the take-up roller 82 are brought into contact with each other, whereby the laminate 10 can be wound up in a roller shape.
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.

Even when a rigid body (for example, a transport roller) other than the take-up roller 82 is in contact with the overcoat layer 14 and an external force is applied to the stacked body 10, 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.
Metal alkoxide is an organometallic compound, as a general formula is represented by R1 (M-OR _2). 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.
As the metal atom M is Si R1 (Si-OR _2), for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra script silane, methyl trimethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, Examples thereof include dimethyldimethoxysilane and dimethyldiethoxysilane.

As the metal atom M is Zr R1 (Si-OR _2), for example, can be exemplified tetramethoxysilane zirconium, tetraethoxy zirconium, tetra-isopropoxide Bo alkoxy zirconium, tetra script alkoxy zirconium.
As the metal atom M is Ti R1 (Si-OR _2), for example, it can be exemplified tetramethoxysilane titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra script alkoxy titanium such.

As the metal atom M is Al R1 (Si-OR ₂₎ may, for example, tetramethoxysilane aluminum, tetraethoxy aluminum, tetraisopropoxy aluminum, tetra script alkoxy aluminum.
Moreover, when adding the inorganic particle which consists of an inorganic substance to the overcoat layer 14, it is preferable to use the extender whose particle size is larger than this kaolinite which is a kind of clay mineral, for example.

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”).
Further, 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 of the base material 11 (set transport direction). .
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 uses an inline roll-to-roll method to form an atomic layer on one surface 11a of the base material 11 by using a roll-to-roll method in a predetermined direction (one direction). This is an apparatus for sequentially forming the deposited 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 pressing rollers. 28, an intermediate chamber 29, an overcoat layer forming part 31, 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 roll shape with an outer surface 21 a having a cylindrical surface, and the outer surface 21 a is in contact with the other surface 11 b of the substrate 11. The support member 21 rotates in the B direction so that the base material 11 supplied from the base material winding roller 36 is changed to the plasma pretreatment unit 24, the plurality of atomic layer deposition film forming units 26, and the guide roller 27 in this order. Let it pass. The outer surface 21 a of the support member 21 functions as a guide surface for conveying 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 the support member 21 is in contact with the other surface 11 b of the base material 11 and the outer surface 21 a of the support member 21. The base material 11 is supplied to. 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 faces the one surface 11 a of the substrate 11 that passes between the substrate feeding roller 37 and the atomic layer deposition film forming unit 26. Has been placed.
The plasma pretreatment unit 24 includes a processing chamber 41 that performs plasma pretreatment on 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, one surface 11a of the substrate 11 is modified by exposing one surface 11a of the substrate 11 to an oxygen plasma atmosphere (specifically, one surface 11a of the substrate 11 is modified). Changing the functional group of the surface 11a).
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 example of forming an aluminum oxide (Al ₂ O ₃ ) film.
The plurality of film forming units 43 are arranged between the plasma pretreatment unit 24 and the guide roller 27 so as to face one surface 11 a of the substrate 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 includes one surface 11 a of the base material 11 positioned before and after the precursor adsorption chamber 46 and one surface 11 a of the base material 11 positioned before and after the second precursor supply nozzle 47. Exposed.

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 by-products that are adsorbed on the one surface 11a of the substrate 11 by passing through the precursor adsorption chamber 46 is passed. In addition to removing the substances, the second precursor supply nozzle 47 is passed through an extra second precursor (for example, H ₂ O) that is adsorbed on one surface 11a of the substrate 11 and By-product removal is performed.

The “second precursor” in the present invention refers to a substance that causes the first precursor (TMA in this embodiment) to undergo oxidation, nitridation, or oxynitridation 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, trimethylaluminum (TMA) adsorbed on one surface 11 a of the base material 11 reacts with water, so that the atomic layer deposition film 12 is reacted. Thus, 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 is formed on one surface 11a. An (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 (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 of the film 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 are disposed at positions that can contact the outer peripheral portion of one surface 12 of the atomic layer deposition film 12 conveyed by the outer surface 21 a of the support member 21.
The width W2 of the roller surface 51a in contact with the one surface 12a of the atomic layer deposition film 12 can be set to a value of about 5 to 10% of the width W1 of the base material 11, for example.
In this way, the substrate 11 in contact with only the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12 and having the atomic layer deposition film 12 formed thereon is used as an overcoat layer formation chamber 61 (hereinafter referred to as a second processing chamber). The overcoat layer forming chamber 61 is sometimes referred to as a “second processing chamber”.) By having the guide roller 27 that guides the overcoat layer forming chamber 61 into the second processing chamber 61, a conventional guide that contacts the entire one surface 12 a of the atomic layer deposition film 12. Compared with the case where a roller is used, 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 introduction port 29-1 and a second introduction port 29-2.
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.

Thus, by having the intermediate chamber 29 which passes when conveying the base material 11 from the first processing chamber to the second processing chamber, for example, between the first processing chamber and the second processing chamber. If the degree of vacuum differs greatly, the degree of vacuum is changed stepwise by setting the degree of vacuum of the intermediate chamber 29 to a value between the degree of vacuum of the first processing chamber and the degree of vacuum of the second processing chamber. be able to.
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 substrate 11 on which the atomic layer deposition film 12 is formed is transferred to the second processing chamber via the intermediate chamber 29, so that the gas used in the first processing chamber and the first chamber Mixing with the gas used in the second 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 introduction port 29-2. 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 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 12 a of the atomic layer deposition film 12. By having the overcoat layer forming chamber 61 (second processing chamber) for forming (see FIG. 1), it is possible to suppress the movement of the gas used in the second processing chamber into the first processing chamber. In both cases, it is possible to suppress the movement of the gas used in the first processing chamber 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 comes into 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, so that the atomic layer deposition film 12 is in contact with the other surface 11b. The transport direction of the formed 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 conveyed by the first roller 62 and comes into contact with 14a (see FIG. 1) in which the overcoat layer 14 is formed on one surface 12a of the atomic layer deposition film 12, whereby the substrate 11 is transferred to the laminated body take-up unit 33 (specifically, the dancer roller 81 constituting the laminated body take-up part 33) disposed in the overcoat layer forming chamber 61 while changing the carrying direction of 11. .

The raw material tank 65 is connected to a sprayer 69 via a raw material supply pipe 66. 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 may 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 substrate 11 immediately after passing through the first roller 62. It is placed in a possible position.
The coating material sprayed into the gas state on 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 laminate 10 that has passed through the second roller 63 is conveyed to the laminate winding portion 33 (specifically, the dancer roller 81 that constitutes the laminate winding portion 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 63. The dancer roller 81 has a roller surface that comes into contact with one surface 11 b of the base material 11 constituting the laminate 10.

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, since the roller surface of the take-up roller does not directly contact one surface of the atomic layer deposition film, it is possible to suppress the occurrence of scratches caused by the take-up roller on the atomic layer deposition film.
According to the laminated body manufacturing apparatus of the first embodiment, the atomic layer deposition film 12 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. By having an overcoat layer forming chamber 61 (second processing chamber) for forming the overcoat layer 14 (see FIG. 1) on one surface 12a, the gas used in the second processing chamber is the first processing. It is possible to suppress movement into the room, and it is possible to suppress movement of gas used in the first processing chamber 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.

  Further, the base material 11 on which the atomic layer deposition film 12 is formed is brought into contact with only the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12, and is guided into the overcoat layer formation chamber 61 (second processing chamber). By having the guide roller 27, scratches caused by the guide roller 27 are generated in the atomic layer deposition film 12 as compared with the case where a conventional guide roller that contacts the entire one surface 12 a of the atomic layer deposition film 12 is used. Can be suppressed.

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, by contacting the one surface 14a of the overcoat layer 14 that constitutes the laminate 10, the laminate take-up portion 33 is provided by having the laminate take-up portion 33 that winds the laminate 10 into a roll shape. Since the roller surface of the take-up roller 82 is not in direct contact with the one surface 12a of the atomic layer deposition film 12, it is possible to prevent the atomic layer deposition film 12 from being damaged due to the take-up roller 82. .

<The manufacturing method of the laminated body of 1st Embodiment>
FIG. 7 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 and FIG. 7, a method for manufacturing the laminate according to the first embodiment will be described.
When the processing of the flowchart shown in FIG. 7 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 cylindrical support member 21 in a direction toward the plasma pretreatment unit 24. At this time, the base material 11 is transported so that the other surface 11 b is in contact with the outer surface 21 a of the support member 21.

In STEP1, one surface 11a of the substrate 11 is subjected to plasma pretreatment. Specifically, the one surface 11a of the substrate 11 is modified by exposing the one surface 11a of the substrate 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 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). Forming 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, the excess (excess) first precursor (for example, trimethylaluminum (TMA)) is removed, and the by-product adsorbed on the one surface 11a of the substrate 11 treated with STEP1 is removed. Removal is performed.

  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 as a precursor on one surface 11 a of the substrate 11.
Thereafter, the base material 11 having the precursor adsorbed on one surface is led out from the precursor adsorption chamber 46 and is purged between the precursor adsorption chamber 46 and the second precursor supply nozzle 47. In chamber 45, 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 monolayer aluminum oxide (Al ₂ O ₃ ) layer is formed on 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 one surface 11 a of the base material 11, the above processing is performed using 70 film forming portions 43. By performing the cycle, 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 one processing chambers, the first processing chamber disposed 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 FIG. 2 and FIG. 4), the base material 11 on which the atomic layer deposition film 12 is formed on one surface 11 a is the first surface disposed in the overcoat layer forming chamber 61 from the outer surface 21 a of the support member 21. It is conveyed in the direction toward the roller 62 (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 substrate 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 The roller surfaces 51a of the pair of guide roller bodies 51 come into contact with each other.
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 treatment) by the guide roller 27 that contacts only the outer peripheral portion of the one surface 12a of the atomic layer deposition film 12. Compared to the case of using a conventional guide roller that is in contact with the entire one surface 12a of the atomic layer deposition film 12 by being guided into the chamber), the damage caused by the guide roller 27 on the atomic layer deposition film 12 is reduced. Occurrence can be suppressed.

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 substrate 11 on which the atomic layer deposition film 12 is formed is in contact with the roller surface of the first roller 62. Further, the base material 11 on which the atomic layer deposition film 12 is formed is transported 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, The overcoat 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) formed into a gaseous state on one surface 12a of the atomic layer deposition film 12 from the coating nozzle. By spraying acrylic monomers or acrylic oligomers such as acrylate, acetal acrylate, butadiene acrylate, melamine acrylate, or photoinitiators such as benzoin ethers, benzophenones, xanthones, acetophenone derivatives, etc. A layer (a 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 a mechanical strength higher than that of the atomic layer deposition film 12, 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. The roller 82 can further suppress the atomic layer deposition film 12 from being damaged when the laminated body 10 is wound up in a roller shape.

Further, even when a rigid body (for example, the roller 63) other than the take-up roller 82 comes into contact with the overcoat layer 14, it is possible to suppress damage to the one surface 12 a 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 the atomic layer deposition film 12 so as to be thicker than the thickness of the atomic layer deposition film 12, It is possible to further prevent the atomic layer deposition film 12 from being damaged when the take-up roller 82 is brought into contact with the take-up roller 82 and the take-up roller 82 takes up the laminated body 10 into a roller shape.

Further, even when a rigid body (for example, the roller 63) other than the take-up roller 82 comes into contact with the overcoat layer 14, it is possible to suppress damage to the one surface 12 a 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 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 take-up roller 82 winds up the laminate 10 into a roller shape. Since the surface does not come into direct contact with one surface 12a of the atomic layer deposition film 12, it is possible to suppress the occurrence of scratches caused by the winding roller 82 on the atomic layer deposition film 12.

At this time, the dancer roller 81 and the winding roller 82 are disposed in the overcoat layer forming chamber 61.
As a result, it is possible to reduce the number of particles that are caught during winding, and it is possible to reduce barrier deterioration during winding.
In addition, since the number of times one surface 14a of the overcoat layer 14 contacts the roller surface after the overcoat layer 14 is formed can be reduced, the risk of scratches due to the roller can also be reduced.

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, For example, the generation of scratches due to contact between the atomic layer deposition films 12 can be suppressed).
When the winding process of STEP5 is finished, the process shown in FIG. 7 is finished.

  According to the laminate manufacturing method of the first embodiment, the overcoat layer is 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. By forming the overcoat layer 14 on the one surface 12a of the atomic layer deposition film 12 in the formation chamber 61 (second processing chamber), 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.

Further, by arranging the take-up roller 82 in the overcoat layer forming chamber 61 (second processing chamber), particle adhesion to the laminate 10 is reduced, and deterioration of the gas barrier property after take-up can be suppressed.
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 substrate 11 on which the atomic layer deposition film 12 is formed is attached 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. In comparison with the case of using a conventional guide roller that is in contact with the entire one surface 12a of the atomic layer deposition film 12, the generation of scratches due to the guide roller 27 is reduced in the atomic layer deposition film 12. Can be suppressed.

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, by contacting the one surface 14a of the overcoat layer 14 that constitutes the laminate 10, the laminate take-up portion 33 is provided by having the laminate take-up portion 33 that winds the laminate 10 into a roll shape. Since the roller surface of the take-up roller 82 is not in direct contact with the one surface 12a of the atomic layer deposition film 12, it is possible to prevent the atomic layer deposition film 12 from being damaged due to the take-up roller 82. .

<Laminated body manufacturing apparatus according to a modification of the first embodiment>
FIG. 8 is a front view schematically showing a schematic configuration of a laminated body manufacturing apparatus according to a modification of the first embodiment. In FIG. 8, the same components as those in the laminate manufacturing apparatus 20 of the first embodiment shown in FIG.
The laminated body 10 shown in FIG. 1 is replaced with the laminated body manufacturing apparatus 20 of 1st Embodiment shown in FIG. 2, using the laminated body manufacturing apparatus 80 which concerns on the modification of 1st Embodiment shown in FIG. It is possible to manufacture.

Here, with reference to FIG. 8, 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 a flash vapor deposition method) constituting the laminate manufacturing apparatus 20 of the first embodiment. Except for having a coat layer forming part 91 (an overcoat layer forming part for forming the overcoat layer 14 by vacuum vapor deposition), it is configured in the same manner as the laminate manufacturing apparatus 20.

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, an overcoat layer forming unit except that a main roller 83, guide rollers 85 and 86, rollers 87 and 88, an evaporation source 89, and a heating device (not shown) are included. The configuration is the same as 31.

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 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.

  As described above, the guide roller 85 is in contact with 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. Thus, as compared with the case where a conventional guide roller that contacts the entire one surface 12a of the atomic layer deposition film 12 is used, it is possible to suppress the generation of scratches caused by the guide roller 27 on the atomic layer deposition film 12. it can.

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 the overcoat layer 14 by adhering to one surface 12a of the atomic layer deposition film 12 formed on the substrate 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 modified example 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, the method similar to the manufacturing method of the laminated body of 1st Embodiment except forming the overcoat layer 14 by a vacuum evaporation method. Can be manufactured.
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. 9 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. 9, 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. 9, 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 one surface 11 a of the substrate 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.
Thus, the undercoat layer 101 is disposed between the base material 11 and the atomic layer deposition film 12, and is in contact with one surface 11 a of the base material 11 and the atomic layer deposition film 12. Contains an inorganic substance and / or an organic polymer. Thereby, for example, when the undercoat layer 101 contains an inorganic material, 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. Therefore, a two-dimensional atomic layer deposition film 12 that grows in one surface direction 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.
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. 10: is a front view which shows schematic structure of the laminated body manufacturing apparatus which concerns on the 2nd Embodiment of this invention. 10, the same components as those in the laminate manufacturing apparatus 20 according to the first embodiment shown in FIG.
Next, with reference to FIG. 10, the laminated body manufacturing apparatus 110 which concerns on 2nd Embodiment used when manufacturing the laminated body 100 shown in FIG. 9 is demonstrated.
The laminate manufacturing apparatus 110 of the second embodiment is similar to the laminate manufacturing apparatus 20 except that the configuration of the laminate manufacturing apparatus 20 of the first embodiment further includes an undercoat layer forming unit 111. Composed.
The undercoat layer forming unit 111 is disposed so as to face one surface 11 a of the substrate 11 transported 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 one surface 11a of the base material 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, and also an overcoat. A processing chamber such as the layer forming chamber 61 may be provided separately.

The laminated body manufacturing apparatus 110 having the above-described configuration is provided with an undercoat layer on one surface 11a of the base material 11 by in-line roll-to-roll processing of the belt-like base material 11 extending in a predetermined direction (one direction). 101, 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, an inorganic substance is placed between one surface 11a of the base material 11 and the atomic layer deposition film 12 so as to be in contact with the base material 11 and the atomic layer deposition film 12. When the undercoat layer 101 including the inorganic substance and / or the organic polymer is formed by including the undercoat layer forming portion 111 that forms the undercoat layer 101 including the organic polymer, In the thickness 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. 11 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. 9-11, the manufacturing method of the laminated body which concerns on 2nd Embodiment is demonstrated.
When the processing of the flowchart shown in FIG. 11 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 is in contact with the outer surface 21 a of the support member 21.

In STEP 11, plasma pretreatment is performed on one surface 11 a of the substrate 11 by the same method as in STEP 1 described in FIG. 7.
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 STEP12.
In STEP 12, the undercoat layer 101 is formed on 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, atoms having a desired thickness are formed on one surface 101 a of the undercoat layer 101 by the atomic layer deposited film forming unit 26 having a plurality of film forming units 43 by the same method as in STEP 2 described in FIG. 7. A layer deposited film 12 is formed (atomic layer deposited 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 guide roller 27 that contacts only the outer peripheral portion of the one surface 12 a of the atomic layer deposition film 12 is disposed at the rearmost stage via the intermediate chamber 29 by a method similar to STEP 3 described in FIG. 7. The base material 11 on which the undercoat layer 101 and the atomic layer deposition film 12 are formed is guided from the film forming portion 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 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 into 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. 11 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 one surface 11a of the substrate 11 before the atomic layer deposition film forming step. In the atomic layer deposition film forming step, an inorganic substance and / or an organic high layer exposed from one surface 101a of the undercoat layer 101 is formed on one surface 101a of the undercoat layer 101. For example, when the undercoat layer 101 containing an inorganic substance is formed by forming the atomic layer deposition film 12 so as to bind to the molecule, the precursor of the atomic layer deposition film 12 is one of the undercoat layers 101. A two-dimensional atomic layer deposition film 12 that grows in the direction of one surface 101a of the undercoat layer 101 is formed to bond to the inorganic substance exposed from the surface 101a. It becomes Rukoto.

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 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 various modifications can be made within the scope of the gist of the present invention described in the claims. Deformation / change is possible.

FIG. 12 is a front view showing a schematic configuration of another laminated body manufacturing apparatus. In FIG. 12, 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. 12, the laminate manufacturing apparatus 120 is configured by providing an undercoat layer forming unit 111 shown in FIG. 10 in the configuration of the laminate manufacturing apparatus 80 according to the modification of the first embodiment. Also good.

The laminated body manufacturing apparatus 120 having such a configuration can obtain the same effect as the laminated body 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 the flash vapor deposition method or the vacuum vapor deposition method has been described as an example. However, the overcoat layer 14 is formed by the chemical vapor deposition method (for example, the CVD method). The coat 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.

  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 carrying out with a belt, a better quality overcoat layer can be formed, and as a result, the gas barrier property can be improved.

Furthermore, by winding the substrate in the same room as the overcoat layer, particle adhesion to the substrate can be reduced and scratches due to contact with the roller can be reduced, so that a stable gas barrier property can be obtained. I can do it.
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 ... The other side, 12 ... Atomic layer deposition film, 14 ... Overcoat layer, 20, 80, 110, 120 DESCRIPTION OF SYMBOLS ... Laminated body manufacturing apparatus, 21 ... Support member, 21a ... Outer surface, 23 ... Base material conveyance part, 24 ... Plasma pretreatment part, 26 ... Atomic layer deposited film formation part, 27, 85, 86 ... Guide roller, 28 ... Presser 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 part, 32, 87 ... Roller, 32a, 37a, 51a, 54a, 83a ... Roller surface, 33 ... Laminate winding part, 36 ... Roller for winding substrate, 37 ... Roller for feeding substrate , 41 ... processing chamber, 43 ... film forming section, 45 Purging 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 ... 1st roller, 63 ... 2nd roller, 65 ... Raw material tank, 66 ... Raw material supply piping, 68 ... Raw material supply pump, 69 ... Sprayer, 72 ... Vaporizer, 74 ... Gas supply piping, 76 ... Coating Nozzle, 78 ... Light irradiation part, 81 ... Dancer roller, 82 ... Winding roller, 83 ... Main roller, 87, 88 ... Roller, 89 ... Evaporation source, 101 ... Undercoat layer, 111 ... Undercoat layer forming part, W1 , W2 ... width, A, B, C ... direction, D, E, F ... area

Claims (13)

In the production of a laminate in which at least an atomic layer deposition film and an overcoat layer are laminated in this order on one surface side of a band-shaped substrate, the atomic layer deposition film and the overcoat layer are formed in-line. A method for producing a laminate,
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 removed from the first processing chamber by a guide roller that contacts only the outer peripheral portion of one surface of the atomic layer deposition film opposite to the base. A base material guiding process for guiding into the two processing chambers;
An overcoat layer forming step of forming an overcoat layer on one surface of the atomic layer deposition film guided into the second processing chamber;
After the overcoat layer is formed, the winding roller is brought into contact with one surface of the overcoat layer opposite to the atomic layer deposition film in the second processing chamber. A winding step of winding the laminate into a roller shape,
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 such 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 at least one of an inorganic substance and an organic polymer on one surface of the base material,
In the atomic layer deposition film forming step, one of the inorganic substance and the organic polymer exposed from one surface of the undercoat layer with respect to one surface of the undercoat layer opposite to the base material The method for producing a laminate according to any one of claims 1 to 3, wherein the atomic layer deposition film is formed so as to be bonded.   In the base material guiding step, the base material is transferred to the first 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. It guides to the said 2nd process chamber from any one of Claims 1-4, The manufacturing method of the laminated body of any one of Claims 1-4 characterized by the above-mentioned.   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 laminated body manufacturing apparatus for forming a laminated body including an atomic layer deposition film formed on a side surface of the base material and the one surface side of the base material by an in-line roll-to-roll method,
A support member for supporting the other surface opposite to the one surface of the base by an outer surface made of a cylindrical surface;
A transport unit that transports the base material in the transport direction along the outer surface of the support member;
Atoms that are arranged on the outer surface of the support member in a state where the base material can be introduced into and led out from the first processing chamber, and form the atomic layer deposition film on one surface of the base material in the first processing chamber. A layer deposited film forming unit;
An overcoat layer forming unit that forms an overcoat layer on one surface of the atomic layer deposition film in a second processing chamber disposed downstream of the atomic layer deposition film formation unit in the 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;
Laminate winding, which is disposed downstream of the overcoat layer forming portion and winds the laminate in a roll shape by contacting one surface of the overcoat layer constituting the laminate in a second processing chamber. Torubu,
The laminated body manufacturing apparatus characterized by having.   The laminate manufacturing apparatus according to claim 9, further comprising a pressing roller that presses the base material on which the atomic layer deposition film is formed against a roller surface of the first guide roller.   11. The laminated body manufacturing apparatus according to claim 9, wherein the overcoat layer forming portion includes a second guide roller that contacts only an outer peripheral portion of one surface of the atomic layer deposition film. .   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. The laminate manufacturing apparatus according to any one of claims 9 to 11.   An undercoat layer forming portion that is disposed in a front stage of the atomic layer deposited film forming portion in the transport direction and forms an undercoat layer containing at least one of an inorganic substance and an organic polymer on one surface of the base material; It has, The laminated body manufacturing apparatus of any one of Claims 9-12 characterized by the above-mentioned.

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