JP6743829B2 - Laminate and gas barrier film - Google Patents

Description

The present invention relates to a laminate including an atomic layer deposition film formed on a surface of a substrate by an atomic layer deposition method, and a gas barrier film including the laminate.

The method of forming a thin film on the surface of an object using a gas phase that makes a substance move at the atomic or molecular level like a gas is roughly classified into chemical vapor deposition (CVD) and physical vapor phase. There is a growth method (PVD: Physical Vapor Deposition).

Typical PVD include a vacuum vapor deposition method and a sputtering method. In particular, in the sputtering method, a high quality thin film excellent in film quality and uniformity of film thickness, although the apparatus cost is generally high. Therefore, it is widely applied to display devices such as liquid crystal displays.

In CVD, a raw material gas is introduced into a vacuum chamber, and one or more gases are decomposed or reacted on a substrate by thermal energy to grow a solid thin film. At this time, in order to promote the reaction at the time of film formation or to lower the reaction temperature, there are some that use plasma or a catalyst (Catalyst) reaction in combination, such as PECVD (Plasma Enhanced CVD) and Cat-CVD. being called. The characteristic feature of such CVD is that there are few film formation defects, and it is mainly applied to semiconductor device manufacturing processes such as film formation of gate insulating films.

In recent years, the deposition method (ALD method: Atomic Layer Deposition) has been receiving attention. The ALD method is a method in which a substance adsorbed on the surface is formed one by one at an atomic level by a chemical reaction on the surface, and is classified into the category of CVD. The ALD method is distinguished from general CVD in so-called CVD (general CVD) in which a single gas or a plurality of gases are simultaneously used to react on a substrate to grow a thin film. is there. On the other hand, the ALD method uses a precursor (hereinafter, referred to as “first precursor”), or a gas rich in activity also called a precursor and a reactive gas (also a precursor in the ALD method). Therefore, the precursors are hereinafter referred to as "second precursors") alternately, and a special thin film is grown one by one at the atomic level by adsorption on the substrate surface and subsequent chemical reaction. This is a film forming method.

A specific film-forming method of the ALD method utilizes a so-called self-limiting effect in which, when the surface is covered with a certain gas, the gas is not further adsorbed in the surface adsorption on the substrate. The unreacted precursor is exhausted when only one layer of the body is adsorbed. Then, a reactive gas is introduced to oxidize or reduce the precursor to obtain only one thin film having a desired composition, and then the reactive gas is exhausted. The above processing is set as one cycle, and this cycle is repeated to grow a thin film. Therefore, in the ALD method, the thin film grows two-dimensionally. Further, the ALD method is characterized in that it has few film-forming defects as compared with the conventional vacuum vapor deposition method, the sputtering method and the like, as well as the general CVD method.

Therefore, it is expected to be applied to a wide range of fields such as food and pharmaceutical packaging fields and electronic component fields.

Further, the ALD method includes 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 plasma activated ALD (PEALD: Plasma Enhanced ALD) or simply plasma ALD.

The technology itself of the ALD method was introduced in 1974 by Dr. Proposed by Tuomo Sumtola. Generally, the ALD method is being applied in the semiconductor field such as a gate insulating film because a high-quality and high-density film can be obtained. is there. Further, the ALD method has a characteristic that there is no slanting effect, that is, there is no phenomenon that sputtering particles are obliquely incident on the substrate surface to cause film formation variation, as compared with other film formation methods, so that there is a gap through which gas can enter. If it is possible, film formation is possible. Therefore, the ALD method is applicable to MEMS (Micro Electro Mechanical Systems) and the like for coating of lines and holes on a substrate having a high aspect ratio with a large depth-width ratio and for coating of three-dimensional structures. Is expected.

However, the ALD method also has drawbacks. That is, in order to perform the ALD method, there is a point of using a special material and a cost increase due to it, but the biggest drawback is that the film forming rate is slow. For example, the film forming rate is about 5 to 10 times slower than that of a normal film forming method such as vacuum evaporation or sputtering.

The target for forming a thin film by the ALD method using the film forming method as described above is a small plate-shaped substrate such as a wafer or a photomask, or a large-area substrate having no flexibility such as a glass plate. , Or a substrate having a large area and flexibility such as a film, and the like. Corresponding to these applications, in mass production equipment for forming thin films on these substrates, various substrate handling methods have been proposed and put into practical use depending on cost, ease of handling, film-forming quality, etc. ing.

For example, in the case of a wafer, a single substrate is supplied to a film forming apparatus to form a film, and then a single-wafer type film forming apparatus in which the next substrate is replaced and film formation is performed again There is a batch-type film forming apparatus that performs the same film forming.

Further, as an example of forming a film on a glass substrate or the like, there is an in-line type film forming apparatus for sequentially carrying out film formation while sequentially transporting the substrate to a portion serving as a film formation source. Further, there is a so-called roll-to-roll coating film forming apparatus which mainly unwinds a flexible substrate from a roll, performs film formation while conveying, and winds the substrate onto another roll. The latter includes not only the flexible substrate but also a flexible sheet that allows the substrate to be film-formed to be continuously conveyed, or a web coating film-forming apparatus that carries out continuous film formation by placing it on a tray that is partially flexible.

With respect to the film forming method and the substrate handling method by any of the film forming apparatuses, the combination of the film forming apparatuses having the highest film forming rate is adopted in view of cost, quality and easiness of handling.

Note that as a related technique, a technique of forming a barrier layer on the surface of a plastic film by performing atomic layer deposition by the ALD method is disclosed (for example, see Patent Document 1). According to this technique, it is possible to realize a barrier film having excellent barrier properties by performing atomic layer deposition by the ALD method.

JP, 2012-096432, A

As described above, the laminated body in which the atomic layer deposition film is provided on the surface of the base material by the ALD method is widely known, and these laminated bodies are used for a gas barrier film having a high gas barrier property. However, the atomic layer deposition film may be easily scratched by an external force. When the atomic layer deposition film is damaged by some external force, a through hole extending in the film thickness direction of the atomic layer deposition film may be formed depending on the size of the damage. When a through hole in the film thickness direction is formed in the atomic layer deposition film in this manner, gas flows in and out of the base material through the through hole, so that the gas barrier property is deteriorated.

Further, as another problem, when a gas barrier film using a laminate having such an easily scratched atomic layer deposited film is manufactured, a rigid body contacts the atomic layer deposited film after the atomic layer deposited film is formed. Unless it is a production line that does not do so, it becomes a factor that reduces the gas barrier property. Therefore, when the gas barrier film is manufactured using the laminate, the gas barrier property is deteriorated when the gas barrier film is wound into a roll in the manufacturing process. For this reason, there is a problem in that the gas barrier film cannot be transported and stored in a roll form.

The present invention has been made in view of such circumstances, and a laminated body in which an atomic layer deposited film formed on the surface of a base material is not easily scratched by an external force, and a gas barrier property is enhanced, and the laminated body. An object is to provide a gas barrier film including the body.

The present invention relates to a sheet-shaped laminate that is wound into a roll, and includes a base material, a layer provided on one surface of the base material, and a layer having adhesiveness on both surfaces, and the other surface of the base material. An atomic layer deposition film made of an inorganic material is provided, and the adhesive force of the layer having adhesiveness on both sides with respect to the atomic layer deposition film is 10 cN/25 mm or more and 200 cN/25 mm or less.

The present invention also relates to a gas barrier film containing the above-mentioned laminate.

According to the present invention, the surface of the atomic layer deposition film that covers the base material is bonded to the layers having adhesiveness on both sides, so that the layer having adhesiveness on both sides protects the surface of the atomic layer deposition film. As a result, it is possible to prevent the external surface from damaging one surface of the atomic layer deposited film, specifically, to form a scratch having a depth reaching the base material from the one surface side of the atomic layer deposited film due to the external force. It will be possible.

Thereby, for example, even when the laminated body is transported and stored in a roll shape, it is possible to suppress deterioration of the gas barrier property, and it is possible to achieve desired durability and gas barrier property. In other words, it is possible to reduce the possibility that a scratch such as gas flowing in and out of the atomic layer deposited film will occur in the atomic layer deposited film. This makes it possible to maintain high durability and gas barrier properties of the laminate and the gas barrier film comprising the laminate, and to provide a highly reliable barrier film.

FIG. 1 is a cross-sectional view showing the structure of the laminated body according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing a state in which the laminated body according to the first embodiment of the present invention is wound by a roller. FIG. 3 is a cross-sectional view showing the structure of the laminated body according to the second embodiment of the present invention. FIG. 4 is a cross-sectional view showing a state in which the laminated body according to the second embodiment of the present invention is wound by a roller.

(First embodiment)
Hereinafter, the first embodiment will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing the structure of the laminated body according to the first embodiment of the present invention. Further, FIG. 2 is a cross-sectional view showing a state when the laminated body according to the first embodiment of the present invention is wound by a roller.

As shown in FIG. 1, the laminated body comprises a base material 1 and a protective film 2 having adhesiveness on both sides of one surface 1a of the base material 1 and a side of the base material 1 on which the protective film is bonded. The atomic layer deposition film 3 (hereinafter referred to as "ALD film 3") is formed along the other surface 1b on the opposite side. The protective film 2 includes, for example, a base material layer and an adhesive layer. According to this embodiment, when the surface 3a of the atomic layer deposited film of the laminate is wound in a roll shape with the roller surface side of the winding roller, as shown in FIG. The surface 2a opposite to the surface on the first side and the surface 3a of the ALD film 3 can be bonded to each other, and the ALD film 3 can be protected.

The base material 1 is a film-shaped base material made of a plastic material, and is preferably transparent. Examples thereof include plastic materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide film (PI), polyethylene (PE), polypropylene (PP) and polystyrene (PS). In addition, it is not limited to these, and can be appropriately selected in consideration of heat resistance, strength physical properties, electrical insulation properties, and the like.

The substrate 1 preferably has a glass transition point (Tg) of 50° C. or higher, but is not limited thereto.

The thickness of the substrate 1 is 25 μm or more in consideration of suitability as a packaging material for electronic parts such as electroluminescence elements and precision parts, suitability as a gas barrier film, and roll-to-roll transport and film formation. It is preferably 200 μm or less.

In order to convey the base material by roll-to-roll and form the ALD film, the thickness of the base material is required to be 50 μm or more. As will be described later, in the first embodiment, the thickness of the base material required for forming the ALD film 3 can be the sum of the thickness of the base material 1 and the thickness of the protective film 2. .. Therefore, if the thickness of the base material 1 is 25 μm or more and the thickness obtained by adding the thickness of the base material 1 and the thickness of the protective film 2 is 50 μm or more, the roll-to-roll of the base material 1 and the protective film 2 is It is possible to carry and form an ALD film.

The protective film 2 is not particularly limited in the laminate of the present invention, and various protective films having adhesiveness, which are used in the production of functional films, can be used.

Therefore, the protective film 2 may be one in which a pressure-sensitive adhesive is applied to both surfaces of the base material layer, or the protective film itself may have adhesiveness.

When the protective film 2 has a base material layer coated with an adhesive, examples of the base material layer include polyester resins such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP) and the like. Examples thereof include polyolefin resins and acrylic resins such as polymethylmethacrylate, but are not limited thereto. Examples of the pressure-sensitive adhesive include acrylic type, urethane type, rubber type, silicone type, and fluorine type, but are not limited to these. Further, the above-mentioned pressure-sensitive adhesive may be applied using a composition containing a solvent. At this time, examples of the coating method of the adhesive layer include, but are not limited to, a die coater method, a gravure roll coater method, and a spray coater method.

Moreover, as the protective film 2 having an adhesive property, one in which an adhesive layer made of an adhesive resin is laminated on both surfaces of a base material layer can be mentioned. The resin used as the base material layer is not particularly limited as long as it is a thermoplastic resin having excellent adhesiveness to the adhesive layer. Examples include, but are not limited to, polyolefin resins such as polyethylene and polypropylene. Examples of the adhesive layer include ethylene/vinyl acetate copolymers, ethylene/methyl methacrylate copolymers, copolymers such as ethylene-α-olefin copolymers, and mixtures thereof. It is not limited to. Examples of the production method include, but are not limited to, a method in which a base material layer and an adhesive layer are extrusion-molded.

The adhesive force of the surface 2a of the protective film to the surface 3a of the ALD film 3 is preferably 10 cN/25 mm or more and 200 cN/25 mm or less, and more preferably 10 cN/25 mm or more and 100 cN/25 mm or less.

When the adhesive force of the surface 2a of the protective film 2 is weaker than 10 cN/25 mm, it may be easily peeled off by some contact, so that when it comes into contact with a roller or the like, rubbing occurs and the surface of the ALD film 3 is damaged. However, the gas barrier property may be deteriorated, which is not preferable. On the other hand, when the adhesive force of the surface 2a of the protective film 2 is stronger than 200 cN/25 mm, the ALD film 3 is less likely to be scratched because it is not peeled off even when it comes into contact with a roller or the like during bonding. However, since it has a strong adhesive force and cannot be easily peeled off, careless force is applied when peeling off the protective film 2 that is pasted at the time of unwinding the wound laminate, the surface of the ALD film 3 is damaged, and the gas barrier It is not preferable because the property may be deteriorated.

Further, the adhesive force of the other surface of the protective film 2 to the surface 1a of the substrate 1 (the surface opposite to the surface 2a to be bonded to the ALD film 3) is preferably 10 cN/25 mm or more and 200 cN/25 mm or less. Since it does not have to be peeled off after unwinding, it may be 200 cN/25 mm or more.

The thickness of the protective film 2 is preferably 10 μm or more and 100 μm or less. As described above, the total thickness of the base material 1 and the protective film 2 needs to be 50 μm or more. Therefore, the thickness of the protective film 2 may be 10 μm or more and 100 μm or less, and the total thickness of the base material 1 and the protective film 2 may be 50 μm or more.

When the thickness of the protective film 2 is thinner than 10 μm, handling becomes difficult and wrinkles may occur when the protective film 2 is attached to the base material 1. The unevenness due to the wrinkles to be bonded is transferred to the ALD substrate during winding, and the ALD film 3 may be scratched due to deformation, twisting, and twisting, which is not preferable.

Further, when the thickness of the protective film 2 is thicker than 100 μm, it is necessary to apply more winding tension in order to wind the protective film 2 without loosening, as compared with the case where the thickness is thin. However, winding up with a high tension causes winding tightness, and a large force is applied in the winding core direction. Then, especially on the winding core side of the film, a strong pressing pressure is applied to the ALD film 3, which may deteriorate the barrier property, which is not preferable. In addition, it is not preferable because it is expensive in terms of cost.

When the laminate is used as a gas barrier film, the protective film 2 may be used in a state of being peeled from the base material 1, or the protective film 2 may be used in a state of being stuck to the base material 1. ..

The ALD film 3 is a film formed by the ALD method.

The ALD film 3 may be an inorganic oxide film such as AlO _x , TiO _x , SiO _x , ZnO _x , and SnO _x , an inorganic nitride film, an inorganic oxynitride film, or a mixed film of these films and elements. Further, the ALD film 3 may be an oxide film made of another element, a nitride film, an oxynitride film, or a mixed film thereof.

The thickness of the ALD film 3 is preferably 2 nm or more and 500 nm or less, and more preferably 2 nm or more and 100 nm or less. If the thickness of the ALD film 3 is smaller than 2 nm, the function as a gas barrier layer cannot be sufficiently fulfilled. On the other hand, when the film thickness of the ALD film 3 is larger than 500 nm, cracks are likely to occur in the gas barrier layer or it becomes difficult to control the optical characteristics.

The ALD film 3 formed on the surface 1b of the base material 1 has an excellent barrier property, but when the ALD film 3 is thin, external contact or the like causes scratches or pinholes in the ALD film 3. there is a possibility. In such a case, it may cause deterioration of the gas barrier performance of the laminate.

Therefore, in order to prevent the ALD film 3 from being scratched, pinholes, or the like due to external contact and improve durability, first, the protective film 2 is attached to the surface 1a of the base material 1 and then The ALD film 3 is formed on the surface 1b of the substrate 1 opposite to the side where the protective film is attached to form a laminate, and the laminate is then wound into a roll.

With this embodiment, the surface 2a of the protective film 2 and the surface 3a of the ALD film 3 when the surface 3a of the ALD film 3 of the laminated body is wound in a roll shape with the roller surface side of the winding roller. And can be pasted together. At this time, the surface 2a of the protective film 2 is in contact with the surface 3a of the ALD film 3 and adheres thereto, so that the ALD film 3 can be protected.

In this way, first, the protective film 2 is attached to the surface 1a of the substrate 1, and then the ALD film 3 is formed on the surface 1b of the substrate 1 opposite to the side where the protective film is attached. The ALD film 3 does not come into direct contact with other base materials during winding. That is, the surface 3a of the ALD film 3 is adhered to the surface 2a of the protective film 2 at the time of winding, so that the gas barrier property can be maintained even when wound in a roll shape, and the durability and the durability of the laminate can be improved. The gas barrier property can be enhanced.

Since the surface 3a of the ALD film 3 is attached to the surface 2a of the protective film 2 during winding, the ALD film 3 is scratched by an external force in the laminated body including the base material 1, the protective film 2, and the ALD film 3 described above. It will be difficult. That is, it is possible to suppress the possibility that the ALD film 3 is damaged such that gas flows in and out in the film thickness direction of the ALD film 3. Therefore, the laminate can be used as a gas barrier film.

In addition, after being unrolled, the laminated body wound by the roller based on the above-described embodiment is, as a separate step, as a protective layer on the surface of the ALD film 3 as an overcoat layer while maintaining the gas barrier property of the ALD film 3. It is possible to form a laminated body provided with.

Further, since the ALD film 3 is formed on the surface 1b of the base material 1 after the protective film 2 is attached to the surface 1a of the base material 1, the thickness of the base material necessary for forming the ALD film 3 is The thickness of the base material 1 and the thickness of the protective film 2 can be added. Therefore, in the laminated body according to the above-described embodiment, the thickness of the base material 1 is equal to the thickness of the base material 1 compared to the thickness of the base material when the protection film is attached after forming the ALD film 3 on the base material 1. The thickness of can be reduced. As a result, when the wound rolls have the same diameter, the roll of the laminate according to the above-described embodiment is better than the roll of the laminate in which the ALD film 3 is formed on the substrate 1 and then the protective film is attached. Therefore, it is possible to increase the number of portions of the base material 1 and the ALD film 3 required to function as a gas barrier film.

[Summary]
As described above, the protective film is adhered along the outer surface of the base material, and the ALD film, which is the barrier layer, is formed along the surface of the base material opposite to the side to which the protective film is adhered. By laminating the ALD film and the protective film having an appropriate adhesive force at the time of winding, the barrier property can be maintained even after winding. Therefore, according to the laminated body of the first embodiment, by laminating the protective film having the adhesive layer on the ALD film at the time of winding, the laminated body of the laminated body is less affected by stress such as environmental change. The gas barrier property can be enhanced.

(Second embodiment)
Hereinafter, the second embodiment will be described with reference to the drawings. The second embodiment is different from the first embodiment in that an adhesive layer 4 is formed along one surface 1a of the base material 1.

FIG. 3 is a cross-sectional view showing the structure of the laminated body according to the second embodiment of the present invention. Further, FIG. 4 is a cross-sectional view showing a state when the laminated body according to the second embodiment of the present invention is wound by a roller.

As shown in FIG. 3, the laminate has a base material 1, an adhesive layer 4 formed along one surface 1a of the base material 1, and a side of the base material 1 opposite to the side on which the adhesive layer 4 is formed. Of the atomic layer deposition film 3 (hereinafter referred to as "ALD film 3") formed along the other surface 1b of the. According to this embodiment, when the surface 3a of the ALD film 3 of the laminated body is wound in a roll shape with the roller surface side of the winding roller, as shown in FIG. , And the surface 3a of the ALD film 3 can be bonded to each other, and the ALD film 3 can be protected.

The material, the glass transition point (Tg), and the thickness of the base material 1 are the same as those in the first embodiment, and thus the description thereof is omitted here. For the same reason as in the first embodiment, the thickness of the base material 1 may be 25 μm or more, and the total thickness of the base material 1 and the adhesive layer 4 may be 50 μm or more.

The adhesive layer 4 is made of an adhesive. There is no particular limitation on the type of the pressure-sensitive adhesive, and the pressure-sensitive adhesive used in the production of the functional film can be used. Examples of the pressure-sensitive adhesive include, but are not limited to, acrylic, rubber, urethane, silicone, epoxy, polyolefin, and fluorine. Further, the above-mentioned pressure-sensitive adhesive may be applied using a composition containing a solvent. At this time, examples of the coating method of the adhesive layer include, but are not limited to, a die coater method, a gravure roll coater method, and a spray coater method.

When the laminate is wound up, the adhesive force of the surface 4a of the adhesive layer 4 to the surface 3a of the ALD film 3 is preferably 10 cN/25 mm or more and 200 cN/25 mm or less, and 10 cN/25 mm or more and 100 cN/25 mm or less. It is more preferable to have. When the adhesive force of the adhesive layer 4 is less than 10 cN/25 mm, sufficient adhesive force cannot be obtained and the film may be easily peeled off by some contact. Therefore, rubbing or the like occurs when contacting a roller or the like, and thus the ALD film 3 It is not preferable because it may scratch the surface and reduce the gas barrier property. On the other hand, when the adhesive force of the adhesive layer 4 is stronger than 200 cN/25 mm, the ALD film 3 is less likely to be scratched because the adhesive layer 4 is not peeled off even when it is brought into contact with a roller or the like during bonding. However, since it has a strong adhesive force and cannot be easily peeled off, careless force is applied when the wound laminate is unwound, the surface of the ALD film 3 may be damaged, and the gas barrier property may be deteriorated, which is not preferable.

The thickness of the adhesive layer 4 is preferably 1 μm or more and 40 μm or less. As described above, the total thickness of the base material 1 and the adhesive layer 4 needs to be 50 μm or more. Therefore, the thickness of the adhesive layer 4 may be 1 μm or more and 40 μm or less, and the total thickness of the base material 1 and the adhesive layer 4 may be 50 μm or more. If the thickness of the adhesive layer 4 is less than 1 μm, sufficient adhesive force with the ALD film 3 cannot be obtained, and peeling may occur easily during winding, which is not preferable. In addition, it may be difficult to sufficiently prevent the influence of scratches or scratches on the ALD film 3 due to contact with a roller or the like, which is not preferable. Further, when the thickness of the adhesive layer 4 is larger than 40 μm, excessive force is applied to the surface of the ALD film 3 when unwinding the wound laminate, the gas barrier property is lowered, and the surface of the ALD film 3 is lowered. This is not preferable because the adhesive layer 4 may remain. In addition, it is not preferable because it is expensive in terms of cost.

The ALD film 3 is the same as that in the first embodiment, and therefore its description is omitted here.

The ALD film 3 formed on the surface 1b of the base material 1 has an excellent barrier property, but when the ALD film 3 is thin, external contact or the like causes scratches or pinholes in the ALD film 3. there is a possibility. In such a case, it may cause deterioration of the gas barrier performance of the laminate. Therefore, in order to prevent the ALD film 3 from being scratched, pinholes, or the like due to external contact and improve durability, first, the adhesive layer 4 is formed on the surface 1a of the substrate 1, and then the adhesive layer 4 is formed. The ALD film 3 is formed on the surface 1b of the substrate 1 opposite to the side on which the adhesive layer 4 is formed to form a laminate, and then the laminate is wound into a roll.

According to this embodiment, when the one surface 3a of the ALD film 3 of the laminate is used as the roller surface side of the winding roller and is wound into a roll, the surface 4a of the adhesive layer 4 (the surface 1a on the base material side and The surface on the opposite side) and the surface 3a of the ALD film 3 can be bonded together. At this time, the surface 4a of the adhesive layer 4 comes into contact with the surface 3a of the ALD film 3 and adheres thereto, and thus the ALD film 3 can be protected.

In this way, the laminated body in which the adhesive layer 4 is first formed on the one surface 1a of the substrate 1 and then the ALD film 3 is formed on the surface 1b of the substrate 1 opposite to the side on which the adhesive layer is formed is However, the ALD film 3 does not come into direct contact with other base materials during winding. That is, the surface 3a of the ALD film 3 is adhered to the surface 4a of the adhesive layer 4 during winding, whereby the gas barrier property can be maintained when wound in a roll shape, and the durability of the laminate is improved. The gas barrier property can be enhanced.

Since the one surface 3a of the ALD film 3 is bonded to the one surface 4a of the adhesive layer 4 during winding, the laminate composed of the base material 1, the adhesive layer 4, and the ALD film 3 is unlikely to be scratched by the external force. Become. That is, it is possible to suppress the possibility that the ALD film 3 is damaged such that gas flows in and out in the film thickness direction of the ALD film 3. Therefore, the laminate can be used as a gas barrier film.

In addition, the adhesive layer 4 in the laminated body realized based on the above embodiment is formed on one surface of the base material 1 so as to face the ALD film 3 and is formed on a base material different from the base material 1. Not a thing. Therefore, after unwinding the laminated body wound by the take-up roller, the surface of the ALD film 3 as a protective layer is formed as a protective layer in another step while maintaining the gas barrier property of the ALD film 3 without generating wasteful waste material. A laminated body provided with a coat layer or the like can be formed.

In addition, since the ALD film 3 is formed on the surface 1b of the base material 1 after forming the adhesive layer 4 on the surface 1a of the base material 1, the thickness of the base material necessary for forming the ALD film 3 is The thickness of the material 1 and the thickness of the adhesive layer 4 may be added together. Therefore, in the laminate according to the above embodiment, the thickness of the adhesive layer 4 is larger than the thickness of the adhesive layer 4 when the adhesive layer is formed after the ALD film 3 is formed on the substrate 1. The thickness of can be reduced. As a result, when the wound roll diameters are the same, the roll of the laminate according to the above-described embodiment is more than the roll of the laminate in which the adhesive layer 4 is formed after the ALD film 3 is formed on the base material 1. Therefore, it is possible to increase the number of portions of the base material 1 and the ALD film 3 required to function as a gas barrier film.

[Summary]
As described above, the pressure-sensitive adhesive layer is formed along one surface of the outer surface of the base material, and the ALD film, which is a gas barrier layer, is formed along the surface of the base material opposite to the side on which the pressure-sensitive adhesive layer is formed. By laminating the ALD film and an adhesive layer having an appropriate adhesive force at the time of winding, the gas barrier property can be maintained even after winding. Therefore, according to the laminate of the present invention, by sticking the adhesive layer on the ALD film at the time of winding, it is possible to maintain the gas barrier property of the laminate high without being affected by stress such as environmental change. it can.

The first embodiment and the second embodiment of the laminated body of the present invention have been described above in detail with reference to the drawings, but the specific configuration of the present invention is limited to the contents of the above-described embodiments. is not. Further, the present invention can be applied to a gas barrier film including the laminate realized by the above invention.

(Example of the first embodiment)
First, a specific example of the laminated body realized based on the above-described first embodiment will be described. Here, a method of forming the gas barrier layer made of the ALD film 3 will be described.

[Atomic layer deposition film formation]
A TiO ₂ film (barrier) was formed as the ALD film 3 on the other surface of the PET film having a thickness of 100 μm prepared by bonding the protective film on one surface, which was prepared as the substrate 1, by the ALD method using a batch type ALD film forming apparatus. Layer) was deposited.

Titanium tetrachloride (TiCl ₄ ) was used as a source gas when forming the TiO ₂ film. Further, the raw material gas at the same time, the N ₂ is a process gas, and O ₂ and N ₂ is a purge gas, and O ₂ is the reaction gas and plasma discharge gas was supplied to each deposition chamber (chamber) in .. At this time, the pressure in the film forming chamber was 10 to 50 Pa.

Further, a 13.56 MHz power supply was used as a plasma excitation power supply, and plasma discharge was performed in the ICP mode.

The supply time of each gas was set as follows. Specifically, the supply time of TiCl ₄ and the process gas was 1 sec, the supply time of the purge gas was 60 sec, and the supply time of the reaction gas/discharge gas was 5 sec.

Then, simultaneously with the supply of the reaction gas and the discharge gas, a plasma discharge was generated in the ICP mode. The output power of the plasma discharge at this time was 250 watts. Further, as a gas purge after plasma discharge, O ₂ (supply amount of 60 sccm) and N ₂ (supply amount of 100 sccm) serving as purge gas were supplied for 4 sec. The film forming temperature of the TiO ₂ film was 90°C.

The deposition rate of the TiO ₂ film under the above cycle conditions was as follows. That is, since the unit film forming rate is about 1.1 Å/cycle, when the film forming process was performed for 176 cycles to form a film with a thickness of 20 nm, the total film forming time was 253 min.

[Water vapor permeability and adhesive strength of laminate]
Next, regarding the experimental results of the adhesive force after winding the laminated body realized based on the first embodiment and the water vapor transmission rate (hereinafter, referred to as WVTR) before and after being wound on the winding roller. An example will be described. Here, the adhesive force was measured by 180° peeling between the protective film 2 and the ALD film 3 of a sample obtained by cutting the laminate into strips having a width of 25 mm. A Tensilon universal tester RTC-1250 manufactured by Orientec was used for the test. The peeling speed was 300 mm/min. The water vapor transmission rate is measured by using a water vapor transmission rate measuring device (MOCON Aquatran (registered trademark) manufactured by MOCON) in an atmosphere of 40° C./90% RH. Further, Table 1 is a table comparing WVTRs before and after winding the laminated body.

Hereinafter, the superiority of the example of the first embodiment will be described with reference to Table 1.

<Example 1>
In Example 1, first, on a surface 1a of a base material 1 which is a PET film having a thickness of 100 μm, an acrylic adhesive layer was provided on both surfaces of a base material layer made of polyethylene terephthalate (PET) by a coating method, and a thickness of 30 μm. The protective film 2 was attached. Next, on the surface 1b of the base material 1, as the ALD film 3, an ALD film 2 having a TiO ₂ film formed as a barrier layer with a thickness of about 20 nm is formed on the surface to prepare a sample, and a sample having a diameter of 300 mm for winding is formed. Rolling was carried out by contacting the roller. At this time, the adhesive force between the protective film 2 and the ALD film 3 that were bonded together during winding was 32 cN/25 mm, and the WVTR before and after winding was also measured. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 7.0×10 ⁻³ [g/(m ² ·day)] after winding. there were.

<Example 2>
In Example 2, the lamination of Example 2 was performed in the same manner as in Example 1 except that a protective film having a thickness of 50 μm in which rubber-based adhesive layers were laminated on both sides of a base material layer made of polypropylene (PP) was used. The body was made. At this time, the adhesive force between the protective film 2 and the ALD film 3 that were bonded together during winding was 160 cN/25 mm, and the WVTR before and after winding was also measured. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 7.8×10 ⁻³ [g/(m ² ·day)] after winding. there were.

<Comparative example>
Next, in order to show the superiority of the adhesive force and the WVTR in the laminated body according to the example of the first embodiment, a comparison with a comparative example as shown in Table 1 will be made.

<Comparative Example 1>
In Comparative Example 1, a laminate of Comparative Example 1 was produced by the same method as in Example 1 except that the protective film 2 was not provided. Using a sample on which the protective film 2 was not formed, a winding roller having a diameter of 300 mm was brought into contact with the sample to perform winding. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 2.0×10 ⁻¹ [g/(m ² ·day)] after winding. Met.

<Comparative example 2>
In Comparative Example 2, the same method as in Example 1 was used except that a protective film having a thickness of 35 μm in which an adhesive layer made of an ethylene/vinyl acetate copolymer was provided on both surfaces of a base material layer made of polyethylene (PE) was used. Thus, a laminate of Comparative Example 2 was produced. At this time, the adhesive force between the protective film 2 and the ALD film 3 to be stuck together during winding was 4 cN/25 mm, and the WVTR before and after winding was also measured. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 3.1×10 ⁻² [g/(m ² ·day)] after winding. there were.

<Comparative example 3>
In Comparative Example 3, the same method as in Example 1 was used except that a protective film having a thickness of 40 μm formed by coating a rubber-based adhesive layer on both surfaces of a base material layer made of polypropylene (PP) was used. A laminate of Comparative Example 3 was produced. At this time, the adhesive force between the protective film 2 and the ALD film 3 that were bonded together during winding was 330 cN/25 mm, and the WVTR before and after winding was also measured. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 3.7×10 ⁻² [g/(m ² ·day)] after winding. there were.

(Example of Second Embodiment)
Next, a specific example of the laminated body realized based on the second embodiment will be described. A film forming method for forming a TiO ₂ film as the gas barrier layer made of the ALD film 3 will be described.

[Atomic layer deposition film formation]
A batch type ALD film-forming apparatus was used on the other surface of the PET film having a thickness of 100 μm, which was prepared as the base material 1 and had an adhesive layer formed on one surface, in the same manner as in the example of the first embodiment. A TiO ₂ film (gas barrier layer) was formed as the ALD film 3 by the ALD method.

[Evaluation method of laminate]
Next, in the laminated body realized based on the above-described embodiment, the measurement of the adhesive force after being wound on the winding roller, the measurement of the water vapor transmission rate (hereinafter referred to as WVTR) before and after the winding, and the winding The subsequent scratches on the surface of the ALD film 3 were evaluated.

<Measurement of adhesive strength and water vapor transmission rate>
The adhesive force and the water vapor transmission rate were measured by the same method as in the example of the first embodiment.

<Evaluation of surface scratches>
The surface scratches were evaluated by observing the surface of the ALD film 3 after winding the laminate (after unwinding) using an optical microscope. At this time, the observation area was about 2 mm×3 mm, and the number of scratches having a diameter of 20 μm or more was counted. It was confirmed that there were almost no scratches on the surface of the laminate before winding.

Table 2 shows the configurations of the laminates according to Examples 3 to 5 and Comparative Examples 4 to 6, the measured values of the adhesive strength, the water vapor permeability before and after winding, and the number of scratches after winding.

Hereinafter, examples will be described with reference to Table 2.

<Example 3>
In Example 3, first, the acrylic adhesive layer 4 having a thickness of 5 μm was formed on the one surface 1 a of the substrate 1 which was a PET film having a thickness of 100 μm. Next, on the other surface 1b of the base material 1, an ALD film 3 having a TIO ₂ film formed as a gas barrier layer with a thickness of about 20 nm was formed to prepare a sample, which was then brought into contact with a take-up roller having a diameter of 300 mm and taken up. Was carried out. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 which were bonded together during winding was 15 cN/25 mm. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 7.1×10 ⁻³ [g/(m ² ·day)] after winding. there were. The number of scratches on the surface after winding was four.

<Example 4>
In Example 4, a laminated body of Example 4 was produced in the same manner as in Example 3 except that the rubber-based adhesive layer 4 was formed on the surface 1a of the base material 1 to have a thickness of 10 μm. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 which were attached at the time of winding was 160 cN/25 mm. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 7.6×10 ⁻³ [g/(m ² ·day)] after winding. there were. The number of scratches on the surface after winding was 5.

<Example 5>
In Example 5, on the surface 1b of the base material 1, trimethyl aluminum (TMA; Tri-Methyl Aluminum) was used as a source gas, and an ALD film 3 having an Al ₂ O ₃ film of about 20 nm formed as a gas barrier layer was formed. A layered product of Example 5 was produced in the same manner as in Example 3 except for the above. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 which were bonded together during winding was 15 cN/25 mm. The measured value of WVTR is 5.1×10 ⁻³ [g/(m ² ·day)] before winding and 7.2×10 ⁻³ [g/(m ² ·day)] after winding. there were. The number of scratches on the surface after winding was four.

In any of the laminates of Examples 3 to 5, by providing the adhesive layer 4 having an adhesive force to the ALD film 3 of 10 to 200 cN/25 mm, the occurrence of scratches on the ALD film 3 after winding is suppressed, As a result, it was possible to suppress a decrease in water vapor permeability after winding.

<Comparative example>
Next, in order to show the superiority of the adhesive force, WVTR, and the number of scratches on the surface in the laminate according to the example of the second embodiment, a comparison will be made with a comparative example as shown in Table 2.

<Comparative example 4>
In Comparative Example 4, a laminated body of Comparative Example 4 was produced in the same manner as in Example 3 except that the adhesive layer 4 was not formed on the surface 1a of the base material 1. Using the sample in which the adhesive layer 4 was not formed, it was wound by contacting it with a winding roller having a diameter of 300 mm. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 2.0×10 ⁻¹ [g/(m ² ·day)] after winding. Met. The number of scratches on the surface after winding was 100. In the laminated body according to Comparative Example 4, it was not possible to prevent the ALD film 3 from being scratched after winding, and the water vapor permeability after winding was significantly reduced.

<Comparative Example 5>
In Comparative Example 5, a laminated body of Comparative Example 5 was produced in the same manner as in Example 3 except that the rubber-based adhesive layer 4 was formed on the one surface 1a of the base material 1 to have a thickness of 15 μm. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 which were attached at the time of winding was 330 cN/25 mm. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 3.5×10 ⁻² [g/(m ² ·day)] after winding. there were. The number of scratches on the surface after winding was 40. Also in the laminate according to Comparative Example 5, it was not possible to prevent the ALD film 3 from being scratched after winding, and the water vapor permeability after winding was significantly reduced. It is considered that this is because the adhesive force of the adhesive layer 4 was too strong, so that an inadvertent force was applied when the laminate was unwound and the surface of the ALD film 3 was damaged.

<Comparative example 6>
In Comparative Example 6, a laminated body of Comparative Example 6 was produced in the same manner as in Example 3 except that the acrylic adhesive layer 4 was formed on the one surface 1a of the base material 1 to have a thickness of 6 μm. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 which were bonded together during winding was 5 cN/25 mm. The measured value of WVTR is 5.0×10 ⁻³ [g/(m ² ·day)] before winding and 2.4×10 ⁻³ [g/(m ² ·day)] after winding. there were. The number of scratches on the surface after winding was 50. Also in the laminated body according to Comparative Example 6, it was not possible to prevent the ALD film 3 from being scratched after winding, and the water vapor permeability after winding was significantly reduced. It is considered that this is because the adhesive strength of the adhesive layer 4 was insufficient, the adhesive layer 4 was easily separated from the ALD film 3, and the surface of the ALD film 3 was scratched due to rubbing or the like.

INDUSTRIAL APPLICABILITY The laminate of the present invention is not limited to the use of electronic components such as electroluminescence elements (EL elements), liquid crystal displays, and semiconductor wafers, but is also effective for packaging films such as pharmaceuticals and foods, and packaging films for precision components. Can be used.

1 Base material 2 Protective film 3 Atomic layer deposition film (ALD film)
4 Adhesive layer

Claims (9)

A sheet-shaped laminated body wound in a roll,
Base material,
A layer provided on one surface of the base material and having adhesiveness on both surfaces,
Provided on the other surface of the base material, and comprising an atomic layer deposition film made of an inorganic material,
A layered product, wherein an adhesive force of the layer having adhesiveness on both sides with respect to the atomic layer deposition film is 10 cN/25 mm or more and 200 cN/25 mm or less. The layered product according to claim 1, wherein the layer having adhesiveness on both sides is a protective film having a substrate layer and an adhesive layer provided on both sides of the substrate layer. The thickness of the said protective film is 10 micrometers or more and 100 micrometers or less, The laminated body of Claim 2 characterized by the above-mentioned. The layered product according to claim 1, wherein the layer having adhesiveness on both sides is an adhesive layer. The thickness of the said adhesive layer is 1 micrometer or more and 40 micrometers or less, The laminated body of Claim 4 characterized by the above-mentioned. The laminated body according to claim 1, wherein the atomic layer deposited film has a thickness of 2 nm or more and 500 nm or less. The atomic layer deposition film is a film including at least one layer of an inorganic oxide film, an inorganic nitride film and an inorganic oxynitride film,
The laminated body according to claim 1, wherein the inorganic oxide film, the inorganic nitride film, and the inorganic oxynitride film contain at least one kind of Al, Ti, Si, Zn, and Sn. A gas barrier film comprising the laminate according to claim 1. The gas barrier film according to claim 8, wherein the water vapor transmission rate of the laminate is 0.01 [g/(m ² ·day)] or less.

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