WO2017073037A1 - Corps stratifié et film de barrière contre les gaz - Google Patents

Corps stratifié et film de barrière contre les gaz Download PDF

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Publication number
WO2017073037A1
WO2017073037A1 PCT/JP2016/004640 JP2016004640W WO2017073037A1 WO 2017073037 A1 WO2017073037 A1 WO 2017073037A1 JP 2016004640 W JP2016004640 W JP 2016004640W WO 2017073037 A1 WO2017073037 A1 WO 2017073037A1
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Prior art keywords
film
ald
winding
base material
thickness
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PCT/JP2016/004640
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English (en)
Japanese (ja)
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喬文 堀池
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凸版印刷株式会社
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Priority to JP2017547610A priority Critical patent/JP6743829B2/ja
Publication of WO2017073037A1 publication Critical patent/WO2017073037A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00

Definitions

  • the present invention relates to a laminate comprising an atomic layer deposition film formed on the surface of a substrate by an atomic layer deposition method, and a gas barrier film comprising the laminate.
  • the method of forming a thin film on the surface of an object using a gas phase that makes the substance move at the atomic or molecular level like a gas can be broadly divided into chemical vapor deposition (CVD) and physical vapor phase. There is a growth method (PVD: Physical Vapor Deposition).
  • PVD vapor deposition
  • sputtering is generally used to form a high-quality thin film that is high in equipment cost but excellent in film quality and film thickness uniformity. Therefore, it is widely applied to display devices such as liquid crystal displays.
  • CVD is a method in which 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 during film formation or to lower the reaction temperature, there are also those that use plasma and a catalyst (Catalyst) reaction together, such as PECVD (Plasma Enhanced CVD) and Cat-CVD, respectively. being called.
  • PECVD Plasma Enhanced CVD
  • Cat-CVD Cat-CVD
  • ALD method Atomic Layer Deposition
  • This ALD method is a method in which a substance adsorbed on the surface is formed one layer at a time by a chemical reaction on the surface, and is classified into the category of CVD.
  • the ALD method is distinguished from general CVD by so-called CVD (general CVD) in which a thin film is grown by reacting on a substrate using a single gas or a plurality of gases simultaneously. is there.
  • the ALD method uses a precursor (hereinafter referred to as a “first precursor”), or an active gas called a precursor and a reactive gas (also referred to as a precursor in the ALD method).
  • the precursor is hereinafter referred to as a “second precursor”
  • a 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 formation method of the ALD method uses a so-called self-limiting effect in which, when the surface is covered with a certain gas in the surface adsorption on the substrate, no further gas adsorption occurs. When only one layer is adsorbed, the unreacted precursor is exhausted. Subsequently, a reactive gas is introduced, and the precursor is oxidized or reduced to obtain only one thin film having a desired composition, and then the reactive gas is exhausted. The above process is defined as one cycle, and this cycle is repeated to grow a thin film. Therefore, in the ALD method, the thin film grows two-dimensionally.
  • the ALD method is characterized in that it has fewer film-forming defects than the conventional CVD or the like, as well as the conventional vacuum deposition method and sputtering.
  • the ALD method includes a method of using plasma to activate the reaction in the step of decomposing the second precursor and reacting with the first precursor adsorbed on the substrate.
  • This method is called plasma activated ALD (PEALD: Plasma Enhanced ALD) or simply plasma ALD.
  • the ALD method is capable of forming a high-quality and high-density film, and is therefore being applied in the field of semiconductors such as a gate insulating film.
  • ITRS International Technology Roadmap for Semiconductors
  • the ALD method has a feature that there is no slanting effect as compared with other film forming methods, that is, there is no phenomenon in which sputtered particles are incident on the substrate surface and the film forming variation does not occur. If so, film formation is possible. Therefore, the ALD method can be applied to the coating of lines and holes on a substrate having a high aspect ratio with a large depth to width ratio, as well as to MEMS (Micro Electro Mechanical Systems) related to coating of three-dimensional structures. Expected.
  • the ALD method also has drawbacks. That is, in order to perform the ALD method, a special material is used and the cost is increased. However, the biggest drawback is that the film forming speed is low. For example, the film formation rate is about 5 to 10 times slower than a film formation method such as normal vacuum deposition 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-like substrate such as a wafer or a photomask, or a substrate having a large area and no flexibility such as a glass plate. Or a substrate having a large area and flexibility such as a film.
  • mass production facilities for forming thin films on these substrates have been proposed and put to practical use by various substrate handling methods depending on cost, ease of handling, film formation quality, etc. ing.
  • a single substrate is supplied to a film forming apparatus to form a film, and then the wafer is replaced with the next substrate to form a film again, or a plurality of substrates are set together and all wafers are set.
  • a batch type film forming apparatus for performing the same film forming.
  • an in-line type film forming apparatus that performs film formation at the same time while sequentially transporting the substrate to a part serving as a film formation source.
  • a so-called roll-to-roll coating film forming apparatus in which a flexible substrate is mainly unwound from a roll and film is formed while being conveyed, and the substrate is wound on another roll.
  • the latter includes not only a flexible substrate but also a flexible coating sheet that can continuously convey a substrate to be deposited, or a web coating deposition apparatus that continuously deposits on a tray that is partially flexible.
  • the film forming method and the substrate handling method using any of the film forming apparatuses a combination of film forming apparatuses having the fastest film forming speed is adopted in view of cost, quality, and ease of handling.
  • a technique for 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, a barrier film excellent in barrier properties can be realized by performing atomic layer deposition by the ALD method.
  • laminates in which an atomic layer deposition film is provided on the surface of a substrate by the ALD method are widely known, and these laminates are used for gas barrier films having high gas barrier properties.
  • the atomic layer deposited film may be easily damaged by an external force. If 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 generated depending on the size of the scratch. When through-holes in the film thickness direction are formed in the atomic layer deposition film in this way, gas enters and exits from the base material through the through-holes, so that gas barrier properties are deteriorated.
  • the present invention has been made in view of such circumstances, and a laminated body having improved gas barrier properties so that an atomic layer deposited film formed on the surface of a substrate is not easily damaged by an external force, and the laminated body. It aims at providing the gas barrier film containing a body.
  • the present invention relates to a sheet-like laminate wound in a roll shape, and is provided on a base material, a layer provided on one side of the base material and having adhesiveness on both sides, and on the other side of the base material.
  • an atomic layer deposited film made of an inorganic material, and the adhesive strength of the layer having adhesiveness to both sides of the atomic layer deposited 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 comprising the above laminate.
  • the surface of the atomic layer deposition film covering the substrate is bonded to the adhesive layer on both sides, so that the adhesive layer on both sides protects the surface of the atomic layer deposition film.
  • FIG. 1 is a cross-sectional view showing the configuration of the laminate according to the first embodiment of the present invention.
  • 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 up by a roller.
  • FIG. 3 is a cross-sectional view showing the configuration of the laminate according to the second embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing a state when the laminated body of the second embodiment of the present invention is wound with a roller.
  • FIG. 1 is a cross-sectional view showing the configuration of the laminate in the first embodiment of the present invention.
  • FIG. 2 is sectional drawing which shows the state at the time of winding up the laminated body of the 1st Embodiment of this invention with a roller.
  • the laminate includes a base 1 and a side 1 a of the base 1 bonded with a protective film 2 having adhesiveness on both sides, and a side of the base 1 bonded with the protective film. It is composed of an atomic layer deposition film 3 (hereinafter referred to as “ALD film 3”) formed along the other surface 1b on the opposite side.
  • the protective film 2 consists of a base material layer and an adhesion layer, for example.
  • the substrate 1 is a film-like substrate made of a plastic material, and is preferably transparent.
  • plastic materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide film (PI), polyethylene (PE), polypropylene (PP), and polystyrene (PS).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide film
  • PE polyethylene
  • PE polypropylene
  • PS polystyrene
  • it is not limited to these, It can select suitably considering heat resistance, an intensity
  • 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 ⁇ m or more in consideration of appropriateness as a packaging material for electronic parts such as electroluminescence elements and precision parts, proper processing as a gas barrier film, and conveyance and film formation by roll-to-roll. It is preferable that it is 200 micrometers or less.
  • the thickness of the substrate In order to transport the substrate by roll-to-roll and form an ALD film, the thickness of the substrate needs to be 50 ⁇ m or more. As will be described later, in the first embodiment, the thickness of the base material required when forming the ALD film 3 can be set to a thickness obtained by adding 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 ⁇ m or more and the thickness of the base material 1 and the thickness of the protective film 2 is 50 ⁇ m or more, the base material 1 and the protective film 2 are roll-to-roll. Transport and ALD film formation are possible.
  • Protective film 2 is not particularly limited in the laminate of the present invention, and various protective films having adhesiveness used in the production of functional films can be used.
  • the protective film 2 may be one in which an adhesive is applied to both surfaces of the base material layer, or the protective film itself may be adhesive.
  • the base material layer include polyester resins such as polyethylene terephthalate (PET), polyethylene (PE), and polypropylene (PP). Examples thereof include, but are not limited to, polyolefin resins and acrylic resins such as polymethyl methacrylate.
  • the adhesive include acrylic, urethane, rubber, silicone, and fluorine, but are not limited thereto.
  • the pressure-sensitive adhesive may be applied using a composition to which a solvent is added.
  • examples of the method for applying the adhesive layer include, but are not limited to, a die coater method, a gravure roll coater method, and a spray coater method.
  • the protective film 2 having adhesiveness a film in which an adhesive layer made of an adhesive resin is laminated on both surfaces of the base material layer can be mentioned.
  • Resin used as a base material layer will not be restrict
  • examples thereof include, but are not limited to, polyolefin resins such as polyethylene and polypropylene.
  • the adhesive layer include copolymers such as ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene- ⁇ -olefin copolymer, and mixtures thereof. It is not limited to.
  • Examples of the production method include, but are not limited to, those obtained by extrusion molding of a base material layer and an adhesive layer.
  • the adhesive strength 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.
  • 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 any contact, so that the surface of the ALD film 3 is scratched when it comes into contact with a roller or the like. This is not preferable because the gas barrier property may be lowered.
  • the adhesive force of the surface 2a of the protective film 2 is stronger than 200 cN / 25 mm, the ALD film 3 is not easily damaged because it does not peel off even when contacting with a roller or the like.
  • the adhesive force is strong and cannot be easily peeled off, an unintentional force is applied when the laminated protective film 2 is peeled off when the laminated body is unwound, and the surface of the ALD film 3 is damaged, resulting in a gas barrier. This is not preferable because the property may be lowered.
  • the adhesive strength of the other surface of the protective film 2 to the surface 1a of the substrate 1 is desirably 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 ⁇ m or more and 100 ⁇ m or less. As described above, the thickness obtained by adding the thickness of the substrate 1 and the thickness of the protective film 2 needs to be 50 ⁇ m or more. Therefore, the thickness of the protective film 2 is 10 ⁇ m or more and 100 ⁇ m or less, and the combined thickness of the substrate 1 and the protective film 2 may be 50 ⁇ m or more.
  • the thickness of the protective film 2 is less than 10 ⁇ m, handling becomes difficult, and thus wrinkles or the like may occur at the time of bonding to the base material 1. Unevenness due to the bonding flaw is transferred to the ALD base material at the time of winding, and the ALD film 3 may be damaged due to deformation, twisting / collision, etc., which is not preferable.
  • the thickness of the protective film 2 is thicker than 100 ⁇ m, it is necessary to apply a winding tension more than when the thickness is small in order to wind up without loosening.
  • winding is generated by winding with high tension, and a large force is applied in the winding core direction. Then, a strong pressing pressure is applied to the ALD film 3 particularly on the winding core side of the film, and the barrier property may be deteriorated.
  • the ALD film 3 is a film formed by the ALD method.
  • ALD film 3 AlO x, TiO x, SiO x, ZnO x, inorganic oxide film such as SnO x, inorganic nitride, inorganic oxynitride film, or may be a mixed film of these films and elements. Furthermore, the ALD film 3 may be an oxide film, a nitride film, an oxynitride film, or a mixed film made of other elements.
  • 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.
  • the thickness of the ALD film 3 is smaller than 2 nm, the function as a gas barrier layer cannot be performed sufficiently.
  • the film thickness of the ALD film 3 is larger than 500 nm, the gas barrier layer is easily cracked or it is difficult to control the optical characteristics.
  • the ALD film 3 formed on the surface 1b of the substrate 1 has excellent barrier properties. However, when the ALD film 3 is thin, scratches, pinholes, etc. are generated in the ALD film 3 due to external contact or the like. there is a possibility. In such a case, the gas barrier performance of the laminate is reduced.
  • the protective film 2 is bonded to the surface 1a of the substrate 1, and then The ALD film 3 is formed on the surface 1b opposite to the side where the protective film of the base material 1 is bonded to form a laminate, and the laminate is then wound into a roll.
  • the surface 2a of the protective film 2 and the surface 3a of the ALD film 3 are wound when the ALD film 3 of the laminate is wound in a roll shape with the surface 3a of the winding roller side of the winding roller. Can be pasted together. At this time, the surface 2 a of the protective film 2 can contact and adhere to the surface 3 a of the ALD film 3 to protect the ALD film 3.
  • the laminated body which first bonded the protective film 2 to the surface 1a of the base material 1, and then formed the ALD film 3 on the surface 1b opposite to the side where the protective film of the base material 1 was bonded.
  • the ALD film 3 does not come into direct contact with another substrate. That is, when the surface 3a of the ALD film 3 is bonded to the surface 2a of the protective film 2 during winding, the gas barrier property can be maintained when the roll is wound, and the durability of the laminate can be increased. Gas barrier property can be improved.
  • the laminate composed of the base material 1, the protective film 2, and the ALD film 3 since the surface 3a of the ALD film 3 is bonded to the surface 2a of the protective film 2 during winding, the ALD film 3 is damaged by an external force. It becomes difficult. That is, the possibility that the ALD film 3 is damaged such that gas enters and exits in the film thickness direction of the ALD film 3 can be suppressed. Therefore, the laminate can be used as a gas barrier film.
  • the laminated body wound up with the roller based on the said embodiment is an overcoat layer etc. as a protective layer on the surface of ALD film 3 as a separate process after unwinding, maintaining the gas barrier property of ALD film 3 Can be formed.
  • the thickness of the base material required when forming the ALD film 3 is It can be set as the thickness which added the thickness of the base material 1 and the thickness of the protective film 2. Therefore, in the laminated body which concerns on the said embodiment, the base material 1 is the part of the thickness of the protective film 2 rather than the thickness of the base material in the case of bonding the protective film after forming the ALD film 3 on the base material 1. Can be reduced in thickness.
  • the roll of the laminated body which concerns on the said embodiment is more than the roll of the laminated body which bonded the protective film after forming the ALD film 3 on the base material 1. Further, it is possible to increase the portions of the base material 1 and the ALD film 3 necessary for functioning as a gas barrier film.
  • a protective film is bonded along the outer surface of the base material, and an ALD film that is a barrier layer is formed along the surface opposite to the side on which the protective film of the base material is bonded.
  • the barrier property can be maintained even after winding. Therefore, according to the laminate according to the first embodiment, the protective film having an adhesive layer on the ALD film is bonded to the ALD film at the time of winding so that the laminate is not significantly affected by stress such as environmental changes. Gas barrier properties can be increased.
  • the second embodiment is different from the first embodiment in that an adhesive layer 4 is formed along one surface 1a of the substrate 1.
  • FIG. 3 is a cross-sectional view showing the configuration of the laminate according to the second embodiment of the present invention.
  • FIG. 4 is sectional drawing which shows the state at the time of winding up the laminated body which concerns on the 2nd Embodiment of this invention with a roller.
  • the laminate includes a base material 1, an adhesive layer 4 formed along one surface 1 a of the base material 1, and a side opposite to the side on which the adhesive layer 4 of the base material 1 is formed. And an atomic layer deposition film 3 (hereinafter referred to as “ALD film 3”) formed along the other surface 1b.
  • ALD film 3 atomic layer deposition film 3
  • the thickness of the substrate 1 may be 25 ⁇ m or more, and the thickness obtained by adding the thickness of the substrate 1 and the thickness of the adhesive layer 4 may be 50 ⁇ m or more.
  • the adhesive layer 4 is made of an adhesive.
  • the adhesive utilized in manufacture of a functional film can be utilized.
  • the adhesive include, but are not limited to, acrylic, rubber, urethane, silicone, epoxy, polyolefin, and fluorine.
  • the pressure-sensitive adhesive may be applied using a composition to which a solvent is added.
  • examples of the method for applying the adhesive layer include, but are not limited to, a die coater method, a gravure roll coater method, and a spray coater method.
  • 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. More preferably.
  • the adhesive strength of the adhesive layer 4 is weaker than 10 cN / 25 mm, sufficient adhesive strength cannot be obtained, and the adhesive layer 4 may be easily peeled off by any contact. This is not preferable because the surface of the film may be scratched and the gas barrier property may be lowered.
  • the adhesive strength of the adhesive layer 4 is stronger than 200 cN / 25 mm, the ALD film 3 is not easily damaged because it does not peel off even when contacting with a roller or the like.
  • the adhesive strength is strong and does not easily peel off, an unintended force is applied when the wound laminate is unwound, and the surface of the ALD film 3 may be damaged and the gas barrier property may be lowered.
  • the thickness of the adhesive layer 4 is desirably 1 ⁇ m or more and 40 ⁇ m or less. As described above, the thickness obtained by adding the thickness of the substrate 1 and the thickness of the adhesive layer 4 needs to be 50 ⁇ m or more. Therefore, the thickness of the adhesive layer 4 is 1 ⁇ m or more and 40 ⁇ m or less, and the combined thickness of the substrate 1 and the adhesive layer 4 may be 50 ⁇ m or more.
  • the thickness of the adhesive layer 4 is smaller than 1 ⁇ m, it is not preferable because sufficient adhesive force with the ALD film 3 cannot be obtained and may be easily peeled off during winding. In addition, it is not preferable because it may be difficult to sufficiently prevent the effects of scratches and scratches on the ALD film 3 due to the contact of a roller or the like.
  • the thickness of the adhesive layer 4 is larger than 40 ⁇ m, excessive force is applied to the surface of the ALD film 3 when the wound laminate is unwound, resulting in a decrease in gas barrier properties or on the surface of the ALD film 3. This is not preferable because the adhesive layer 4 may remain. Moreover, it is not preferable because it is expensive.
  • ALD film 3 is the same as that of the first embodiment, description thereof is omitted here.
  • the ALD film 3 formed on the surface 1b of the substrate 1 has excellent barrier properties. However, when the ALD film 3 is thin, scratches, pinholes, etc. are generated in the ALD film 3 due to external contact or the like. there is a possibility. In such a case, the gas barrier performance of the laminate is reduced. Therefore, in order to prevent the ALD film 3 from being scratched or pinholes due to external contact or the like, and to improve durability, first, the adhesive layer 4 is formed on the surface 1a of the substrate 1, and then The ALD film 3 is formed on the surface 1b opposite to the side on which the adhesive layer 4 is formed of the base material 1 to form a laminate, and then the laminate is wound into a roll.
  • the surface 4a of the adhesive layer 4 (the surface 1a on the substrate side and the surface 1a) The opposite surface) and the surface 3a of the ALD film 3 can be bonded together.
  • the surface 4a of the adhesive layer 4 can contact and adhere to the surface 3a of the ALD film 3 to protect the ALD film 3.
  • the laminate in which the adhesive layer 4 is first formed on one surface 1a of the substrate 1 and then the ALD film 3 is formed on the surface 1b opposite to the side on which the adhesive layer of the substrate 1 is formed is
  • the ALD film 3 does not come into direct contact with another substrate. That is, when the surface 3a of the ALD film 3 is bonded to the surface 4a of the adhesive layer 4 when winding, the gas barrier property can be maintained when the roll is wound, and the durability of the laminate can be increased. Gas barrier property can be improved.
  • the one surface 3a of the ALD film 3 is bonded to the one surface 4a of the adhesive layer 4 at the time of winding. Become. That is, the possibility that the ALD film 3 is damaged such that gas enters and exits in the film thickness direction of the ALD film 3 can be suppressed. Therefore, the laminate can be used as a gas barrier film.
  • the adhesive layer 4 in the laminate 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. For this reason, after unwinding the laminated body wound up by the winding roller, the surface of the ALD film 3 is overcoated as a protective layer in a separate process while maintaining the gas barrier property of the ALD film 3 without producing wasteful waste.
  • a laminate provided with a coat layer or the like can be formed.
  • the thickness of the substrate necessary for forming the ALD film 3 is determined based on the thickness of the substrate. It can be set as the thickness which added the thickness of the material 1 and the thickness of the adhesion layer 4.
  • the base material 1 is equal to the thickness of the adhesive layer 4 rather than the thickness of the base material when the adhesive layer is formed after forming the ALD film 3 on the base material 1. Can be reduced in thickness.
  • the roll of the laminated body which concerns on the said embodiment is more than the roll of the laminated body which formed the adhesion layer 4 after forming the ALD film 3 on the base material 1. Further, it is possible to increase the portions of the base material 1 and the ALD film 3 necessary for functioning as a gas barrier film.
  • an adhesive layer is formed along one surface of the outer surface of the base material, and an ALD film that is a gas barrier layer is formed along the surface opposite to the side on which the adhesive layer is formed of the base material.
  • the gas barrier property can be maintained even after the winding by performing the bonding of the ALD film and the adhesive layer having an appropriate adhesive force at the time of winding. Therefore, according to the laminate of the present invention, by adhering the adhesive layer on the ALD film at the time of winding, the gas barrier property of the laminate can be maintained high without being affected by stress such as environmental changes. it can.
  • Example of the first embodiment First, specific examples of the laminated body realized based on the first embodiment will be described. Here, a method for forming a gas barrier layer made of the ALD film 3 will be described.
  • a TiO 2 film (barrier) was prepared as an ALD film 3 on the other side of a PET film having a thickness of 100 ⁇ m prepared as a base material 1 and having a protective film bonded on one side by an ALD method using a batch type ALD film forming apparatus. Layer).
  • titanium tetrachloride TiCl 4
  • 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 .
  • the pressure in the film forming chamber was set to 10 to 50 Pa.
  • a plasma discharge was performed in the ICP mode using a 13.56 MHz power source as a plasma excitation power source.
  • 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.
  • plasma discharge was generated in the ICP mode simultaneously with the supply of the reaction gas / discharge gas.
  • the output power of the plasma discharge at this time was 250 watts.
  • O 2 (supply amount: 60 sccm) and N 2 (supply amount: 100 sccm) serving as purge gases were supplied for 4 seconds.
  • the deposition temperature of the TiO 2 film was 90 ° C.
  • the deposition rate of the TiO 2 film under the cycle conditions as described above was as follows. That is, since the unit film formation rate was about 1.1 liters / cycle, when 176 cycles of film formation were performed to form a film with a thickness of 20 nm, the total film formation time was 253 min.
  • the water vapor transmission rate is obtained by measuring the water vapor transmission rate in an atmosphere of 40 ° C./90% RH using a water vapor transmission rate measuring device (MOCON Aquatran (registered trademark) manufactured by MOCON).
  • Table 1 is a table comparing WVTRs before and after winding of the laminates.
  • Example 1 In Example 1, first, a 30 ⁇ m thick acrylic adhesive layer is provided on both surfaces of a base material layer made of polyethylene terephthalate (PET) on a surface 1a of a base material 1 which is a 100 ⁇ m thick PET film by a coating method. The protective film 2 was bonded together. Next, on the surface 1b of the substrate 1, as ALD film 3, on the surface, the TiO 2 film to form about 20nm film-formed ALD film 2 to prepare a sample as a barrier layer, for winding diameter 300mm Winding was carried out in contact with a roller.
  • PET polyethylene terephthalate
  • the adhesive force between the protective film 2 and the ALD film 3 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 lamination of Example 2 was performed in the same manner as in Example 1 except that a protective film having a thickness of 50 ⁇ m in which a rubber-based adhesive layer was laminated on both surfaces of a base material layer made of polypropylene (PP). The body was made. At this time, the adhesive force between the protective film 2 and the ALD film 3 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.
  • the laminated body of the comparative example 1 was produced by the method similar to Example 1 except not having the protective film 2.
  • FIG. Using a sample on which this protective film 2 was not formed, the sample was wound by being brought into contact 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.
  • Comparative Example 2 In Comparative Example 2, the same method as in Example 1 except that a 35 ⁇ m-thick protective film 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 strength between the protective film 2 and the ALD film 3 bonded together during winding was 4 cN / 25 mm, and the WVTR before and after winding was measured together. 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 ⁇ m formed by applying a rubber-based adhesive layer on both sides 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 bonded together at the time of winding was 330 cN / 25 mm, and the WVTR before and after winding was measured together. 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 the second embodiment Next, specific examples 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.
  • a batch-type ALD film forming apparatus was used on the other side of a 100 ⁇ m-thick PET film prepared as the base material 1 and having an adhesive layer formed on one side 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.
  • the surface scratches were evaluated by observing the surface of the ALD film 3 after winding (after unwinding) the laminate 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 ⁇ m or more was counted. In addition, it confirmed that there was almost no damage
  • Table 2 shows the configurations of the laminates according to Examples 3 to 5 and Comparative Examples 4 to 6, measured values of adhesive strength, water vapor permeability before and after winding, and the number of scratches after winding.
  • Example 3 In Example 3, first, an acrylic pressure-sensitive adhesive layer 4 having a thickness of 5 ⁇ m was formed on one surface 1a of the substrate 1 which is a PET film having a thickness of 100 ⁇ m. Next, an ALD film 3 having a TIO 2 film of about 20 nm formed as a gas barrier layer is formed on the other surface 1b of the substrate 1 to prepare a sample, which is brought into contact with a winding roller having a diameter of 300 mm and wound. Carried out. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 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 the 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 with a thickness of 10 ⁇ m on the surface 1a of the substrate 1. At this time, the adhesive strength between the adhesive layer 4 and the ALD film 3 bonded together during 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 An ALD film 3 in which trimethylaluminum (TMA) was used as a source gas and an Al 2 O 3 film of about 20 nm was formed as a gas barrier layer on the surface 1b of the substrate 1 was formed. Except for this, the laminate of Example 5 was made in the same manner as in Example 3. At this time, the adhesive force between the adhesive layer 4 and the ALD film 3 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.
  • TMA trimethylaluminum
  • any of the laminates of Examples 3 to 5 by providing the adhesive layer 4 having an adhesive force with respect to the ALD film 3 of 10 to 200 cN / 25 mm, generation 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.
  • the laminated body of the comparative example 4 was produced by the method similar to Example 3 except not forming the adhesion layer 4 in the surface 1a of the base material 1.
  • 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.
  • wound of the ALD film 3 after winding cannot be prevented, and the water-vapor-permeation rate after winding fell significantly.
  • Comparative Example 5 a laminate of Comparative Example 5 was produced in the same manner as in Example 3 except that the rubber-based adhesive layer 4 was formed with a thickness of 15 ⁇ m on one surface 1a of the substrate 1. At this time, the adhesive strength between the adhesive layer 4 and the ALD film 3 bonded together during 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.
  • Comparative Example 6 a laminate of Comparative Example 6 was produced in the same manner as in Example 3 except that the acrylic adhesive layer 4 having a thickness of 6 ⁇ m was formed on one surface 1a of the substrate 1. At this time, the adhesive strength between the adhesive layer 4 and the ALD film 3 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.
  • the laminate of the present invention is effective not only for the use of electronic components such as electroluminescence elements (EL elements), liquid crystal displays, and semiconductor wafers, but also for packaging films for pharmaceuticals and food, packaging films for precision parts, etc. Can be used.
  • EL elements electroluminescence elements
  • liquid crystal displays liquid crystal displays
  • semiconductor wafers but also for packaging films for pharmaceuticals and food, packaging films for precision parts, etc. Can be used.

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Abstract

La présente invention concerne : un corps stratifié ayant des caractéristiques de barrière contre les gaz améliorées par prévention qu'un film déposé par couche atomique formé sur une surface d'un matériau de base soit aisément rayé en raison d'une force externe ; et un film de barrière contre les gaz comprenant le corps stratifié. Ce corps stratifié en forme de feuille enroulée dans un état de rouleau est caractérisé en ce qu'il est pourvu de : un matériau de base ; une couche, qui est disposée sur une surface du matériau de base, et qui présente une adhérence sur les deux surfaces ; et un film déposé par couche atomique qui est disposé sur l'autre surface du matériau de base, et qui est formé d'un matériau inorganique. Le corps stratifié est également caractérisé en ce que, par rapport au film déposé par couche atomique, la force adhésive de la couche ayant l'adhérence sur les deux surfaces n'est pas inférieure à 10 cN/25 mm mais pas supérieure à 200 cN/25 mm.
PCT/JP2016/004640 2015-10-27 2016-10-20 Corps stratifié et film de barrière contre les gaz WO2017073037A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009148896A (ja) * 2007-11-30 2009-07-09 Toyobo Co Ltd 積層ポリイミドフィルム及びその製造方法
JP2012096432A (ja) * 2010-11-01 2012-05-24 Sony Corp バリアフィルム及びその製造方法
JP2015003464A (ja) * 2013-06-21 2015-01-08 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP2015132007A (ja) * 2014-01-15 2015-07-23 凸版印刷株式会社 積層体の製造方法、及び積層体製造装置
EP2927346A1 (fr) * 2012-11-29 2015-10-07 LG Chem, Ltd. Procédé de revêtement permettant de réduire la dégradation d'une couche barrière

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Publication number Priority date Publication date Assignee Title
WO2014123201A1 (fr) * 2013-02-08 2014-08-14 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
EP3284592A4 (fr) * 2015-04-16 2019-04-17 Toppan Printing Co., Ltd. Stratifié et film formant barrière aux gaz

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009148896A (ja) * 2007-11-30 2009-07-09 Toyobo Co Ltd 積層ポリイミドフィルム及びその製造方法
JP2012096432A (ja) * 2010-11-01 2012-05-24 Sony Corp バリアフィルム及びその製造方法
EP2927346A1 (fr) * 2012-11-29 2015-10-07 LG Chem, Ltd. Procédé de revêtement permettant de réduire la dégradation d'une couche barrière
JP2015003464A (ja) * 2013-06-21 2015-01-08 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP2015132007A (ja) * 2014-01-15 2015-07-23 凸版印刷株式会社 積層体の製造方法、及び積層体製造装置

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