JP2009269192A - Method of manufacturing laminate, laminate, multilayer film, and laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a laminate that prevents the decline of the smoothness and coverage of an upper layer (an inorganic film) in the method of manufacturing the laminate in which a lower layer with a coating film containing a radiation curable monomer or oligomer cured by radiation is formed, and the inorganic film is formed on the lower layer by a vacuum deposition method. <P>SOLUTION: Before a curing process, the coating film on a substrate is treated by a first pressure over a first prescribed time. In the curing process, the coating film on the substrate is treated by a second pressure higher than the first pressure over a second prescribed time. In a vacuum deposition process, it is treated by a third pressure lower than the first pressure over a third prescribed time. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate production method, a laminate, a laminate film, and a laminate sheet, and in particular, a laminate production method in which a lower layer is provided on a base material and an inorganic film is provided on the lower layer by a vacuum film formation method. About.

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

  In addition, film formation (thin film formation) by a vacuum film formation method such as sputtering or plasma CVD is used for manufacturing these functional films.

  In order to perform film formation efficiently and with high productivity by a vacuum film formation method, film formation is continuously performed on a long base material.

  As equipment for carrying out such a film forming method, a supply roll formed by winding a long base material (web-shaped base material) in a roll shape, and a winding for winding a film-formed base material in a roll shape. A so-called roll-to-roll film forming apparatus using a take-off roll is known. This roll-to-roll film forming device inserts a long base material from a supply roll to a take-up roll through a predetermined path passing through a film forming chamber for forming a film on the base material by plasma CVD, and supplies it. The film formation is continuously performed on the substrate to be conveyed in the film formation chamber while the base material is fed out from the roll and the film-formed base material is wound up by the take-up roll.

  By the way, functional films such as a gas barrier film and a protective film are not necessarily a single layer. For example, an organic film mainly composed of a polymer is formed on a base material such as a plastic film, and the film is formed thereon. A functional film (laminated film) formed by forming an inorganic film made of an inorganic material is also known.

As an example, Patent Document 1 discloses an organic film obtained by curing a composition containing a hexafunctional acrylate or methacrylate monomer or oligomer, an aluminum oxide, a silicon oxide, and a composite oxide of indium and tin. In addition, a gas barrier film in which an inorganic film made of an oxide selected from a composite oxide of indium and cerium or the like is laminated is disclosed.
JP 2002-264274 A

  By the way, on a base material such as a plastic film, a lower layer obtained by curing a coating film containing a radiation curable monomer by radiation is provided, and a laminated film such as a laminated film in which an inorganic film is provided on the lower layer by a vacuum film forming method. In the body, there was a problem that foam marks appeared when the coating film as the lower layer was cured by radiation, and the smoothness and coverage of the upper layer (inorganic film) provided on the lower layer were lowered.

  The present invention has been made in view of such circumstances, and a lower layer obtained by curing a coating film containing a radiation curable monomer or oligomer by radiation is provided, and an inorganic film is formed on the lower layer by a vacuum film forming method. It aims at providing the manufacturing method of the laminated body which can suppress the fall of the smoothness of an upper layer (inorganic film) and a coverage in the manufacturing method of the provided laminated body.

  In order to achieve the above object, in order to achieve the above object, the invention described in claim 1 provides a coating film by applying a coating solution containing a radiation curable monomer or oligomer on a substrate. A lower layer is formed by a coating step, a heating step of heat-treating the coating film to dry the solvent in the coating solution, and a curing step of curing the coating film after the heat treatment with radiation, and on the lower layer An upper layer is formed by a vacuum film forming step of forming an inorganic film by a vacuum film forming method, and before the curing step, the coating film on the substrate is passed over a first predetermined time before the curing step, In the curing step, the coating film on the substrate is treated with a second pressure higher than the first pressure for a second predetermined time in the curing step, and in the vacuum film-forming step, Processing at a third pressure lower than the first pressure for a third predetermined time It provides a method for producing a laminate characterized by and.

  The inventor of the present application diligently studied a method capable of suppressing the occurrence of foaming marks when the coating film serving as the lower layer is cured by radiation and suppressing the decrease in the smoothness and coverage of the upper layer (inorganic film). As a result, the pressure conditions in the curing process for curing the lower coating film with radiation, the pressure conditions before the curing process, and the pressure conditions in the vacuum film forming process for providing the upper layer performed after the curing process are as described above. I got the knowledge that it can be solved by being.

  According to claim 1, before the curing step, the coating film on the substrate is processed at the first pressure for a first predetermined time, and in the curing step, the coating film on the substrate is treated for the second predetermined time. The coating film becomes a lower layer by processing at a second pressure higher than the first pressure over a period of time, and processing at a third pressure lower than the first pressure for a third predetermined time in the vacuum film formation step. It is possible to suppress the appearance of foaming marks when the resin is cured by radiation, and to suppress the smoothness of the upper layer (inorganic film) and the decrease in coverage.

  Note that “reducing pressure before the curing step” as used herein may be reduced in the heating step of drying the solvent in the coating solution by heat-treating the lower coating film, and the heating step and the curing step. It means that the pressure may be reduced between.

According to a second aspect of the present invention, in the first aspect, the first predetermined time is 1 to 120 sec, the first pressure is in the range of 5 to 1030 hPa, the second predetermined time is 1 to 120 sec, the second The pressure is in the range of 100 to 1600 hPa, the third predetermined time is in the range of 1 to 120 sec, and the third pressure is in the range of 1 × 10 ^{−5 to 5} hPa.

According to claim 2, before the curing step, the coating film on the substrate is treated at 5 to 1030 hPa for 1 to 120 seconds, and in the curing step, the coating film on the substrate is 5 to 1030 hPa for 1 to 120 seconds. When the coating film that is the lower layer is cured by radiation by processing at a higher 100 to 1600 hPa and processing at 1 × 10 ^{−5 to 5} hPa, which is lower than ^{5 to} 1030 hPa for 1 to 120 seconds in the vacuum film formation step It is possible to suppress the occurrence of foaming marks, and to suppress the smoothness of the upper layer (inorganic film) and the decrease in coverage. A longer decompression time is more effective in suppressing the occurrence of foaming marks, but if it exceeds 120 seconds, it is not preferable because productivity decreases industrially.

  According to a third aspect of the present invention, in the first or second aspect, the curing step is performed in an environment purged with an inert gas.

  According to claim 3, by performing the curing step in an environment purged with an inert gas, the occurrence of foaming marks is further suppressed when the coating film as the lower layer is cured by radiation, and the upper layer (inorganic film) ) Can be suppressed.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the lower layer has a thickness of 100 to 500 nm, and the upper layer has a thickness of 5 to 40 nm.

  The present invention is particularly effective when a laminate having a lower layer thickness of 100 to 500 nm and an upper layer thickness of 5 to 40 nm is produced.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the coating liquid has a degassing step of degassing before coating.

  According to claim 5, by applying a deaeration treatment before applying a coating solution containing a radiation curable monomer or oligomer, it is possible to further suppress the occurrence of foaming marks when cured by radiation. it can.

  A sixth aspect of the invention is characterized in that, in any one of the first to fifth aspects, the lower layer is composed of two or more layers.

  According to claim 6, it is possible to further suppress the occurrence of foaming marks on the surface where the lower layer is in contact with the upper layer by providing the coating film so that the lower layer has two or more layers.

  The invention according to claim 7 is a laminate manufactured by the manufacturing method according to any one of claims 1 to 6.

The invention of claim 8 is characterized in that, in claim 7, the firing marks on the surface of the laminate are 10 μm or less in size, and the number per 1 m ² is 5000 or less.

According to the method for producing a laminate of the present invention, it is possible to provide a laminate in which the firing mark on the surface of the laminate (lower layer) is 10 μm or less and the number per 1 m ² is 5000 or less. it can. Therefore, the smoothness of the upper layer (inorganic film) and a decrease in the coverage can be suppressed.

  The invention of claim 9 is a laminated film characterized in that the substrate of the laminate according to claim 7 or 8 is a film, and the invention of claim 10 is a laminate according to claim 7 or 8. The laminated sheet is characterized in that the body substrate is a sheet.

  The present invention is effective whether the substrate is a film or a sheet.

  According to the present invention, there is provided a lower layer obtained by curing a coating film containing a radiation curable monomer or oligomer by radiation, and an inorganic film is provided on the lower layer by a vacuum film forming method. Moreover, the manufacturing method of the laminated body which can suppress the fall of the smoothness of an upper layer (inorganic film | membrane) and a coverage can be provided.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The present invention will be described with reference to the following preferred embodiments, but can be modified in many ways without departing from the scope of the present invention, and other embodiments than the present embodiment can be used. be able to. Accordingly, all modifications within the scope of the present invention are included in the claims. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to”.

  Hereinafter, the manufacturing method of the laminated body of this invention is demonstrated. In addition, although the case where the base material of a laminated body is a film below is demonstrated, the laminated body of this invention is not limited to a laminated | multilayer film, and the same holds true also when the base material of a laminated body is a sheet | seat.

  In FIG. 1, the conceptual diagram of the laminated | multilayer film manufactured by the manufacturing method of the laminated body of this invention is shown.

  As shown in FIG. 1, the manufacturing method of the present invention forms (forms) an organic film 12 mainly composed of a predetermined polymer on the surface of a base material B (film raw fabric). A laminated film (hereinafter also referred to as a functional film) 10 is manufactured by forming an inorganic film 14 thereon by a vacuum film forming method.

  As an example, the laminate manufacturing method includes an organic film forming apparatus 20 that forms the organic film 12 on the surface of the base material B, and an inorganic film forming apparatus that forms the inorganic film 14 on the organic film 12 (surface). 22 is used to manufacture the laminated film 10.

  FIG. 2A conceptually shows an example of an organic film forming apparatus 20 that performs the method for manufacturing a laminate of the present invention.

  The organic film forming apparatus 20 includes a coating unit 26, a heating unit 28, and a UV irradiation unit 30. A coating solution containing a radiation curable monomer or oligomer prepared in advance is applied to the base material B. Then, the organic film 12 is formed by drying with the heating means 28 and polymerizing with the UV irradiation device 30.

  The organic film forming apparatus 20 forms an organic film by roll-to-roll, and the base material B is loaded on the rotating shaft 32 as a base material roll 40 and is formed in an organic film while being conveyed in the longitudinal direction. The base material Bo formed with an organic film is wound around the winding shaft 34 as a roll 42.

  The base material B sent out from the base material roll 40 is first transported to the coating means 26. In the coating means 26, a coating solution containing a radiation curable monomer or oligomer that becomes the organic film 12 prepared in advance is applied to the surface of the base material B. All the usual liquid application methods can be used for applying the coating liquid.

  The substrate B is then conveyed to the heating means 28. The heating unit 28 dries the solvent in the coating solution applied by the coating unit 26. There is no particular limitation on the heating method of the coating liquid, and the coating liquid can be heated before reaching the UV irradiation device 30 depending on the conveyance speed of the base material B, such as heating with a heater or heating with warm air. Any known heating means can be used.

  Next, the base material B is conveyed to the UV irradiation device 30. In the UV irradiation device 30, the coating solution applied by the coating unit 26 and heated and dried by the heating unit 28 is irradiated with UV (ultraviolet rays) to polymerize a radiation curable monomer or oligomer, thereby forming the organic film 12. Film.

  Next, the base material roll 42 around which the base material B on which the organic film 12 is formed is loaded into the inorganic film forming apparatus 22 as conceptually shown in FIG.

  The inorganic film forming apparatus 22 forms (forms) the inorganic film 14 on the surface of the substrate Bo (that is, the surface of the organic film 12) by a vacuum film forming method, and includes a supply chamber 50, a film forming chamber 52, And a winding chamber 54.

  Similarly to the organic film forming apparatus 20, the inorganic film forming apparatus 22 is an apparatus that performs film formation by roll-to-roll. The inorganic film 14 is formed while the substrate Bo is fed from the base roll 42 and conveyed in the longitudinal direction. The functional film 10 having the organic film 12 and the inorganic film 14 formed thereon is wound into a roll shape by a winding shaft 58.

  The supply chamber 50 includes a rotation shaft 56, a guide roller 60, and a vacuum exhaust unit 61. In the inorganic film forming apparatus 22, the base material roll 42 on which the substrate Bo formed by forming the organic film 12 on the substrate B is wound is loaded on the rotation shaft 56 of the supply chamber 50. When the substrate roll 42 is loaded on the rotating shaft 56, the substrate Bo passes through a predetermined transport path from the supply chamber 50 through the film forming chamber 52 to the winding shaft 58 of the winding chamber 54 ( Sent through). Also in the inorganic film forming apparatus 22, the feeding of the substrate Bo from the base roll 42 and the winding of the functional film 10 on the winding shaft 56 are performed in synchronization, and a long substrate Bo is transferred to a predetermined transport path. The inorganic film 14 is continuously formed on the substrate Bo while being conveyed in the longitudinal direction.

  In the supply chamber 50, the rotating shaft 56 is rotated clockwise in the drawing by a driving source (not shown) to send out the substrate Bo from the base roll 42, and a predetermined path is guided by the guide roller 60 to form the substrate Bo. Send to chamber 52.

  Further, a vacuum exhaust means 61 is disposed in the supply chamber 50, and the inside of the supply chamber 50 is depressurized to a predetermined degree of vacuum (pressure) corresponding to the film formation pressure in the film formation chamber 52. This prevents the pressure in the supply chamber 50 from adversely affecting the pressure (film formation) in the film formation chamber 52. The evacuation unit 61 may be a publicly known one as with the evacuation unit 72 of the film formation chamber 52 described later.

  The guide roller 60 that contacts the organic film 12 in a vacuum is preferably a stepped roller that contacts only the end of the substrate Bo (the end in the direction (width direction) orthogonal to the transport direction).

  In addition to the illustrated members, the supply chamber 50 includes various members (transports) for transporting the substrate Bo along a predetermined path, such as a pair of transport rollers and a guide member that regulates the position in the width direction of the substrate Bo. Means). However, during the formation of the inorganic film 14, the inside of the supply chamber 50 is at a degree of vacuum corresponding to the pressure in the film formation chamber, so that the member that contacts the organic film 12 is the same as the guide roller 60 that is a stepped roller. Suppose that it has the structure which contacts only the edge part of the board | substrate Bo.

  The substrate Bo is guided by the guide roller 60 and transferred to the film forming chamber 52. In the film forming chamber 52, the inorganic film 14 is formed (formed) on the surface of the substrate Bo (that is, the surface of the organic film 12) by a vacuum film forming method. In the illustrated example, the film forming chamber 52 includes a drum 62, film forming means 64 a, 64 b, 64 c, and 64 d, guide rollers 68 and 70, and a vacuum exhaust means 72. In the case where the film formation chamber 52 performs film formation by sputtering, plasma CVD, or the like, the film formation chamber 52 is further provided with a high-frequency power source or the like.

  The substrate Bo is transferred to the film forming chamber 52 from a slit 74 a formed in a partition wall 74 that separates the supply chamber 50 and the film forming chamber 52.

  In addition, the inorganic film forming apparatus 22 in the illustrated example is preferably provided with a vacuum evacuation unit in the supply chamber 50 and the winding chamber 54, and the supply chamber 50 and the winding chamber are arranged according to the film forming pressure in the film forming chamber 52. Although the chamber 54 is also evacuated, the apparatus for carrying out the present invention is not limited to this. For example, the supply amount 50 and the take-up chamber 54 are not provided with a vacuum evacuation unit, and a slit through which the substrate Bo passes can be provided with a minimum size that allows the substrate B to pass through without contacting the substrate B. By doing so, the film forming chamber 52 may be configured to be substantially airtight. Alternatively, the supply chamber 50 and the take-up chamber 54 are provided with a sub-chamber through which the substrate B passes between the supply chamber 50 and the take-up chamber 54 and the film formation chamber 52 without providing a vacuum exhaust means. The sub chamber may be evacuated by a vacuum pump.

  In the case where a sub chamber or the like is provided upstream of the film forming chamber 52 (upstream in the transport direction of the substrate B), when the means for transporting the substrate inside the sub chamber or the like is also in contact with the organic film 12, It is necessary to have a configuration in which only the end portion of the substrate Bo is in contact.

  The drum 62 of the film forming chamber 52 is a cylindrical member that rotates counterclockwise in the drawing around the center line.

  The substrate Bo supplied from the supply chamber 50 and guided along the predetermined path by the guide roller 68 is wound around a predetermined area on the peripheral surface of the drum 62 and is supported / guided by the drum 62 while passing through the predetermined transport path. The inorganic film 14 is formed on the surface (on the organic film 12) by the film forming means 64a to 64d and the like. When the film formation chamber 52 performs film formation by sputtering, plasma CVD, or the like, the drum 62 may be grounded (earthed) so as to act as a counter electrode, or a high-frequency power source. May be connected.

  The film forming means 64a to 64d are for forming the inorganic film 14 on the surface of the base material B by a vacuum film forming method.

  Here, in the manufacturing method of the present invention, the formation method of the inorganic film 14 is not particularly limited, and a known vacuum film formation method (vapor phase deposition) such as CVD, plasma CVD, sputtering, vacuum deposition, ion plating, or the like. Law) is all available.

  Therefore, the film forming means 64a to 64d are configured by various members according to the vacuum film forming method to be performed.

  For example, if the film forming chamber 52 performs the film formation of the inorganic film 14 by ICP-CVD (inductively coupled plasma CVD), the film forming means 64a to 64d include induction coils for forming an induction magnetic field, And a gas supply means for supplying a reaction gas to the film formation region.

  If the film forming chamber 52 is for depositing the inorganic film 14 by the CCP-CVD method (capacitive coupling type plasma CVD), a large number of film forming means 64 a to 64 d are formed on the surface facing the drum 46 in a hollow shape. The high-frequency electrode and the shower electrode acting as the reactive gas supply means are connected to the reactive gas supply source.

  If the film forming chamber 52 is for depositing the inorganic film 14 by the CVD method, the film forming means 64a to 64d are configured to include a reaction gas introducing means and the like.

  Further, if the film forming chamber 52 is for depositing the inorganic film 14 by sputtering, the film forming means 64a to 64d have a target holding means, a high frequency electrode, a sputtering gas supply means, and the like. Is done.

  The vacuum evacuation means 72 evacuates the inside of the film forming chamber 52 so as to obtain a degree of vacuum corresponding to the formation of the inorganic film 14 by a vacuum film forming method.

  There is no particular limitation on the vacuum exhaust means 72, and a vacuum pump such as a turbo pump, a mechanical booster pump, and a rotary pump, an auxiliary means such as a cryocoil, an ultimate vacuum degree and an exhaust amount adjusting means, etc. are used. Various known (vacuum) evacuation means used in vacuum film forming apparatuses can be used.

  The substrate Bo, that is, the functional film 10 on which the inorganic film 14 is formed by the film forming means 64 a to 64 d while being supported / conveyed by the drum 62, is guided to a predetermined path by the guide roller 70, and is conveyed to the winding chamber 54. Then, it is wound up in a roll shape by the winding shaft 58.

  The laminated film roll wound up in a roll is used for the next step.

  Thus, the lower layer (organic film 12) which hardened the coating film containing the radiation curable monomer or oligomer with the radiation was provided, and the laminated body which provided the inorganic film 14 by the vacuum film-forming method on the lower layer was manufactured. In the method, there is a problem that foam marks appear when the lower coating film is cured by radiation, and the smoothness and coverage of the upper layer (inorganic film 14) provided on the lower layer are lowered. .

  Therefore, the present invention provides a coating process in which a coating liquid containing a radiation curable monomer or oligomer is applied on a substrate to provide a coating film, and the coating film is heated to dry the solvent in the coating liquid. A lower layer is formed by a heating step and a curing step in which the coating film after the heat treatment is cured by radiation, and an upper layer is formed by a vacuum film forming step in which an inorganic film is formed on the lower layer by a vacuum film forming method. Before, the coating film on the substrate is treated at a first pressure for a first predetermined time, and in the curing step, the coating film on the substrate is higher than the first pressure for a second predetermined time. In the vacuum film forming process, the second coating is processed at a third pressure lower than the first pressure for a third predetermined time, thereby foaming when the lower coating film is cured by radiation. Suppressing the appearance of marks, smoothness and coverage of the upper layer (inorganic film) It was decided to suppress the bottom. That is, the inventor of the present application applies pressure conditions in a curing process in which a coating film as a lower layer is cured by radiation, pressure conditions before the curing process, and pressure conditions in a vacuum film forming process in which an upper layer is formed after the curing process. However, by being in the above range, it is possible to suppress the appearance of foaming marks when the coating film as the lower layer is cured by radiation, and to suppress the smoothness of the upper layer (inorganic film) and the decrease in coverage. I got the knowledge.

  Note that “reducing pressure before the curing step” as used herein may be reduced in the heating step of drying the solvent in the coating solution by heat-treating the lower coating film, and the heating step and the curing step. It means that the pressure may be reduced between.

Specifically, first, in the heating process by the heating means 28 in the organic film forming apparatus 20 of FIG. 2A, the coating film on the substrate is depressurized at 5 to 1030 hPa for 1 to 120 seconds, or the heating means 28 is used. And a UV irradiating device 30 are provided with a decompression means (not shown), and the coating film on the substrate is decompressed at 5 to 1030 hPa for 1 to 120 seconds by a decompression process by the decompression means. And in the hardening process by UV irradiation apparatus 30, the coating film on a base material is pressure-reduced for 1 to 120 seconds at 100-1600 hPa. Further, in the vacuum film formation step in the film formation chamber 52 of the inorganic film formation apparatus 22 in FIG. 2B, the pressure is reduced at 1 × 10 ^{−5 to 5} hPa for 1 to 120 seconds.

  Here, the pressure reducing method is not particularly limited, and vacuum pumps such as turbo pumps, mechanical booster pumps, and rotary pumps, further auxiliary means such as cryocoils, adjusting means for ultimate vacuum and displacement, etc. are used. Is possible.

  The curing step is preferably performed in an environment purged with an inert gas. By performing the curing process in an environment purged with an inert gas, it suppresses the appearance of foam marks when the coating film that is the lower layer is cured by radiation, and the smoothness and coverage of the upper layer (inorganic film) Can be suppressed.

  In the present invention, the thickness of the lower layer (organic film 12) is preferably 100 to 500 nm, and the thickness of the upper layer (inorganic film 14) is preferably 5 to 40 nm.

  Moreover, it is preferable to perform the deaeration process which deaerates the air in a coating liquid before application | coating liquid. By applying a deaeration treatment before applying the coating solution containing the radiation curable monomer or oligomer, it is possible to further suppress the occurrence of foam marks when cured by radiation.

  In the present invention, it is also preferable that the lower layer (organic film 12) has two or more layers. In order to make the lower layer into two layers, in the organic film forming apparatus 20 shown in FIG. 2 (A), a coating solution containing a radiation curable monomer or oligomer is applied by the coating means 26, and the heating means 28 is used. It is dried and polymerized by the UV irradiation device 30. Further, the organic film forming device 20 applies a coating solution containing a radiation curable monomer or oligomer on the coating film by the coating means 26, and heating means. The organic film 12 is formed by drying at 28 and polymerizing with the UV irradiation device 30. Alternatively, in the organic film forming apparatus 20 ′ shown in FIG. 3, a coating solution containing a radiation curable monomer or oligomer is applied by the coating means 26, dried by the heating means 28, and polymerized by the UV irradiation apparatus 30. On the coating film, a coating solution containing a radiation curable monomer or oligomer is applied by the coating means 26 ′, dried by the heating means 28 ′, and polymerized by the UV irradiation apparatus 30 ′. An organic film 12 composed of layers is formed.

  Thus, by providing the coating film so that the lower layer has two or more layers, it is possible to further suppress the occurrence of foam marks on the surface where the lower layer is in contact with the upper layer.

The laminate manufactured by the method for manufacturing a laminate of the present invention has a surface shot mark of 10 μm or less, and the number of the shot marks on the surface per 1 m ² can be 5000 or less. Accordingly, the smoothness of the upper layer (inorganic film) and the decrease in coverage are suppressed.

  The lower layer (organic film 12) is preferably smooth and has high film hardness. The smoothness of the organic film 12 is preferably 10 nm or less, and more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm square.

The film hardness of the lower layer (organic film 12) preferably has a certain degree of hardness. Preferred hardness, 100 N / mm ² or more is preferable as the indentation hardness as measured by nanoindentation method, 200 N / mm ² or more is more preferable. The pencil hardness is preferably HB or higher, more preferably H or higher.

  In the present invention, the base material B on which the organic film 12 and the inorganic film 14 are formed is not particularly limited, and various organic films described later such as various resin films such as a PET film and various metal sheets such as an aluminum sheet. 12 and various base materials (base films) used for various functional films such as a gas barrier film, an optical film, and a protective film, as long as the inorganic film 14 can be formed by vacuum film formation. All are available.

  Moreover, the base material B may have a surface on which various films such as a protective film and an adhesive film are formed.

  The coating film for forming the organic film 12 is a film containing a radiation curable monomer or oligomer as a main component. Specifically, the monomer or oligomer used is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

  In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  Examples of the photopolymerization initiator or photopolymerization initiator system used include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660 and acyloin described in US Pat. No. 2,448,828. Ether compounds, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3549367, a combination of a triarylimidazole dimer and a p-aminoketone, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, US Pat. No. 4,239,850 Trihalomethyl-triazine compounds described, USA And tri halomethyl oxadiazole compounds as described in Patent No. 4,212,976 A1. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example. The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the coating solution. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. The irradiation energy ^is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 2000 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.

  Examples of a method for forming the organic film 12 include a normal solution coating method, a vacuum film forming method, and the like.

  Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294. It can apply | coat by the extrusion-coating method which uses-.

In addition, acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air. Therefore, in the present invention, when these are used as the organic film 12, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. In addition, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

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

  When manufacturing a protective film for various devices and devices such as a display device such as an organic EL display or a liquid crystal display as a laminated film, a silicon oxide film or the like may be formed as the inorganic film 14.

  Furthermore, when manufacturing an optical film such as a light reflection preventing film, a light reflection film, and various filters as a laminated film, a film made of a material having or expressing the desired optical characteristics is used as the inorganic film 14. A film may be formed.

  Especially, since the inorganic film 14 having excellent gas barrier properties can be formed by the excellent surface smoothness of the organic film 12, the present invention is most suitable for the production of gas barrier films.

  In the manufacturing method of the present invention, the inorganic film 14 is not limited to be formed by using the four film forming units 48a to 48d in the inorganic film forming chamber, and is not more than 3 or 5 or more. May be used to form an inorganic film.

  Furthermore, the inorganic film 14 is not limited to a single layer, and may be a plurality of layers. When a plurality of inorganic films are formed, each layer may be the same or different from each other.

  As mentioned above, although the manufacturing method of the laminated body of this invention was demonstrated in detail, this invention is not limited to the said embodiment, You may perform various improvement and a change in the range which does not deviate from the summary of this invention. Of course.

  For example, as shown in FIG. 2 and FIG. 3, after forming the organic film 12 with the organic film forming apparatus 20, the substrate Bo on which the organic film 12 is formed is wound into a roll to form a substrate roll 42. The embodiment has been described in which the base material roll 42 is loaded into the inorganic film forming apparatus 22 and the base material Bo is sent out from the base material roll 42 to form the inorganic film 14. However, the present invention is not limited thereto. First, the embodiment in which the base film Bo on which the organic film 12 is formed is not wound in a roll shape and the inorganic film 14 is continuously formed as it is is also established.

  Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

  98 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 900 g of methyl ethyl ketone solvent. To the resulting solution, 2 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Fine Chemicals Co., Ltd.) was added, and the mixture was stirred and dissolved to obtain a coating solution.

  The substrate used was a TAC (triacetyl cellulose film) manufactured by Fuji Film Co., Ltd., having a thickness of 80 μm and a width of 200 mm. The running speed of the film was 10 m / min.

After passing through a roll heated to 90 ° C., a coating solution containing a polymerizable compound having the above composition was continuously applied for 50 m with a # 6 wire bar in the coating step. After the coating solution was applied, it was dried at 100 ° C. in the heating step. Next, a UV irradiation apparatus (Light Hammer 10, 240 W / cm, manufactured by Fusion UV Systems) equipped with a D-Bulb having a strong emission spectrum at 350 to 400 nm as a UV light source is used. At 30, UV irradiation was performed at 0.4 W / cm ² and 0.4 J / cm ² for 1 second at a position 5 mm from the focal point to polymerize the polymerizable compound. Then, it stood to cool to room temperature, the elongate film (base material Bo) was obtained, and it wound up.

  In the UV irradiation, nitrogen gas having a purity of 99.9999% was used as an inert gas. The temperature of nitrogen gas was 22 ° C.

  Next, an aluminum oxide film having a thickness of 40 nm was formed as the inorganic film 14 on the organic film 12 by using a sputtering apparatus. The aluminum oxide film used aluminum as a target, argon as a discharge gas, and oxygen as a reaction gas.

  In the laminated film manufactured as described above, the decompression conditions before the curing process, the decompression conditions in the curing process, and the decompression conditions in the vacuum film formation process were tested under the conditions shown in Experiments 1 to 24 in Table 1 below. Went.

  Evaluation was made on foam suppression and film formability of the surface of the laminated film produced under the conditions of Experiments 1 to 24. And comprehensive evaluation was determined from the evaluation result of bubble suppression and film formability. The evaluation results are shown in Table 1.

  For the evaluation of foam suppression, ◎ if there is no trace of foam, ◯ if there is a trace of very weak undulation, and if there is a trace but there was no effect on the aluminum oxide film Δ, the case where the aluminum oxide film was cracked by traces of bubbles was marked with x. Regarding the evaluation of film formability, ◎ if the film could be formed uniformly without defects, ◯ if the film has a partially non-uniform part, ○ Δ, where a defect causing a practical problem occurred is marked with ×. The overall evaluation is ◎ if both evaluations are ◎, ◯ if both evaluations are ○, △ if either evaluation is △, either evaluation is × The thing is set to x, and the thing whose both evaluation is x is set to xx. Further, ◯ △ is an intermediate evaluation between ◯ and △.

  From the above results, the coating step of applying the coating liquid containing the radiation curable monomer or oligomer on the substrate of the present invention to provide the coating film, and the solvent in the coating liquid by heating the coating film By a vacuum film forming process in which a lower layer (organic layer) is formed by a heating process for drying the film and a curing process in which the coating film after the heat treatment is cured by radiation, and an inorganic film is formed on the lower layer by a vacuum film forming method. An upper layer is formed, and the coating film on the substrate is processed at a first pressure for a first predetermined time before the curing step, and the coating film on the substrate is processed for a second predetermined time in the curing step. The overall evaluation becomes Δ or more by processing at the second pressure higher than the first pressure and processing at the third pressure lower than the first pressure for the third predetermined time in the vacuum film forming process. Therefore, according to the present invention, the smoothness of the upper layer (inorganic film) and the decrease in the coverage were suppressed. It can be seen that it is possible to obtain a layer substance.

Further, before the curing step, the coating film on the substrate is depressurized at 5 to 1030 hPa for 1 to 120 sec, and in the curing step, the coating film on the substrate is depressurized at 100 to 1600 hPa for 1 to 120 sec. In the vacuum film-forming step, the overall evaluation becomes ◯ Δ or more by reducing the pressure at 1 × 10 ^{−5 to 5} hPa for 1 to 120 seconds. Therefore, by reducing the pressure within this numerical range, the upper layer (inorganic It can be seen that it is possible to obtain a laminate in which the smoothness of the film) and the decrease in coverage are suppressed.

The figure which shows the laminated | multilayer film manufactured by the manufacturing method of the laminated | multilayer film of this invention The figure which shows an example of the film-forming apparatus which enforces the manufacturing method of the laminated body of this invention The figure which shows another example of the film-forming apparatus which enforces the manufacturing method of the laminated body of this invention

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Laminated film, 12 ... Organic film, 14 ... Inorganic film, 20 ... Organic film-forming apparatus, 22 ... Inorganic film-forming apparatus, 26 ... Application | coating means, 28 ... Drying means, 30 ... UV irradiation apparatus, 52 ... Film-forming chamber , 64a, 64b, 64c, 64d ... film forming means

Claims (10)

A coating step of applying a coating solution containing a radiation-curable monomer or oligomer on a substrate to provide a coating film; a heating step of heating the coating film to dry the solvent in the coating solution; and A lower layer is formed by a curing step of curing the coating film after heat treatment with radiation,
Forming an upper layer by a vacuum film forming step of forming an inorganic film on the lower layer by a vacuum film forming method;
Prior to the curing step, the coating film on the substrate is treated with a first pressure for a first predetermined time,
In the curing step, the coating film on the substrate is treated at a second pressure higher than the first pressure for a second predetermined time,
In the vacuum film-forming step, the laminated body is processed at a third pressure lower than the first pressure over a third predetermined time. The first predetermined time is 1 to 120 seconds, the first pressure is in the range of 5 to 1030 hPa,
The second predetermined time is 1 to 120 sec, the second pressure is in the range of 100 to 1600 hPa,
2. The method for manufacturing a laminate according to claim 1, wherein the third predetermined time is 1 to 120 sec, and the third pressure is in a range of 1 × 10 ^{−5 to 5} hPa.   The method for producing a laminate according to claim 1, wherein the curing step is performed in an environment purged with an inert gas.   The thickness of the said lower layer is 100-500 nm, and the thickness of the said upper layer is 5-40 nm, The manufacturing method of the laminated body of any one of Claims 1-3 characterized by the above-mentioned.   The method for producing a laminate according to any one of claims 1 to 4, wherein the coating liquid has a degassing step of degassing before coating.   The said lower layer is comprised by 2 or more layers, The manufacturing method of the laminated body of any one of Claims 1-5 characterized by the above-mentioned.   A laminate produced by the production method according to any one of claims 1 to 6. 8. The laminate according to claim 7, wherein the firing mark on the surface of the laminate has a size of 10 μm or less, and the number per 1 m ² is 5000 or less.   The laminated film according to claim 7 or 8, wherein the laminate is a film.   A laminate sheet, wherein the substrate of the laminate according to claim 7 or 8 is a sheet.

Images