JP2009269193A - Laminate and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a laminate with a good coverage of an upper layer 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 an inorganic film is formed on the lower layer by a vacuum film forming method. <P>SOLUTION: The laminate is produced through a process (a) in which a coating liquid containing the radiation curable monomer or oligomer is applied on a substrate to form the coating film, the coating film is heated/treated, and an organic layer is formed by radiation-curing the treated coating film, a process (b) for forming the lower layer including at least two organic layers by repeating the process (a), and a process (c) for forming an inorganic layer on the lower layer by the vacuum film forming method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated body and a method for producing the same, and more particularly to a laminated body in which a lower layer is provided on a substrate and an inorganic film is provided on the lower layer by a vacuum film forming method and a method for producing the laminated body.

  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 in which a coating film containing a radiation curable monomer is cured 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 is a problem in that foreign matter adheres to the base material, so that a partial coating failure of the lower layer occurs, and a defect occurs in the upper layer (inorganic film) provided on the lower layer.

  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 is an object of the present invention to provide a method for manufacturing a laminate having a good coverage of the upper layer.

  In order to achieve the above object, in order to achieve the above object, the invention according to claim 1 is applied by applying (a): a coating solution containing a radiation curable monomer or oligomer on a substrate. Providing a film, heat-treating the coating film, curing the heat-treated coating film with radiation, and forming an organic layer; and (b): repeating step (a) to form two or more layers There is provided a method for producing a laminate, comprising: a step of forming a lower layer including an organic layer; and (c): a step of forming an inorganic film on the lower layer by a vacuum film forming method.

  The inventor of the present application diligently studied a method for suppressing the occurrence of defects in the upper layer (inorganic film) provided on the lower layer due to the partial coating failure of the lower layer due to the adhesion of foreign matter to the base material. As a result, a coating solution containing a radiation curable monomer or oligomer is applied, heat-treated to dry the coating film, and radiation-cured after the heat treatment. It was found that the problem can be solved by applying the liquid, heating to dry the coating film, and radiation curing after the heating.

  That is, in the case where the first lower layer is provided, the foreign matter adhering to the base material cannot be completely covered with the coating film, so that there is a possibility that the film defect partially appears. When the second layer is provided on the eye, the smoothness is improved by the first coating layer, so that it becomes easy to cover the partial film defect portion. Therefore, since the inorganic film is provided by the vacuum film formation method on the lower layer where partial film failure does not occur, it is possible to suppress the occurrence of defects in the upper layer (inorganic film).

  According to claim 1, (a): a coating liquid containing a radiation-curable monomer or oligomer is applied on a substrate to provide a coating film, the coating film is heat-treated, and the heat-treated film A step of curing the coating film with radiation to form an organic layer, (b): a step of forming a lower layer including two or more organic layers by repeating step (a), and (c): the lower layer The upper layer (inorganic film) of the laminated body can be suitably formed by the method for producing a laminated body including a step of forming an inorganic film on the surface by a vacuum film forming method. can do.

  The invention of claim 2 is characterized in that, in claim 1, the base material is a film.

  The invention of claim 3 is characterized in that, in claim 2, the coating in step (a) is performed by bar coating or gravure coating, and the coating in step (a) repeated last in step (b) is die coating. To do.

  When the base material is a film, it is effective to remove foreign matters adhering to the base material by applying the coating in the step (a) to the base material by bar coating or gravure coating. And the smoothness of the lower layer which provides an upper layer improves by making application | coating in a process (b) into die application | coating which can apply | coat uniform thickness. Therefore, since it is possible to suppress the appearance of defects due to foreign matters adhering to the base material of the upper layer (inorganic film) formed by the vacuum film forming method, it is possible to obtain a laminated body with a high coverage of the upper layer. Can do.

  According to a fourth aspect of the present invention, in the second or third aspect, the step (a) and the step (b) are performed in series.

  According to the fourth aspect, by forming the lower layer without winding up in the middle of forming the lower layer in the coating apparatus provided with the coating means at two or more locations, foreign matter does not newly adhere to the coating surface. Therefore, it is possible to further suppress the occurrence of partial coating failure in the lower layer.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the lower layer has a thickness of 100 to 1000 nm, and the upper layer has a thickness of 5 to 40 nm.

  The present invention is particularly effective when manufacturing a laminate having a lower layer thickness of 100 to 1000 nm and an upper layer thickness of 5 to 40 nm.

  A sixth aspect of the present invention is a laminated body manufactured by the manufacturing method according to any one of the first to fifth aspects.

A seventh aspect of the invention is characterized in that, in the sixth aspect, the uppermost foreign material in the lower layer has a size of 1000 nm or less, and the number per 1 m ² is 500,000 or less.

According to the method for producing a laminate of the present invention, it is possible to provide a laminate in which the uppermost foreign material in the lower layer has a size of 1000 nm or less and the number per 1 m ² is 500,000 or less. Accordingly, it is possible to suppress a decrease in the coverage of the upper layer (inorganic film).

  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. It is possible to provide a method for producing a laminate having a good coverage of the upper layer.

  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 also holds also about the case where 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 a laminated body is shown.

  As shown in FIG. 1, the manufacturing method of a laminated body forms (forms) the organic film 12 which has a predetermined polymer as a main component on the surface of the base material B (film raw fabric). An inorganic film 14 is formed thereon by a vacuum film forming method to manufacture a laminate (hereinafter also referred to as a laminated film) 10.

  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 implements the method for manufacturing a laminate.

  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 42 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 base material 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 substrate Bo is sent out from the base roll 42, and the inorganic film 14 is transferred while being conveyed in the longitudinal direction. The functional film 10 having the organic film 12 and the inorganic film 14 formed thereon is wound up in 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 in which the base material Bo formed by forming the organic film 12 on the base material 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 conveyance path from the supply chamber 50 through the film forming chamber 52 to the winding shaft 58 of the winding chamber 54. (Passed through). Also in the inorganic film forming apparatus 22, the feeding of the base material Bo from the base material roll 42 and the winding of the functional film 10 on the winding shaft 56 are performed in synchronization with each other to form a long base material Bo in a predetermined manner. The inorganic film 14 is continuously formed on the base material Bo while being transported in the longitudinal direction along the transport path.

  In the supply chamber 50, the rotating shaft 56 is rotated clockwise in the drawing by a driving source (not shown) to feed the substrate Bo from the substrate roll 42, and a predetermined path is guided by the guide roller 60. It is sent to the film formation 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 base material Bo (the end in the direction (width direction) perpendicular to the transport direction).

  In addition to the illustrated members, the supply chamber 50 includes various members for transporting the base material Bo along a predetermined path, such as a pair of transport rollers and a guide member for regulating the position of the base material Bo in the width direction. (Conveying means) may be included. 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 base material Bo.

  The substrate Bo is guided by the guide roller 60 and conveyed to the film forming chamber 52.

  The film forming chamber 52 forms (forms) the inorganic film 14 on the surface of the base material 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 chamber 50 and the winding chamber 54 are not provided with a vacuum evacuation unit, and a slit through which the base material Bo passes can be provided at a minimum without allowing the base material B to pass through the slit. The film forming chamber 52 may be configured to be substantially airtight by setting the size to the above. Alternatively, the supply chamber 50 and the winding chamber 54 are provided with a sub-chamber through which the substrate B passes between the supply chamber 50 and the winding chamber 54 and the film forming 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 formation chamber 52 (upstream in the transport direction of the base material B), the means for transporting the base material in the sub-chamber or the like is also in contact with the organic film 12. Needs to be configured to contact only the end of the base material Bo.

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

  The base material Bo supplied from the supply chamber 50 and guided to a predetermined path by the guide roller 68 is hung around a predetermined area on the peripheral surface of the drum 62 and supported / guided by the drum 62 while being predetermined. The inorganic film 14 is formed on the surface (on the organic film 12) by the film forming means 64a to 64d. 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 units 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 enters the winding chamber 54. It is conveyed and wound into a roll by a 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 in that foreign matter adheres to the base material, so that partial coating failure of the lower layer occurs, and a defect occurs in the upper layer (inorganic film) provided on the lower layer.

  Therefore, the present invention applies a coating solution containing a radiation-curable monomer or oligomer on a substrate to provide a coating film, heat-treats the coating film, and cures the coating film after the heat treatment with radiation. The lower layer consisting of two or more layers was formed by repeating a round of steps, and an inorganic film was formed on the lower layer by a vacuum film formation method.

  The inventor of the present application diligently studied a method for suppressing the occurrence of defects in the upper layer (inorganic film) provided on the lower layer due to the partial coating failure of the lower layer due to the adhesion of foreign matter to the base material. As a result, (a): a coating solution containing a radiation curable monomer or oligomer is applied on a base material to provide a coating film, the coating film is heat-treated, and the heat-treated coating film is cured by radiation. A step of forming an organic layer, (b): a step of forming a lower layer including two or more organic layers by repeating step (a), and (c): an inorganic layer formed by vacuum film formation on the lower layer. The knowledge that it can eliminate by manufacturing a laminated body with the process of forming a film | membrane was acquired.

  If foreign material adheres to the base material, when a lower layer is provided, the foreign material 15 attached to the base material B may not be completely covered with the coating film 12a as shown in FIG. In this case, if an inorganic film is formed on the lower layer by a vacuum film forming method, a defect occurs in the inorganic film (upper layer). Therefore, as shown in FIG. 3B, the coating film 12b is formed by applying the same coating solution once more, and the lower layer 12 is formed to eliminate the film defect. Even if it is provided, defects are less likely to occur in the upper layer (inorganic film).

  Specifically, in the organic film forming apparatus 20 shown in FIG. 2A, a coating solution containing a radiation curable monomer or oligomer as a lower layer is applied twice or more. That is, in the organic film forming apparatus 20 shown in FIG. 2A, a coating solution containing a radiation curable monomer or oligomer is applied by the applying means 26, dried by the heating means 28, and the UV irradiation apparatus 30. In the organic film forming apparatus 20, a coating solution containing a radiation curable monomer or oligomer is applied by the coating means 26, dried by the heating means 28, and then irradiated with UV. The organic film 12 is formed by polymerization using the apparatus 30. The same coating solution is used for the first coating and the second and subsequent coatings, but the solvent composition may be different.

  Further, the first layer (lowermost layer) to the second layer (uppermost layer) are preferably applied in a series as shown in the organic film forming apparatus 20 ′ in FIG. A coating solution containing a radiation curable monomer or oligomer is applied by the coating means 26, dried by the heating means 28, polymerized by the UV irradiation device 30, and the radiation curable monomer is formed on the coating film 12b. Alternatively, the organic film 12 is formed by applying a coating solution containing an oligomer by the coating means 26 ', drying it by the heating means 28', and polymerizing it by the UV irradiation device 30 '. By forming the organic film forming apparatus 20 'without winding it in the middle of the formation of the lower layer, it is possible to prevent foreign matter from newly adhering to the coating surface, and further suppress the partial coating failure of the lower layer. can do.

  Further, the lower layer (organic film) and the upper layer (inorganic film) may be formed in series using the laminated film manufacturing apparatus 24 shown in FIG.

  In the present invention, the thickness of the lower layer (organic film 12) is preferably 100 to 1000 nm, and the thickness of the upper layer (inorganic film 14) is preferably 5 to 40 nm.

In the laminate manufactured by the method for manufacturing a laminate of the present invention, the foreign material in the lowermost upper layer (in the case of two layers, the coating film 12b) has a size of 1000 nm or less, and the number per 1 m ² is 500,000. It can be as follows. Accordingly, a decrease in the coverage of the upper layer (inorganic film) is suppressed.

  As described above, according to the method for producing a laminate of the present invention, a lower layer obtained by curing a coating film containing a radiation curable monomer or oligomer with radiation is provided, and an inorganic layer is formed on the lower layer by a vacuum film forming method. In the method for manufacturing a laminated body provided with a film, a foreign body in the lower layer (organic film) can be suppressed to provide a method for manufacturing a laminated body with a good upper layer coverage.

  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.

  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.

[Comparative example]
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.

[Example]
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 # 3 wire bar in the coating step. After the coating solution was applied, it was dried at 100 ° C. in the heating step. Next, using the ultraviolet irradiation device (Light Hammer 10, 240 W / cm, manufactured by Fusion UV Systems) as a UV light source, 0.4 W / cm ² , 0.4 J at a position of 5 mm from the focal point in the UV irradiation device 30. The polymerizable compound was polymerized by UV irradiation for 1 ^second at / cm ² . Then, it stood to cool to room temperature and wound up the long film. Further, after the long film was heated to 90 ° C. and passed, a coating solution containing a polymerizable compound having the above composition was continuously applied for 50 m with a # 3 wire bar in the coating step. Next, the UV irradiation device is used as a UV light source, and the UV irradiation device 30 is irradiated with UV 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. It was. 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.

(Evaluation)
The surface of the laminated film manufactured under the above conditions is observed by SEM, and the foreign material in the lower layer (organic film 12) of the laminated body has a size of 1000 nm or less and the number per 1 m ² is 500000 or less. Was marked with ◯, and others were marked with ×. The observation results are shown in Table 1.

  As can be seen from the above results, according to the present invention, (a): a coating solution containing a radiation-curable monomer or oligomer is applied on a substrate to provide a coating film, and the coating film is heat-treated, (B): a step of forming a lower layer including two or more organic layers by repeating step (a); c): Since a layered product is produced by the step of forming an inorganic film on the lower layer by a vacuum film forming method, foreign matter in the lower layer can be suppressed, so that the upper layer (inorganic film) has a good coverage. You can get a body.

The figure which shows the laminated film manufactured by the manufacturing method of a laminated film The figure which shows an example of the apparatus which enforces the manufacturing method of a laminated body The figure which shows the laminated | multilayer film manufactured by the manufacturing method of the laminated body of this invention The figure which shows an example of the apparatus which enforces the manufacturing method of the laminated body of this invention The figure which shows another example of the 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, 20 '... Organic film-forming apparatus, 22 ... Inorganic film-forming apparatus, 24 ... Laminated film manufacturing apparatus, 26, 26' ... Coating means, 28, 28 '... drying means, 30, 30' ... UV irradiation device, 52 ... deposition chamber, 64a, 64b, 64c, 64d ... deposition means

Claims (7)

(A): A coating liquid containing a radiation curable monomer or oligomer is applied on a substrate to provide a coating film, the coating film is heat-treated, and the coating film after the heat treatment is cured by radiation. A step of forming an organic layer,
(B): a step of forming a lower layer including two or more organic layers by repeating step (a);
(C): forming an inorganic film on the lower layer by a vacuum film formation method;
The manufacturing method of the laminated body characterized by including.   The method for producing a laminate according to claim 1, wherein the substrate is a film.   The production of a laminate according to claim 2, wherein the coating in the step (a) is performed by bar coating or gravure coating, and the coating in the step (a) repeated last in the step (b) is die coating. Method.   The method for producing a laminate according to claim 2 or 3, wherein the step (a) and the step (b) are performed in series.   The method for producing a laminate according to any one of claims 1 to 4, wherein the lower layer has a thickness of 100 to 1000 nm, and the upper layer has a thickness of 5 to 40 nm.   A laminate produced by the production method according to any one of claims 1 to 5. The layered product according to claim 6, wherein the uppermost foreign material in the lower layer has a size of 1000 nm or less, and the number per 1 m ² is 500,000 or less.

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