JP5522521B2 - Moisture-proof laminate - Google Patents

Description

  The present invention relates to a moisture-proof laminate, and more specifically, a laminate such as a sheet or film for packaging used for food, non-food and pharmaceutical packaging, electronic equipment-related members, etc., and particularly requires high water vapor barrier properties. The present invention relates to a moisture-proof laminate applied to the field.

  In the field of electronic devices that can be made flexible, such as organic devices such as organic EL and electronic paper, and in the medical packaging field, water vapor changes the contents and shortens the product life. There is a need for packaging materials or films having barrier properties.

  In response to such a demand, for example, Patent Document 1 discloses an element main body that has an organic electroluminescent layer between a substrate and a first electrode layer and a second electrode layer and is in contact with one surface side of the substrate. And an organic electroluminescent device having a structure in which an organic layer and an inorganic layer are alternately formed and laminated, and a barrier layer in contact with the surface of the device body opposite to the substrate. . In this organic electroluminescent element, the barrier layer formed of a laminate of an organic layer and an inorganic layer has a function of preventing permeation of moisture and oxygen. Patent Document 2 discloses a gas barrier transparent laminate having a structure in which a transparent plastic substrate having a moisture absorption retention capability is sandwiched between transparent laminates including a vapor-deposited thin film layer.

JP 2003-17244 A (Claims etc.) JP 2006-7565 A (Claims etc.)

  However, the technique described in Patent Document 1 has a drawback that it is not suitable for mass production because it takes time to form a barrier layer and the film cannot be formed at once. Also in the technique described in Patent Document 2, in addition to the fact that the plastic substrate alone cannot arbitrarily control the rate of moisture absorption, when an inorganic moisture absorbent is dispersed in the plastic substrate, In this case, the inorganic moisture absorbent absorbs moisture contained in the water, so that the ability of the inorganic moisture absorbent is not sufficiently exhibited, and it is difficult to control the moisture absorption amount. Furthermore, in the technique described in Patent Document 2, it is necessary to laminate several layers of the plastic substrate in order to obtain a high moisture-proof property, and there is a problem that the laminated body is easily thickened.

  Therefore, the object of the present invention is to solve the above problems, and can be manufactured at a low cost without going through many manufacturing processes, can exhibit a high level of moisture-proof performance with a thin layer, and can control the moisture absorption amount. The object is to provide a moisture-proof laminate that is easy.

  As a result of diligent study, the present inventor made a moisture-proof laminated body having a structure in which a moisture-absorbing layer using a binder resin and a moisture-adsorbing substance having no moisture absorption is sandwiched between vapor-deposited films having high moisture resistance, The inventors have found that the above problems can be solved, and have completed the present invention.

That is, the moisture-proof laminate of the present invention is a moisture-proof laminate having at least two layers of vapor-deposited films, and at least one moisture-absorbing layer sandwiched between the vapor-deposited films,
The moisture-absorbing layer comprises a binder resin having a moisture content of 1% or less, and a moisture-adsorbing substance; and
The vapor-deposited film has an inorganic oxide vapor-deposited film formed by physical vapor deposition and a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are An organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M). A first gas barrier coating film comprising a gas barrier composition comprising at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method; An inorganic oxide vapor-deposited film formed by vapor deposition or chemical vapor deposition, and a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² , M, n, m, and n + m are Represents the same as above) A second gas barrier coating film comprising a gas barrier composition containing at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method; Are formed sequentially,
The moisture-absorbing layer is in the form of a film, and the film-like moisture-absorbing layer and the vapor-deposited film are laminated by dry lamination using an adhesive.

  In the present invention, in place of the second gas barrier coating film, a primer layer made of a composition containing a polyester resin or a polyurethane resin as a main component of the vehicle may be formed.

  In the present invention, the moisture adsorbing substance of the moisture absorption layer is at least one selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, sulfates, metal halides, perchloric acid, and organic substances. A chemical moisture-adsorbing substance consisting of Furthermore, it is preferable that the weight ratio of the binder resin and the moisture adsorbing substance in the moisture absorption layer is 80 to 40 parts by mass of the moisture adsorbing substance with respect to 20 to 60 parts by mass of the binder resin.

  According to the present invention, by using a binder resin having a moisture content of 1% or less in the moisture absorption layer, the moisture absorption capability of the moisture absorption layer can be controlled, and the moisture absorption layer is sandwiched between vapor deposition films having high moisture resistance. By adopting the configuration, it is possible to realize a moisture-proof laminate that can be manufactured at low cost without passing through many manufacturing steps and that can exhibit a high level of moisture-proof performance with a thin layer.

It is typical sectional drawing which shows one structural example of the moisture-proof laminated body of this invention. It is typical sectional drawing which shows one structural example of the vapor deposition film which concerns on this invention. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the present invention, the following description shows an example of the embodiment, and it goes without saying that the present invention is not limited thereto.
The moisture-proof laminate of the present invention has a structure in which at least two vapor-deposited films are provided, and at least one moisture-absorbing layer is sandwiched between the layers. In FIG. 1, typical sectional drawing which shows the example of 1 structure of the moisture-proof laminated body of this invention is shown.

  The moisture-proof laminated body 10 of an example of this invention shown in figure has the laminated structure which consists of two layers of the vapor deposition films 1, and the 1 layer of moisture absorption layer 2 pinched | interposed between the layers. Among these, the moisture absorption layer 2 has substantially no hygroscopicity, specifically, a binder resin having a moisture content of 1% or less and a moisture adsorbing substance, and the deposited film 1 is shown in FIG. As described above, on one surface of the substrate 3, an inorganic oxide vapor-deposited film 4 by physical vapor deposition, a first gas barrier coating film 5, and inorganic by physical vapor deposition or chemical vapor deposition are used. An oxide vapor deposition film 6 and a second gas barrier coating film 7 are sequentially formed. The vapor deposition film 1 sandwiches the moisture absorption layer 2 so that the base material 3 is on the outside air side. In the present invention, by using the binder resin having no hygroscopicity in the moisture absorbing layer 2 as described above, the moisture absorbing ability of the moisture absorbing layer 2 can be controlled, and the moisture absorbing layer 2 has high moisture resistance. It was possible to obtain a moisture-proof laminate that can exhibit a high level of moisture-proof performance even with a thin layer by being sandwiched between the vapor-deposited films 1. Moreover, the moisture-proof laminated body of this invention also has the advantage that it can be manufactured by a simpler and low-cost process compared with the past.

The vapor-deposited film 1 used in the present invention has extremely high moisture-proof performance due to the above configuration. Hereinafter, the structure of this vapor deposition film 1 is demonstrated in detail. The vapor-deposited film 1 according to the present invention has an inorganic oxide vapor-deposited film 4 by a physical vapor deposition method and a general formula R ¹ _n M (OR ² ) _m (where, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. The first gas barrier comprising a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Coating film 5, inorganic vapor-deposited film 6 by physical vapor deposition or chemical vapor deposition, and general formula R ¹ _n M (OR ² ) _m (wherein R ¹ , R ² , M, n, m and n + m are the same as above. And a second gas barrier by a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. The conductive coating film 7 is sequentially formed.

The said vapor deposition film 1 which concerns on this invention is produced as follows. That is, first, a plasma-treated surface with an inert gas is provided on one surface of the substrate 3, and an inorganic oxide vapor deposition film 4 is formed on the plasma-treated surface by physical vapor deposition. Next, an oxygen gas plasma treatment surface is provided on the surface of the inorganic oxide vapor-deposited film 4, and at least one kind represented by the general formula R ¹ _n M (OR ² ) _m is formed on the plasma treatment surface. The first gas barrier coating film 5 is provided using a gas barrier composition containing the above alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method. . Next, an inorganic oxide vapor deposition film 6 formed by physical vapor deposition or chemical vapor deposition is provided on the surface of the first gas barrier coating film 5, and oxygen vapor is deposited on the inorganic oxide vapor deposition film 6. A plasma-treated surface with gas is provided, and at least one alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a polyvinyl alcohol-based resin, and / or ethylene A second gas barrier coating film 7 containing a vinyl alcohol copolymer and made of a gas barrier composition obtained by polycondensation by a sol-gel method is provided.

  In the vapor deposition film 1 according to the present invention, a primer layer made of a composition containing a polyester resin or a polyurethane resin as a main component of the vehicle may be provided in place of the second gas barrier coating film 7. Also in this case, it is possible to obtain a vapor-deposited film with extremely high moisture resistance, and the desired effect of the present invention is achieved.

  Further, in the vapor deposition film 1, a plasma treatment surface by an inert gas is provided on the surface of the first gas barrier coating film 5, and a physical vapor deposition method or a chemical vapor deposition method is formed on the plasma treatment surface. It is also possible to provide a vapor-deposited film 6 of inorganic oxide. Also in this case, instead of the second gas barrier coating film 7, a primer agent layer made of a composition containing a polyester resin or a polyurethane resin as a main component of the vehicle may be provided.

  The base material 3 of the vapor deposition film 1 is a basic material constituting the vapor deposition film 1, and is a base material that holds a vapor deposition film of an inorganic oxide or a gas barrier coating film. Resin films or sheets that can withstand conditions such as formation and processing of vapor-deposited films and the like and that can satisfactorily hold them without impairing their characteristics can be used. Specifically, for example, polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins) ), Poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylon resins, polyurethane resins, acetal resins, and cellulose resins Any film or sheet can be used. In the present invention, among the above-described resin films or sheets, it is particularly preferable to use a polyester resin, polyolefin resin, or polyamide resin film or sheet.

  In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, such as extrusion method, cast molding method, T-die method, cutting method, inflation method, etc. Using the film forming method, a method of forming the above various resins alone, or a method of forming a multilayer co-extrusion film using two or more resins, and further using two or more resins, Various resin films or sheets are manufactured by a method of mixing and forming before forming a film, and further, for example, using a tenter method, a tubular method, etc. Various resin films or sheets formed by stretching in the direction can be used. In the present invention, the film thickness of various resin films or sheets is preferably 6 to 200 μm, more preferably 9 to 100 μm.

  In forming a film using one or more of the above-mentioned various resins, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release, etc. Various plastic compounding agents and additives can be added for the purpose of improving or modifying the property, flame retardancy, antifungal property, electrical properties, strength and the like. The addition amount can be any amount from a very small amount to several tens of percent depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

  In the present invention, the plasma treatment surface with an inert gas is provided on one surface of the substrate 3 and the surface of the first gas barrier coating film 5, and the substrate 3 and physical vapor deposition are provided. Close adhesion between the inorganic oxide vapor-deposited film 4 by the method, or between the first gas barrier coating film 5 and the inorganic oxide vapor-deposited film 6 by physical vapor deposition or chemical vapor deposition In order to prevent the occurrence of delamination and the like, the tight adhesion between the layers is improved and the layers are firmly adhered to each other.

  Such a plasma-treated surface with an inert gas can be formed by using a plasma surface treatment method or the like that performs surface modification using a plasma gas generated by ionizing a gas by arc discharge. That is, in the present invention, the plasma processing surface can be formed by performing the plasma processing by the plasma surface processing method using an inert gas such as nitrogen gas, argon gas, helium gas as the plasma gas. In the present invention, as the plasma gas, a mixed gas obtained by adding oxygen gas to the above inert gas can also be used.

  In the present invention, when forming a plasma-treated surface with an inert gas, an inorganic oxide vapor-deposited film by physical vapor deposition is used on one surface of the substrate, or the first gas barrier coating film. It is preferable to perform in-line plasma treatment immediately before forming a vapor-deposited film of an inorganic oxide by physical vapor deposition or chemical vapor deposition on the surface, whereby the substrate or the first gas barrier property can be obtained. It is possible to remove moisture, dust and the like on the surface of the coating film and to smoothen and activate the surface.

  Furthermore, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of the conditions such as the plasma output, the kind of plasma gas, the supply amount of the plasma gas, the treatment time, etc. Furthermore, in the present invention, as a method for generating plasma, for example, devices such as direct current glow discharge, high frequency discharge, microwave discharge, etc. can be used.

  Next, the vapor deposition film of the inorganic oxide by the physical vapor deposition method according to the present invention is formed on the plasma-treated surface with an inert gas provided on one surface of the substrate 3 or the first gas barrier coating film 5. (When the plasma processing surface by an inert gas is provided on the surface of the first gas barrier coating film 5, it is provided on the plasma processing surface). Such a vapor deposition film can be composed of not only a single layer film composed of one layer but also a multilayer film composed of two or more layers, such as a vacuum deposition method, a sputtering method, an ion plating method, an ion cluster beam method, etc. It can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method). Specifically, for example, a vacuum deposition method in which a metal or a metal oxide is used as a raw material, heated and vaporized, and vapor-deposited on a plasma-treated surface with an inert gas provided on one surface of the substrate, An oxidation reaction deposition method in which a metal or a metal oxide is used as a raw material, oxygen is introduced and oxidized to deposit on a plasma-treated surface with an inert gas provided on one side of the substrate, and an oxidation reaction is performed by plasma. A vapor deposition film can be suitably formed using a plasma-assisted oxidation reaction vapor deposition method or the like that is subsidized by the above. In this case, as a heating method for the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.

  Hereinafter, a method for forming a vapor-deposited film of an inorganic oxide by the physical vapor deposition method will be described with specific examples. FIG. 3 is a schematic configuration diagram illustrating an example of a take-up vacuum deposition apparatus. As shown in the drawing, in this case, first, in the vacuum chamber 32 of the take-up type vacuum vapor deposition apparatus 31, the substrate 1 having a plasma treatment surface with an inert gas on one surface is fed out from the unwinding roll 33, and then The fed substrate 1 is guided to the cooled coating drum 35 via a guide roll 34 or the like as necessary. Here, in the present invention, as shown in the figure, for example, a magnetron sputtering device 45 for performing plasma treatment or the like is disposed between the guide roll 34 and the cooling coating drum 35, and the Before the material 1 is fed out and the fed substrate 1 is guided to the cooling coating drum 35, plasma treatment with an inert gas is performed on one surface of the substrate 1 to form a plasma treatment surface in-line. You can also.

  Thereafter, vapor deposition heated by irradiating an electron beam 38 with, for example, an electron gun 37 on a plasma-treated surface with an inert gas provided on one surface of the substrate 1 guided on the cooling coating drum 35. A source 39, for example, metal aluminum, aluminum oxide or the like is evaporated in the crucible 36, and if necessary, oxygen gas from an oxygen gas cylinder 40 disposed outside the take-up vacuum deposition apparatus 31 from an oxygen gas outlet 41. For example, a vapor deposition film of an inorganic oxide such as aluminum oxide is formed through the mask 42 while jetting and the like. Next, the base material 1 on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is sent out through a guide roll 43 or the like, if necessary, and taken up on a take-up roll 44. The base material 1 which further provided the vapor deposition film | membrane of the inorganic oxide on the plasma processing surface by the provided inert gas can be obtained. In the above, the vapor deposition source 39 is heated by an electron beam heating method (EB) or the like in which an electron beam 38 is irradiated by an electron gun 37 or the like.

  In the present invention, the one side of the substrate 1 is subjected to plasma treatment with an inert gas by the magnetron sputtering apparatus 45 or the like to form a plasma treatment surface in-line, via the plasma treatment surface, The adhesion between the base material and the deposited film of the inorganic oxide can be improved. Alternatively, after forming the inorganic oxide vapor-deposited film, the surface of the deposited inorganic oxide vapor-deposited film is subjected to plasma treatment with oxygen gas or the like to form a plasma-treated surface in-line. Alternatively, the adhesion with the second gas barrier coating film can be improved. Furthermore, in the present invention, using the above-described winding type vacuum vapor deposition apparatus, first, a vapor deposition film of the first layer of inorganic oxide is formed, and then the vapor deposition of this inorganic oxide is performed in the same manner. An inorganic oxide vapor deposition film is further formed on the film, or by using the above-described winding-type vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is also possible to form a vapor-deposited film of an inorganic oxide composed of two or more multilayer films.

  Note that the same procedure as described above can be applied to the case where the vapor deposition film is provided on the surface of the first gas barrier coating film 5 or the plasma treatment surface with an inert gas provided on the surface.

  In the present invention, the inorganic oxide vapor deposition film can be basically used as long as it is a thin film on which a metal oxide is vapor-deposited. For example, silicon (Si), aluminum (Al), magnesium (Mg) Of metals such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) It is possible to use a deposited film of a product. Among these, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) is preferable. Moreover, in this invention, the vapor deposition film | membrane of the inorganic oxide which mixed the metal or the oxide of a metal by 1 type, or 2 or more types of mixtures by dissimilar material can also be comprised.

The metal oxide vapor-deposited film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and its notation is, for example, SiO _X , AlO _X , MgO. MO X _(in the formula, M represents a metal element, the value of X, each range differs by the metal element) as _X, etc. represented by. As the range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) ) Is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, titanium (Ti) is 0 to 2, lead ( Pb) can take values ranging from 0 to 1, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. Further, in the above, when X = 0, it is a complete metal and is not transparent and cannot be used at all. In addition, the upper limit of the range of X is a completely oxidized value. In the present invention, generally, examples other than silicon (Si) and aluminum (Al) are scarce, silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5 to 1. A value in the range of .5 can be preferably used.

  In the present invention, the thickness of the vapor-deposited film of the inorganic oxide varies depending on the metal to be used or the kind of the metal oxide, but is, for example, in the range of 50 to 2000 mm, preferably 100 to 1000 mm. It can be arbitrarily selected and formed.

  Next, the oxygen-treated plasma-treated surface in the present invention is the surface of the inorganic oxide vapor-deposited film 4 by physical vapor deposition or the inorganic oxide vapor-deposited film by physical vapor deposition or chemical vapor deposition. 6, which is provided in close contact between the vapor-deposited film 4 of the inorganic oxide and the first gas barrier coating film 5 by physical vapor deposition, or by physical vapor deposition or chemical vapor. By improving the close adhesion between the vapor-deposited film 6 of the inorganic oxide by the phase growth method and the second gas barrier coating film 7 or the primer layer, the layers are firmly adhered, and delamination (delamination) ) And the like.

  In the present invention, the plasma-treated surface with oxygen gas is subjected to surface modification using plasma gas generated by ionizing the gas by arc discharge, like the plasma-treated surface with inert gas described above. It can be formed using a processing method or the like. In this case, as the plasma gas, oxygen gas or a mixed gas of oxygen gas and an inert gas such as nitrogen gas, argon gas, helium gas, or the like can be used.

  Further, in the present invention, the plasma treatment surface with oxygen gas is immediately after the inorganic oxide vapor deposition film formed by physical vapor deposition is formed on the plasma treatment surface with an inert gas provided on one surface of the substrate, or Immediately after forming an inorganic oxide vapor deposition film by physical vapor deposition or chemical vapor deposition on the surface of the first gas barrier coating film, these inorganic oxide vapor deposition films by physical vapor deposition, or It can also be formed by performing in-line plasma discharge treatment with oxygen gas on the surface of the deposited inorganic oxide film by physical vapor deposition or chemical vapor deposition.

  Furthermore, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of the conditions such as the plasma output, the kind of plasma gas, the supply amount of the plasma gas, the treatment time, etc. Furthermore, in the present invention, as a method for generating plasma, for example, devices such as direct current glow discharge, high frequency discharge, microwave discharge, etc. can be used.

Next, the first or second gas barrier coating film according to the present invention will be described. As described above, the first or second gas barrier coating film has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms). M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and polyvinyl alcohol And a gas barrier composition obtained by polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. It is formed. Therefore, the first or second gas barrier coating film is prepared by preparing the gas barrier composition and then applying the composition on the vapor-deposited film of the inorganic oxide by the physical vapor deposition method or the physical vapor deposition. On the inorganic oxide vapor-deposited film by the chemical vapor deposition method or the chemical vapor deposition method, a coating film is provided by coating through a plasma-treated surface with oxygen gas, and then in the range of 20 ° C. to 180 ° C. and above It can form by heat-processing for 10 second-10 minutes at the temperature below melting | fusing point of a base material.

  In the present invention, the first or second gas barrier coating film may be formed by applying the gas barrier composition on an inorganic oxide vapor-deposited film by the physical vapor deposition method, or by the physical vapor deposition method or After coating a vapor-deposited film of an inorganic oxide by a chemical vapor deposition method through a plasma-treated surface with oxygen gas and stacking two or more coating films, heat treatment similar to the above is performed, and 2 It may be formed as a composite polymer layer having multiple layers.

Here, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. Further, as the partial hydrolyzate of the alkoxide, it is not necessary that all of the alkoxy groups are hydrolyzed, and one or more hydrolyzed ones and a mixture thereof may be used. As the hydrolysis condensate, a dimer or more of a partially hydrolyzed alkoxide, specifically, a 2 to 6 mer can be used.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , examples of the metal atom represented by M include silicon, zirconium, titanium, aluminum, and the like. Can include, for example, silicon. Furthermore, in this invention, the alkoxide of 2 or more types of different metal atoms can also be mixed and used in the same solution. Furthermore, specific examples of the organic group represented by R ¹ in the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group and n-octyl group. Furthermore, specific examples of the organic group represented by R ² in the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, methyl group, ethyl group, n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like can be mentioned. In the present invention, these alkyl groups contained in the same molecule may be the same or different.

From the above, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si. Such alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group). Here, as Ra, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or the like is used. Specific examples of the alkoxysilane include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉ ) ₄ or the like can be used.

In the present invention, the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m is represented by the general formula Rb _n Si (ORc) _4-m (where n represents an integer of 0 or more). M represents an integer of 1 to 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, and an n-butyl group). Specific examples of the alkylalkoxysilane include, for example, methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si ( OCH _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) can be used ₂ or the like. In addition, said alkoxysilane, alkyl alkoxysilane, etc. can be used individually or in mixture of 2 or more types. Furthermore, the polycondensation product of the said alkoxysilane can also be used in this invention, Specifically, a polytetramethoxysilane, a polytetraethoxysilane, etc. can be mentioned, for example.

Furthermore, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a zirconium alkoxide in which M is Zr can also be used. Specific examples of the zirconium alkoxide include, for example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n Butoxyzirconium Zr (OC ₄ H ₉ ) _{4 and the} like can be mentioned.

Furthermore, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can also be used. Specific examples of such titanium alkoxides include, for example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra n Butoxytitanium Ti (OC ₄ H9) _{4 and the} like can be mentioned.

Furthermore, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can also be used. Specific examples of the aluminum alkoxide include, for example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum Al (OC ₂ H ₅ ) ₄ , tetraisopropoxyaluminum Al (iso-OC ₃ H ₇ ) ₄ , tetra n Butoxy aluminum Al (OC ₄ H ₉ ) _{4 and the} like can be mentioned.

  In the present invention, the alkoxide may be used in combination of two or more. In particular, by using a mixture of alkoxysilane and zirconium alkoxide, it is possible to improve the toughness, heat resistance, and the like of the obtained deposited film. The amount of zirconium alkoxide used in this case can be in the range of 10 parts by mass or less, preferably about 5 parts by mass, with respect to 100 parts by mass of alkoxysilane. When the amount of zirconium alkoxide used exceeds 10 parts by mass, the formed gas barrier coating film is likely to be gelled, and the brittleness of the film is increased, so that the gas barrier coating film is liable to peel off. .

  Further, in the present invention, by using a mixture of alkoxysilane and titanium alkoxide, there is an advantage that the heat conductivity of the obtained gas barrier coating film is lowered and the heat resistance of the deposited film is remarkably improved. The amount of titanium alkoxide used in this case can be in the range of 5 parts by mass or less, preferably about 3 parts by mass with respect to 100 parts by mass of the alkoxysilane. If the amount of titanium alkoxide used exceeds 5 parts by mass, the brittleness of the gas barrier coating film to be formed becomes large and the gas barrier coating film is liable to peel off, which is not preferable.

  Next, as the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer for forming the first or second gas barrier coating film, the polyvinyl alcohol resin or the ethylene / vinyl alcohol copolymer is used alone. Each of them can be used, and a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, by using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, physical properties such as gas barrier properties, water resistance, and weather resistance of the obtained gas barrier coating film can be remarkably improved. . In particular, by using a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, in addition to the above physical properties such as gas barrier properties, water resistance and weather resistance, hot water resistance and gas barrier properties after hydrothermal treatment It is possible to form a gas barrier coating film that is remarkably excellent.

  In the present invention, a coating layer formed of a gas barrier composition containing the polyvinyl alcohol resin, a coating layer formed of a gas barrier composition containing an ethylene / vinyl alcohol copolymer, and The coating layer formed of a gas barrier composition containing a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer may be appropriately laminated with a plurality of layers.

  In the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio is, as a weight ratio, polyvinyl alcohol-based resin: ethylene / vinyl alcohol copolymer = 10: 0. 0.05 to 10: 6 is preferable, and a blending ratio of about 10: 1 is more preferable.

  In the present invention, the content of the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer can be in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. Is about 20 to 200 parts by mass. When the content of the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer exceeds 500 parts by mass, the brittleness of the gas barrier coating film increases, and the water resistance and weather resistance of the obtained vapor-deposited film also decrease. On the other hand, if it is less than 5 parts by mass, the gas barrier properties are lowered, which is not preferred.

  In the present invention, as the polyvinyl alcohol resin, those obtained by saponifying polyvinyl acetate can be generally used. Such polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetic acid groups remain, fully saponified polyvinyl alcohol resins in which no acetic acid groups remain, or modified polyvinyl alcohols in which OH groups have been modified. Alcohol-based resins may be used and are not particularly limited. Specific examples of such polyvinyl alcohol resins include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (ken) Degree of conversion = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer is used. be able to. Specific examples include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which acetic acid groups remain only a few mol% or no acetic acid groups remain. However, the saponification degree preferable from the viewpoint of gas barrier properties is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. Furthermore, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, particularly 20 to 45 mol%. It is preferable to do. Specific examples of such an ethylene / vinyl alcohol copolymer include Eval EP-F101 (ethylene content; 32 mol%) manufactured by Kuraray Co., Ltd., and Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. %) Etc. can be used.

  In preparing the gas barrier composition according to the present invention, for example, a silane coupling agent or the like can be added. As such a silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used, and an organoalkoxysilane having an epoxy group is particularly suitable. Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. . The silane coupling agent may be used alone or in combination of two or more. In this invention, the usage-amount of the said silane coupling agent can be in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. When the amount of the silane coupling agent used exceeds 20 parts by mass, the gas barrier coating film to be formed tends to have increased rigidity and brittleness, and the insulating property and workability of the gas barrier coating film tend to decrease. It is not preferable.

  As the sol-gel method catalyst used in the gas barrier composition, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used, and N, N-dimethylbenzylamine is particularly preferable. The amount used is preferably 0.01 to 1.0 part by mass, particularly about 0.03 part by mass, per 100 parts by mass of the total amount of alkoxide and silane coupling agent. The acid used in the gas barrier composition is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent, or the like. Examples of such acids include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid. The amount of the acid used is 0.001 to 0.05 mol, particularly about 0.01 mol, relative to the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety). preferable.

  In the gas barrier composition, water in the range of 0.1 to 100 mol, preferably 0.8 to 2 mol can be used with respect to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density. It becomes. Such a porous polymer is not preferable because the gas barrier property of the deposited film cannot be improved. On the other hand, if the amount of water is less than 0.8 mol, the hydrolysis reaction is difficult to proceed, which is not preferable.

  Furthermore, as an organic solvent used for the said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol etc. can be used, for example. Here, in the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in a state of being dissolved in a coating solution containing the alkoxide or the silane coupling agent. Therefore, the type of the organic solvent is appropriately selected. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, n-butanol is preferably used. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (trade name) can be used. The amount of the organic solvent used is usually 30 parts per 100 parts by mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. It is -500 mass parts.

  The gas barrier coating film according to the present invention is specifically formed as follows, for example. That is, first, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a metal An alkoxide or the like is mixed to prepare a gas barrier composition (coating liquid). Here, in this gas barrier composition (coating liquid), a polycondensation reaction gradually proceeds. Next, according to a conventional method, the gas barrier composition (coating liquid) is applied on an inorganic oxide vapor-deposited film or the like formed on one surface of the substrate by a conventional method and dried. As a result, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer proceeds, and a coating film is formed. Preferably, the above coating operation is further repeated to laminate a plurality of coating films composed of two or more layers. Finally, the substrate coated with the above-described coating liquid is at a temperature of about 20 ° C. to 180 ° C. and below the melting point of the substrate, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to Heat treatment is performed for 10 minutes, and a gas barrier coating film of the above gas barrier composition is formed in one layer or two or more layers on an inorganic oxide vapor deposition film or the like formed on one surface of the substrate. be able to. The vapor-deposited film of the present invention having a gas barrier coating film formed in this manner is extremely excellent in gas barrier properties.

  The operation of the gas barrier coating film forming method according to the present invention will be described with reference to an example in which alkoxysilane is used as the alkoxide. First, the alkoxysilane and the metal alkoxide are hydrolyzed by the added water. . At that time, the acid serves as a catalyst for hydrolysis. Next, protons are taken from the generated hydroxyl groups by the action of the sol-gel catalyst, and hydrolyzed products are dehydrated and polycondensed. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group. In addition, due to the action of the base catalyst, ring opening of the epoxy group also occurs and a hydroxyl group is generated. Furthermore, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. Furthermore, since the reaction system includes a polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the coalescence also occurs. The polycondensate produced is, for example, a composite polymer containing an inorganic part composed of a bond such as Si-O-Si, Si-O-Zr, Si-O-Ti, and an organic part derived from a silane coupling agent. Configure. In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and having a portion derived from a silane coupling agent is first formed. This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. This OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel catalyst (base catalyst), and then polycondensation proceeds. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—: It is considered that a composite polymer having a Si bond, for example, represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

  The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition (coating liquid) increases during preparation. When this gas barrier composition (coating liquid) is applied onto a vapor-deposited film of an inorganic oxide provided on one surface of the substrate, and heated to remove the solvent and the alcohol produced by the polycondensation reaction, The polycondensation reaction is completed, and a transparent coating layer is formed. When a plurality of coating layers are laminated, the composite polymers in the interlayer coating layers are also condensed, and the layers are firmly bonded to each other. Moreover, since the organic reactive group in the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the inorganic oxide vapor-deposited film and the like, the surface of the inorganic oxide vapor-deposited film and the like Adhesiveness and adhesion with the coating layer are also good.

  In the method of the present invention, the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.5 mol, relative to 1 mol of the alkoxide, so that the linear polymer described above is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular cohesive energy is high. Since the chain rigidity is also high, good gas barrier properties are exhibited.

  In the present invention, the inorganic oxide vapor-deposited film and the like and the first or second gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction. And the adhesiveness between these improves and it can exhibit the effect of a more favorable gas barrier property by the synergistic effect of these two layers.

  Examples of the method for applying the gas barrier composition include application means such as a roll coat such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator and the like once or a plurality of times. With this coating, a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed. Further, condensation is carried out by heating and drying at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C., for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, under a normal environment. In other words, the first or second gas barrier coating film can be formed. Furthermore, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied in advance on the inorganic oxide vapor-deposited film, if desired, before corona discharge treatment or plasma treatment. Processing can also be performed arbitrarily.

  Next, the inorganic oxide deposited film formed by the chemical vapor deposition method according to the present invention will be described. The vapor deposition film of the inorganic oxide by the chemical vapor deposition method is the surface of the first gas barrier coating film described above (in the case of providing a plasma treatment surface with an inert gas on the surface of the first gas barrier coating film, For example, a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like. In addition to a single layer film composed of one layer, a multilayer film composed of two or more layers can also be used.

  Specifically, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material on the surface of the first gas barrier coating film, etc., and an inert gas such as argon gas or helium gas is used as a carrier gas. A vapor deposition film of an inorganic oxide such as silicon oxide is formed using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. As the low-temperature plasma generator, for example, generators such as high-frequency plasma, pulse wave plasma, and microwave plasma can be used. In particular, in order to obtain a highly active and stable plasma, generation by a high-frequency plasma method is possible. It is preferred to use an apparatus.

  Hereinafter, a method for forming a vapor-deposited film of an inorganic oxide by the low-temperature plasma chemical vapor deposition method will be described with a specific example. FIG. 4 is a schematic configuration diagram showing an example of a low-temperature plasma chemical vapor deposition apparatus. The illustrated plasma chemical vapor deposition apparatus 51 includes a supply chamber 52 for supplying a substrate, a pretreatment chamber 53, a film forming chamber 54, a post treatment chamber 55, and a winding chamber 56 for winding the substrate after film formation. Etc. In the present invention, first, the base material provided with the first gas barrier coating film or the like wound around the unwinding roll 57 is guided to the pretreatment chamber 53 via the guide roll 58 or the like. Thereafter, in the pretreatment chamber 53, for example, a magnet 59 or the like is used as necessary to generate plasma, and plasma discharge treatment or the like is performed while supplying plasma gas from the gas supply chamber 60 through the gas supply pipe 61. Then, a pretreatment such as forming a plasma treatment surface on the surface of the first gas barrier coating film is performed.

  Next, the base material is guided to the film forming chamber 54 via the auxiliary rolls 62, 63 and the like, and is conveyed onto the peripheral surface of the cooling / electrode drum 64 at a predetermined speed. Then, while supplying a vapor deposition monomer gas such as an organosilicon compound, oxygen gas, inert gas, etc. from the raw material volatilization supply device 65 and the gas supply device 66, etc. The mixed gas composition for vapor deposition is introduced into the film forming chamber 54 kept in a vacuum through the supply nozzle 67, and the first gas barrier coating of the substrate conveyed on the peripheral surface of the cooling / electrode drum 64 is performed. Plasma is generated by glow discharge plasma 68 on the film or the like, and irradiated with this to form a deposited film of an inorganic oxide such as silicon oxide. At this time, a predetermined power is applied to the cooling / electrode drum 64 from a power source (not shown) arranged outside the film forming chamber 54, and in the vicinity of the cooling / electrode drum 64, A magnet 69 or the like is arranged to promote the generation of plasma.

  Next, the base material on which the deposited film of inorganic oxide such as silicon oxide is formed is guided to the post-treatment chamber 55 through the guide rolls 70 and 71 and the like. Thereafter, in the post-processing chamber 55, as described above, for example, a magnet 72 or the like is used to generate plasma as necessary, and the plasma is supplied from the gas supply chamber 73 through the supply pipe 74 while supplying plasma gas. After performing a discharge treatment or the like, a post-treatment such as forming a plasma treatment surface on the surface of the vapor-deposited film of the inorganic oxide is performed. Next, a vapor-deposited film of an inorganic oxide such as silicon oxide is formed as described above, and a base material whose surface is post-treated as necessary is guided to a winding chamber 56 via a guide roll 75 or the like. Thereafter, the base material is taken up on the take-up roll 76 in the take-up chamber 56, whereby an inorganic oxide vapor deposition film can be formed by the plasma chemical vapor deposition method. Although not shown, the plasma chemical vapor deposition apparatus 51 is equipped with a vacuum pump or the like, thereby maintaining the degree of vacuum in the film forming chamber.

  At this time, in the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas or inert gas supplied from the gas supply device, and this mixed gas is supplied through the raw material supply nozzle. Introduce into the vacuum chamber. In this case, the content of the organosilicon compound in the mixed gas is 1 to 40% by volume, the oxygen gas content is 10 to 70% by volume, and the inert gas content is 10 to 60% by volume. For example, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14.

On the other hand, since a predetermined voltage is applied from the power source to the cooling / electrode drum, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. This glow discharge plasma is derived from one or more gas components in the mixed gas, and in this state, the substrate is transported at a constant speed, so that the glow discharge plasma causes the cooling / electrode drum peripheral surface to A vapor deposition film of an inorganic oxide such as silicon oxide can be formed on the upper substrate. Note that the degree of vacuum in the vacuum chamber at this time is preferably adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, particularly 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Moreover, it is preferable to adjust the conveyance speed of a base material to 10-300 m / min, especially 50-150 m / min.

Further, in the plasma chemical vapor deposition apparatus, an inorganic oxide vapor deposition film such as silicon oxide is formed on the substrate in the form of a thin film in the form of SiO _X while oxidizing the plasma source gas with oxygen gas. Therefore, the deposited vapor-deposited film of inorganic oxide such as silicon oxide is a continuous layer that is dense and has few gaps and is rich in flexibility and flexibility, such as the first gas barrier coating film on the substrate, etc. It has excellent adhesion. Further, in the present invention, the surface of the base material is cleaned by SiO _X plasma, and polar groups, free radicals, etc. are generated on the surface of the base material, so that a deposited film of inorganic oxide such as silicon oxide is formed. And the first gas barrier coating film and the like on the substrate have an advantage of higher close adhesion. Furthermore, as described above, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ^{−. The} degree of vacuum is lower than that of 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, which is adjusted to ² Torr and is a degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method. Therefore, it is possible to shorten the vacuum state setting time at the time of replacing the raw material of the base material, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is A thin film is formed by closely adhering to the surface of the first gas barrier coating film on the substrate, and is usually represented by the general formula SiO _X (where X represents a number of 0 to 2). It is a continuous thin film mainly composed of silicon oxide. Such a silicon oxide vapor-deposited film is a silicon oxide vapor-deposited film represented by the general formula SiO _X (where X represents a number from 1.3 to 1.9) in terms of transparency and adhesion. A thin film mainly composed of is preferable. In the above, the value of X varies depending on the molar ratio between the vapor deposition monomer gas and the oxygen gas, the energy of the plasma, etc. In general, although the gas permeability decreases as the value of X decreases, The film itself is yellowish and the transparency is poor.

The silicon oxide vapor-deposited film is mainly composed of silicon oxide, and at least one compound selected from the group consisting of carbon, hydrogen, silicon and oxygen is chemically bonded, etc. It contains by. For example, when a compound having a C—H bond, a compound having a Si—H bond, a compound having a Si—C bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, The case where the organosilicon compound or a derivative thereof is contained by a chemical bond or the like is included. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process. In this invention, it is 0.1-50 mass% suitably as content of the said compound in the vapor deposition film of a silicon oxide, More preferably, it is 5-20 mass%. If this content is less than 0.1% by mass, the impact resistance, spreadability, flexibility, adhesion, etc. of the deposited silicon oxide film will be insufficient, and scratches and cracks will occur due to bending and the like. It becomes easy and it becomes difficult to maintain high adhesiveness stably. On the other hand, when the content exceeds 50% by mass, the gas barrier property expected as a secondary effect on the deposited film of silicon oxide is lowered, which is not preferable. In the present invention, it is preferable that the content of the compound in the silicon oxide vapor deposition film increases in the depth direction from the surface of the silicon oxide vapor deposition film. Thereby, on the surface of the deposited film of silicon oxide, the impact resistance and the like can be enhanced by the above-described compound and the like, and the affinity and the like with other base materials are increased and the adhesion thereof is enhanced. Since the content of the compound is large at the interface with the first gas barrier coating film or the like on the base material, the first gas barrier coating film on the base material and the silicon oxide vapor deposition film are closely bonded. The property becomes strong.

  In the present invention, the deposited film of silicon oxide is subjected to, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS). The physical properties as described above can be confirmed by performing elemental analysis using a method of analyzing by ion etching in the depth direction. In the present invention, the thickness of the silicon oxide vapor-deposited film is preferably 30 to 2000 mm, more preferably 50 to 500 mm. If the thickness is greater than 2000 mm, particularly more than 500 mm, cracks and the like are likely to occur in the film, which is not preferable. On the other hand, if the thickness is less than 30 mm, it is difficult to achieve the effect. Is not preferable. The film thickness of the deposited silicon oxide film can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name RIX2000 type) manufactured by Rigaku Corporation. Further, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas, the method of slowing the vapor deposition rate, etc. Is mentioned.

  In the present invention, the monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor-deposited film of an inorganic oxide such as silicon oxide may be, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxy Silane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used. Among these, it is particularly preferable to use 1.1.3-3 tetramethyldisiloxane or hexamethyldisiloxane as a raw material from the viewpoints of handling properties, characteristics of the formed continuous film, and the like. Moreover, in this invention, argon gas, helium gas, etc. can be used as inert gas, for example.

Next, a primer layer (not shown) that can be used in place of the second gas barrier coating film in the present invention will be described. Such a primer layer is a physical gas phase on the surface of the first gas barrier coating film (or the surface of the first gas barrier coating film when the plasma processing surface with an inert gas is provided). After an inorganic oxide vapor deposition film is formed by a growth method or a chemical vapor deposition method, the inorganic oxide vapor deposition film is provided on the surface of the inorganic oxide vapor deposition film through a plasma treatment surface using oxygen gas. The primer layer is composed of a composition having a polyester resin or polyurethane resin as a main component of the vehicle, and the silane coupling agent is 0.05 to 0.05% with respect to 1 to 30% by mass of the polyester resin or polyurethane resin. 10% by mass, preferably 0.1 to 5% by mass, filler is added in a proportion of 0.1 to 20% by mass, preferably 1 to 10% by mass, and further, if necessary, a stabilizer, a curing agent, It is formed using a polyester-based or polyurethane-based resin composition prepared by adding additives such as crosslinking agents, lubricants, UV absorbers, etc., and adding a solvent, diluent, etc. and mixing them well. The Specifically, for example, the polyester-based or polyurethane-based resin composition is coated with oxygen on the surface of the inorganic oxide vapor-deposited film by a coating method such as roll coating, gravure coating, knife coating, dip coating, or spray coating. The primer layer according to the present invention is coated through a plasma-treated surface with a gas, and then the coating film is dried to remove a solvent, a diluent, and the like, and further an aging treatment is performed as necessary. Can be formed. In the present invention, the thickness of the primer agent layer, for ^{example, 0.1g / m 2 ~1.0g / m} 2 ( dry) are preferred.

  In the present invention, by using the primer layer as described above, it is possible to improve the tight adhesion between the vapor-deposited film of the inorganic oxide and the moisture absorption layer and the like, and to improve the elongation of the primer layer, for example, It is possible to improve post-processing suitability such as laminating, and to prevent the occurrence of cracks or the like in the inorganic oxide vapor-deposited film during the post-processing.

  As the polyurethane resin, for example, a polyurethane resin obtained by a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound can be used. Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. A one-component or two-component curable polyurethane resin obtained by a reaction of the polyfunctional isocyanate with a hydroxyl group-containing compound such as polyether polyol, polyester polyol, or polyacrylate polyol can be used. By using such a polyurethane-based resin, the adhesion between the inorganic oxide vapor-deposited film and the moisture-absorbing layer is improved and the elongation of the primer layer is improved, for example, post-processing such as laminating. The suitability can be improved, and the occurrence of cracks and the like in the inorganic oxide vapor-deposited film during such post-processing can be prevented.

  The polyester-based resin is produced, for example, by polycondensation of one or more aromatic saturated dicarboxylic acids having a basic skeleton such as terephthalic acid with one or more saturated dihydric alcohols. A thermoplastic polyester resin can be used. As the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4,4-dicarboxylic acid and the like can be used. Examples of the saturated dihydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, and neopentyl glycol. An alicyclic glycol such as glycol and cyclohexanedimethanol, an aromatic diol such as 2.2-bis (4′-β-hydroxyethoxyphenyl) propane and naphthalenediol can be used.

  In the present invention, as the polyester resin, specifically, for example, a thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, a thermoplastic produced by polycondensation of terephthalic acid and tetramethylene glycol. Polybutylene terephthalate resin, thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, thermoplastic polyethylene produced by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol Terephthalate resin, thermoplastic polyethylene terephthalate resin produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, terephthalic acid and isophthalic acid Thermoplastic polyethylene terephthalate resin produced by co-polycondensation of Chi glycol and propylene glycol, a polyester polyol resin, etc. can be used.

  In the present invention, in addition to the saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, One or more aliphatic saturated dicarboxylic acids such as sebacic acid and dodecanoic acid can be added and copolycondensed, and the amount used is an aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, It is preferable to set it as 1-10 mass%. In the present invention, by using the polyester-based resin as described above, the close adhesion and the like are improved and the degree of elongation of the primer agent layer is improved. The occurrence of cracks and the like in the inorganic oxide vapor-deposited film during such post-processing can be prevented.

  Furthermore, in the above, as the silane coupling agent constituting the polyurethane-based or polyester-based resin composition, organic functional silane monomers having binary reactivity can be used. For example, γ-chloropropyltrimethoxy Silane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycid Xylpropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane , Γ-U One or more kinds such as an aqueous solution of raidpropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-aminopropylsilicone can be used.

  In the silane coupling agent as described above, a functional group at one end of the molecule, usually chloro, alkoxy, or acetoxy group, is hydrolyzed to form a silanol group (SiOH), which is an inorganic oxide. For example, a reaction such as a dehydration condensation reaction is caused by some action with an active group on the surface of the metal or the oxide film deposited on the surface of the deposited metal film or a functional group such as a hydroxyl group. In addition, a silane coupling agent is modified on the film surface of the inorganic oxide vapor-deposited film by a covalent bond or the like, and further, a strong bond to the film surface of the inorganic oxide vapor-deposited film of the silanol group itself by adsorption or hydrogen bond Form. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent reacts with a substance constituting the hygroscopic layer or an adhesive layer to form a strong bond. Therefore, this makes it possible to form a strong laminated structure with high laminate strength in the present invention. In other words, in the present invention, the inorganic and organic properties of the silane coupling agent are used to improve the tight adhesion between the vapor-deposited film of the inorganic oxide and the moisture-absorbing layer. It is something to enhance.

  Next, in the present invention, as the filler used in the polyurethane-based or polyester-based resin composition, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder and the like can be used. . Such a filler adjusts the viscosity or the like of a polyurethane-based or polyester-based resin composition to improve its coating suitability, and binds with a polyurethane-based or polyester-based resin as a binder resin via a silane coupling agent, It improves the cohesive strength of the coating film.

  As described above, a suitable vapor deposition film according to the present invention has a plasma treatment surface with an inert gas, an inorganic oxide vapor deposition film by physical vapor deposition, and a plasma with oxygen gas on one surface of a substrate. A treatment surface, a first gas barrier coating film, a plasma treatment surface with an inert gas if necessary, an inorganic oxide vapor deposition film by physical vapor deposition or chemical vapor deposition, a plasma treatment surface with oxygen gas, and A layer in which a second gas barrier coating film is sequentially laminated, or a plasma-treated surface with an inert gas, an inorganic oxide vapor-deposited film by physical vapor deposition, or a plasma-treated surface with oxygen gas on one surface of a substrate A first gas barrier coating film, a plasma-treated surface with an inert gas if necessary, an inorganic oxide vapor-deposited film by physical vapor deposition or chemical vapor deposition, Ma treated surface, and consists of those successively laminated a primer agent layer composed of a composition mainly vehicle a polyester resin or polyurethane resin.

  Next, the moisture absorption layer 2 in the present invention is composed of a binder resin having a moisture content of 1% or less and a moisture adsorbing substance. The binder resin used for the moisture-absorbing layer 2 is not particularly limited as long as the moisture content is in the range of 1% or less. Among them, the moisture-absorbing substance can be highly filled, and the moisture contained or adhered to the binder resin itself. It is preferable to use a polyolefin-based resin from the viewpoint of maintaining the physical properties of the moisture-absorbing layer such as pinhole resistance, puncture strength, stiffness (flexibility), etc. In the present invention, the moisture content of the binder resin means the moisture content of the binder resin alone before producing the moisture-proof laminate, and can be measured based on, for example, the Karl Fischer method. In the present invention, the moisture content of the binder resin is preferably as low as possible.

  Moreover, as the moisture-adsorbing substance used for the moisture-absorbing layer 2, a chemically-adsorbing substance that has no re-wetting property and maintains a solid shape even when moisture is absorbed can be suitably used. Specific examples include alkali metal oxides, alkaline earth metal oxides, sulfates, metal halides, perchloric acid, and organic substances.

Among these, examples of the alkali metal oxide include sodium oxide (Na ₂ O) and potassium oxide (K ₂ O). Examples of the alkaline earth metal oxide include calcium oxide (CaO) and magnesium oxide ( MgO), barium oxide (BaO), and the like. As sulfates, calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga) ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), nickel sulfate (NiSO ₄ ), and the like, and anhydrous salts are particularly preferable.

Further, as metal halides, calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₃ ), copper chloride (CuCl ₂ ), calcium bromide (CaBr ₂ ) , Cerium bromide (CeBr ₃ ), selenium bromide (SeBr ₄ ), vanadium bromide (VBr ₂ ), magnesium bromide (MgBr ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), fluoride niobium _(NbF 5), barium iodide _(BaI 2), there may be mentioned such as magnesium iodide (MgI _2), in particular is suitable anhydrous salt. Furthermore, examples of perchlorate include magnesium perchlorate (Mg (ClO ₄ ) ₂ ), barium perchlorate (Ba (ClO ₄ ) ₂ ) and the like, and anhydrous salts are particularly preferred. . Even when an organic substance is used as the chemically adsorbing substance, it is necessary to chemically adsorb moisture and maintain a solid state even when moisture is absorbed.

  As a weight ratio of the binder resin and the moisture-adsorbing substance in the moisture-absorbing layer 2, in order to ensure high moisture-absorbing performance of the moisture-absorbing layer 2, the moisture-adsorbing substance is used in an amount of 80 to 40 with respect to 20 to 60 parts by mass of the binder resin. It is preferable to mix by mass part. More preferably, the weight ratio is 70 to 30 parts by mass of the moisture-adsorbing substance with respect to 30 to 50 parts by mass of the binder resin. When the weight ratio of the binder resin is higher than the above range and the weight ratio of the moisture-adsorbing substance is low, sufficient moisture absorption performance may not be obtained. On the other hand, when the weight ratio of the binder resin is lower than the above range and the weight ratio of the moisture-adsorbing substance is high, the ratio of the moisture-adsorbing substance is high. Also, the melt viscosity becomes excessively high. In addition, about the thickness of the moisture absorption layer 2, it does not specifically limit, It can determine with a use in the range of 25-300 micrometers.

  In the present invention, an adhesive layer, an anchor coat layer, or an adhesive layer can be disposed between the vapor deposition film 1 and the moisture absorption layer 2 as necessary. Moreover, when laminating the vapor deposition film 1 and the moisture absorption layer 2 through an adhesive, the binder resin of the moisture absorption layer is used as a protective layer to prevent adhesion failure due to the unevenness of the moisture absorption layer 2 and to prevent the moisture absorption agent from peeling off. It is also possible to laminate the same resin layer. In addition, when performing said lamination | stacking, pre-treatments, such as a corona treatment, an ozone treatment, a flame | frame treatment, etc. can be arbitrarily given to the surface mutually laminated | stacked as needed.

  Examples of the adhesive constituting the adhesive layer include a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester, or these and methyl methacrylate, acrylonitrile, styrene, or the like. Polyacrylic acid ester adhesives made of copolymers, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc. Agent, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive Agent, reactive (meth) acrylic adhesive, chloroprene rubber, ni Rirugomu, styrene - rubber adhesive comprising a butadiene rubber, a silicone-based adhesive, an alkali metal silicate, may be mentioned inorganic adhesive or the like made of a low-melting-point glass or the like. Moreover, the composition system of the adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of film / sheet type, powder type, solid type, etc. Further, the adhesion mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

When forming the adhesive layer, the adhesive is applied to one side of both of the layers by, for example, a roll coating method, a gravure roll coating method, a coating method such as a kiss coating method, or a printing method, The solvent or the like may be dried, and the coating or printing amount is preferably 0.1 to 10 g / m ² (dry state).

  Moreover, as an anchor coating agent which comprises the said anchor coat layer, anchor coating agents, such as isocyanate type (urethane type), a polyethyleneimine type, a polybutadiene type, an organic titanium type, can be used, for example. Furthermore, as a pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, a known rubber-based, acrylic-based, or silicone-based pressure-sensitive adhesive can be used.

  In particular, as the anchor coating agent and adhesive, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc. Polyether polyurethane resins obtained by reaction of polyfunctional isocyanates such as aliphatic polyisocyanates with hydroxyl group-containing compounds such as polyether polyols, polyester polyols, and polyacrylate polyols, polyester polyurethane resins, or It is preferable to use a material mainly composed of a polyacrylate polyurethane resin. The anchor coat layer or adhesive layer formed using the anchor coat agent or adhesive as described above is a thin film that is soft, flexible and flexible, has a high tensile elongation, and is an inorganic oxide. It acts as a film having flexibility, flexibility, etc. on the deposited film of the object, improves the post-processing suitability of the deposited film of the inorganic oxide at the post-processing such as laminating, and the inorganic oxide at the post-processing The effect of preventing the occurrence of cracks and the like in the deposited film can be obtained, and the laminate strength can be increased.

  In the present invention, the anchor coat layer made of the anchor coat agent and the adhesive layer made of the adhesive have a tensile elongation in the range of 100 to 300% based on JIS K 7113 standard. If the tensile elongation is less than 100%, the flexibility of the laminate is lost, and cracks and the like on the vapor-deposited film of inorganic oxide tend to occur, which is not preferable. On the other hand, if the tensile elongation exceeds 300%, the adhesive strength as an anchor coating agent or an adhesive is not sufficient, and the required laminate strength is hardly exhibited, which is not preferable.

  In the present invention, a known film forming method such as an inflation film forming method or a T-die film forming method can be used as a method for manufacturing the moisture absorbing layer 2 when the moisture absorbing layer 2 is formed in a film shape. In this case, as a method for laminating the vapor-deposited film 1 and the film-like moisture absorbing layer 2, a known method such as a dry laminating method using an adhesive, a heat laminating method, or an extrusion laminating method can be appropriately used. In addition, when the binder resin that does not absorb moisture and the moisture-adsorbing substance constituting the moisture-absorbing layer 2 are prepared as a liquid mixture, the liquid mixture is known to have a satisfactory coating amount, such as a die coater or a comma coater. The moisture absorption layer 2 can be formed by coating on the vapor deposition film 1 using the coating method.

  The moisture-proof laminate of the present invention can be widely used as, for example, a packaging sheet or film used for food, non-food and pharmaceutical packaging, electronic equipment-related members, etc., and has high moisture-proof properties. In particular, it can be suitably used in fields where high water vapor barrier properties are required, such as the field of electronic devices that can be made flexible such as organic devices such as organic EL elements and electronic paper, and the field of medical packaging. it can.

Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
<Preparation of vapor deposition film 1>
First, a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was used as a base material, and this was mounted on a feed roll of a take-up vacuum deposition apparatus shown in FIG. Next, this PET film is conveyed at a line speed of 600 mm / min, argon gas 500 sccm (in which the amount per minute is shown in milliliters) is introduced using a magnetron sputtering apparatus, and plasma treatment is performed at an output of 20 kW. A plasma-treated surface with an inert gas was formed on one surface of the substrate. Further, an aluminum oxide film having a thickness of 20 nm is deposited on this plasma-treated surface by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source in accordance with the following deposition conditions. A film was formed.

(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ⁻⁴ mbar,
Degree of vacuum in the winding chamber; 2 × 10 ⁻² mbar,
Electron beam power; 25 kW,
Film transport speed: 600 m / min

  Thereafter, using another magnetron sputtering apparatus, oxygen gas of 1000 sccm was introduced, plasma treatment was performed at an output of 5 kW, and a plasma treatment surface with oxygen gas was formed on the surface of the aluminum oxide vapor deposition film. Formed and wound up.

  On the other hand, according to the composition shown in Table 1 below, an ethyl silicate 40 prepared in advance in an EVOH solution (composition a) in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water, A hydrolyzed liquid (composition b) composed of isopropyl alcohol, acetylacetone aluminum and ion-exchanged water was added and stirred, and a liquid mixture (composition c) composed of an aqueous polyvinyl alcohol solution, acetic acid, isopropyl alcohol and ion-exchanged water prepared in advance was prepared. In addition, the mixture was stirred to prepare a colorless and transparent gas barrier composition.

Next, the gas barrier composition prepared above is coated on the plasma-treated surface with oxygen gas on the vapor deposition layer formed on the PET film as the substrate, and heated at 100 ° C. for 30 seconds. The first gas barrier coating film having a coating amount of 0.4 g / m ² (dry state) was formed by processing.

  Next, the base film on which the first gas barrier coating film is formed as described above is again attached to the unwinding roll of the winding type vacuum vapor deposition apparatus shown in FIG. 3, and conveyed at a line speed of 600 mm / min. Argon gas of 500 sccm was introduced using a magnetron sputtering apparatus, and plasma treatment was performed at an output of 20 kW to form a plasma treatment surface with an inert gas on the first gas barrier coating film formation surface. Further, an aluminum oxide film having a thickness of 20 nm is deposited on this plasma-treated surface by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source in accordance with the following deposition conditions. A film was formed.

(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ⁻⁴ mbar,
Degree of vacuum in the winding chamber; 2 × 10 ⁻² mbar,
Electron beam power; 25 kW,
Film transport speed: 600 m / min

  Thereafter, using another magnetron sputtering apparatus, oxygen gas of 500 sccm is introduced, plasma treatment is performed at an output of 3 kW, and a plasma treatment surface by oxygen gas is formed on the surface of the aluminum oxide vapor deposition layer. And wound up.

  On the other hand, according to the composition shown in Table 2 below, an ethyl silicate 40 prepared in advance in an EVOH solution (composition a) in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water, A hydrolyzed liquid (composition b) consisting of isopropyl alcohol, acetylacetone aluminum and ion-exchanged water is added and stirred. Further, a polyvinyl alcohol aqueous solution prepared in advance, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged A liquid mixture (composition c) consisting of water was added and stirred to prepare a colorless and transparent gas barrier composition.

Next, the plasma-treated surface of the deposited aluminum oxide film formed above is coated with the colorless and transparent gas barrier composition prepared above by a gravure roll coating method, and heat-treated at 100 ° C. for 30 seconds to be applied. A second gas barrier coating film having an amount of 0.4 g / m ² (dry state) was formed. On this second gas barrier coating film, an epoxy silane coupling agent (8.0% by mass) and an antiblocking agent (1.0% by mass) are sufficiently added to the initial condensation product of the polyester resin. The primer resin composition kneaded in is coated at a film thickness of 0.2 g / m ² (dry state) by the gravure roll coating method to form a primer agent layer, and the vapor deposition film 1 according to the present invention is produced. did.

<Preparation of moisture absorption layer 2>
40 parts by mass of linear low density polyethylene (LLDPE) as a binder resin (manufactured by Ube Maruzen Co., Ltd., Umerit 1540F MFR = 4 (190 ° C., 2.16 kg)) and calcium oxide (CaO as a moisture adsorbing substance) ) 60 parts by mass were mixed and melt-kneaded using a single screw extruder, and resin pellets for forming the hygroscopic layer 2 were prepared using a granulator. Using the pellets for forming the hygroscopic layer 2, a film-like hygroscopic layer 2 was obtained by using an inflation film forming machine.

The film-like moisture-absorbing layer 2 is sandwiched between the two vapor-deposited films 1 and bonded by a dry laminating method through an isocyanate-based adhesive, whereby a vapor-deposited film (12 μm) / adhesive layer (4 g / m ^2). ) / Hygroscopic layer (30 μm) / Adhesive layer (4 g / m ² ) / Vapor deposited film (12 μm) The layer of Example 1 was prepared.

<Example 2>
A moisture-proof laminate of Example 2 was produced in the same manner as in Example 1 except that the deposited film 1 produced without forming the second gas barrier coating film was used. The layer structure of this moisture-proof laminate was vapor deposition film (12 μm) / adhesion layer (4 g / m ² ) / moisture absorption layer (30 μm) / adhesion layer (4 g / m ² ) / deposition film (12 μm).

<Example 3>
The moisture-proof layer of Example 3 was the same as Example 2 except that the pellet for forming the moisture-absorbing layer 2 was coextruded using a multilayer T-die extruder and the vapor-deposited film 1 was pseudo-adhered by thermal lamination. A conductive laminate was produced. The layer structure of the moisture-proof laminate was vapor deposition film (12 μm) / moisture absorption layer (30 μm) / vapor deposition film (12 μm).

<Comparative Example 1>
A moisture-proof laminate of Comparative Example 1 was produced in the same manner as in Example 2 except that the hygroscopic layer 2 was not provided. The layer structure of this moisture-proof laminate was vapor deposition film (12 μm) / adhesive layer (4 g / m ² ) / vapor deposition film (12 μm).

<Comparative example 2>
A moisture-proof laminate of Comparative Example 2 was produced in the same manner as in Example 2 except that the weight ratio of the binder resin to the moisture-adsorbing substance in the moisture-absorbing layer 2 was changed to binder resin: moisture-adsorbing substance = 100: 0. did. The layer structure of this moisture-proof laminate was vapor deposition film (12 μm) / adhesion layer (4 g / m ² ) / moisture absorption layer (30 μm) / adhesion layer (4 g / m ² ) / deposition film (12 μm).

<Comparative Example 3>
A moisture-proof laminate of Comparative Example 3 was produced in the same manner as in Example 2 except that a film obtained by depositing silica on a PET film having a thickness of 12 μm by a vacuum deposition method was used as the deposited film 1. The layer structure of this moisture-proof laminate was vapor deposition film (12 μm) / adhesion layer (4 g / m ² ) / moisture absorption layer (30 μm) / adhesion layer (4 g / m ² ) / deposition film (12 μm).

<Comparative Example 4>
A moisture-proof laminate of Comparative Example 4 was produced in the same manner as in Example 2 except that 6-nylon was used as the binder resin for the moisture absorption layer. The layer structure of this moisture-proof laminate was vapor deposition film (12 μm) / adhesion layer (4 g / m ² ) / moisture absorption layer (30 μm) / adhesion layer (4 g / m ² ) / deposition film (12 μm).

  In Table 3 below, the conditions of the moisture-proof laminate in each of the above Examples and Comparative Examples are shown.

＊１）水分吸着性物質：ＣａＯ

* 1) Moisture-absorbing substance: CaO

<Evaluation test>
The moisture-proof laminates produced in Examples 1 and 2 and Comparative Examples 1 to 3 were measured under the conditions of a temperature of 40% and a humidity of 90% RH, manufactured by MOCON, USA (model name: PERMATRAN). ) Was used to measure the water vapor transmission rate (water vapor barrier property).

Moreover, the binder resin of the moisture absorption layer of the moisture-proof laminated body produced in the said Examples 1-3 and Comparative Examples 1-4 (Examples 1-3 and Comparative Examples 1-3: LLDPE, Comparative Example 4: 6-nylon) The moisture content before producing the moisture-proof laminate was measured using a Karl Fischer moisture measuring device (manufactured by Hiranuma Sangyo Co., Ltd., AQ-7).
These measurement results are shown in Table 4 below.

  As shown in the said table | surface, in the moisture-proof laminated body of Examples 1-3, it was confirmed that the high water vapor | steam barrier property is obtained using the lamination technique for general purpose packaging. On the other hand, in the moisture-proof laminated body of the comparative example 1, since the moisture absorption layer was not provided, barrier property fell compared with the Example. Moreover, in the moisture-proof laminated body of the comparative example 2, the hygroscopic agent was not contained in the moisture absorption layer, and the effect of high moisture-proofness was not enough. Furthermore, in the moisture-proof laminated body of the comparative example 3, the barrier property of a vapor deposition film was not enough, and the water vapor | steam barrier property in the whole laminated body was a low thing compared with an Example. Furthermore, in Comparative Example 4, the moisture content of the binder resin was high, the moisture absorption performance was deactivated, and the effect of high moisture resistance was not sufficient.

DESCRIPTION OF SYMBOLS 1 Deposition film 2 Hygroscopic layer 3 Base material 4 Inorganic oxide deposition film 5 1st gas barrier coating film 6 Inorganic oxide deposition film 7 2nd gas barrier coating film 10 Moisture-proof laminated body 31 Winding type vacuum deposition Apparatus 32 Vacuum chamber 33 Unwinding roll 34 Guide roll 35 Coating drum 36 Crucible 37 Electron gun 38 Electron beam 39 Deposition source 40 Oxygen gas cylinder 41 Oxygen gas outlet 42 Mask 43 Guide roll 44 Winding roll 45 Magnetron sputtering apparatus 51 Plasma chemical vapor Phase growth apparatus 52 Supply chamber 53 Pretreatment chamber 54 Film formation chamber 55 Posttreatment chamber 56 Winding chamber 57 Unwinding roll 58 Guide roll 59 Magnet 60 Gas supply chamber 61 Gas supply pipes 62 and 63 Auxiliary roll 64 Cooling / electrode drum 65 Raw material volatilization supply device 66 Gas supply device 67 Raw material supply Nozzle 68 glow discharge plasma 69 magnet 70, 71 guide roll 72 Magnet
73 Gas supply chamber 74 Supply pipe 75 Guide roll 76 Winding roll

Claims (4)

A moisture-proof laminate comprising at least two vapor-deposited films, wherein at least one moisture-absorbing layer is sandwiched between the vapor-deposited films,
The moisture-absorbing layer comprises a binder resin having a moisture content of 1% or less, and a moisture-adsorbing substance; and
The vapor-deposited film has an inorganic oxide vapor-deposited film formed by physical vapor deposition and a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are An organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M). A first gas barrier coating film comprising a gas barrier composition comprising at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method; An inorganic oxide vapor-deposited film formed by vapor deposition or chemical vapor deposition, and a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² , M, n, m, and n + m are Represents the same as above) A second gas barrier coating film comprising a gas barrier composition containing at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method; Ri but name are sequentially formed,
The wicking layer is a film-like, film-like absorbent wet layer and the deposition film, moisture resistance laminate characterized by Rukoto such is laminated by dry lamination using an adhesive.   The moisture-proof laminate according to claim 1, wherein a primer agent layer made of a composition comprising a polyester resin or a polyurethane resin as a main component of the vehicle is formed in place of the second gas barrier coating film.   Chemical moisture adsorption comprising at least one selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, sulfates, metal halides, perchloric acid and organic substances as the moisture adsorbing substance of the moisture absorption layer The moisture-proof laminate according to claim 1, wherein the moisture-proof laminate is an organic substance.   The weight ratio of the binder resin and the moisture adsorbing substance in the moisture absorption layer is 80 to 40 parts by mass of the moisture adsorbing substance with respect to 20 to 60 parts by mass of the binder resin. Moisture-proof laminate.

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