JP5568897B2 - Gas barrier laminated film for vacuum insulation, vacuum insulation, home appliances and houses - Google Patents

Description

  The present invention relates to a gas barrier laminated film for vacuum heat insulating material and a vacuum heat insulating material obtained by sealing a core material under reduced pressure with the gas barrier laminated film for vacuum heat insulating material, and more specifically, refrigerator, rice cooker, pot, cooler box, transportation Containers, fuel tanks for hydrogen, system baths, eco-cute hot water tanks, thermal insulation, housing walls, and vacuum insulation materials used for heat insulation walls around cars, airplanes, ships, trains, OA equipment, etc. is there.

  In recent years, reduction of greenhouse gases has been promoted in order to prevent global warming, and in order to achieve energy saving, efforts are being made to cut off heat transfer with a vacuum heat insulating material and reduce energy required for air conditioning. Such a vacuum heat insulating material can exhibit high heat insulating performance with a thickness of 10 mm or less, and is an effective material used for refrigerators and the like in order to widen the interior space.

  In order to maintain the heat insulation performance of such a vacuum heat insulating material for a long time, an excellent gas barrier property is required for a laminate for a vacuum heat insulating material used for a jacket material. As a covering material used in such a vacuum heat insulating material, a heat seal layer, an aluminum vapor deposition layer, a laminate film composed of a protective layer and an aluminum foil, the aluminum foil does not cover the heat seal portion of the laminate film There exists a vacuum heat insulating material made into the magnitude | size (patent document 1). It is said that a vacuum heat insulating material with high heat insulating performance can be obtained even when used at a high temperature by laminating aluminum foil having a size that does not cover the heat seal portion of the laminate film.

  In addition, as an outer cover material, an intermediate coating layer (B layer) formed by applying a vapor-deposited thin film layer (A layer) and a coating agent containing at least a water-soluble polymer to at least one side of a base material made of a plastic material and drying by heating. In addition, a laminated body in which vapor-deposited thin film layers (C layers) are sequentially laminated is also disclosed (Patent Document 2). In Patent Document 2, when a vapor deposition film such as aluminum is used as a gas barrier layer, a pinhole or a crack is generated in the vapor deposition film and gas barrier properties are lowered, and a vapor deposition thin film layer (A layer) is disclosed. A high gas barrier property is secured by sequentially laminating an intermediate coating layer (B layer) and a vapor deposition thin film layer (C layer) obtained by applying a coating agent containing a water-soluble polymer to the substrate and drying by heating. It is.

  In addition, there is also a laminate material having a laminate structure having two or more gas barrier layers made of a metal foil layer or a vapor deposition layer with a plastic film layer interposed therebetween (Patent Document 3). When the outer cover material of the vacuum heat insulating material is bent, small holes are formed in the gas barrier layer of the outer cover material, and the performance over time may be deteriorated. By using a covering material of a laminate structure having two or more gas barrier layers consisting of a metal foil layer or a vapor deposition layer with a protective layer being a plastic film layer interposed therebetween, and covering at least one heat transfer surface of the core material Even if at least one portion of the jacket material is bent, the shape of the ridge line generated in the metal foil layer or the vapor deposition layer constituting the two gas barrier layers is slightly different, so that the deterioration of the gas barrier property can be minimized. And so on.

  Furthermore, a transparent barrier film layer composed of a base plastic film layer / ceramic vapor deposition layer is provided as a barrier layer, and the transparent barrier film layer is formed by a special plasma using a holo anode plasma treatment device before vapor deposition of the vapor deposition layer. There is also a jacket material characterized by plasma pretreatment (Patent Document 4). It is said that the barrier property similar to that of aluminum foil can be secured by subjecting the base plastic film to plasma pretreatment with special plasma using a holo anode plasma processor.

On the other hand, as a gas barrier film, there is also a moisture-proof film formed by laminating a transparent film in which a vapor deposition film of silicon oxide is formed on polyvinyl alcohol and a transparent film having a silicon oxide thin film on one side (Patent Document 5). A vapor deposition film of silicon oxide is formed on polyvinyl alcohol, which is originally considered to have gas barrier properties, to ensure high gas barrier properties. In the examples, a transparent film in which silicon monoxide having a purity of 99.9% was heated and evaporated by an electron beam heating method to form a transparent vapor-deposited film of silicon oxide on polyvinyl alcohol, and silicon terephthalate by the above-described method. forming a transparent film with a deposit of oxides, the deposition film by pairs direction and laminated using a urethane-based adhesive, to obtain a moisture-proof film. Furthermore, there is also a highly rigid moisture-proof film in which a heat seal layer is formed on the moisture-proof film described in Patent Document 5 (Patent Document 6).

  Further, on both surfaces of a substrate made of a transparent plastic material, a vapor-deposited thin film layer made of an inorganic oxide, a water-soluble polymer, and (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride A gas barrier laminate film is also disclosed, in which a gas barrier coating layer obtained by applying a coating agent mainly containing an aqueous solution containing at least one of the above or a water / alcohol mixed solution and heating and drying is sequentially laminated ( Patent Document 7).

JP 2001-032992 A Japanese Patent Laid-Open No. 2004-130654 JP 2006-064034 A JP 2008-008400 A Japanese Patent No. 2820469 Japanese Patent No. 2816998 JP 2002-166487 A

  However, as described in Patent Document 1, an excellent gas barrier property can be obtained by using a laminate in which aluminum foil is laminated, and there is an advantage that the inside of the jacket material is maintained at a high degree of vacuum over a long period of time. However, since the heat conductivity of aluminum itself is large, there is a problem that sufficient heat insulation performance cannot be obtained due to heat conduction through the jacket material.

  Further, the vacuum heat insulating materials disclosed in Patent Document 2, Patent Document 3, and Patent Document 4 are also used when the heat insulating material is fitted into the walls of the inner box and the outer box as a heat insulating layer such as a refrigerator. It was necessary to bend the bonded end portion, and cracks were easily generated by the bending, and the gas barrier property deteriorated with time, and the gas barrier property was not sufficient.

  On the other hand, the polyvinyl alcohol used in Patent Documents 5 and 6 is inherently excellent in gas barrier properties, but has a hydrophilic functional group in the structure, so that the gas barrier properties are likely to deteriorate under high humidity. In order to improve the gas barrier property of such a film having a hydrophilic functional group under high humidity, there is a method of forming a vapor deposition film, but a vapor deposition film of silicon oxide or silicon nitride is formed on one side thereof. However, gas barrier properties may not be sufficient.

  Further, as a gas barrier laminate film having a hydrophilic functional group, an ethylene vinyl copolymer is also known. However, like polyvinyl alcohol, the gas barrier property tends to be lowered under high humidity. Therefore, development of a film that is more excellent in gas barrier properties is desired even for a film such as polyvinyl alcohol or ethylene vinyl copolymer that is likely to have a gas barrier property that is likely to deteriorate under high humidity.

  In Patent Document 7, a predetermined coating agent is applied on the deposited film in order to ensure gas barrier properties. However, as a transparent plastic material, a polyester film such as polyethylene terephthalate or polyethylene naphthalate is targeted. There is no description regarding films of polyvinyl alcohol and ethylene-vinyl acetate copolymer.

Therefore, an object of the present invention is to provide a gas barrier laminated film for a vacuum heat insulating material that can prevent generation of cracks due to bending and maintain high gas barrier properties.
Another object of the present invention is to provide a gas barrier laminate film for a vacuum heat insulating material that can maintain a high gas barrier property even under high humidity using a film made of polyvinyl alcohol or an ethylene vinyl copolymer as a base film. .

  In addition, the present invention provides sufficient heat insulation performance with less heat conduction through the gas barrier laminated film for vacuum heat insulating material, the inside of the gas barrier laminated film for vacuum heat insulating material is maintained at a high vacuum, and the heat insulating performance is maintained for a long time. An object of the present invention is to provide a vacuum insulating material that can be used.

  As a result of detailed examination of the gas barrier laminated film for vacuum heat insulating material, the present inventor has found that the gas barrier layer in which a deposited film having a thickness of 150 to 4000 angstroms is formed on both surfaces of a base film made of a polyvinyl alcohol resin is a base material. Gas barrier properties such as oxygen permeability and water vapor permeability can be dramatically improved by preventing water vapor permeation of the film from both sides, and as such a deposited film, plasma chemical vapor deposition (PE-CVD) is used. When a silicon oxide vapor deposition film is formed, the silicon-containing vapor deposition film is flexibly prepared. Therefore, even when a vapor deposition film is formed on both sides of the base film, the obtained gas barrier laminate film can be maintained flexibly. , A heat-sealing layer is laminated on the innermost layer of such a gas barrier layer, polyethylene terephthalate, nylon, etc. on the outermost layer Gas barrier laminate film obtained by laminating the outer layer, useful as an envelope material of the vacuum heat insulating material, and completed the present invention.

That is, the present invention is a gas barrier laminate film for vacuum heat insulating material formed by laminating a gas barrier layer and the heat-fusible resin layer, said gas barrier layer on both sides of the polyvinyl alcohol Ruff Irumu, plasma chemical vapor deposition A silicon-containing vapor-deposited film formed by the method is laminated at a thickness of 150 to 4000 angstroms, and each of the vapor-deposited films has a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² Represents 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. Gas barrier properties obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by.)), A polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier laminated film for a vacuum heat insulating material, which is a gas barrier film provided with a gas barrier coating film of the composition and having a water vapor permeability of 0.08 g / m ² · day or less , is provided.

The present invention also provides a vacuum heat insulating material obtained by sealing a core material under reduced pressure with the gas barrier laminated film for a vacuum heat insulating material.
Furthermore, this invention provides the household appliance and house which mounted | wore with the vacuum heat insulating material.

  The gas barrier film constituting the gas barrier laminate film for a vacuum heat insulating material of the present invention is formed by forming a silicon-containing vapor deposition film having a predetermined thickness on both surfaces of a base film made of a polyvinyl alcohol resin, so that the vapor deposition film is formed only on one surface. Compared with the case of forming, water vapor permeability and oxygen permeability can be drastically reduced. For this reason, in order to obtain equivalent barrier properties, the layer configuration can be simplified, which is advantageous in terms of cost and environment.

  In particular, the gas barrier film constituting the gas barrier laminated film for vacuum heat insulating material of the present invention is obtained by depositing carbon-containing silicon oxide by supplying organic-containing silicon oxide oxide as a deposition monomer by plasma chemical vapor deposition. In addition to the gas barrier properties, adhesion between the base film and the carbon-containing silicon oxide can be secured, and flexibility such as extensibility, flexibility and flexibility can be imparted to the vapor deposition layer.

  The gas barrier coating film constituting the gas barrier laminated film for a vacuum heat insulating material of the present invention has a polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and at least one alkoxide chemically reacted with each other, Since an extremely strong three-dimensional network composite polymer layer is formed and laminated on a vapor-deposited film having excellent flexibility, an extremely high gas barrier property can be secured, and transparency, impact resistance, and hot water resistance are excellent.

Since the vacuum heat insulating material of the present invention does not use a metal foil as the outermost layer, it can prevent thermal cross-linking and can exhibit excellent heat insulating properties which are the original characteristics of the vacuum heat insulating material.
Moreover, since the vacuum heat insulating material of this invention is excellent in gas barrier property and bending workability, it can be used conveniently for a household appliance and a house.

FIG. 1 is a view for explaining the layer structure of a gas barrier film constituting the gas barrier laminated film for a vacuum heat insulating material of the present invention, and a vapor-deposited film (20) of carbon-containing silicon oxide on both surfaces of a base film (10). It is a figure which shows that the gas barrier coating film (30) is laminated | stacked on the said vapor deposition film (20). FIG. 2 is a view for explaining the layer structure of the gas barrier laminate film (A) for a vacuum heat insulating material of the present invention, and a heat-fusible resin layer (on the gas barrier coating film (30) of the gas barrier film (70). It is a figure which shows the aspect on which 40) and a plastic base film (50) are laminated | stacked. FIG. 3 is a view for explaining the layer structure of the gas barrier laminate film (A) for vacuum heat insulating material according to the present invention, in which an adhesive layer for dry lamination is applied to the gas barrier coating film (30) of the gas barrier film (70). It is a figure which shows the aspect on which a heat-fusible resin layer (40) and a plastic base film (50) are laminated | stacked through. FIG. 4 is a view for explaining the layer structure of the gas barrier laminated film (A) for vacuum heat insulating material of the present invention. The dry lamination adhesive layer (30) is formed on the gas barrier coating film (30) of the gas barrier film (70). 60), the heat-fusible resin layer (40) and the plastic substrate film (50) are laminated, and the outer layer (80) is further laminated via the dry lamination adhesive layer (60). (50) shows a mode of lamination. FIG. 5 is a cross-sectional view of a preferred embodiment of the vacuum heat insulating material (C) formed by sealing the core material (B) under reduced pressure with the gas barrier laminated film for vacuum heat insulating material (A) of the present invention. FIG. 6 is a schematic configuration diagram showing an example of a low-temperature plasma chemical vapor deposition apparatus. FIG. 7 is a schematic configuration diagram showing an example of a low temperature plasma chemical vapor deposition apparatus having a plurality of film forming chambers.

The first of the present invention is a gas barrier laminated film for a vacuum heat insulating material formed by laminating a gas barrier layer and a heat-fusible resin layer,
In the gas barrier layer, a silicon-containing vapor-deposited film is laminated on both surfaces of a polyvinyl alcohol-based resin film with a thickness of 150 to 4000 angstroms, and each of the vapor-deposited films has a general formula R ¹ _n M (OR ² ) _m (wherein In the formula, 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 at least one alkoxide represented by M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. A gas barrier film for a vacuum heat insulating material, which is a gas barrier film provided with a gas barrier coating film of the obtained gas barrier composition, the second of the present invention is the above vacuum heat insulating material It is a vacuum heat insulating material formed by sealing a core material under reduced pressure with a gas barrier laminate film.

  Polyvinyl alcohol resin has a hydrophilic group in its structure, so the gas permeation rate increases at high humidity and the gas barrier property is likely to be lowered. However, by forming a vapor deposition film with a thickness of 150 to 4000 angstroms on both sides Further, the gas barrier property can be remarkably improved, and further higher gas barrier property can be secured by laminating a predetermined gas barrier coating film. A gas barrier laminated film obtained by laminating such a gas barrier film as a gas barrier layer on a heat-sealing layer is excellent in gas barrier properties and heat insulating properties, and therefore can be suitably used as a vacuum heat insulating material. Moreover, the vacuum heat insulating material which uses the said gas-barrier laminated | multilayer film for vacuum heat insulating materials as a packaging material which seals a core material under reduced pressure is excellent in bending workability, and can be used conveniently for a household appliance and a house. Hereinafter, the present invention will be described in detail.

(1) Layer structure of gas barrier laminated film for vacuum heat insulating material The gas barrier laminated film for vacuum heat insulating material of the present invention is formed by laminating a gas barrier layer and a heat-fusible resin layer. As shown in FIG. 1, the gas barrier layer has a carbon-containing silicon oxide vapor-deposited film (20) on both surfaces of a base film (10), and a gas-barrier coating film (30) is formed on each of the vapor-deposited films. This is a laminated gas barrier film (70).

  Therefore, the gas barrier laminated film for vacuum heat insulating material of the present invention is obtained by laminating the heat-fusible resin layer (40) on the gas barrier film (70). As shown in FIG. The material film (50) may be laminated. Further, as shown in FIG. 3, the gas barrier laminated film (A) for vacuum heat insulating material according to the present invention is such that the heat-fusible resin layer (40) and the plastic substrate film (50) are bonded for dry lamination. It may be bonded through the agent layer (60). When the plastic substrate film (50) and the heat-fusible resin layer (40) are laminated on the vapor deposition film (20) of the gas barrier film (70), the water vapor barrier property is further improved.

  Furthermore, as shown in FIG. 4, the gas barrier laminated film (A) for vacuum heat insulating material of the present invention has an outer layer (80) on the outside of the plastic substrate film (50), and an adhesive layer for dry lamination ( 60) or the like.

(2) Vacuum heat insulating material The vacuum heat insulating material of the present invention is obtained by sealing the core material (B) under reduced pressure with the gas barrier laminated film (A) for vacuum heat insulating material. The vacuum heat insulating material (C) of the present invention, wherein the core material (B) is hermetically sealed with a gas barrier laminated film (A) for a vacuum heat insulating material comprising a gas barrier film (70) and a heat-fusible resin layer (40). ) Is shown in FIG. As shown in FIG. 5, in the vacuum heat insulating material (C) of the present invention, at least the gas barrier film (70) and the heat-fusible resin layer (from the outermost layer toward the innermost layer) 40) is vacuum-sealed with a gas barrier laminated film (A) for a vacuum heat insulating material. The core material (B) is covered and depressurized with two gas barrier laminated films (A) for vacuum heat insulating material facing the heat-fusible resin layer (40), and the gas barrier laminated film for vacuum heat insulating material is obtained. The overlapping portion (90) of the film (A) is heat-sealed and sealed.

In the vacuum heat insulating material of the present invention, the decompression of the core material (B) is preferably 0.1 to 10 Pa, more preferably 1 to 5 Pa. If it is this range, it is excellent in vacuum heat insulation.
The vacuum heat insulating material (C) of the present invention is obtained by sealing the core material (B) with two gas barrier laminated films (A) for vacuum heat insulating material under reduced pressure, but the shape of the core material (B) is suitable for use. It can be appropriately selected depending on the case. FIG. 5 shows one embodiment of a vacuum heat insulating material obtained by sealing a rectangular core material under reduced pressure, but is not limited to such a flat plate, and is suitable for the location of the vacuum heat insulating material. The shape can be selected as appropriate.

(3) Gas barrier laminated film for vacuum heat insulating material The gas barrier laminated film (A) for vacuum heat insulating material of the present invention is formed by laminating a gas barrier layer and a heat-fusible resin layer, and the gas barrier layer comprises polyvinyl alcohol. A silicon-containing vapor-deposited film is laminated on both sides of the resin film with a thickness of 150 to 4000 angstroms, and each of the vapor-deposited films has a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² represents 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 the valence of M. A gas barrier property obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by (1)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Gas barrier coating film is a gas barrier film provided by Narubutsu.

  Since the polyvinyl alcohol-based resin film has a hydrophilic group in the structure, the gas permeation rate is increased under high humidity and the gas barrier property is easily lowered. However, a vapor deposition film having a thickness of 150 to 4000 angstroms is formed on both surfaces. Thus, the gas barrier property can be remarkably improved, and further higher gas barrier property can be secured by laminating a predetermined gas barrier coating film.

(I) Base film The base film which comprises the gas barrier film used by this invention is a polyvinyl alcohol-type resin film. For example, there are a polyvinyl alcohol film and an ethylene vinyl copolymer film. Although these are inherently excellent in gas barrier properties, the gas barrier properties are likely to be lowered under high humidity. An object of the present invention is to provide a gas barrier laminate film that uses these films that are inherently excellent in gas barrier properties and can ensure high gas barrier properties even under high humidity.

  Polyvinyl alcohol may be partially saponified polyvinyl alcohol in which several tens of percent of acetate groups remain, or completely saponified polyvinyl alcohol in which no acetate groups remain. Moreover, the modified polyvinyl alcohol by which the hydroxyl group was modified | denatured may be sufficient, and it does not specifically limit. However, from the viewpoint of gas barrier properties, the preferable degree of saponification is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.

  The ethylene / vinyl alcohol copolymer is obtained by saponification of a copolymer of ethylene and vinyl acetate, that is, a random copolymer of ethylene-vinyl acetate, and has several tens of acetate groups. The saponification product is not particularly limited, including a partially saponified product remaining in mol% to a completely saponified product in which only a few mol% of acetic acid groups remain or no acetic acid groups remain. However, from the viewpoint of gas barrier properties, the preferable degree of saponification is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%.

  As the polyvinyl alcohol-based resin film, any of an unstretched film of the resin and a film stretched in a uniaxial direction or a biaxial direction can be used. A stretched film is preferable in terms of excellent water resistance and heat resistance.

  In the present invention, as the film, for example, the above-mentioned resin is used, and the above-mentioned various resins are formed by using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, and the like. Can be used alone, and for example, a film formed by stretching in a uniaxial or biaxial direction using a tenter method or a tubular method can be used.

In this invention, as a film thickness of a polyvinyl alcohol-type resin film, it is 8-100 micrometers, More preferably, it is 12-30 micrometers.
In addition, when the above resin is used and the film is formed, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, Various plastic compounding agents and additives can be added for the purpose of improving and modifying antifungal properties, electrical properties, strength, etc. The amount of addition is extremely small to tens of percent Depending on the purpose, it can be optionally added.

  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. Furthermore, a modifying resin or the like can also be used.

  In addition, as a polyvinyl alcohol-type resin film, a commercial item may be sufficient, the product name "BOVLON" by Nippon Synthetic Chemical Industry Co., Ltd. as a biaxially stretched polyvinyl alcohol film, and the Kuraray company as a biaxially stretched ethylene vinyl alcohol copolymer film. There is a product name "EVAL".

(Ii) Surface treatment In this invention, when forming the vapor deposition film | membrane of carbon containing silicon oxide in one surface of the said base film, you may surface-treat a base film previously. As a result, the adhesion to the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film can be improved. Similarly, surface treatment may be performed on the vapor deposition layer.

  Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

  In addition, a primer coating agent, an undercoat agent, an anchor coating agent, a vapor deposition anchor coating agent, or the like can be arbitrarily applied in advance to the surface of various films used in the present invention for surface treatment. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefins such as polyethylene or polypropylene. A resin composition containing a resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. For example, immediately before forming a vapor-deposited film of carbon-containing silicon oxide by chemical vapor deposition described later, in-line plasma treatment removes moisture, dust, etc. on the surface of the substrate film and smoothes the surface. Surface treatment such as activation, activation, etc. can be made possible. In addition, plasma treatment can be performed after vapor deposition to improve adhesion. In the present invention, as the plasma treatment, it is preferable to perform the plasma discharge treatment in consideration of the plasma output, the type of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

  In the present invention, the adhesion of the carbon-containing silicon oxide vapor-deposited film, the heat-fusible resin layer, the printed layer and other layers and films is also improved on the surface of the film other than the base film. Therefore, any of the above surface treatments may be performed.

(Iii) Vapor deposition film of carbon-containing silicon oxide The vapor deposition film of carbon-containing silicon oxide is preferably formed using an organic silicon compound as a vapor deposition monomer by chemical vapor deposition. As the chemical vapor deposition method, for example, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like can be used. Among these, it is particularly desirable to manufacture by film formation using a low temperature plasma chemical vapor deposition method.

  In the present invention, specifically, on one surface of the base film, a film-forming monomer gas composed of one or more organic silicon compounds is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas. Of carbon-containing silicon oxide made of silicon oxide or the like using a low temperature plasma chemical vapor deposition method using oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. It can be manufactured by forming a single layer film consisting of one layer of a vapor deposition film, a multilayer film consisting of two or more layers, or a composite film.

  In the above, as a low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, microwave plasma can be used, and in the present invention, in order to obtain a highly active stable plasma, It is desirable to use a high frequency plasma generator.

An example of a method for forming a vapor-deposited film of carbon-containing silicon oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 6 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.
The plasma chemical vapor deposition apparatus (100) of FIG. 6 forms a carbon-containing silicon oxide layer on a base film supply chamber (110), a first film formation chamber (120) including a vacuum chamber, and the base film. It is comprised from the winding chamber (150) which winds up the converted film. The substrate film (101) is unwound from an unwinding roll (111) disposed in the substrate film supply chamber (110), and the substrate film (101) is assisted in the first film formation chamber (120). It is conveyed on the circumferential surface of the cooling / electrode drum (122) at a predetermined speed via the roll (121). On the other hand, vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. is supplied from a gas supply device (125), a raw material volatilization supply device (124), etc. This is introduced into the first film formation chamber (120) through the raw material supply nozzle (127). The mixed gas composition for vapor deposition is supplied onto the substrate film (101) conveyed on the peripheral surface of the cooling / electrode drum (122), and plasma is generated and irradiated by glow discharge plasma (128) for oxidation. A vapor-deposited film of carbon-containing silicon oxide such as silicon is formed. Subsequently, the base film (101) on which the vapor-deposited film of carbon-containing silicon oxide such as silicon oxide is formed is transferred to the winding chamber (150) through the auxiliary roll (123), where the winding roll (151) is transferred. ), A film having a deposited film of carbon-containing silicon oxide by plasma chemical vapor deposition can be produced.

  A predetermined power is applied to the cooling / electrode drum (122) from a power source (160) disposed outside the first film formation chamber (120), and in the vicinity of the cooling / electrode drum (122), The generation of plasma is promoted by disposing a magnet (129). Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, 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. When the substrate film is conveyed in this state, the glow discharge plasma causes the substrate on the peripheral surface of the cooling / electrode drum to be conveyed. A vapor-deposited film of carbon-containing silicon oxide such as silicon oxide can be formed on the film. In FIG. 6, reference numeral (153) denotes a vacuum pump.

In the present invention, a vapor deposition film of carbon-containing 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. However, it is closely bonded to one surface of the base film to form a dense thin film having high flexibility, etc., and generally has the general formula SiO _x C _y (where x is 0.5 to 3.0). , Y is 0.1 to 2.5)) and is a continuous thin film mainly composed of silicon oxide. The carbon-containing silicon oxide vapor-deposited film has a general formula SiO _x C _y (where x is 1.3 to 1.9 and y is 0.5 to 1.0 from the viewpoint of transparency, barrier properties, and the like. It is preferably a thin film mainly composed of a vapor-deposited film of carbon-containing silicon oxide represented by: The value of x varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. In general, the gas permeability decreases as the value of x decreases, and the film itself becomes yellowish. It becomes tinged and becomes less transparent.

In the present invention, the vapor-deposited film of carbon-containing silicon oxide is mainly composed of silicon oxide, and further, at least one compound of carbon, hydrogen, silicon or oxygen or at least one compound composed of two or more elements is formed by chemical bonding or the like. It consists of the vapor deposition film to contain. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and 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 vapor-deposited film of carbon-containing silicon oxide may be varied by changing the conditions of the vapor deposition process. Under the present circumstances, as content which said compound contains in the vapor deposition film | membrane of carbon containing silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. When the content is less than 0.1% by mass, the impact resistance, spreadability, flexibility and the like of the vapor-deposited film of carbon-containing silicon oxide are insufficient, and scratches, cracks, etc. are likely to occur due to bending, etc. In some cases, it is difficult to stably maintain the barrier property. On the other hand, if it exceeds 50% by mass, the barrier property may be deteriorated.

  In the present invention, the surface of the base film is cleaned by plasma, and polar groups, free radicals, and the like are generated on the surface. Therefore, the carbon-containing silicon oxide film made of silicon oxide or the like formed into a film The close adhesiveness with the base film is high.

  Further, in the present invention, in the vapor-deposited film of carbon-containing silicon oxide, the content of the above compound may increase or decrease from the surface of the vapor-deposited film of carbon-containing silicon oxide in the depth direction. For example, in the case of decreasing from the surface in the depth direction, this improves the impact resistance and the like by the above compound on the surface of the carbon-containing silicon oxide vapor deposition film, and on the other hand, at the interface with the base film Since the content of the compound is small, the tight adhesion between the base film and the carbon-containing silicon oxide deposited film becomes strong. Such a vapor-deposited film of carbon-containing silicon oxide is not limited to the case where it is composed of one layer, and may be a multilayer film in which two or more layers are laminated, for example.

  In order to form the multilayer deposition layer, a chemical vapor deposition apparatus (100) having a plurality of vacuum chambers as deposition chambers is used to form carbon-containing silicon oxide deposition films having different compositions. be able to. FIG. 7 is used to illustrate the case of having a three-layer deposited film. The plasma chemical vapor deposition apparatus (100) of FIG. 7 includes a base film supply chamber (110), a first film formation chamber (120), a second film formation chamber (130), a third film formation chamber (140), And it is comprised from the winding chamber (150) which winds up the film which formed the carbon-containing silicon oxide layer on the base film, and laminated | stacked it. In the base film supply chamber (110), the base film (101) is fed from the unwinding roll (111) to the first film formation chamber (120), and the base film (101) is further transferred to the auxiliary roll (121). ) On the circumferential surface of the cooling / electrode drum (122) at a predetermined speed. In the first film formation chamber (120), a raw material volatilization supply device (124), a gas supply device (125), etc. are used to form a film-forming monomer gas, oxygen gas, inert gas, and the like. The above-mentioned mixed gas composition for film formation is introduced into the first film formation chamber (120) through the raw material supply nozzle (127) while supplying the other and the like and adjusting the mixed gas composition for film formation composed of them. Then, a plasma is generated by glow discharge plasma (128) on the substrate film (101) conveyed on the peripheral surface of the cooling / electrode drum (122), and this is irradiated with silicon oxide. A first carbon-containing silicon oxide layer made of, for example, is formed.

  The base film (101) obtained by forming the carbon-containing silicon oxide film of the first layer in the first film forming chamber (120) is transferred to the second film forming chamber via the auxiliary rolls (123), (131) and the like. (130), and then, in the same manner as described above, the base film (101) on which the carbon-containing silicon oxide film of the first layer is formed is cooled and conveyed onto the peripheral surface of the electrode drum (132) at a predetermined speed. To do. Thereafter, in the same manner as described above, from the raw material volatilization supply device (134), the gas supply device (135), etc., the film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organic silicon compounds are removed. Supplying the above-mentioned mixed gas composition for film formation into the second film formation chamber (130) through the raw material supply nozzle (137) while adjusting the mixed gas composition for film formation comprising them, and On the carbon-containing silicon oxide film of the first layer of the base film (101) obtained by forming the carbon-containing silicon oxide film of the first layer conveyed on the cooling / electrode drum (132) peripheral surface, Plasma is generated by glow discharge plasma (138) and irradiated to form a second-layer carbon-containing silicon oxide film made of silicon oxide or the like.

  Further, the carbon-containing silicon oxide films of the first layer and the second layer are formed in the second film formation chamber (130), and the laminated base film (101) is added to the auxiliary rolls (133), (141), etc. Then, the substrate film (101) formed by forming the carbon-containing silicon oxide films of the first layer and the second layer at a predetermined speed is delivered to the third film formation chamber (140) through It is conveyed on the circumferential surface of the cooling / electrode drum (142). Next, a film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organic silicon compounds are supplied from the raw material volatilization supply device (144) and the gas supply device (145), and the like. The film-forming mixed gas composition is introduced into the third film-forming chamber (140) through the raw material supply nozzle (147) while adjusting the film-forming mixed gas composition. The carbon-containing silicon oxide films of the first layer and the second layer transported on the peripheral surface of the electrode drum (142) are formed, and on the carbon-containing silicon oxide film of the second layer of the laminated base film 1, Plasma is generated by glow discharge plasma (148) and irradiated to form a third-layer carbon-containing silicon oxide film made of silicon oxide or the like.

  Next, the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are formed as described above, and the base film (101) on which these layers are stacked is wound through the auxiliary roll (143). It takes out to a take-up chamber (150), and then winds up to a take-up roll (151).

  Each cooling / electrode drum (122), (132), (142) disposed in each of the first, second, and third film forming chambers (120), (130), (140). A predetermined power is applied from a power source (160) arranged outside each of the first, second, and third film forming chambers (120), (130), (140), and Magnets (129), (139), and (149) are arranged in the vicinity of the cooling / electrode drums (122), (132), and (142) to promote the generation of plasma. Although not shown, the plasma chemical vapor deposition apparatus is provided with a vacuum pump or the like, and it is needless to say that each film forming chamber or the like can be adjusted to be kept in vacuum. In addition, although the above is illustrated with three layers, a film formation chamber can be arbitrarily prepared to have a multilayer structure of four or more layers.

In the above, the inside of the vacuum chamber is decompressed by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable. Further, in the present invention, regardless of whether the vapor-deposited film of carbon-containing silicon oxide is composed of a single layer or a multilayer, the degree of vacuum when forming the vapor-deposited film of carbon-containing silicon oxide such as silicon oxide is Each vacuum chamber is decompressed by a vacuum pump and adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the degree of vacuum when forming a vapor-deposited film of carbon-containing silicon oxide such as silicon oxide by a conventional vacuum vapor deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the vacuum state setting time at the time of replacing the film, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized. Note that when there are a plurality of film formation chambers, the degree of vacuum may be the same or different in each chamber.

  Moreover, it is desirable to adjust the conveyance speed of a base film to about 10-300 m / min, Preferably, it is about 50-200 m / min. In plasma chemical vapor deposition, a predetermined voltage is applied to the cooling / electrode drum from the power source, so that glow discharge plasma is generated in the vicinity of the opening of the material supply nozzle in the film forming chamber and the cooling / electrode drum. Generated. The glow discharge plasma is derived from one or more gas components contained in the film-forming mixed gas composition. When the base film is transported at a constant speed within the above range, the glow discharge plasma causes the cooling to occur. A carbon-containing silicon oxide film made of silicon oxide or the like can be uniformly formed on the base film on the electrode drum peripheral surface.

In addition, in the mixed gas composition for film formation composed of the raw material organosilicon compound, oxygen gas, and inert gas, the gas mixing ratio of each gas component is that of the film forming monomer gas composed of one kind of organosilicon compound. The content is preferably adjusted in the range of 1 to 40% by mass, the oxygen gas content in the range of 0.1 to 70% by mass, and the inert gas content in the range of 1 to 60% by mass. In the case where the vapor deposition layer is composed of multiple layers, the ratio of the raw material monomer gas to oxygen gas (O ₂ ) may be changed in each vapor deposition layer. As a result, the amount of carbon in the carbon-containing silicon oxide film formed can be increased or decreased. When the amount of carbon increases, the number of C—C bonds and Si—CH ₃ bonds increases, and the flexibility is high. A water-repellent carbon-containing silicon oxide film having a high barrier property against water vapor can be formed. Further, when the carbon content in the carbon-containing silicon oxide layer formed into a film is reduced, Si—CH ₃ bonds are reduced and flexibility is inferior, but high gas barrier properties against oxygen and the like can be maintained. .

  In the present invention, the vapor-deposited film of carbon-containing silicon oxide uses, 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 above-mentioned physical properties can be confirmed by performing analysis by performing ion etching in the depth direction and performing elemental analysis of the deposited film of carbon-containing silicon oxide.

  In the present invention, the total film thickness of each vapor-deposited film of carbon-containing silicon oxide is preferably 150 to 4000 mm, more preferably 150 to 2000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 150 mm, it may be difficult to achieve a barrier effect. The film thickness 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 a means of changing the film thickness of the carbon-containing silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. Can be done by.

  In the case of the above-described multi-layer structure consisting of three layers, the thickness of the carbon-containing silicon oxide film constituting the first layer is preferably about 30 to 2000 inches, and the carbon-containing oxidation constituting the second layer. The film thickness of the silicon film is 20 to 2000 mm, preferably 30 to 1000 mm, and the carbon-containing silicon oxide film constituting the third layer has a film thickness of 20 to 2000 mm, preferably The range of 30 to 1000 mm is desirable. In the above, if the total is less than 150 mm, it is not preferable because the barrier property of itself does not develop, and if it exceeds 4000 mm, the film tends to crack and the like. This is not preferable because cracks tend to occur during winding. In the above, as a means for changing the film thickness of the carbon-containing silicon oxide layer, there is a method or a method of increasing the volume velocity of the layer, that is, increasing the amount of the monomer gas for film formation and the oxygen gas. It can be performed by a method of slowing the film forming speed.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of carbon-containing silicon oxide such as silicon oxide, 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, etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  In the present invention, a gas barrier laminated film can be produced by forming a vapor deposition film on one side of the base film by the above method and then forming the vapor deposition method on the other side of the base film again.

(Iv) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, 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. Contains the above alkoxide, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, and polycondensation by sol-gel method in the presence of sol-gel method catalyst, acid, water, and organic solvent A coating film comprising a gas barrier composition formed by coating the composition on a carbon-containing silicon oxide vapor deposition film on the base film to provide a coating film, 30 seconds at a temperature below the melting point of the base film It can be formed by heat treatment for 10 minutes.

  Further, the gas barrier composition is applied onto a carbon-containing silicon oxide vapor-deposited film on the base film, and two or more coating films are stacked, and the temperature of the base film is 20 ° C. to 180 ° C. You may heat-process for 30 second-10 minutes at the temperature below melting | fusing point, and may form the composite polymer layer which laminated | stacked two or more gas barrier coating films.

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. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.
In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such alkoxysilane, tetramethoxysilane Si (OCH _{3) 4,} tetraethoxysilane _{Si (OC 2 H 5) 4} , tetrapropoxysilane _{Si (O C 3 H 7)} 4, tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like can be exemplified.

When n is 1 or more, the general formula Rb _n Si (ORc) _4-m (wherein m represents an integer of 1, 2, 3; Rb and Rc are methyl, ethyl, Group, n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include 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) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

Further, in the present invention, condensation polymerization of the above alkoxysilanes can also be used, specifically, for example, can be used poly tetramethoxysilane, polytetra eth Kishishiran, and other like.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxy zirconium Zr (OCH _{3) 4,} tetraethoxy zirconium _{Zr (OC 2 H 5) 4} , tetraisopropoxy zirconium _{Zr (iso- O C 3 H 7} ) 4, tetra-n-butoxy zirconium Zr (OC ₄ H _{9 4} ) Others can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra ethoxy titanium _{Ti (OC 2 H 5) 4} , tetraisopropoxy titanium _{Ti (iso- O C 3 H 7} ) 4, tetra-n-butoxy titanium _{Ti (OC 4 H 9) 4} , can be exemplified other like.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is o -OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film is coated. This is not desirable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film is coated.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer.

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  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 can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, 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%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention 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 is 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 a polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Gas barrier composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. . For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, sulfuric, hydrochloric, mineral acids such as nitric acid, and acetic, tartaric, etc. organic acids, may use other like. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative 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, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel method catalyst. It is -500 mass parts.

In the present invention, the gas barrier laminate film can be produced by the following method.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, the above gas barrier composition is applied onto the vapor-deposited film of carbon-containing silicon oxide on the base film and dried by a conventional method. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film coated with the gas barrier composition is heated at 50 to 300 ° C. and at a temperature not higher than the melting point of the base film, preferably at a temperature in the range of 70 to 200 ° C. for 0.05 to 60 minutes. To do. Thus, a gas barrier laminated film in which one or more gas barrier coating films of the gas barrier composition are formed on the carbon-containing silicon oxide vapor deposition film can be produced.

  A gas barrier laminate film obtained using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a gas barrier laminate film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, A gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied onto the coating film to form a second coating film, and a composite layer thereof is formed. A gas barrier laminate film with improved properties can be produced.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the gas barrier laminated film according to the present invention.

The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.
The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by hydrolysis by the action of the sol-gel method catalyst, and the hydrolyzed products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）を、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾル−ゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

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 the existing acid as a catalyst. The OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds. To do. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム上の炭素含有酸化珪素の蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム上の炭素含有酸化珪素の蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied on the vapor-deposited film of carbon-containing silicon oxide on the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed. A transparent coating film is formed on the deposited carbon-containing silicon oxide film. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the organic reactive group of the silane coupling agent or the hydroxyl group generated by hydrolysis is bonded to the hydroxyl group on the surface of the base film or the vapor-deposited film of carbon-containing silicon oxide on the base film. The adhesion between the material film or the surface of the carbon-containing silicon oxide vapor deposition film and the coating film is also good. Thus, in the present invention, the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction. The adhesion between the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer 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 aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). In particular, when used for so-called gas-filled packaging filled with N ₂ , CO ₂ gas, etc., the excellent gas barrier property is extremely effective for holding the filled gas. Furthermore, the gas barrier laminate film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

(V) Heat-fusible resin layer As the heat-fusible resin layer (40), it is possible to use polyolefin-based resins having various heat sealability that can be melted by heat and fused to each other. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) acrylic resin, one or more films made of a resin such as polyvinyl chloride resin or sheet or coated film and the like can be used.

  The heat-fusible resin layer may be a single layer or a multilayer made of one of the above resins, and the thickness of the heat-fusible resin layer is 15 to 130 μm. If the thickness is less than 15 μm, scratches and cracks may occur in the deposited film of carbon-containing silicon oxide.

(Vi) Plastic base film The plastic base film that can be used in the present invention is excellent in mechanical, physical, and chemical strength, and particularly excellent in heat resistance, moisture resistance, pinhole resistance, puncture resistance, and the like. Resin films can be widely used. For example, at least one of a polyester resin, a polyamide resin, a polyaramid resin, a polypropylene resin, a polycarbonate resin, a polyacetal resin, a fluorine resin, and the like can be suitably used. In the present invention, polyester resins such as polyethylene terephthalate, nylon resins, and polypropylene resins can be preferably used.

  In the present invention, the plastic substrate film may be any of an unstretched film of the resin and a film stretched in a uniaxial direction or a biaxial direction. In the present invention, it is particularly preferable to use a stretched nylon film, a biaxially stretched plastic substrate film or a biaxially stretched polypropylene film.

  In the present invention, the thickness of the plastic substrate film is not particularly limited as long as strength, puncture resistance, rigidity and the like can be ensured, but is preferably 6 to 100 μm, more preferably 9 to 50 μm.

(Vii) Anchor coat layer In this invention, a heat-fusible resin layer can be laminated | stacked by extrusion formation on the vapor deposition layer (20) and gas barrier coating film of a gas barrier film (70).

  When the heat-fusible resin layer (40) is formed by extrusion, the heat-fusible resin layer is preferably formed on the vapor-deposited film or the gas barrier coating film via an anchor coating agent. Examples of the anchor coating agent to be used include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, a thin film rich in flexibility and flexibility can be formed, its tensile elongation is improved, and it acts as a film having flexibility, flexibility, etc. on the vapor deposition film and gas barrier coating film. Improves processability such as laminating and printing, and avoids the occurrence of cracks in the deposited film and gas barrier coating film, and tight adhesion between the gas barrier laminated film and the heat-fusible resin layer The laminate strength can be improved.

In the present invention, the anchor coating agent is coated by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and the solvent, diluent or the like is dried, and the anchor according to the present invention is applied. An anchor coat layer with a coating agent can be formed. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). The anchor coat layer made of the anchor coat agent preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

(Viii) Laminating adhesive In the present invention, the gas barrier film (70) is laminated with a heat-fusible resin layer (40), a plastic substrate film (50), and the like to form a gas barrier laminated film for vacuum insulation (A ) Can be laminated using a dry laminate lamination method via a laminating adhesive (60).

  The adhesive for laminating comprises a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives Polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive type (meta ) Acrylic acid adhesive, chloroprene rubber, nitrile Beam, styrene - inorganic adhesive made of butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of low-melting glass, it is possible to use other adhesives.

  More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, a thin film rich in flexibility and flexibility can be formed, its tensile elongation is improved, and it acts as a film having flexibility, flexibility, etc. on the vapor deposition film and gas barrier coating film. Further, processability such as laminating and printing can be improved, and the occurrence of cracks or the like in the deposited film or gas barrier coating film can be avoided. The laminate adhesive layer made of the above-mentioned laminate adhesive preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

  The composition system of these adhesives 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 a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like.

Although there is no limitation in the usage-amount of the adhesive agent for lamination, Generally, it is 0.1-10 g / m < ² > (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

(Ix) Outer layer As the outer layer (80) constituting the gas barrier laminated film (100) for a vacuum heat insulating material, it has excellent properties in mechanical, physical, chemical, etc., and has excellent strength. A resin film or sheet excellent in heat resistance, moisture resistance, pinhole resistance, puncture resistance, and the like can be used. Specifically, a film or sheet of tough resin such as polyester resin, polyamide resin, polypropylene resin, or the like can be used. These films or sheets can be used as unstretched films, or stretched films stretched in a uniaxial direction or biaxial direction, but biaxially stretched films are used in terms of mechanical or heat resistance. preferable. The outer layer (80) is laminated in order to enhance physical properties such as strength of the gas barrier laminated film (100) for vacuum heat insulating material, and a plurality of outer layers (80) may be provided depending on the required quality. Thickness is 9-50 micrometers, and is determined according to the material structure and required quality which are used for the laminated body for vacuum heat insulating materials.

(X) Gas Barrier Laminate Film Production Method The gas barrier laminate film for a vacuum heat insulating material of the present invention uses an organosilicon compound as a monomer for vapor deposition by chemical vapor deposition on one side of a base film made of polyvinyl alcohol resin. To form a vapor-deposited film of carbon-containing silicon oxide, and then, on the other side, an organic silicon compound is supplied as a vapor-deposition monomer by chemical vapor deposition to form a vapor-deposited film of carbon-containing silicon oxide. A gas barrier laminated film (A) for a vacuum heat insulating material can be produced by laminating a heat-sealing layer (40) according to a conventional method. As the lamination method, the dry lamination method described above or an extrusion lamination method in which a thermoplastic resin is hot melt extruded from a T die and bonded together are used. Moreover, an outer layer (80), a printing layer, etc. can be provided in the gas barrier laminated film (A) for a vacuum heat insulating material. In addition, the gas barrier laminated film (A) for vacuum heat insulating material has an oxygen permeability and a water vapor permeability of 0.5 (cc / m ² · day) and 0.2 (g / m ² · day), respectively, as gas barrier properties. ) Or less, preferably 0.1 (cc / m ² · day), or 0.1 (g / m ² · day) or less.

The gas barrier film used in the present invention can be extremely improved in gas barrier properties by adjusting the thickness of the deposited film to 150 to 4000 angstroms. At that time, an organic silicon compound is supplied as a vapor deposition monomer by a chemical vapor deposition method to form a vapor deposition film of carbon-containing silicon oxide, whereby a hydrocarbon having a CH ₃ site in the vapor deposition film, SiH ₃ silyl, Hydrosilica such as SiH ₂ silylene and hydroxyl derivatives such as SiH ₂ OH silanol can be derived. Thereby, the impact resistance, spreadability, flexibility, etc. of the deposited film of carbon-containing silicon oxide can be improved, and scratches, cracks, etc. due to bending can be prevented. In particular, the surface of the base film is cleaned by plasma, and polar groups, free radicals, and the like are generated on the surface. Therefore, a carbon-containing silicon oxide film made of silicon oxide or the like to be formed into a film and the base film The tight adhesion of the material becomes high. Furthermore, by forming a gas barrier coating film, the laminate strength can be increased and the gas barrier property can be improved.

  As a result, the obtained gas barrier film can be wound up according to a conventional method to form a raw roll. If silicon, silicon monoxide, trisilicon tetranitride, or the like is simply supplied as a deposition source, the deposited film is not flexible, so that it is difficult to wind it as a raw roll. However, by forming the vapor deposition film by the above method, even a thick vapor deposition film of 150 to 4000 angstroms can form the raw fabric roll.

  In addition, since the raw fabric roll of the obtained gas barrier film has high hygroscopicity, it is preferable to perform moisture-proof packaging with aluminum foil or the like. When this gas barrier film is used and another gas barrier film or an outer layer is laminated with an adhesive for dry lamination, a gas barrier coating film (30) is deposited on the vapor deposition film (20) of the gas barrier film (70). ), And another layer can be laminated on the gas barrier coating film (30) by applying an adhesive for dry lamination. In such a case, a gas barrier coating film is formed. It is preferable to take up the film and perform moisture-proof packaging with aluminum foil or the like. Furthermore, when a heat seal layer is laminated on the obtained film, when a primer is previously applied to the vapor deposition film (20), the primer-coated film is wound and moisture-proof packaging is performed using an aluminum foil or the like. In this way, moisture absorption is prevented by wrapping the raw roll in each process, preventing moisture absorption of the obtained gas barrier film and the gas barrier laminated film for vacuum insulation material of the present invention, and ensuring high gas barrier properties. can do.

(4) Core material The core material (B) used in the vacuum heat insulating material of the present invention is a porous material having a core material porosity of 50% or more, more preferably 90% or more, and a wide range of materials having low thermal conductivity. Can be used.

  Examples of substances constituting such a core material include powder, foam, and fiber. The powder may be either inorganic or organic, and includes dry silica, wet silica, conductive powder, pearlite, and the like. A mixture of dry silica and conductive powder is advantageous when used in a temperature range in which an increase in internal pressure occurs because deterioration in the heat insulation performance associated with an increase in internal pressure of the vacuum heat insulating material is small. Furthermore, when a substance having a small infrared absorptance such as titanium oxide, aluminum oxide or indium-doped tin oxide is added as a radiation suppressing material, the infrared absorptivity of the core material can be reduced. Examples of the foam include urethane foam, styrene foam, phenol foam, and the like. Among these, a foam that forms open cells can be preferably used. Furthermore, as a fiber body, there exist an inorganic type and an organic type, and an inorganic fiber can be used conveniently from a viewpoint of heat insulation performance. Examples of such inorganic fibers include glass wool, glass fiber, alumina fiber, silica alumina fiber, silica fiber, and rock wool. It has low thermal conductivity and is easier to handle than powder.

  The core material (B) used in the present invention is not limited to the case of using these alone, and may be a composite material in which two or more kinds are mixed. In the present invention, it is preferable to use a core material that can be deformed into such a curved surface because it is intended to be used for a vehicle body that frequently uses curved surfaces such as railways and subways. Glass wool, glass fiber, alumina fiber, silica alumina fiber, silica fiber, rock wool and the like can be suitably used.

(5) Manufacture of vacuum heat insulating material The vacuum heat insulating material of the present invention is prepared by previously preparing a gas barrier laminated film for vacuum heat insulating material in advance as described above, and opposing the innermost layer of the obtained gas barrier laminated film for vacuum heat insulating material, The core material is placed on the outer periphery of the core material by using a bag making machine, the remaining three gas barrier laminated films are heat sealed, and then attached to a vacuum sealing machine. The opening can be sealed and manufactured in a state where the pressure is reduced to 3 Pa.

(6) Use of vacuum heat insulating material The vacuum heat insulating material of the present invention has a low thermal conductivity and is extremely excellent in heat insulating properties. For this reason, it can use suitably for household appliances, such as a refrigerator, a rice cooker, a pot, and a cooler box, and houses, such as an OA apparatus and a housing wall. Furthermore, it is also suitable for transportation containers, hydrogen fuel tanks, system buses, eco-cute hot water tanks, heat insulation boxes, and heat insulating walls around the heat generating parts of cars, airplanes, ships, trains, and the like.

Next, the present invention will be described in more detail by showing specific examples.
Example 1
(1) A biaxially stretched polyvinyl alcohol film having a thickness of 12 μm having corona-treated surfaces on both sides is used as a base film, and this is mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then the conditions shown below Then, a vapor-deposited film of carbon-containing silicon oxide having a thickness of 200 mm was formed on the biaxially stretched polyvinyl alcohol film.

(Deposition conditions)
Deposition film; corona-treated surface introduction gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm)
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar
Cooling and electrode drum power supply: 10kW
Line speed: 100 m / min
(2) Immediately after forming a vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the surface of the vapor deposition film, and the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7. Using a mixed gas consisting of 0: 2.5 (unit: slm), performing oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min, the carbon-containing silicon oxide A plasma-treated surface was formed in which the surface tension of the deposited film was improved to 54 dyn / cm or more.

(3) A carbon-containing silicon oxide vapor deposition film having a thickness of 200 mm is formed on the other surface of the base film in the same manner as in the above (1), and immediately after the vapor deposition film is formed, , Using a glow discharge plasma generator, using a mixed gas of power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm), mixed gas pressure 6 Oxygen / argon mixed gas plasma treatment was performed at × 10 ⁻⁵ Torr and a treatment speed of 420 m / min to form a plasma treated surface in which the surface tension of the deposited film of carbon-containing silicon oxide was improved to 54 dyn / cm or more.

  (4) To the mixed solution of composition a prepared according to the composition shown in Table 1, the previously prepared hydrolyzed solution of composition b is added and stirred to obtain a colorless and transparent barrier coating solution, which is a gravure roll coating method (3) is coated on the plasma-treated surface of the vapor-deposited film on both sides of the film, and then heat-treated at 180 ° C. for 60 seconds to form a gas barrier coating film having a thickness of 0.3 μm (in the dry operation state). This formed a gas barrier film.

（５） 前記ガスバリア性塗布膜を形成したガスバリア性フィルムの一方に厚さ１２μｍのポリエチレンテレフタレートフィルムを、他面に厚さ５０μｍのポリエチレンフィルムをそれぞれドライラミネート用接着剤を介して積層し、更に前記ポリエチレンテレフタレートフィルムの外側に厚さ１５μｍの延伸ポリアミドフィルムをドライラミネート用接着剤を介して積層し、前記ガスバリア性フィルムの最外層に延伸ポリアミドフィルム、最内層にポリエチレンフィルムが積層された真空断熱材用ガスバリア性積層フィルムを製造した。なお、上記（１）、上記（３）の蒸着処理の後、および前記ガスバリア性塗布膜の形成後は、直ちにフィルムにアルミ箔による防湿包装を行った。

(5) A 12 μm thick polyethylene terephthalate film is laminated on one side of the gas barrier film on which the gas barrier coating film is formed, and a 50 μm thick polyethylene film is laminated on the other side via an adhesive for dry lamination, For vacuum heat insulating materials, a stretched polyamide film with a thickness of 15 μm is laminated on the outside of the polyethylene terephthalate film via an adhesive for dry lamination, and the stretched polyamide film is laminated on the outermost layer of the gas barrier film and the polyethylene film is laminated on the innermost layer. A gas barrier laminate film was produced. In addition, after the vapor deposition process of said (1) and said (3), and after formation of the said gas-barrier coating film, the moisture-proof packaging by aluminum foil was performed to the film immediately.

  (6) About the obtained gas barrier film and the gas barrier laminated film for vacuum heat insulating materials, oxygen permeability and water vapor permeability were measured under the following conditions. The results are shown in Tables 2 and 3. In Tables 2 and 3, the oxygen permeability is 0.1 or less and the water vapor permeability is 0.02 or less means that it is below the measurement limit value.

Moreover, the heat conductivity was measured with the following method about the obtained gas-barrier laminated film for vacuum heat insulating materials. The results of thermal conductivity are shown in Table 3.
(I) Measurement of oxygen permeability:
Measurement was performed with a measuring instrument (model name: OX-TRAN 2/21) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.

(Ii) Measurement of water vapor permeability:
The measurement was performed with a measuring instrument (model name, Permatran 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH. The results are shown in Table 1.

(Iii) Thermal conductivity The thermal conductivity was measured by JIS A1412-3 heat flow meter method using a thermal conductivity measuring device Auto Lambda HC-074 manufactured by Eihiro Seiki.

(Example 2)
(1) A double-sided vapor-deposited film of an ethylene vinyl copolymer in the same manner as in Example 1 except that a biaxially stretched film of a 12 μm-thick ethylene vinyl copolymer having corona-treated surfaces on both sides was used as the base film. A gas barrier film was obtained.

  (2) A gas barrier laminated film for a vacuum heat insulating material was produced in the same manner as in Example 1 except that the gas barrier film obtained in (1) above was used instead of the gas barrier film of Example 1.

(3) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for vacuum heat insulating material was heated. Conductivity was measured. The results are shown in Tables 2 and 3.

(Example 3)
(1) Using the gas barrier film of Example 1, a polyethylene terephthalate film having a thickness of 12 μm on one side of the coating film having a gas barrier property, and a polyethylene film having a thickness of 50 μm on the other side via an adhesive for dry lamination. A gas barrier laminated film for a vacuum heat insulating material, in which a polyethylene terephthalate film was laminated on the outermost layer of the gas barrier film and a polyethylene film was laminated on the innermost layer, was manufactured.

(2) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for vacuum heat insulating material was heated. Conductivity was measured. The results are shown in Tables 2 and 3.

(Example 4)
(1) Using the gas barrier film of Example 2, a stretched polypropylene film with a thickness of 25 μm on one side of the gas barrier coating film and a polyethylene film with a thickness of 50 μm on the other side, respectively, via an adhesive for dry lamination A gas barrier laminated film for a vacuum heat insulating material was manufactured by laminating and stretching a polypropylene film as an outermost layer of the gas barrier film and a polyethylene film as an innermost layer.

(2) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for vacuum heat insulating material was heated. Conductivity was measured. The results are shown in Tables 2 and 3.

(Example 5)
(1) Using the gas barrier film of Example 1, a stretched polyamide film having a thickness of 15 μm on one side of the gas barrier coating film and a polyethylene film having a thickness of 50 μm on the other side via an adhesive for dry lamination, respectively. A gas barrier laminated film for a vacuum heat insulating material was produced by laminating and stretching a polyamide film on the outermost layer of the gas barrier film and a polyethylene film on the innermost layer.

(2) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for vacuum heat insulating material was heated. Conductivity was measured. The results are shown in Tables 2 and 3.

(Comparative Example 1)
(1) A biaxially stretched polyvinyl alcohol film having a thickness of 12 μm having corona-treated surfaces on both sides is used as a base film, and this is mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then the conditions shown below Then, a vapor-deposited film of carbon-containing silicon oxide having a thickness of 200 mm was formed on the stretched polyvinyl alcohol film.

(Deposition conditions)
Deposition film; corona-treated surface introduction gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm)
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar
Cooling and electrode drum power supply: 10kW
Line speed: 100 m / min
(2) Immediately after forming a vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the surface of the vapor deposition film, and the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7. Using a mixed gas of 0: 2.5 (unit: slm), oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min, and a silicon oxide vapor deposition film is formed. A plasma-treated surface with the surface tension improved to 54 dyn / cm or more was formed.

(3) Next, a gas barrier coating film was formed on one of the plasma-treated surfaces of the deposited film in the same manner as in Example 1 to obtain a gas barrier film.
(4) A polyethylene film having a thickness of 50 μm is laminated on the gas barrier coating film of the comparative gas barrier film and a polyethylene terephthalate film having a thickness of 12 μm is laminated on the other surface via an adhesive for dry lamination, and the polyethylene terephthalate film is further laminated. A gas barrier property for comparative vacuum heat insulating material in which a stretched polyamide film having a thickness of 15 μm is laminated on the outside of the gas barrier film via an adhesive for dry lamination, and a stretched polyamide film is laminated on the outermost layer of the gas barrier film and a polyethylene film is laminated on the innermost layer. A laminated film was produced. In addition, after the vapor deposition process of said (1) and said (3) and formation of the said gas-barrier coating film, the film was immediately moisture-proof-packed with aluminum foil.

(5) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for comparative vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for comparative vacuum heat insulating material. The thermal conductivity of was measured. The results are shown in Tables 2 and 3.

(Comparative Example 2)
(1) A biaxially stretched film of ethylene vinyl copolymer having a thickness of 12 μm having corona-treated surfaces on both sides as a base film is mounted on a take-up roll of a take-up vacuum deposition apparatus, and then this is fed out. The following deposition conditions are applied by vacuum deposition using an electron beam (EB) heating system while supplying oxygen gas to the corona-treated surface of a biaxially stretched film of ethylene vinyl copolymer using aluminum as a deposition source. Thus, a vapor deposition film of aluminum oxide having a thickness of 200 mm was formed.

(Deposition conditions)
Deposition surface: Corona-treated surface,
Deposition source: Aluminum,
Degree of vacuum in the deposition chamber (before oxygen introduction): 2 to 10 × 10 ⁻⁵ mbar,
Degree of vacuum in the deposition chamber (after oxygen introduction): 1 to 10 × 10 ⁻⁴ mbar,
Line speed: 600 m / min,
(2) Immediately after forming the 200 nm thick aluminum oxide vapor deposition film as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 9 kW, oxygen gas (O ₂ ): argon gas. Using a mixed gas of (Ar) = 7.0: 2.5 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min. A plasma-treated surface with the surface tension of the vapor deposition film surface of aluminum oxide improved to 54 dyn / cm or more was formed to obtain an aluminum vapor deposition film (1).

  (3) The above (1), (2) except that a 12 μm stretched polyethylene terephthalate film having corona-treated surfaces on both sides is used as a base film instead of a biaxially stretched film of ethylene vinyl copolymer having a thickness of 12 μm. ) To obtain an aluminum deposited film (2).

(4) The said aluminum vapor deposition film (1) and the aluminum vapor deposition film (2) were adhere | attached through the adhesive layer for dry lamination, and the gas-barrier film was obtained.
(5) A gas barrier laminated film for a comparative vacuum heat insulating material was produced in the same manner as in Example 5 except that the gas barrier film was used instead of the gas barrier film of Example 5.

(6) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for comparative vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for comparative vacuum heat insulating material was measured. The thermal conductivity of was measured. The results are shown in Tables 2 and 3.

(Comparative Example 3)
(1) Using the comparative gas barrier film obtained in Comparative Example 1, dry laminate each of a 50 μm thick polyethylene film on the gas barrier coating film of the comparative gas barrier film and a 12 μm thick polyethylene terephthalate film on the other surface A gas barrier film was produced in which a polyethylene terephthalate film was laminated on the outermost layer of the comparative gas barrier film and a polyethylene film was laminated on the innermost layer.

(2) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for comparative vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for comparative vacuum heat insulating material was measured. The thermal conductivity of was measured. The results are shown in Tables 2 and 3.

(Comparative Example 4)
(1) A carbon-containing oxide having a thickness of 200 mm on both sides of polyethylene terephthalate in the same manner as in Example 1 except that a 12 μm thick biaxially stretched polyethylene terephthalate film having corona-treated surfaces on both sides was used as the base film. A silicon deposited film was formed.

(2) Immediately after forming a vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the surface of the vapor deposition film, and the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7. Using a mixed gas consisting of 0: 2.5 (unit: slm), performing oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min, the carbon-containing silicon oxide A plasma-treated surface was formed in which the surface tension of the deposited film was improved to 54 dyn / cm or more.

(3) In the same manner as in Example 1, a gas barrier coating film was formed on the plasma treated surface to obtain a gas barrier film.
(4) A stretched polyamide film having a thickness of 15 μm is laminated on one side of the gas barrier film on which the gas barrier coating film is formed, and a polyethylene film having a thickness of 50 μm is laminated on the other side via an adhesive for dry lamination, A comparative gas barrier laminate film in which a stretched polyamide film was laminated on the outermost layer and a polyethylene film was laminated on the innermost layer was produced.

  (5) In the same manner as in Example 1, the obtained gas barrier film and the gas barrier laminated film for comparative vacuum heat insulating material were measured for oxygen permeability and water vapor permeability, and the gas barrier laminated film for comparative vacuum heat insulating material. The thermal conductivity of was measured. The results are shown in Tables 2 and 3.

（結果）
（１） 実施例１〜５と比較例１〜４とを比較すると、実施例１〜５の本発明の真空断熱材用ガスバリア性積層フィルムは、いずれも水蒸気透過性が０．０２ｇ／ｍ２・ｄａｙ以下と水蒸気バリア性に優れることが判明した。

(result)
(1) When Examples 1 to 5 and Comparative Examples 1 to 4 are compared, the gas barrier laminated films for vacuum heat insulating materials of Examples 1 to 5 each have a water vapor permeability of 0.02 g / m 2 ···. It was found that the water vapor barrier property was excellent as well as day or less.

  (2) When Examples 1 to 5 and Comparative Examples 1 to 4 are compared, the gas barrier laminate films for vacuum heat insulating materials of Examples 1 to 5 of the present invention each have a thermal conductivity of 0.0032 W after 2 weeks. The gas barrier laminated film for vacuum heat insulating materials of Comparative Examples 1 to 4 was 0.0040 W / m · K or higher, which is higher than the gas barrier laminated film for vacuum heat insulating material of the present invention. showed that. This is considered to be derived from the fact that the gas barrier property is not sufficient, and therefore it is difficult to maintain the vacuum.

  The gas barrier laminated film for vacuum heat insulating materials according to the present invention is excellent in gas barrier properties, heat insulating properties, and flexibility, and can be suitably used as a covering material for vacuum heat insulating materials in home appliances, OA equipment, and houses.

10 ... base film,
20 ... deposited film,
40 ... heat-fusible resin layer,
50 ... plastic base film,
60 ... Laminate adhesive layer,
70: Gas barrier film,
80 ... outer layer,
90 ... Overlapping portion of the gas barrier laminated film for vacuum heat insulating material,
A: Gas barrier laminated film for vacuum heat insulating material,
B ... Core material C ... Vacuum insulation material,
100: Plasma chemical vapor deposition apparatus,
101 ... substrate film,
110 ... Base film supply chamber,
111 ... unwinding roll,
120: first film formation chamber,
121, 123, 131, 133, 141, 143 ... auxiliary rolls,
122, 132, 142 ... cooling / electrode drum,
124, 134, 144 ... Raw material volatilization supply device,
125, 135, 145 ... gas supply device,
127, 137, 147 ... Raw material supply nozzle 128, 138, 148 ... Glow discharge plasma,
129, 139, 149 ... magnets,
130 ... second film formation chamber,
140: third film formation chamber,
150 ... take-up chamber,
153 ... Vacuum pump,
160: Power supply.

Claims (7)

A gas barrier laminated film for a vacuum heat insulating material formed by laminating a gas barrier layer and a heat-fusible resin layer,
The gas barrier layer on both sides of the polyvinyl alcohol Ruff Irumu, silicon-containing deposited film formed by plasma chemical vapor deposition method are stacked in a thickness of 150-4000 Angstroms, and each of the deposition film, 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 the valence of M.) and contains at least one alkoxide represented by the following formula: and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. further, the gas barrier coating film is formed by gas barrier composition obtained by polycondensation by the sol-gel method, gas barrier water vapor permeability is less 0.08g / m ² · day Fi A beam, the gas barrier laminate film for vacuum insulation. The deposition film, a plasma chemical vapor phase growth method is a vapor-deposited film of an organic silicon compound carbon containing silicon oxide formed by supplying a deposition monomer gas-barrier multilayer film for vacuum heat insulating material according to claim 1. Wherein the gas barrier layer, further characterized in that the plastic base film is laminated, the gas barrier laminate film for vacuum heat insulating material according to any one of claims 1-2. The gas barrier laminate film for a vacuum heat insulating material according to claim 3 , wherein the plastic base film and the heat-fusible resin layer are respectively laminated via an adhesive for dry lamination. The vacuum heat insulating material formed by sealing a core material under reduced pressure with the gas-barrier laminated film for vacuum heat insulating materials of any one of Claims 1-4 . Home appliance equipped with the vacuum heat insulating material according to claim 5 . A house equipped with the vacuum heat insulating material according to claim 5 .

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