JP2008155437A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film excellent in gas barrier properties, heat resistance and tearing properties. <P>SOLUTION: The gas barrier laminated film includes a base film, a deposited film of a carbon-containing silicon oxide, a gas barrier coating film and a coating thin film of a polyurethane resin composition. The deposited film of the carbon-containing silicon oxide is a deposited film of the carbon-containing silicon oxide deposited on one face of the base film by supplying an organosilicon compound by a chemical gas phase growing method as a depositing monomer. The gas barrier coating film comprises at least one or more kinds of alkoxides of formula R<SP>1</SP><SB>n</SB>M(OR<SP>2</SP>)<SB>m</SB>(wherein R<SP>1</SP>and R<SP>2</SP>are each a 1-8C organic group, M is a metal atom, n is an integer of ≥0, m is an integer of ≥1, and n+m is a valence of M), a polyvinyl alcohol based resin and/or an ethylene-vinyl alcohol copolymer, and furthermore, is a gas barrier coating film of a gas barrier composition obtained by polycondensation by a sol-gel method. This gas barrier laminated film is excellent in retort resistance and boiling resistance. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a gas barrier laminate film, and more particularly to a gas barrier laminate film having excellent gas barrier properties that prevent permeation of oxygen, water vapor, etc., transparency, and excellent tearability.

  Conventionally, as packaging materials for filling and packaging foods, beverages, chemicals, miscellaneous goods, etc., various kinds of materials that block or block the transmission of oxygen gas, water vapor, etc. to prevent alteration, discoloration, etc. of the contents. A barrier laminate having the following form has been developed and proposed.

There is a pouch for retort as an application of such a barrier laminate, and generally a sterilization process is performed at a temperature of about 110 to 130 ° C. and a pressure of 1 to 3 kgf / cm ² · G for about 20 to 60 minutes. As a barrier laminate material used under such retort conditions, there is a packaging material using a metal foil such as aluminum, which is frequently used as having high gas barrier properties without being affected by temperature and humidity. However, when metal foil is used, the contents cannot be confirmed, and the metal foil remains as an incombustible material when discarded after use. For this reason, the barriering laminated material which can see through the content without using metal foil is developed.

  For example, as a barrier laminate used under the above retort conditions, there is a film in which a barrier coat layer is provided on a vapor deposition layer in order to further improve the barrier property (Patent Documents 1 and 2). In Patent Document 1, a primer layer, a vapor deposition thin film layer, a gas barrier film layer, and a seal layer are sequentially laminated on a transparent plastic material. A primer layer is provided to improve adhesion, and examples of the primer layer include a mixture of a polyester resin alone, a polyester resin and one or more mixed resins selected from an isocyanate resin, an epoxy resin, and a melamine resin. Has been. According to the above configuration, it is assumed that transparency and gas barrier properties are excellent, and delamination or the like is not generated in a seal after boiling and retort sterilization.

  In addition, the gas barrier film laminate described in Patent Document 2 is one in which a primer layer, a vapor-deposited thin film layer, a gas barrier coating layer, and an overcoat layer are sequentially laminated on a plastic material. In order to improve adhesion, a primer layer is provided, and examples of the primer layer include acrylic polyols, isocyanate compounds, and silane coupling agents. In Patent Document 2, an adhesive primer layer having excellent heat resistance and dimensional stability is provided on at least one surface of a plastic substrate, and then a vapor-deposited thin film layer / gas barrier film layer is provided as a gas barrier layer, and further excellent in heat resistance. Since it has a protective layer, it has gas barrier properties similar to those of metal foils, and it can suppress deterioration of barrier properties after various sterilization treatments such as boil sterilization and retort sterilization. The overcoat layer is made of a composition containing a styrene / maleic anhydride copolymer, thereby absorbing / relaxing stress from an adhesive portion or a sealant layer by boil / retort treatment, and depositing a thin film layer and a gas barrier property. It is said to protect the coating layer.

  On the other hand, in a gas barrier laminated film having a vapor deposition film, there is also a technique for improving adhesion without providing a primer layer between a substrate and a vapor deposition film layer (Patent Document 3). In Patent Document 3, after a polyethylene terephthalate film provided with a vapor deposition layer made of an inorganic oxide is immersed in treated water and a part of the vapor deposition layer is removed, X-ray photoelectron spectroscopy measurement of the film surface is performed, and C1s A strong adhesion vapor-deposited film having a functional group ratio (COO / C-C) determined from waveform analysis of 0.23 or less is disclosed. When the inorganic oxide is removed by immersion in an aqueous solution to which an amine-based alkali has been added, and the functional group ratio (COO / C-C) is 0.23 or less, the PET film and the inorganic oxide layer are It shows extremely good adhesion.

  Furthermore, there is also a film for retort use comprising a vapor-deposited film of carbon-containing silicon oxide, a gas barrier coating film, an intermediate substrate and a heat-sealable resin layer on a substrate film (Patent Document 4). According to the patent document, a laminate having strength and the like by an intermediate base material and having various properties such as heat resistance, moisture resistance, heat sealability, pinhole resistance, puncture resistance, transparency, and the like. It is said that it is a material.

Furthermore, as a characteristic requested | required of the packaging material, the tearability at the time of opening is also requested | required besides the intensity | strength in the said retort processing and boil processing. Even if easy opening is ensured by V-notch, U-notch, I-notch, etc., if the film itself is not torn easily, it is not easy to open after the notch, and even if it tears, more force is required than necessary. , Troubles such as not being able to tear in a straight line may occur, and clothes and furniture may be soiled. For this reason, there is also a gas barrier film that ensures tearability as well as gas barrier properties (Patent Document 5). Patent Document 5 discloses a gas barrier easily tearable polyester film in which a gas barrier organic layer is laminated on at least one side of a biaxially stretched film made of a raw material in which a predetermined modified PBT and PET are mixed at a predetermined ratio. The gas ariatic organic layer comprises a compound (A) having two or more hydroxyl groups in the molecule, and a compound in which at least one carboxyl group is bonded to each of three or more consecutive carbon atoms in the molecule ( B) and the mass ratio (A / B) of A to B is 65/35 to 15/85.
Japanese Patent Laid-Open No. 10-722 JP 2004-106443 A JP 2005-59265 A JP 2005-178802 A JP 2006-21378 A

  However, the laminates described in Patent Documents 1 to 4 do not have sufficient tearability, and the laminate material described in Patent Document 5 does not have sufficient gas barrier properties.

  Therefore, the present invention is excellent in heat resistance, pressure resistance, water resistance, tearability, excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc., and also excellent in transparency, especially processing such as retort processing. It is intended to provide a gas barrier laminate film that can withstand the heat treatment associated with the above, and can reduce the weight and weight of containers and packaging waste, and is excellent in filling and packaging of contents, quality maintenance, and the like.

  As a result of examining the gas barrier film in detail, the present inventor formed a vapor deposition film of carbon-containing silicon oxide on one surface of the base film by vapor-depositing organic-containing silicon oxide or the like by chemical vapor deposition. A highly flexible carbon-containing silicon oxide vapor-deposited film can be formed on a base film, and a gas barrier coating film comprising a polyvinyl alcohol resin, a metal alkoxide, a silane coupling agent, etc. on the vapor-deposited thin film Water resistance can be imparted, and when a coating film made of a predetermined polyurethane resin composition is provided on the gas barrier coating film, a gas barrier coating layer or a print layer that can be provided thereon, Adhesion with the heat seal layer can be ensured, and delamination during retort treatment and boil treatment by ensuring the above adhesion and flexibility. It can be prevented, and found that improved tear resistance of the gas barrier laminate film by avoidance of delamination, and have completed the present invention.

  The gas barrier laminate film according to the present invention can ensure adhesion between the base film and the organic silicon oxide with gas barrier properties by depositing the organic silicon oxide by plasma chemical vapor deposition. And flexibility, such as extensibility, flexibility, and flexibility, can be given to the above-mentioned vapor deposition layer.

  In the gas barrier coating film used in the gas barrier laminate film of the present invention, the polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and one or more alkoxides chemically react with each other to form an extremely strong tertiary Since the original reticulated composite polymer layer is formed and laminated on the vapor-deposited film having excellent flexibility, it is possible to secure a very high gas barrier property and to become a barrier gas barrier laminated film having excellent transparency, impact resistance and hot water resistance. .

  In particular, the present invention has a coating thin film made of a polyurethane-based resin composition containing a silane coupling agent and a filler on the gas barrier coating film, and thus has excellent adhesion to a printed layer and a heat seal layer to be further provided. Further, delamination in retort processing and boil processing for sterilization can be avoided.

  Furthermore, combined with the improvement of the adhesion strength, the integrity of the gas barrier laminate film is strengthened, so that the gas barrier laminate film having excellent tearability is obtained.

The first of the present invention is a gas barrier laminated film having a base film, a carbon-containing silicon oxide vapor deposition film, a gas barrier coating film, and a coating thin film made of a polyurethane resin composition,
An organic silicon compound is supplied as a vapor deposition monomer by chemical vapor deposition to provide a vapor deposition film of carbon-containing silicon oxide on one surface of the base film, and the general formula R is formed on the surface of the vapor deposition film of carbon-containing silicon oxide. ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. In addition, a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method is provided,
And it is a gas barrier laminated film which provided the coating thin film by the polyurethane-type resin composition containing a silane coupling agent and a filler on the surface of a gas barrier coating film. Hereinafter, the present invention will be described in detail.

(1) Layer constitution of film As shown in FIG. 1 (a), the gas barrier laminate film of the present invention comprises a base film (10), a carbon-containing silicon oxide vapor deposition film (20), a gas barrier coating film (30 ) And a coating thin film (40). Furthermore, as shown in FIG.1 (b), you may have a surface treatment layer (10 ') and (20') on a base film (10) and a vapor deposition film (20), respectively. Moreover, as shown in FIG.1 (c), you may have a printing layer (50) on the coating thin film (40) further. Further, as shown in FIG. 1 (d), an adhesive layer (60) for dry lamination and a heat seal layer (70) may be further provided on the coating thin film (40), as shown in FIG. 1 (e). In addition, a printed layer (50) may be provided on the coating thin film (40), and an adhesive layer (60) for dry lamination and a heat seal layer (70) may be further provided on the printed layer (50). The print layer (50) may be full-surface printing or partial printing.

(2) Base Film The base film that can be used in the present invention is excellent in chemical or physical strength, withstands the conditions for forming each carbon-containing silicon oxide film, and the carbon-containing silicon oxide. A resin film that can be satisfactorily maintained without impairing film properties such as a film can be used. Specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile ruptage-styrene copolymer ( ABS resins), poly (meth) acrylic resins, polycarbonate resins, polyvinyl alcohol resins, saponified ethylene-vinyl ester copolymers, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, various nylons, etc. Various resin films such as polyamide resin, polyurethane resin, acetal resin, cellulose resin, and the like can be used. In the present invention, among the above resin films, it is particularly preferable to use a polyester resin, polyolefin resin, or polyamide resin film. As the base film, any of an unstretched film of the above resin and a film stretched in a uniaxial direction or a biaxial direction can be used.

  In the present invention, as the above-mentioned various resin films, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc. The above-mentioned film forming method is used to form a film of each of the above-mentioned various resins alone, or to form a multilayer co-extrusion film using two or more kinds of resins, Using the above resins, various resin films are manufactured by a method of forming a film by mixing before forming into a film, and if necessary, for example, a tenter method or a tubular method, etc. Various resin films that are stretched in a uniaxial or biaxial direction using the above can be used.

  In the present invention, the film thickness of various resin films is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

  It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can also be used.

(3) Surface treatment In this invention, although the vapor deposition film | membrane of carbon containing silicon oxide is formed in one surface of 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, a carbon-containing silicon oxide vapor-deposited film, a gas barrier coating film, a coating thin film made of a polyurethane resin composition, a heat seal layer, and a printing layer are also applied to the surface of a resin film other than the base film. In order to improve adhesion with other layers and films, any of the above surface treatments may be performed. For example, in the present invention, when a coating thin film made of a polyurethane resin composition is formed on the gas barrier coating film, the gas barrier coating film is subjected to plasma treatment, and the plasma treatment surface is coated with the polyurethane resin composition. A thin film may be formed. Moreover, when forming a printing layer on the said gas barrier coating film, a plasma process may be previously performed to a gas barrier coating film and a printing layer may be formed. Alternatively, an undercoat agent may be applied to a coating thin film made of a polyurethane resin composition, and then a molten resin that can constitute the heat seal layer may be laminated by melt extrusion.

(4) Vapor-deposited film of carbon-containing silicon oxide A vapor-deposited film of carbon-containing silicon oxide is formed by chemical vapor deposition using an organosilicon compound as a vapor deposition monomer. 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 produce a film by using a low temperature plasma chemical vapor deposition method.

  In the present invention, specifically, on one surface of the substrate 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 deposited film of carbon-containing silicon oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 2 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.

  The plasma chemical vapor deposition apparatus (100) of FIG. 2 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 base film (101) is unwound from an unwinding roll (111) disposed in the base film supply chamber (110), and the base film (101) is assisted in the first film forming 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, an oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organosilicon compound, etc. are supplied from a gas supply device (125) and a raw material volatilization supply device (124) to prepare a mixed gas composition for vapor deposition. This is introduced into the first film forming 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 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. The cooling / electrode drum (122) is applied with a predetermined power from a power source (160) disposed outside the first film forming 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. 2, reference numeral (153) represents 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. Is closely bonded to one surface of the base film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous thin film mainly composed of silicon oxide. The carbon-containing silicon oxide vapor-deposited film is a carbon-containing material represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency, barrier properties, and the like. A thin film mainly composed of a silicon oxide vapor deposition film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, 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 SiOx plasma, and polar groups, free radicals, etc. are generated on the surface, so that the carbon-containing silicon oxide made of silicon oxide or the like to be formed into a film is formed. The tight adhesion between the membrane and the substrate 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 vapor deposition film of carbon-containing silicon oxide having different compositions is formed by using a chemical vapor deposition apparatus (100) having a plurality of vacuum chambers as deposition chambers. be able to. FIG. 3 is used to illustrate the case of having a three-layer deposited film. The plasma chemical vapor deposition apparatus (100) of FIG. 3 includes a base film supply chamber (110), a first film forming chamber (120), a second film forming chamber (130), a third film forming chamber (140), And it is comprised from the winding chamber (150) which rolls 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 forming 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 forming 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 forming chamber (120) through the raw material supply nozzle (127) while supplying the others and adjusting the mixed gas composition for film formation comprising 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 supplied to the second film forming chamber through the auxiliary rolls (123), (131) and the like. (130), and then, similarly to the above, the base film (101) formed by forming the first layer of carbon-containing silicon oxide film is cooled and transported 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 monomer gas for film formation, oxygen gas, inert gas, etc. composed of one or more kinds of organosilicon compounds are added. Supplying the above-mentioned mixed gas composition for film formation into the second film forming 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 first and second carbon-containing silicon oxide films are formed in the second film forming 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-forming chamber (140) through It is conveyed on the circumferential surface of the cooling / electrode drum (142). Next, a monomer gas for film formation consisting of one or more organic silicon compounds, oxygen gas, inert gas, and the like are supplied from the raw material volatilization supply device (144), 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 film of the first layer and the second layer conveyed on the peripheral surface of the electrode drum (142) is formed into a film, and the second layer of the carbon-containing silicon oxide film of the base film 1 is laminated, 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) disposed 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 can be prepared to be kept in vacuum. In addition, although the above is exemplified by three layers, a film forming 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 depressurized by a vacuum pump and adjusted to a degree of vacuum of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a degree of vacuum 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 time for setting the vacuum state at the time of replacing the original film, and the degree of vacuum is easily stabilized, and the film forming process is stabilized. When there are a plurality of film forming chambers, the degree of vacuum may be the same or different in each chamber.

  Moreover, it is desirable that the conveyance speed of the base film is adjusted to about 10 to 300 m / min, preferably about 50 to 200 m / min. In plasma chemical vapor deposition, since a predetermined voltage is applied to the cooling / electrode drum from the power source, 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 the film formation 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. When said deposited layer is a multilayer, in each deposited layer, the ratio of the film for monomer gas and oxygen gas as the raw material (O ₂₎ may be changed respectively. 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 formed carbon-containing silicon oxide layer 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 the carbon-containing silicon oxide vapor-deposited film is preferably about 60 to 4000 mm, more preferably 100 to 1000 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 60 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 multilayer structure composed of the three layers described above, the thickness of the carbon-containing silicon oxide film constituting the first layer is desirably about 20 to 200 mm, preferably about 30 to 100 mm. The film thickness of the carbon-containing silicon oxide film constituting the two layers is preferably about 20 to 200 mm, preferably about 30 to 100 mm, and the film thickness of the carbon-containing silicon oxide film constituting the third layer is The range of 20 to 200 mm, preferably 30 to 100 mm is desirable. In the above, if it is 20 mm or less, its own barrier properties are not expressed, and if it exceeds 200 mm, cracks and the like are likely to occur in the film. In particular, the base film is wound during film formation. This is not preferable because cracks tend to be easily formed. Further, in the above, as a means for changing the film thickness of the carbon-containing silicon oxide layer, the volume velocity of the layer is increased, that is, a method for increasing the amount of monomer gas for film formation and 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.

(5) 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 to 1 at a temperature not higher than the melting point of the base film. It can be formed by minute heat treatment.

  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 an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by 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.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

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} , tetra i propoxy zirconium _{Zr (iso-0C 3 H 7} ) 4, tetra-n-butoxy zirconium Zr (OC ₄ H _{9) 4} , etc. 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 Examples thereof include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-0C ₃ H ₇ ) ₄ , tetra n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and the 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 (is0-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, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. 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 20 ° C. to 180 ° C. and below the melting point of the base film, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 minutes. To process. 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 or the like, 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.

(6) Coating thin film The coating thin film of the polyurethane resin composition of the present invention is made of a polyurethane resin composition containing a silane coupling agent and a filler, and the coating thin film is the gas barrier coating film or its surface treatment layer. Formed on top.

  As the silane coupling agent used for the coating thin film, bifunctional organofunctional silane monomers can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane. , Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ -Mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β -Hide Kishiechiru)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl silicone - can be used one or more of the aqueous solution or the like of the emission.

  In the silane coupling agent as described above, a functional group at one end of the molecule, usually chloro, alkoxy, or acetoxy group is hydrolyzed to form a silanol group (SiOH), which is the barrier coating. Silane coupling occurs on the barrier coating film by causing a reaction such as a reaction such as dehydration condensation reaction with silicon contained in the film or an active group on the barrier coating film, for example, a functional group such as a hydroxyl group. The agent is modified with a covalent bond or the like, and further, a strong bond is formed by adsorption of the silanol group itself onto the barrier coating film or hydrogen bond. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto on the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. For example, an adhesive layer for laminating It reacts with substances constituting the anchor coat layer and other layers to form a strong bond. As a result, in the present invention, the barrier coating film and the heat-sealable resin layer are firmly and closely bonded via the adhesive bond layer, the anchor coat layer, and the like by the chemical bond as described above. Strength can be increased and a strong laminated structure with high laminate strength can be formed. In particular, in the present invention, a monomer for depositing an organic silicon compound is used to form a vapor-deposited film of carbon-containing silicon oxide, but the organosilicon compound such as tetraethoxysilane used for forming the vapor-deposited film is coated with the gas barrier coating. Since the silane coupling agent is used in common for the gas barrier coating film and the coating thin film, each thin film is strongly bonded to each other by containing the components in common. Conceivable. In particular, by laminating a coating layer containing a silane coupling agent, adhesion between the gas barrier coating film and the laminating adhesive layer or anchor coat layer is ensured, and thus laminated on these. Adhesion with the heat seal layer is also ensured, and laminate strength and the like are improved.

  As the filler, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. This is to improve the coating suitability and the like of the polyurethane resin composition by adjusting the viscosity and the like.

  Specific examples of the polyurethane-based resin include a polymer obtained by reaction of a polyfunctional isocyanate and a hydroxyl group-containing compound, specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene. Polyfunctional isocyanates such as aromatic polyisocyanates such as polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate, and polyether polyols, polyester polyols, polyacrylate polyols, etc. One-pack or two-pack polyurethane resins obtained by reaction with a hydroxyl group-containing compound can be used. Thus, in the present invention, by using the polyurethane-based resin as described above, the degree of elongation of the coating thin film is improved, and the post-processing suitability such as laminating or bag making is improved. It prevents the occurrence of cracks in the thin film of inorganic oxide during processing.

  As said polyurethane-type resin composition, a silane coupling agent, about 0.05-10 mass% with respect to a polyurethane-type resin, 1-30 mass%, Preferably, about 0.1-5 mass%, a filler Add about 0.1 to 20% by mass, preferably about 1 to 10% by mass, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. Is added arbitrarily, a solvent, a diluent, etc. are added and mixed well to prepare a polyurethane resin composition. Thus, in the present invention, the polyurethane resin composition as described above is applied onto the inorganic oxide thin film by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods. After coating, the coating film is dried to remove the solvent, diluent, etc., and the coating thin film according to the present invention can be formed. In addition, in this invention, as a film thickness of the coating thin film by a polyurethane-type resin composition, about 0.01-50 micrometers, for example, Preferably, about 0.1-5 micrometers is desirable.

(7) Laminating adhesive In the present invention, a substrate such as a heat seal layer can be laminated on the surface of the coating thin film via a laminating adhesive using a dry laminating method. In addition, when any two layers are laminated, they can be adhered by a dry laminate lamination method via a laminating adhesive.

  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, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide It can act and improve processing aptitude, such as lamination processing and printing processing, and can avoid generation of a crack etc. to a barrier thin film layer which consists of inorganic oxides. 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.

(8) Printed layer In the present invention, a desired printed pattern layer can be formed between any of the layers forming the gas barrier laminate film. As the printed pattern layer, for example, a normal gravure ink composition, an offset ink composition, a letterpress ink composition, a screen ink composition, and other ink compositions are used on the coating layer, for example, , Gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, by forming a desired printing pattern consisting of characters, figures, patterns, symbols, etc. be able to.

  Regarding the ink composition, examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resins, polyamide resins, alkyd resins, epoxy resins, unsaturated polyester resins, thermosetting poly (meth) acrylic resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins , Maleic resin, Fiber resins such as rocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more of fats and oils and other resins can be used. In the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, a filler, Light stabilizers such as additives, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, solvent, dilution Ink compositions having various forms obtained by sufficiently kneading with an agent or the like can be used.

  The print layer may be printed by surface printing or reverse printing of a desired printing pattern such as a character, a figure, a symbol, a pattern, or a pattern, and may be full surface printing or partial printing.

(9) Anchor coat layer In the present invention, a heat seal can be laminated on the coating thin film by extrusion. When the heat seal layer is formed by extrusion, the heat seal layer is preferably formed on the coating thin 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, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide Acting, improving processability such as laminating and printing, avoiding the occurrence of cracks in the barrier thin film layer made of inorganic oxide, and tight adhesion between the gas barrier laminate film and the heat seal layer It is possible to improve the property, prevent the occurrence of cracks in the barrier thin film layer made of an inorganic oxide, and improve the laminate strength.

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.

(10) Heat-seal layer As the heat-seal layer, polyolefin resins having various heat-seal properties that can be melted by heat and fused to each other can be used. 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 seal layer may be a single layer or a multilayer composed of one of the above resins, and the thickness of the heat seal 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.

(11) Gas barrier laminate film In the gas barrier laminate film of the present invention, a vapor-deposited film (20) of carbon-containing silicon oxide is previously provided on one surface of the base film (10), and the carbon-containing silicon oxide is further provided. The gas barrier coating film (30) is provided on the surface of the vapor deposition film (20), and the coating thin film (40) is laminated on the gas barrier coating film (30). Moreover, the base film (10) surface-treated beforehand may be used, and a surface treatment process may be appropriately included in the lamination process. In order to produce a gas barrier laminate film using the above-mentioned materials, an ordinary laminate material is laminated, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion method. It can be carried out by a molding method, a coextrusion lamination method, an inflation method, a coextrusion inflation method, or the like.

  In the present invention, a packaging container can be produced using the barrier laminate film as described above. For example, if the packaging container is a flexible packaging bag made of plastic film, etc., use the laminated material manufactured by the method described above, and fold it up with the inner surface of the heat-sealable film facing each other. Alternatively, the two sheets can be overlapped, and the peripheral edge can be heat sealed to provide a seal portion to form a bag. As the bag making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side seal type, two-side seal Heat seal by heat seal type such as mold, three-side seal type, four-side seal type, envelope sticker seal type, palm seal sticker type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Thus, various types of packaging containers according to the present invention can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured. Further, in the present invention, a tube container or the like can be manufactured using the laminated film.

  In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used. In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above. Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

  The packaging container comprising the gas barrier laminate film of the present invention includes various articles such as various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, and the like, particularly liquid seasonings such as liquid seasonings. It is used for filling and packaging shaped articles. When filling and wrapping contents, especially liquid or sticky contents such as liquid seasonings, in the packaging container, the contents may affect the inner surface of the bag and often cause phenomena such as delamination. Therefore, in the laminated material constituting the bag body, the peel strength in water between the inorganic oxide thin film and the heat-sealable resin layer constituting the laminated material is 50 g / 15 mm width or more, and The peel strength at 25 ° C. is desirably 200 g / 15 mm width or more. In the above, when the peel strength in water is less than 50 g / 15 mm width, for example, for use in sterilization in hot water such as boil and retort, or when used under high humidity, a packaging material For example, it is not preferable because sufficient strength cannot be obtained and, for example, the oxygen gas barrier property is deteriorated, and when the peel strength at 25 ° C. is less than 200 g / 15 mm width, It is not preferable because the practical strength cannot be obtained.

  The packaging container manufactured as described above is used for filling and packaging various foods, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other items. It is. In the present invention, in particular, for example, a liquid sachet for filling and packaging soy sauce, sauce, soup, etc., a sachet for filling and packaging rice cake, a soft packaging bag for filling and packaging fresh confectionery, etc., or filling a boil or retort food It is useful as a packaging container for filling and packaging food and drink such as soft packaging bags. In particular, since it has excellent gas barrier properties and excellent peel resistance under retort conditions and boil conditions, it can be suitably used particularly as a pouch for retort.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

Example 1
(1) On the other hand, a biaxially stretched polyethylene terephthalate film with a corona-treated surface and having a thickness of 12 μm is used, and this is attached to a plasma chemical vapor deposition apparatus consisting of three film forming chambers (chambers) as shown in FIG. did. Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.

  On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device (124, 134, 144) and supplied from a gas supply device (125, 135, 145). The mixed gas was mixed with oxygen gas and helium, which was an inert gas, to obtain a raw material gas.

As a raw material gas used in the first film forming chamber (120), the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.0: 5.0: 3.0: 0.4 (unit; slm, standard liter minute)), film forming output: 11 kW, and as a raw material gas used in the second film forming chamber (130), the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1. 0.0: 3.0: 4.0: 0.4 (unit: slm), film forming output: 10 kW, and further, as a raw material gas used in the third film forming chamber (140), a mixing ratio of raw material gases Was set to HMDSO: O ₂ : He: Ar = 1.0: 3.0: 4.0: 0.4 (unit: slm) and film forming output: 10 kW.

  Using the source gas as described above, the source gas is introduced into the first film-forming chamber, the second film-forming chamber, and the third film-forming chamber, respectively. While transporting the biaxially stretched polyethylene terephthalate film at a line speed of 150 m / min, the film thicknesses of the first layer, the second layer, and the third layer on the corona-treated surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm. Were formed into three layers of carbon-containing silicon oxide layers each having a total thickness of 15 nm.

Next, a glow discharge plasma generator is used on the vapor-deposited film surface of carbon-containing silicon oxide, and power is 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm) And the oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a treatment speed of 420 m / min, and the surface tension of the deposited film surface of carbon-containing silicon oxide is 54 dyne / cm or more. A plasma-treated surface was formed by improving.

  (2) On the other hand, a preliminarily prepared hydrolyzate of composition b was added to the mixture of composition a prepared according to the composition shown in Table 1 and stirred to obtain a colorless and transparent barrier coating solution.

上記で製造したバリア性塗工液を使用し、これをグラビアロールコート法により前記（１）のプラズマ処理面上にコーティングし、次いで、２００℃で６０秒間、加熱処理して、厚さ０．３μｍ（乾操状態）のガスバリア性塗布膜を形成した。
（３） シランカップリング剤として、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシランを使用し、該シランカップリング剤１．０質量％、シリカ粉末１．０質量％、ポリウレタン系樹脂１３〜１５質量％、ニトロセルロース３〜４質量％、トルエン３１〜３８質量％、メチルエチルケトン（ＭＥＫ）２９〜３０質量％、イソプロピルアルコール（ＩＰＡ）１５〜１６％からなるポリウレタン系樹脂組成物を調整した。

Using the barrier coating solution produced above, this was coated on the plasma-treated surface of (1) above by a gravure roll coating method, and then heat-treated at 200 ° C. for 60 seconds to obtain a thickness of 0. A gas barrier coating film of 3 μm (dry operation state) was formed.
(3) N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is used as the silane coupling agent, 1.0% by mass of the silane coupling agent, 1.0% by mass of silica powder, and polyurethane resin. A polyurethane resin composition comprising 13 to 15% by mass, 3 to 4% by mass of nitrocellulose, 31 to 38% by mass of toluene, 29 to 30% by mass of methyl ethyl ketone (MEK), and 15 to 16% of isopropyl alcohol (IPA) was prepared. .

Next, the above-mentioned polyurethane resin composition is used to coat the gas barrier coating film surface of (2) above by using a roll coating method, and then dried at 100 ° C. for 5 seconds. A coating thin film (thickness 0.2 g / m ² , dry state) with a polyurethane resin composition was formed to produce a gas barrier laminate film of the present invention.

Comparative Example 1
A comparative gas barrier laminate film 1 was prepared in the same manner as in Example 1 except that the coating thin film described in (3) of Example 1 was not provided.

Comparative Example 2
Using silicon monoxide as a source gas, the degree of vacuum in the deposition chamber is set to 2 × 10 ⁻⁴ mbar, the degree of vacuum in the winding chamber is set to 2 × 10 ⁻² mbar, and electron beam power is set by electron beam physical vapor deposition. A comparative gas barrier laminate film 2 was prepared in the same manner as in Example 1 except that a vapor deposition layer having a film thickness of 30 nm was formed at 25 kw and a film conveyance speed of 300 m / min.

Comparative Example 3
A comparative gas barrier laminate film 3 was prepared in the same manner as in Example 1 except that the gas barrier coating film described in (2) of Example 1 was not provided.

Evaluation method A polyethylene film having a thickness of 60 μm was laminated on the coating thin film surface of Example 1, Comparative Example 1, and Comparative Example 3 or on the gas barrier coating film surface of Comparative Example 2 using a two-component curable laminating adhesive. Laminate A was prepared.

  On the other hand, stretched nylon having a thickness of 15 μm is laminated on the coating thin film surface of Example 1, Comparative Example 1, and Comparative Example 3 or on the gas barrier coating film surface of Comparative Example 2 using a two-component curable adhesive. Then, a laminate B was prepared by further laminating unstretched polypropylene having a thickness of 60 μm using a laminating adhesive.

  II. The following evaluation was performed on the above-mentioned laminated material A and laminated material B.

(1) Evaluation of boil barrier properties:
Laminate A was sealed three-way with a size of 180 × 120 mm, filled with 200 ml of water, sealed, and boiled at 95 ° C. for 30 minutes, and then measured for oxygen permeability and water vapor permeability to evaluate barrier properties. The results are shown in Table 2.

(I) Measurement of oxygen permeability:
The measurement was performed with a measuring instrument (model name, OX-TRAN 2/20) 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 2. In Table 2, the unit of oxygen permeability is [cc / m ² / day · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90 % RH].

(2) Retort barrier property evaluation:
Laminate B was sealed three-way with a size of 180 × 120 mm, sealed after filling with 200 ml of water, subjected to retort treatment at 120 ° C. for 30 minutes, and then measured for oxygen permeability and water vapor permeability to evaluate barrier properties. . The oxygen permeability and water vapor permeability were measured by the same method as the above (i) measurement of oxygen permeability. The results are shown in Table 2.

(3) Retort adhesion evaluation:
Laminated material B is sealed in three directions with a size of 180 x 120 mm, sealed after filling with 150 ml of water, folded in half, and the folded part is fixed with a stainless steel jig, and a retort treatment at 135 ° C for 60 minutes is performed. It was. Thereafter, the end face of the sandwiched portion was observed with an optical microscope to see if there was any peeling such as floating, and the peeling interface was specified for those with peeling. The results are shown in Table 2.

(4) Heat resistant adhesion evaluation:
The laminate strength (N / 15 mm) of the laminated material A was measured at room temperature and 100 ° C. The results are shown in Table 2.

(5) Bending resistance evaluation:
Laminate A was used, and the oxygen permeability after 100 bends was measured using a gelbo flex tester. The oxygen permeability was measured by the same method as (i) measurement of oxygen permeability. The results are shown in Table 2.

(6) Tearability:
A strip-shaped film piece having a length of 205 mm in the longitudinal direction (MD) and a width of 20 mm in the width direction (TD) is sampled from the laminated material A and the laminated material B, and 5 mm in length at the center of one TD side of the film piece. Ten samples with notches (notches) were prepared, and then teared by hand in the MD direction from the notches, and the number of samples reaching the TD pieces facing the sides where the tear propagation ends were notched was evaluated as an evaluation value. . The results are shown in Table 3.

結果
（１） ボイルバリア性、レトルトバリア性評価では、ガスバリア性塗布膜の存在しない比較例３では、他の積層材と比較して、著しく酸素透過度および水蒸気透過度が高い。このことから、ガスバリア性塗布膜の介在によってガスバリア性が向上することがわかる。

Results (1) In the evaluation of the boil barrier property and the retort barrier property, in Comparative Example 3 where the gas barrier coating film does not exist, the oxygen permeability and the water vapor permeability are remarkably higher than those of other laminated materials. From this, it can be seen that the gas barrier property is improved by the intervention of the gas barrier coating film.

  (2) In the evaluation of retort adhesion, peeling was observed in Comparative Example 2 in which a deposited film was formed by electron beam physical vapor deposition using silicon monoxide, but plasma chemical vapor was obtained using hexamethyldisiloxane. No peeling was observed in other laminated materials in which the vapor deposition layer was formed by the phase growth method. From this, it can be seen that the chemical vapor deposition method can further improve the adhesion.

  (3) From the evaluation of heat-resistant adhesion, the laminate material A of Comparative Example 1 having no coating thin film has lower laminate strength than any other laminate material A at both normal temperature and 90 ° C. From this, it can be seen that the heat-resistant adhesion is improved by the intervention of the coating thin film.

(4) From the evaluation of bending resistance, the laminated material A of Example 1 has an oxygen permeability of 0.6 (cc / m ² / day · 23 ° C. · 90% RH) even after 100 times of bending. The gas barrier property is extremely high as compared with the laminated material. From this, the laminated material of Example 1 can satisfy any of boil barrier property, retort barrier property, retort adhesion property, heat resistant adhesion property, and bending resistance, which could not be satisfied by Comparative Examples 1 to 3 alone. Recognize.

  (5) From the evaluation of tearability and the results of (1) to (4) above, the laminated material of Example 1 has excellent boil barrier properties, retort barrier properties, retort adhesion properties, heat resistant adhesion properties, bending resistance properties, and It turns out that it is excellent also in tearability.

  The gas barrier laminate film according to the present invention is excellent in boil barrier property, retort barrier property, retort adhesion property, heat resistant adhesion property, bending resistance, and tearing property, and is useful.

Fig.1 (a)-(e) is a cross-sectional view explaining the gas-barrier laminated | multilayer film of this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of the low temperature plasma chemical vapor deposition apparatus which has a some film forming chamber.

Explanation of symbols

10 ... base film,
10 '... plasma surface treated surface 20 ... deposited film of carbon-containing silicon oxide,
20 '... corona surface treatment surface 30 ... gas barrier coating film,
40 ... coating thin film,
50 ... printing layer,
60 ... Laminate adhesive layer,
70 ... heat seal layer,
100: Plasma chemical vapor deposition apparatus,
101 ... substrate film,
110 ... Base film supply chamber,
111 ... unwinding roll,
120 ... first film forming 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 forming chamber,
140: Third film forming chamber,
150 ... take-up chamber,
153 ... Vacuum pump,
160: Power supply.

Claims (3)

A gas barrier laminate film having a base film, a carbon-containing silicon oxide vapor deposition film, a gas barrier coating film, and a coating thin film made of a polyurethane-based resin composition,
An organic silicon compound is supplied as a vapor deposition monomer by chemical vapor deposition to provide a vapor deposition film of carbon-containing silicon oxide on one surface of the base film, and the general formula R is formed on the surface of the vapor deposition film of carbon-containing silicon oxide. ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. In addition, a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method is provided,
A gas barrier laminate film in which a coating thin film made of a polyurethane resin composition containing a silane coupling agent and a filler is provided on the surface of the gas barrier coating film.   The gas barrier laminate film according to claim 1, wherein the base film is made of a polyester resin film, a polyamide resin film, or a polyolefin resin film.   The gas barrier laminate film according to claim 1, wherein a printing layer is laminated on the gas barrier coating film or the coating thin film, or a surface treatment layer thereof.

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