JP2008143583A - Small bag for liquid, and liquid small bag packaging body filled with liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a small bag for liquid and a liquid small bag packaging body having excellent gas barrier properties, mechanical strength and tearing properties. <P>SOLUTION: The small bag for liquid is formed of a laminated material successively laminating an anchor coat layer of an anchor coat agent and/or an adhesive layer for laminate of an adhesive for laminate, and a heat-sealing resin layer on a coating thin film of a laminate film of gas barrier properties composed of a substrate film, a thin film of a vapor-deposited film of carbon-containing silicon oxide, a gas-barrier coating film and a coating thin film. The small bag has excellent tearing properties, mechanical strength and gas barrier properties, and its transparency can be ensured. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid sachet and a liquid sachet package, and more specifically, has strength and excellent fastness, excellent barrier properties such as oxygen gas and water vapor, and excellent laminate strength. In addition, liquid sachets that do not impair the flavor and taste of the contents during storage, storage or distribution, and liquids or viscosities of soy sauce, sauces, soup stock, spices, liquors for cooking, etc. The present invention relates to a liquid sachet package formed by filling and packaging various liquid or viscous foods and drinks such as seasonings, soups, fruit juices, and the like composed of body.

  Conventionally, as packaging materials for filling and packaging foods, drinks, chemicals, miscellaneous goods, etc., the content of the contents is blocked, blocked by oxygen gas, water vapor, etc. to prevent alteration, discoloration, etc. Barrier laminates having various forms through which objects can be seen through have been developed and proposed.

  For example, there is a film in which a barrier coat layer is provided on the 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 laminated 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 barrier 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.

  On the other hand, soy sauce, sauce, soup stock, spices, liquor for cooking, other seasonings consisting of liquid or viscous products, soups, fruit juices, and other various liquid or viscous food and beverage soy sauces, liquids such as sauces In addition to gas barrier properties, liquid sachets filled and packaged with the above-mentioned seasonings are also required to have particularly fastness and chemical resistance and use a polyamide having excellent mechanical strength as a base film. For example, a thickness of 100 is provided on at least one side of a polyamide-based laminated biaxially stretched film including any two layers of three layers of an aromatic polyamide, an aliphatic polyamide, and a mixture of the aromatic polyamide and the aliphatic polyamide. There is a transparent laminated plastic film having an excellent gas barrier property in which a silicon oxide thin film layer is formed in a range of ˜3000 mm (Patent Document 6). Since polyamide is used as the base material, it is said that the gas barrier property and mechanical strength are both excellent, and the barrier property laminate material in which transparency is ensured.

On the other hand, polyamide is excellent in mechanical strength, but may cause troubles in processing steps such as winding failure during vapor deposition and problems of peeling charging. As a technique for improving such winding failure during the deposition of a polyamide film, there is a technique using a biaxially stretched polyamide film having a static friction coefficient of 0.7 or less and a dynamic friction coefficient of 0.6 or less (Patent Document 7). In Patent Document 7, as a means for reducing the friction coefficient of the biaxially stretched polyamide film, a method of adding inorganic particles or organic polymer to polyamide or applying a slipping agent is exemplified, and the dynamic friction coefficient is 0.34 to 0. Manufactures .73 polyamide films.
Japanese Patent Laid-Open No. 10-722 JP 2004-106443 A JP 2005-59265 A JP 2005-178802 A JP 2006-21378 A Japanese Patent Laid-Open No. 6-190961 JP 59-219337 A

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

  The film described in Patent Document 6 can reduce oxygen permeability and is advantageous in terms of excellent impact resistance and mechanical strength because polyamide is used as a base film. Due to the hygroscopicity based on this, it is easy to cause a dimensional change. For this reason, when the deposited film cannot follow the expansion and contraction of the polyamide film, cracks and pinholes are generated and it is difficult to maintain the barrier performance. In particular, the friction coefficient and the transparency of the film have a trade-off relationship, and as in Patent Document 7, when inorganic particles or organic polymer particles are added to lower the dynamic friction coefficient, the transparency of the film is ensured. It becomes difficult. In addition, when the irregularities on the film surface are increased by the addition of these particles, a gap is easily generated in the vapor deposition layer, and the gas barrier property is lowered.

  In addition, liquid sachets contain various contents, so that depending on the contents, the sachets may be broken by the shape of the contents during filling or transportation, or pinholes may be generated, preserving the contents. May be.

  Therefore, the present invention provides a liquid sachet and a liquid sachet package that have excellent mechanical strength, barrier properties that prevent permeation of oxygen gas, water vapor, and the like, transparency is ensured, and excellent laminate strength. Objective.

  As a result of detailed examination of the gas barrier laminated film constituting the liquid pouch, the inventor has a coefficient of dynamic friction of 0.4 or less, a haze of 6.0% or less, and an ash test performance of 15 mm or less. When a biaxially stretched polyamide film having a surface roughness of 2000 nm or less is used as a base film, slipperiness is improved and static electricity troubles are prevented, so that troubles occurring in the subsequent process of the filling machine can be avoided. When a vapor deposition film of carbon-containing silicon oxide is formed on the surface of the polyamide film having a surface roughness of 2000 nm or less by vapor deposition of organic-containing silicon oxide or the like by chemical vapor deposition, a flexible film is formed on the base film. A vapor-deposited film of high carbon-containing silicon oxide can be formed, and a polyvinyl alcohol resin and a metal alloy are further formed on the vapor-deposited thin film. When a gas barrier coating film made of a oxide, a silane coupling agent or the like is provided, water resistance can be imparted, and further, a coating film made of a predetermined polyurethane resin composition is provided on the gas barrier coating film. Adhesion between the gas barrier coating layer and the printed layer or heat seal layer provided thereon can be secured, delamination can be prevented by ensuring the above adhesion and flexibility, and avoidance of delamination It has been found that the tearability of a gas barrier laminate film is improved, and that the use of the gas barrier laminate film results in a liquid sachet having excellent mechanical strength such as puncture resistance and pinhole resistance during transportation. Was completed.

  The liquid sachet of the present invention uses a biaxially stretched polyamide film having a dynamic friction coefficient of 0.4 or less at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10% as a base film, thereby providing gas barrier properties and transparency. Excellent.

  In addition, since the liquid sachet of the present invention uses a gas barrier laminated film in which an organic-containing silicon oxide oxide is deposited by plasma chemical vapor deposition, the base film and the organic-containing silicon oxide oxide have gas barrier properties. Adhesion can be ensured, and flexibility such as spreadability, flexibility, and flexibility can be imparted to the vapor deposition layer.

  The gas barrier laminate film used in the liquid pouch according to the present invention has a gas barrier coating film on the vapor-deposited layer of organic-containing silicon oxide, and includes a silane coupling agent and a filler on the coating film. Since it has a coating thin film made of a polyurethane-based resin composition, the laminate strength is further improved and the sticking resistance is particularly excellent.

  Further, coupled with the improvement of the adhesion strength, the liquid sachet of the present invention is excellent in tearability.

In the first aspect of the present invention, an anchor coat layer and / or an anchor coat agent and / or a coating film of a gas barrier laminated film comprising a base film, a carbon-containing silicon oxide vapor deposition film, a gas barrier coating film and a coating thin film are provided. A liquid sachet made of a laminated material obtained by sequentially laminating an adhesive layer for laminating with a laminating adhesive and a heat-sealable resin layer,
The gas barrier laminate film has a biaxial structure in which the base film has a dynamic friction coefficient of 0.4 or less, a haze of 6.0% or less, an ash test performance of 15 mm or less, and a surface roughness of at least one surface of 2000 nm or less. It is a stretched polyamide film, and an organic silicon compound is supplied as a vapor deposition monomer by chemical vapor deposition, and a vapor deposition film of carbon-containing silicon oxide is provided on the surface of the base film having a surface roughness of 2000 nm or less. 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, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol-based resin, and / or Or Ethile A gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method, and filled with a silane coupling agent on the surface of the gas barrier coating film. Provided with a coating thin film made of a polyurethane-based resin composition containing an agent,
The liquid sachet is a liquid in which the laminated material is overlapped with the heat-sealable resin layer facing each other to heat-seal the outer periphery and provide a heat-seal portion to form a bag body. It is a small bag. Hereinafter, the present invention will be described in detail.

(1) Gas barrier laminate film and laminate As shown in FIG. 1 (a), the gas barrier laminate film used in the present invention comprises a base film (10), a gas barrier coating film (30), 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. In addition, the laminated material used in the present invention includes, for example, a coating thin film (40) of the gas barrier laminate film shown in FIG. 1 (b), an anchor coat layer made of an anchor coating agent and / or an anchor coat agent as shown in FIG. 1 (d). Alternatively, a laminating adhesive layer (60) by a laminating adhesive and a heat-sealable resin layer (70) are sequentially laminated. For example, in the coating thin film (40) of the gas barrier laminate film shown in FIG. 1 (c), as shown in FIG. 1 (e), the anchor coating layer by the anchor coating agent and / or the laminating adhesive layer by the laminating adhesive is used. (60) and a heat-sealable resin layer (70) may be laminated in sequence. The print layer (50) may be full-surface printing or partial printing.

(2) Base film In the present invention, a polyamide film is used as the base film. The base film used in the present invention has excellent chemical or physical strength, can withstand the conditions for forming an inorganic oxide vapor-deposited film, and impairs the film characteristics of the inorganic oxide vapor-deposited film. Polyamide film that can be held well and has a dynamic friction coefficient of 0.4 or less, more preferably 0.3 or less, and a haze of 6.0% at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10%. Or less, more preferably 4.0% or less, ash test performance is 15 mm or less, more preferably 8 to 12 mm, and at least one surface has a surface roughness of 2000 nm or less, more preferably 1500 nm or less. It is a film.

  The present invention uses a biaxially stretched polyamide film that is excellent in mechanical strength because it aims at a gas barrier laminate film having high durability, but the polyamide film easily absorbs moisture and is inferior in slipperiness. On the other hand, it is difficult to ensure both slipperiness and gas barrier properties, and if inorganic particles are blended to ensure slipperiness, it will not make sense to deposit an inorganic oxide vapor deposition film to ensure gas barrier properties. In some cases, transparency is also reduced. Therefore, in the present invention, a gas barrier laminate film having excellent gas slidability and transparency, preventing wrinkles during winding, having excellent roll winding appearance, and improving laminate adhesive strength and having high gas barrier properties. In order to produce a base film, the dynamic friction coefficient at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10% is 0.4 or less, the haze is 6.0% or less, and the ash test performance is 15 mm or less, It was limited to a biaxially stretched polyamide film having a surface roughness of at least 2000 nm on one surface.

  Such a polyamide film may be an aliphatic polyamide, an aromatic polyamide, or a composition in which these are mixed. Specific examples of preferred polyamides include polycaproamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin Lactam (nylon 12), polyethylenediamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6/6), polyhexamethylene sebacamide (Nylon 6 · 10), Polyhexamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene adipamide (Nylon 8.6), Polydecamethylene adipamide (Nylon 10/6), polydecamethylene sebacamide (nylon 10/10), Polydodecamethylene dodecamide (nylon 12 and 12), metaxylenediamine-6 nylon (MXD6) and the like may be used, and a copolymer containing these as main components may be used. Examples thereof include caprolactam / Laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer And ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, and the like. It is also effective to blend these polyamides with plasticizers such as aromatic sulfonamides, p-hydroxybenzoic acid, esters, elastomer components with low elastic modulus, and lactams as film flexibility modifiers. is there. The polyamide film is a conventionally known polyamide film having a haze of 6.0% or less and a dynamic friction coefficient of 0.4 or less. The ash test performance is 15 mm or less, and the surface roughness of at least one surface is at least. The thing below 2000 nm can be selected and used.

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

  When forming the polyamide film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, mold release properties, flame retardancy, antifungal properties, strength, etc. Various plastic compounding agents, additives, etc. can be added for the purpose of improving and modifying the contents, etc., and the addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. can do.

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

(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.

(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, and the like are generated on the surface. Therefore, a carbon-containing silicon oxide film made of silicon oxide or the like formed into a film And high adhesion between the substrate film and the substrate film.

  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 made of a gas barrier composition formed by coating the composition on a vapor-deposited film of carbon-containing silicon oxide on the substrate film layer to provide a coating film, And 30 seconds at a temperature below the melting point of the base film layer. It can be formed by heating for 10 minutes.

  Also, the gas barrier composition is applied onto the carbon-containing silicon oxide vapor-deposited film on the base film layer, and two or more coating films are stacked, and the base film has a temperature of 20 to 180 ° C. A composite polymer layer in which two or more gas barrier coating films are stacked may be formed by heat treatment at a temperature not higher than the melting point of the layer for 30 seconds to 10 minutes.

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 layer is coated. Therefore, it is not preferable.

  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 layer 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 If it exceeds 500 parts by mass, the brittleness of the gas barrier coating film increases, and the water resistance and weather resistance of the resulting gas barrier laminated 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 gas barrier composition is applied onto the vapor-deposited film of carbon-containing silicon oxide on the base film layer by a conventional method and dried. 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 layer to which the gas barrier composition is applied is 20 ° C. to 180 ° C. and a temperature not higher than the melting point of the base film layer, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 seconds. Heat for minutes. 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、基材フィルム層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、基材フィルム層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 onto the vapor-deposited film of carbon-containing silicon oxide on the base film layer 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 film of carbon-containing silicon oxide on the film layer. 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 layer or the vapor-deposited film of carbon-containing silicon oxide on the base film layer. The adhesion between the substrate film layer or the carbon-containing silicon oxide vapor deposition film surface 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, organic functional silane monomers having binary reactivity 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 base film 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) Substrate layer In the liquid sachet of the present invention, a substrate layer may be further laminated on the other surface of the substrate film. The base material layer is a basic material of the liquid sachet, and is excellent in mechanical, physical and chemical properties, particularly a resin film or sheet having strength and toughness and heat resistance. Specifically, for example, tough materials such as polyester resins, polyamide resins, polyaramid resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyacetal resins, fluorine resins, etc. Resin films or sheets, and the like can be used. As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm. The base material layer may be subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as characters, figures, symbols, patterns, and patterns.

As a base material layer, the various paper base materials which comprise a paper layer may be sufficient, for example. As a paper base material, it has formability, bending resistance, rigidity, etc., for example, a paper base material with high sizing property or unbleached paper, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used. In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² . You may use together the paper base material which comprises a paper layer, and the film | membrane thru | or sheet | seat of various resin as the base material layer mentioned above.

  In addition, since liquid sachets are subjected to severe physical and chemical conditions, the laminated materials constituting liquid sachets are required to have strict packaging suitability, deformation prevention strength, drop impact strength, Various conditions such as pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, and hygiene are required. A material that satisfies the above various conditions can be arbitrarily selected and used as the base material layer. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate. Copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, Poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin Resin, Polycar From films or sheets of known resins such as nate resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers, fluorine resins, diene resins, polyacetal resins, polyurethane resins, nitrocellulose, etc. It can be arbitrarily selected and used. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used. In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

(12) Liquid sachet The liquid sachet of the present invention is provided with a vapor deposition film (20) of carbon-containing silicon oxide on one surface of the base film (10) in advance, and further, a vapor deposition film of the carbon-containing silicon oxide. On the surface of (20), the gas barrier coating film (30) is provided, and the coating thin film of the gas barrier multilayer film formed by laminating the coating thin film (40) on the gas barrier coating film (30), This is a liquid sachet made of a laminated material in which an anchor coat layer by an anchor coat agent and / or an adhesive layer for laminating by an adhesive for laminating, and a heat-sealable resin layer are sequentially laminated.

  As a method for producing a laminated material, a method for laminating a normal packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, etc. Method, coextrusion inflation method, etc. Thus, in the present invention, when the above lamination is performed, surface treatment such as corona treatment or ozone treatment can be performed as necessary as described above.

  In the present invention, a pouch for liquid can be produced using the laminated material. For example, the surface of the heat sealable film of the inner layer of the laminated material is made to face and be folded, or two of them are overlapped, and the peripheral end portion is further heat sealed to provide a seal portion to form a bag body Can be configured. 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 form 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. Various types of liquid sachets according to the present invention can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) can be manufactured.

  In the above, the heat sealing method can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and the like. In the present invention, for example, 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 liquid pouch as described above. In addition, the shape can be any of a rectangular container, a cylindrical shape such as a round shape, and the like.

(13) Liquid sachet package The liquid sachet package of the present invention is a liquid sachet, such as soy sauce, sauce, soup stock, spices, cooking liquor, etc. Filled and packaged with various liquid or viscous foods such as fruit juices and others. The contents can be used for filling and packaging various articles such as chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, etc., in addition to the above-mentioned food and drink.

  The liquid sachet package of the present invention is molded using the above laminated material, and the laminated material is a polyamide having excellent mechanical strength such as sticking resistance, and a carbon-containing silicon oxide vapor-deposited film. By laminating a thin film, gas barrier properties and flexibility are ensured. Further, by laminating a gas barrier coating film and a coating thin film, gas barrier properties and laminate strength are ensured. It is excellent in preservability and is robust against pointing and pinholes that are generated during transportation, and the flavor and taste of the contents are rarely impaired during storage, storage or distribution.

  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 one hand, a biaxially stretched polyamide film having a corona-treated surface and having a thickness of 15 μm (dynamic friction coefficient 0.3, haze 2.4%, ash test performance 12 mm, surface roughness 1500 nm) is used. The plasma chemical vapor deposition apparatus comprising three film forming chambers (chambers) as shown in FIG. 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 = 1.2: 6.0: 0.5: 0.5 (unit; slm, standard liter minute)), film forming output: 10 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. .2: 1.0: 0.5: 0.5 (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 = 1.2: 3.0: 0.5: 0.5 (unit: slm) and film forming output: 10 kW.

  Using the raw material gas as described above, the raw material 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 polyamide film at a line speed of 200 m / min, the film thicknesses of the first layer, the second layer, and the third layer are respectively on the corona-treated surface of the biaxially stretched polyamide film having a thickness of 15 μm. A three-layer carbon-containing silicon oxide layer having a total thickness of 5 nm and a thickness of 15 nm was formed.

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、１８０℃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。

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 180 ° C. for 60 seconds to obtain a thickness of 0. A gas barrier coating film of 3 μm (dry operation state) was formed.

  (3) γ-glycidoxypropyltrimethoxysilane is used as the silane coupling agent, the silane coupling agent 1.2% by mass, the silica powder 1.0% by mass, the polyurethane resin 13-15% by mass, A polyurethane resin composition comprising 3 to 4% by mass of nitrocellulose, 31 to 32% by mass of toluene, 29 to 30% by mass of methyl ethyl ketone (MEK), and 15 to 16% by mass 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 using a gravure roll coating method, and then dried at 100 ° C. for 5 seconds. A coating thin film (thickness 0.3 g / m ² , dry state) of the polyurethane resin composition was formed.

(4) On the coating thin film, a polyurethane-based anchor coating agent was coated in the same manner as described above to form an anchor coat layer having a thickness of 0.2 g / m ² (dry state).

  (5) Further, an ethylene / α-olefin copolymer (LDPE, MI = 8.0, density = 0.911) polymerized using a Ziegler catalyst is melt-extruded onto the anchor coat layer, At that time, an extrusion process was performed while applying ozone treatment to the melt-extruded resin surface to form an adhesive layer having a thickness of 20 μm. Next, 80% by mass of an ethylene / α-olefin copolymer (LLDPE, MI = 7.3, density = 0.900) polymerized by a single site catalyst on the above adhesive layer and ethylene / butene copolymer. A blend comprising 20% by mass of a polymer (MI = 3.5, density = 0.855, butene content 20%) was melt extrusion coated at an extrusion temperature of 290 ° C. and a processing speed of 100 m / min to obtain a thickness. A laminate 1 was produced by forming a 20 μm heat-sealable resin layer.

Example 2
An anchor coat layer was formed in the same manner as in Example 1 (1) to (4).

  Next, an ethylene / α-olefin copolymer (LDPE, MI = 8.0, density = 0.911) polymerized using a Ziegler catalyst is melt-extruded onto the anchor coat layer, Extrusion was performed by an extrusion method while applying ozone treatment to the extruded resin surface to form an adhesive layer having a thickness of 20 μm. Next, on this adhesive layer, 80% by mass of ethylene / α-olefin copolymer (LLDPE, MI = 7.3, density = 0.900) polymerized by a single site catalyst and ethylene / butene copolymer A 20 μm thick heat-sealable resin film obtained by forming a blend of 20% by mass (MI = 3.5, density = 0.855, butene content 20%) using an inflation method is laminated. And the laminated material 2 was manufactured.

Comparative Example 1
In Example 1, a biaxially stretched polyamide film having a thickness of 15 μm was used instead of the biaxially stretched polyamide film having a thickness of 15 μm (dynamic friction coefficient 0.3, haze 2.4%, ash test performance 12 mm, surface roughness 1500 nm). Comparative laminate 1 was prepared in the same manner as in Example 1 except that (dynamic friction coefficient 0.6, haze 2.4%, ash test performance 12 mm, surface roughness 1500 nm) was used.

Comparative Example 2
A comparative laminate 2 was prepared in the same manner as in Example 1 except that the coating thin film formed of the polyurethane resin composition described in (3) of Example 1 was not provided.

Evaluation method The laminate materials manufactured in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were subjected to a laminate strength test and a heat seal strength test. The results are shown in Table 2 below.

(I) Laminate strength test:
Using a peeling tester (Orientec Co., Ltd., model name, Tensilon universal testing machine), sample 15 mm width, peeling angle 90 degrees, peeling speed 50 mm / min, distance between fulcrums 50 mm, peeling method T-shaped peeling conditions The laminate strength test was conducted.

(Ii) Heat seal strength:
Sealing conditions: 140 ° C. × 1 kg / cm ² × 1 second, using the above peeling tester, heat seal under the conditions of sample 15 mm width, peeling speed, 300 mm / min, distance between fulcrums, 50 mm, T-shaped peeling A strength test was performed.

ＩＩ．
実施例１、実施例２、比較例１、比較例２で製造した積層材について、引き裂き性試験を行なった。結果を下記の表３に示す。

II.
A tearability test was performed on the laminates manufactured in Example 1, Example 2, Comparative Example 1, and Comparative Example 2. The results are shown in Table 3 below.

(I) Tearability test:
A 5 mm incision was made at the end of the laminated material, and it was torn by hand with dry (in air) and wet (in water), and the tear feeling was evaluated. In addition, the symbol in Table 3 shows the following.

○ is excellent in tearability,
△ is a tearable,
× indicates poor tearability

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実施例１、実施例２、比較例１、比較例２で製造した積層材および該積層材で構成した液体用小袋について、印刷、貼り合せ、スリット、充填工程でのトラブルについて観察を実施した。結果を下記の表４に示す。

III.
With respect to the laminated materials produced in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 and the liquid sachet composed of the laminated materials, the printing, bonding, slitting, and troubles in the filling process were observed. The results are shown in Table 4 below.

  The liquid sachet according to the present invention is particularly useful because it is excellent in mechanical strength, gas barrier properties, laminate strength, transparency, and is excellent in the preservation of contents.

FIGS. 1A to 1E are cross-sectional views illustrating a gas barrier laminate film used in the present 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 ... base film layer,
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 (6)

For the coating thin film of the gas barrier laminated film consisting of a base film, a carbon-containing silicon oxide vapor-deposited film, a gas barrier coating film and a coating thin film, for laminating with an anchor coating layer by an anchor coating agent and / or a laminating adhesive A liquid sachet made of a laminate in which an adhesive layer and a heat-sealable resin layer are sequentially laminated,
The gas barrier laminate film has a biaxial structure in which the base film has a dynamic friction coefficient of 0.4 or less, a haze of 6.0% or less, an ash test performance of 15 mm or less, and a surface roughness of at least one surface of 2000 nm or less. It is a stretched polyamide film, and an organic silicon compound is supplied as a vapor deposition monomer by chemical vapor deposition, and a carbon-containing silicon oxide vapor deposition film is provided on the surface of the base film having a surface roughness of 2000 nm or less. 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, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol-based resin, and / or Or Ethile A gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method, and filled with a silane coupling agent on the surface of the gas barrier coating film. Provided with a coating thin film made of a polyurethane-based resin composition containing an agent,
The liquid sachet is a liquid in which the laminated material is overlapped with the heat-sealable resin layer facing each other to heat-seal the outer periphery and provide a heat-seal portion to form a bag body. Sachets.   The liquid pouch according to claim 1, wherein a base material layer is further laminated on the other surface of the base film.   3. The liquid pouch according to claim 1, wherein the filler is made of silica particles.   The anchor coat layer by the anchor coat agent and / or the adhesive layer for laminating by the laminating adhesive has a tensile elongation of 100 to 300% based on JIS standard K7113. The liquid pouch according to any one of claims 1 to 3.   The liquid pouch according to any one of claims 1 to 4, wherein a printing layer is laminated on the base material layer, the gas barrier coating film or the coating thin film, or a surface treatment layer thereof.   A liquid sachet package comprising: a liquid sachet according to any one of claims 1 to 5 filled and packaged with a liquid or a viscous material from an opening thereof.

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