JP2009248456A - Laminate for tube and laminated tube - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate for a tube which is excellent in gas-barrier properties and transparency. <P>SOLUTION: In the laminate, a surface olefin resin layer, a gas-barrier laminated film, and a heat sealing layer are laminated in turn. In the gas-barrier laminated film, a vapor deposition film (I) formed by supplying an organosilicon compound to a base film by a chemical vapor deposition method, a gas-barrier coated film (I), the vapor deposition film (II), and the gas-barrier coated film (II) are formed. It is suitable for cylindrical molding and can keep gas-barrier properties high since deterioration by hand-kneading is reduced. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate for a tube, and more specifically, a laminate for a tube in which a surface olefin-based resin layer, a gas barrier laminate film, and a heat seal layer are laminated in this order, and the gas barrier laminate film includes: An organic silicon compound vapor deposition layer, a gas barrier coating film, an organic silicon compound vapor deposition layer, and a gas barrier coating film are laminated in this order on the base film, and are excellent in gas barrier properties, flexibility, and flexibility. The present invention relates to a laminate for a tube and a laminate tube made of the laminate.

  Conventionally, a laminate tube has been manufactured by various methods, and at least one surface resin layer, an intermediate layer, and an inner surface resin layer are sequentially stacked to manufacture a laminated material, and surface resins at both ends thereof are manufactured. The cylindrical body is manufactured by heat-sealing the layer and the inner surface resin layer, and then a head composed of a mouth, a shoulder, etc. is formed in one opening of the cylindrical body, and the mouth There is a laminate tube in which a cap is screwed. The laminated tube manufactured above is, for example, toothpaste, mayonnaise, kneaded wasabi, knead, ketchup, other seasonings, whipped cream, other creams, etc. It can be filled with contents such as foods and beverages such as foods, cosmetics, pharmaceuticals, etc., and the open end can be hermetically sealed to form a tubular packaged product as a bottom seal.

  The laminated material for producing such a laminated tube has been proposed a layer structure in which various plastic films and the like are laminated in order to ensure the function according to the contents in order to protect the contents. Laminates having excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like are frequently used in terms of ensuring high quality retention.

  As such a gas barrier material, usually, an aluminum foil or an aluminum vapor-deposited film, a single-layer film of a polyvinylidene chloride resin, a coextruded film using a polyvinylidene chloride resin, or a polyvinylidene chloride resin composition The coated film etc. by the thing are used. In addition, polyvinyl alcohol resin films, ethylene-vinyl alcohol copolymer films, and the like are used as barrier materials (see, for example, Patent Document 1).

Further, in the material in which the heat-adhesive resin layer is formed by extrusion coating on the inner surface of the base material layer through the stretched plastic film and the anchor coat layer, the anchor coat layer contains 0.1 to 0 of the two-component curable urethane adhesive. There is also a packaging material characterized in that the coating amount is in a range of 0.5 g / m ² (Patent Document 2). In view of the point that when laminated with a two-component curable urethane-based adhesive, the adhesive strength of the adhesive decreases with time when the content containing a large amount of the fragrance component is stored, and finally the adhesive strength between the layers decreases. According to the above configuration, even when filled with a content containing a large amount of a fragrance component, the adhesive strength between the stretched plastic film and the sealant layer can be stably stored without being lost. Since it can be formed by melt-coating a sealant layer made of a resin, it is possible to produce an inexpensive and stable packaging material. In FIG. 3 of Patent Document 2, a tubular container is described as an example of a packaging container made of the packaging material.

Further, an inorganic oxide vapor-deposited film is provided on one surface of the surface polyolefin-based resin layer and the base film, and a gas barrier coating film made of a gas barrier composition is further formed on the surface of the inorganic oxide vapor-deposited film. Also disclosed is a tube container packaging material in which an intermediate layer made of a barrier film provided with a film and a backside polyolefin-based resin layer are sequentially laminated (Patent Document 3). A tube container using a polyvinyl alcohol-based resin film, an ethylene-vinyl alcohol copolymer film or the like as a barrier material is excellent in gas barrier properties in an absolutely dry state, but prevents permeation of oxygen gas, water vapor, etc. in a wet state. It was made in view of the fact that the gas barrier property may be remarkably lowered, and has the strength by the above configuration, and has excellent gas barrier property, heat resistance, heat seal property, pinhole resistance, puncture resistance, transparent It is said to have excellent properties, etc., and its contents are packed and packaged, stored, etc.
Japanese Patent Laid-Open No. 5-8352 (Claims, Examples, etc.) JP-A-11-254595 JP 2005-144812 A

  However, as described in Patent Document 1 and the like, it is excellent in gas barrier properties when aluminum foil is used as a barrier material, but after use, incineration treatment as waste waste may lack its incineration suitability, Also lacks transparency.

Moreover, the laminated material described in Patent Document 2 is intended to prevent delamination, and the described laminated material may not have sufficient gas barrier properties.
Furthermore, the tube container packaging material described in Patent Document 3 is excellent in gas barrier properties and transparency, but is more preferable if it has higher gas barrier properties.

  Moreover, the laminated body for tubes is formed to have a diameter of about 2 to 4 cm in order to accommodate kneading, toothpaste, and the like, and it is necessary to maintain a curved state. However, such a curved shape is large for the laminated body. It is a load. In addition, the laminate tube has a large physical handling load compared to other containers, such as squeezed out during use, so that the film constituting the laminate is easily deteriorated, and the gas barrier property is lowered due to film deterioration. There is a case.

  Therefore, an object of the present invention is to provide a laminated body for a tube which is excellent in mechanical strength such as curvature and transparency and excellent in gas barrier properties in actual use, and a laminated tube using the same.

  As a result of examining the laminated body for a tube in detail, the present invention and the like show that a vapor-deposited film obtained by supplying and vapor-depositing an organic silicon compound by chemical vapor deposition on one surface of a base film as a gas barrier laminate is shock resistant. Since it is excellent in properties, spreadability, flexibility, etc., it is possible to avoid the occurrence of scratches and cracks, etc., and it is possible to stably maintain high barrier properties, and to this deposited film, a gas barrier coating film made of a gas barrier composition is applied. And further stacking the vapor deposition film and the gas barrier coating film on the gas barrier coating film in order to ensure higher gas barrier properties, and laminating a heat seal layer and a surface olefin resin layer on the gas barrier laminate. With this simple layer configuration, it was found that gas barrier properties can be kept high by avoiding delamination, and the present invention has been completed.

That is, the present invention is a laminate for a tube in which a surface olefin-based resin layer, a gas barrier laminate film, and a heat seal layer are laminated in this order, and the gas barrier laminate film is formed on one surface of a base film. A vapor-deposited film (I) obtained by supplying an organic silicon compound by chemical vapor deposition is provided on the vapor-deposited film, and a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ , R ²⁾ Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. A gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by the formula (1)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Gas barrier coating film by (I) is provided, and a vapor deposition film (II) obtained by supplying an organic silicon compound by chemical vapor deposition is provided on the gas barrier coating film (I), and the general formula R ¹ _n is provided on the vapor deposition film (II). M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1 or an integer greater than or equal to 1 and n + m represents the valence of M.) and contains at least one alkoxide represented by: a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer; Furthermore, the present invention provides a laminate for a tube, which is a gas barrier laminate film provided with a gas barrier coating film (II) made of a gas barrier composition obtained by polycondensation by a sol-gel method. .

  Moreover, this invention provides the laminated tube which consists of the said laminated body for tubes.

Since the laminated body for tubes of the present invention is excellent in impact resistance, spreadability, flexibility and the like, it is excellent in molding processability when a laminated tube is prepared by bending the laminated body for tubes.
Moreover, the laminated body for tubes of the present invention does not deteriorate in gas barrier properties even when it is bent or manually kneaded, and has high quality retention ability.

  Since the laminated body for tubes of the present invention is transparent, it can be suitably used in the field where the visibility of the contents is required.

1st of this invention is a laminated body for tubes formed by laminating | stacking a surface olefin resin layer, a gas barrier property laminated film, and a heat seal layer in this order, Comprising: The said gas barrier property laminated film is one side of a base film. A vapor-deposited film (I) formed by supplying an organic silicon compound by chemical vapor deposition is provided on the surface, and a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. Gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one or more alkoxides represented by formula (1)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Gas barrier coating film (I) is provided, and a vapor deposition film (II) obtained by supplying an organic silicon compound by chemical vapor deposition is provided on the gas barrier coating film (I), and the general formula R ¹ _n is provided on the vapor deposition film (II). M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1 or an integer greater than or equal to 1 and n + m represents the valence of M.) and contains at least one alkoxide represented by: a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer; Furthermore, the laminate for tubes is a gas barrier laminate film provided with a gas barrier coating film (II) made of a gas barrier composition obtained by polycondensation by a sol-gel method. The second of the present invention is a laminated tube made of the above laminated body for tubes. Hereinafter, the laminated body for tubes and the laminated tube of the present invention will be described in detail.

(1) Configuration of Tube Laminate The tube laminate of the present invention is a tube laminate formed by laminating a surface olefin resin layer, a gas barrier laminate film, and a heat seal layer in this order, and the gas barrier property. The laminated film is provided with a vapor deposition film (I) formed by supplying an organosilicon compound by chemical vapor deposition on one surface of a base film, and the general formula R ¹ _n M (OR ² ) _m is formed on the vapor deposition film. (In the formula, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. N + m represents the valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further includes a sol-gel method. Obtained by polycondensation with A gas barrier coating film (I) made of a barrier composition is provided, and a vapor deposition film (II) obtained by supplying an organosilicon compound to the gas barrier coating film (I) by chemical vapor deposition is provided. II) on the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and 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 ethylene vinyl. A laminate comprising an alcohol copolymer and further provided with a gas barrier coating film (II) made of a gas barrier composition obtained by polycondensation by a sol-gel method. FIG. 1 shows an example of a preferred embodiment of the layer structure of the gas barrier laminate film used in the present invention.

  In FIG. 1, the heat seal layer (10) is bonded to the gas barrier laminate film (30) with a laminating adhesive (20), and the gas barrier laminate film (30) is surface olefin-based with a laminating adhesive (20). It is adhered to the resin layer (40). The gas barrier laminate film (30) includes a base film (31) and a vapor deposition film (33) supplied with an organic silicon compound, a gas barrier coating film (35), and a vapor deposition film (37) supplied with an organic silicon compound. ) And a gas barrier coating film (39) are laminated in this order. In addition, any of the gas barrier laminate films (30) may be directed to the innermost layer side. Therefore, in FIG. 1, the gas barrier coating film (39) constituting the gas barrier laminate film (30) is laminated against the heat seal layer (10) through the laminating adhesive layer (20). However, the base film (31) may be opposed to the heat seal layer (10). Furthermore, in FIG. 1, the aspect by which the printing layer (50) which consists of UV curable resin is formed in a surface olefin resin layer (40) is shown. The printed layer (50) is not formed at both end portions of the tube laminate. Therefore, when the surface olefin-based resin layer (40) has heat-fusibility, both end portions of the tube laminate material. The surface olefin-based resin layer (40) and the heat seal layer (10) are superposed and then heat-sealed to form a cylinder.

  The tube laminate of the present invention is not limited to an embodiment in which the heat seal layer or the surface olefin-based resin layer is bonded to the gas barrier laminate with a laminating adhesive, and is bonded through an extruded molten resin. May be. In FIG. 2, an anchor coat layer (60) is formed on the base film (31) side of the gas barrier laminate film (30) and the gas barrier coating film (39), respectively, and the anchor coat layer (60) is extruded. The aspect laminated | stacked with a heat seal layer (10) and a surface olefin resin layer (40) through a molten tree layer (25), respectively is shown. In addition, as described above, the laminate for a tube of the present invention is such that any surface of the base film (10) of the gas barrier laminate film (30) and the gas barrier coating film (39) is oriented to the innermost layer side. It may be.

(2) Gas barrier laminated film The gas barrier laminated film used in the present invention is provided with a deposited film (I) formed by supplying an organic silicon compound by a chemical vapor deposition method on one surface of a base film. R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents 0 on the film) And m represents an integer of 1 or more, and n + m represents a valence of M.), at least one alkoxide represented by the following formula: polyvinyl alcohol resin and / or ethylene / vinyl alcohol A gas barrier coating film (I) comprising a gas barrier composition obtained by polycondensation by a sol-gel method, and a chemical vapor deposition method on the gas barrier coating film (I). To supply organosilicon compounds The becomes deposited film (II) is provided, the vapor deposition film (II) general formula R ¹ _n M (OR ²⁾ on _m (proviso that in formula, R ^1, R ² is an organic group having 1 to 8 carbon atoms M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M). A gas barrier coating film (II) comprising a gas barrier composition containing an alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method was provided. It is a gas barrier laminate film. In the gas barrier coating film, a polyvinyl alcohol-based resin or ethylene / vinyl alcohol copolymer and one or more alkoxides chemically react with each other to form a strong three-dimensional network composite polymer layer. It acts synergistically with the deposited film, has excellent gas barrier properties that prevent the transmission of oxygen, water vapor, etc., and also has excellent hot water resistance. The gas barrier laminate film of the present invention can ensure higher gas barrier properties by laminating two layers each of the vapor deposition film and the gas barrier coating film.

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

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

In the present invention, the film thickness of the resin film is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.
It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose.

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

(Ii) Surface treatment In this invention, although the vapor deposition film formed by supplying an organosilicon compound to one surface of said base film is formed, you may surface-treat a base film previously. Adhesiveness with the vapor deposition film and gas barrier coating film obtained by this can be improved.

  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 deposition film formed by supplying an organic silicon compound by chemical vapor deposition, which will be described later, by performing plasma treatment in-line, moisture and dust on the surface of the substrate film are removed and Surface treatments such as surface smoothing, 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 processing, it is preferable to perform the plasma discharge processing in consideration of the plasma output, the type of plasma gas, the supply amount of the plasma gas, the processing 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.

(Iii) Deposition film formed by supplying an organosilicon compound The deposited film formed by supplying an organosilicon compound is formed by using an organosilicon compound as a deposition monomer by chemical vapor deposition. As the chemical vapor deposition method, for example, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like can be used. Among these, it is particularly desirable to 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. 1 of an organic silicon compound composed of silicon oxide or the like using a low-temperature plasma chemical vapor deposition method using a gas, further using an oxygen gas as an oxygen supply gas and utilizing a low-temperature plasma generator or the like. It can be produced by forming a single-layer vapor-deposited film composed of layers, a multilayer vapor-deposited film composed 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 formed by supplying an organosilicon compound by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 3 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.
The plasma chemical vapor deposition apparatus (100) of FIG. 3 produces a deposition layer of an organosilicon compound on a substrate film supply chamber (110), a first film formation chamber (120) consisting of a vacuum chamber, and a substrate film. It is comprised from the winding chamber (150) which winds up the film-formed 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 formed by supplying an organosilicon compound made of silicon or the like is formed. Next, the base film (101) on which the vapor deposition film formed by supplying the organosilicon compound made of silicon oxide or the like as described above is transferred to the winding chamber (150) through the auxiliary roll (123). If it winds up to a take-off roll (151), the film which has a vapor deposition film by a plasma chemical vapor deposition method can be manufactured. 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 deposition film formed by supplying an organosilicon compound made of silicon oxide or the like can be formed on the film. In FIG. 3, reference numeral (153) represents a vacuum pump.

In the present invention, a vapor deposition film formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is a base film. Is formed into a dense and flexible thin film, and is usually an oxidation represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon. The vapor-deposited film formed by supplying the organosilicon compound is represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) from the viewpoint of transparency and barrier properties. A thin film mainly composed of a vapor-deposited film obtained by supplying an organosilicon compound 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 deposition film formed by supplying an organosilicon compound is mainly composed of silicon oxide, and further chemistry of at least one compound of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements. It consists of a vapor deposition film contained by bonding or the like. 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 and amount of the compound contained in the deposited film may be changed by changing the conditions of the deposition process. Under the present circumstances, as content contained in said vapor deposition film | membrane which said compound supplies an organosilicon compound, it is 0.1-50 mass%, Preferably it is 5-20 mass%. If the content is less than 0.1% by mass, the impact resistance, spreadability, flexibility, etc. of the deposited film will be insufficient, and scratches, cracks, etc. will easily occur due to bending, and high barrier properties will be stabilized. On the other hand, if it exceeds 50% by mass, the barrier property may be lowered.

  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. The tight adhesion with the film is high.

  Furthermore, in this invention, in the vapor deposition film formed by supplying the organosilicon compound, the content of the above compound may increase or decrease from the surface of the vapor deposition film in the depth direction. For example, when it decreases from the surface in the depth direction, this improves the impact resistance and the like by the above compound on the surface of the deposited film, while the inclusion of the above compound at the interface with the base film. Since the amount is small, the tight adhesion between the base film and the deposited film becomes strong. The vapor deposition film formed by supplying such an organosilicon compound is not limited to a single layer, but may be a multilayer film in which two or more layers are laminated, for example.

  In order to form the above-mentioned multi-layered vapor deposition layer, a chemical vapor deposition apparatus (100) having a plurality of vacuum chambers as film formation chambers is used to supply an organic silicon compound having a different composition. Can be formed. FIG. 4 is used to illustrate the case of having a three-layer deposited film. The plasma chemical vapor deposition apparatus (100) of FIG. 4 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 vapor deposition layer formed by supplying an organosilicon compound on a base film, and laminated | stacked the multilayer. 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 vapor-deposited layer made of an organosilicon compound of the first layer made of or the like is formed into a film.

  The base film (101) obtained by forming the first deposited film in the first film forming chamber (120) is transferred to the second film forming chamber (130) through the auxiliary rolls (123) and (131). Then, in the same manner as described above, the base film (101) obtained by forming the first-layer deposited film is transported onto the cooling / electrode drum (132) peripheral surface at a predetermined speed. 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 organic silicon compounds are 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 A glow discharge plasma (138) is formed on the first layer deposited film of the base film (101) obtained by forming the first layer deposited film transported on the cooling / electrode drum (132) peripheral surface. A plasma is generated by irradiating and irradiating the plasma to form a vapor deposition film formed by supplying a second-layer organosilicon compound made of silicon oxide or the like.

  Further, in the second film forming chamber (130), the first layer and the second layer are formed as a deposited film, and the laminated base film (101) is passed through the auxiliary rolls (133), (141) and the like. Next, the substrate film (101) formed by depositing the first layer and the second layer of the deposited film is cooled to the third film forming chamber (140) at a predetermined speed and the electrode drum (142) as described above. ) Carry on the circumferential surface. 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. Glow discharge plasma (148) is formed on the deposited film of the second layer of the base film 1 formed by stacking the deposited films of the first layer and the second layer conveyed on the peripheral surface of the electrode drum (142). A plasma is generated by irradiating and irradiating the plasma to form a vapor deposition film formed by supplying a third layer organosilicon compound made of silicon oxide or the like.

  Next, the first layer, the second layer, and the third layer of the deposited film are formed into a film, and the base film (101) on which these layers are stacked is wound through the auxiliary roll (143) into the winding chamber ( 150) and then wound on a winding 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, a vapor deposition film formed by supplying an organic silicon compound made of silicon oxide or the like regardless of whether the vapor deposited film formed by supplying an organosilicon compound is constituted by a single layer or a multilayer. The degree of vacuum at the time of formation is adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr by reducing the pressure in each vacuum chamber with a vacuum pump. Is preferred. The degree of vacuum when forming a deposited film by supplying an organic silicon compound made of silicon oxide or the like by a conventional vacuum deposition method is lower than that of 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr. Therefore, it is possible to shorten the time for setting the vacuum state at the time of exchanging the raw material of the base film, and it is easy to stabilize the degree of vacuum, and the film forming process is also 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 vapor deposition film formed by supplying an organosilicon compound made of silicon oxide or the like can be uniformly formed on a 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 deposited film formed by supplying the organic silicon compound formed into a film can be increased or decreased. As the amount of carbon increases, the number of C—C bonds and Si—CH ₃ bonds increases, and flexibility is increased. A water-repellent vapor-deposited film having a high barrier property against water vapor can be formed. Further, when the carbon content in the deposited layer formed into a film is reduced, Si—CH ₃ bonds are reduced and flexibility is inferior, but high gas barrier properties against oxygen and the like can be maintained.

  In the present invention, the vapor deposition film formed by supplying the organosilicon compound is, for example, a surface analysis 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 an elemental analysis of a deposited film obtained by performing an ion etching or the like in the depth direction using an apparatus and supplying an organosilicon compound.

  In the present invention, the total film thickness of the 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. As a means for changing the film thickness of the vapor deposition film, it can be performed by 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 or a method of slowing the vapor deposition rate. .

  In the case of the multilayer structure consisting of the three layers described above, the thickness of the vapor deposition film constituting the first layer is preferably about 20 mm to 200 mm, preferably about 30 mm to 100 mm, and the second layer is The film thickness of the deposited film is about 20 mm to 200 mm, preferably 30 mm to 100 mm, and the film thickness of the vapor deposited film constituting the third layer is about 20 mm to 200 mm, preferably 30 mm. ˜100〜 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. Moreover, in the above, as a means for changing the film thickness of the organosilicon compound layer, a method of increasing the volume velocity of the layer, that is, a method of increasing the amount of monomer gas for forming a film and oxygen gas, or film formation It can be performed by a method of slowing down the speed of performing.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film formed by supplying an organic silicon compound composed of silicon oxide or the like, for example, 1,1,3,3-tetramethyldisiloxane, hexa Methyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane , Phenyltrimethoxysilane, 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.

(Iv) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. It contains the above alkoxide, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and further, in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent, by a sol-gel method. It is a coating film comprising a gas barrier composition formed by polycondensation, and the coating film is provided by coating the composition on the vapor deposition film on the base film, and the coating film is formed at 20 ° C. to 180 ° C. Heat for 30 seconds to 10 minutes at a temperature below the melting point of the substrate film It can be formed by management.

  Further, the gas barrier composition is applied onto the vapor deposition film on the base film, and two or more coating films are stacked, and the temperature is 20 ° C. to 180 ° C. and the melting point of the base film or less. May be heat-treated for 30 seconds to 10 minutes to form a composite polymer layer in which two or more gas barrier coating films are stacked.

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 (OC 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, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n butoxyzirconium Zr (OC ₄ H ₉ ) ₄ , 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 include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra-n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and others.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

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

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

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

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

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

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

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) A polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a catalyst, acid, water, and an organic solvent. The gas barrier composition obtained above. 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 described above is applied and dried by a conventional method on the vapor deposition film formed by supplying the above-described organosilicon compound on the base film. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film coated with the gas barrier composition is heated at 20 ° C. to 180 ° C. and below the melting point of the base film, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 minutes. To process. Thereby, a gas barrier laminated film in which one or two or more gas barrier coating films of the gas barrier composition are formed on the 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 hydrolysis products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

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

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

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

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

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム上の前記蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム上の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 deposition film on the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and the vapor deposition film on the base film. A transparent coating film is formed on the substrate. 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, since the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the base film or the hydroxyl group on the surface of the deposited film on the base film, the base film, or the above-mentioned Adhesiveness between the surface of the deposited film and the coating film is also good. As described above, in the present invention, a vapor deposition film formed by supplying an organosilicon compound and a gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordination bond by a hydrolysis / co-condensation reaction. Therefore, the adhesion between the vapor deposition film formed by supplying the organosilicon compound and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). In particular, when used for so-called gas-filled packaging filled with N ₂ , CO ₂ gas, etc., the excellent gas barrier property is extremely effective for holding the filled gas. Furthermore, the gas barrier laminate film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

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

  The gas barrier laminate film used in the present invention forms the vapor deposition film (I) on the base film as described above, then forms the gas barrier coating film (I), and further forms the vapor deposition film (II) by the above method. And a gas barrier coating film (II) formed by the above method and laminated. However, the vapor deposition films (I) and (II) may be the same or different. Similarly, the gas barrier coating films (I) and (II) may be the same or different. The gas barrier property can be further improved by alternately laminating the deposited film and the gas barrier coating film by two layers. In addition, since the outermost layer of the obtained gas barrier laminate film is a gas barrier coating film (II), there is little risk of damaging the deposited films (I) and (II) when laminating to other films, A decrease in gas barrier properties can be prevented.

(4) Heat seal layer The laminate for a tube of the present invention has a heat seal layer as the innermost layer. Since the innermost layer is a heat seal layer, the innermost layers at both ends of the plate-like tube laminate can be laminated facing each other and thermally fused to form a tube shape.

  The material constituting the heat seal layer used in the present invention may be any material that can be melted by heat and fused to each other. For example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene ( HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic Polyolefin resins such as acid copolymers, ethylene-propylene copolymers, methylpentene polymers, polyethylene or polypropylene are used for unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Acid-modified polyolefin resin modified with acid Polyvinyl acetate resin, polyester resin, polystyrene resin, one or resin comprising more resins other like can be used.

  Furthermore, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst (single site catalyst) can be used as a material constituting the heat seal layer in the present invention.

  As the ethylene-α / olefin copolymer polymerized using a metallocene catalyst, for example, a catalyst using a combination of a metallocene complex and an alumoxane such as a catalyst using a combination of zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst is used. Thus, an ethylene-α / olefin copolymer obtained by polymerization can be used. The metallocene catalyst described above is also called a single-site catalyst because the current catalyst is called a multi-site catalyst with non-uniform active sites, while the active sites are uniform. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Epolyu” manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name “EXACT” manufactured by Exxon Chemical Company, USA ”, An ethylene-α / olefin copolymer polymerized using a metallocene catalyst such as“ AFFINITY ”or a product name“ ENGAGE ”manufactured by Dow Chemical Co., USA be able to.

  In the present invention, as the heat seal layer, for example, one or two or more of the above-mentioned resins are used as a main component, and a desired additive is arbitrarily added thereto, thereby preparing a resin composition, Using the resin composition prepared above, for example, a film or sheet can be formed using a molding method such as a T-die method, an inflation method, or the like, and the above-mentioned backside polyolefin resin layer can be formed.

In the above, it is preferable that the heat seal layer is excellent in low odor and scent retention, etc. in the contents, excellent in strength and the like, and capable of improving waist and the like.
In the present invention, the film thickness of the heat seal layer is 25 to 300 μm, preferably 30 to 200 μm.

  In the present invention, for example, an anti-blocking agent, a lubricant (fatty acid amide, etc.), a flame retardant, an inorganic or organic filler, a dye, a pigment, and the like are optionally added to the heat seal layer. can do.

(4) Surface Olefin Resin Layer In the present invention, a surface olefin resin layer is laminated on the outside of the gas barrier laminate film. A cylindrical trunk | drum can be manufactured by superimposing the surface olefin resin layer and heat seal layer of the both ends of the laminated body for tubes concerning this invention, and heat-seal | fusing. Therefore, it is preferable that the surface olefin-based resin layer can be melted by heating and fused to each other. However, if the innermost layers at both ends of the laminated body for a tube are opposed to each other and overlapped, and the ends are heat-sealed, it can be formed into a cylindrical shape, and is not limited to those having heat-fusibility. The surface olefin-based resin layer is desirably made of a resin having heat sealability that can form a printed pattern by a gravure printing method, a flexographic printing method, an offset printing method, or the like.

  Examples of such surface olefin-based resin layers include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer , An ethylene-propylene copolymer, a methylpentene polymer, a polybutene polymer, an acid-modified polyolefin resin obtained by acid-modifying a polyolefin resin such as polyethylene or polypropylene using an unsaturated carboxylic acid, and other resins may be used. it can.

  Further, in the present invention, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst (single site catalyst) can be used. As the ethylene-α / olefin copolymer polymerized using a metallocene catalyst, for example, a catalyst using a combination of a metallocene complex and an alumoxane such as a catalyst using a combination of zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst is used. Thus, an ethylene-α / olefin copolymer obtained by polymerization can be used. The above metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform.

  Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Epolyu” manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name “EXACT” manufactured by Exxon Chemical Company, USA ”, An ethylene-α / olefin copolymer polymerized using a metallocene catalyst such as“ AFFINITY ”or a product name“ ENGAGE ”manufactured by Dow Chemical Co., USA be able to.

  In the present invention, as the surface olefin resin layer, for example, one or more of the above heat-sealable resins are the main components, and desired additives and the like are arbitrarily added thereto. A resin composition is prepared, and then the above-prepared resin composition is used. This is formed into a film or sheet using a molding method such as a T-die method, an inflation method, or the like. A surface olefin resin layer can be constituted. In the present invention, as the surface olefin-based resin layer, for example, the uneven surface called fish eye is smoothed and flattened, thereby greatly improving the printability by a gravure printing method or a flexographic printing method. It is possible to prevent the occurrence of ink loss or the like constituting the printed pattern layer, to form a very beautiful printed pattern layer, etc., and to improve the occurrence of defective products due to the printing quality. Is desirable.

In the present invention, the film thickness of the surface olefin-based resin layer is 25 to 300 μm, preferably 30 to 200 μm.
(5) Print layer In this invention, you may form a print layer in any layer which comprises the laminated body for tubes.

  The printing layer is composed of one or more ordinary ink vehicles as the main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, and a crosslinking agent. Add one or more additives such as additives, lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and use solvents, diluents, etc. An ink composition obtained by kneading to prepare an ink composition can be used. As such an ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic resin, Natural resin, hydrocarbon resin, polyvinyl chloride resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin , Melamine resin, amino alkyd resin, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc. can be used alone or in combination.

The printing method may be a printing method such as relief printing, screen printing, transfer printing, flexographic printing, or the like in addition to gravure printing.
(6) Laminating adhesive As laminating adhesive constituting the laminating adhesive layer, for example, polyvinyl acetate adhesive, homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester, or the like And polyacrylic acid ester adhesives composed of copolymers of methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid and other monomers Ethylene copolymer adhesive made of copolymer, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin Adhesive, epoxy adhesive, polyurethane adhesive, reactive type (Meth) acrylic adhesives, chloroprene rubber, nitrile rubber, rubber adhesives made of styrene-butadiene rubber, silicone adhesives, alkali metal silicates, inorganic adhesives made of low melting glass, etc. An adhesive can be used.

  The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

In the present invention, the laminating adhesive is applied to one side of both of the layers by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method such as others, or a printing method, Next, the solvent or the like can be dried to form an adhesive layer for laminating, and the coating or printing amount is preferably about 0.1 to 10 g / m ² (dry state).

(7) Anchor coat agent In the present invention, for example, a heat seal layer may be formed by extrusion, and in that case, the heat seal layer can be formed via the anchor coat agent. Examples of the anchor coating agent to be used include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, a thin film rich in flexibility and flexibility can be formed, its tensile elongation is improved, and it acts as a film having flexibility, flexibility, etc. on the above-mentioned thin film, and laminating , Improving processability such as printing, avoiding the occurrence of cracks in the thin film layer, improving the tight adhesion between the gas barrier laminate film and the heat seal layer, Generation | occurrence | production can be prevented and laminate strength can be improved.

The anchor coating agent can be applied by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. The amount of the anchor coating agent used is not particularly limited, but is generally 0.1 to 5 g / m ² (dry state).

(8) Extruded resin layer For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, or metallocene catalyst is used as the melt-extruded resin in the melt-extrusion laminating method. Ethylene-α / olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene Uses acid-modified polyolefin resins such as copolymers, methylpentene polymers, polyolefin resins such as polyethylene, polypropylene, etc., modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. can do.

  In the present invention, when melt extrusion lamination is used, an anchor coating agent such as an isocyanate type, a polyethyleneimine type, or the like can be arbitrarily used. Furthermore, when performing the above lamination, if necessary, for example, pretreatment such as corona treatment, ozone treatment, frame treatment, etc. can be optionally applied to the surface of the substrate to be laminated.

The thickness of the extruded resin layer is 5 to 50 μm, preferably 15 to 30 μm.
(9) Other base materials Since the laminated body for tubes of the present invention is subjected to severe physical and chemical conditions, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing Various conditions such as property, quality maintainability, workability, hygiene, and others are required, and for this purpose, other base materials that satisfy the above conditions can be used arbitrarily. 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 , Polycarbo Films or sheets of known resins such as silicate resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers, fluorine resins, gen resins, polyacetal resins, polyurethane resins, nitrocellulose, etc. Can be arbitrarily selected and used. In the present invention, the film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.

These may be films having any properties such as extrusion film formation, inflation film formation, and coating film.
Furthermore, as other base materials, for example, as a basic material constituting a laminated tube, it has excellent properties in mechanical, physical, chemical, etc., and particularly has strength and toughness. In addition, a resin layer having heat resistance can be used. For example, a strong resin film or sheet such as a polyester resin, a polyamide resin, a polyaramid resin, a polyolefin resin, a polycarbonate resin, a polyacetal resin, a fluorine resin, or the like can be used. As the resin film, 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 5 to 100 μm, preferably 10 to 50 μm.

  In the present invention, as other materials, for example, a light-shielding material having a property of shielding light such as sunlight, or a water-resistant material having a property of not transmitting water vapor, water, or the like is used. This may be a single substrate, or a composite substrate formed by combining two or more substrates. Specifically, for example, water resistant materials having barrier properties such as water vapor and water include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer. A film or sheet of a resin such as a coalescence can be used, and as a light-shielding material, for example, a colorant such as a pigment, and other desired additives such as a pigment are added to the resin and kneaded. Various colored resin films or sheets having light-shielding properties can be used. These materials can be used alone or in combination. The thickness of the film or sheet is arbitrary, but is usually about 5 to 300 μm, more preferably 10 to 100 μm.

(10) Method for producing tube laminate The tube laminate of the present invention is a laminate method used when producing an ordinary laminate material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, Any method such as an extrusion lamination method, a T-die coextrusion molding method, a coextrusion lamination method, an inflation method, or the like can be used.

  For example, a gas barrier laminated film in which the above-described vapor deposition film (I), gas barrier coating film (I), vapor deposition film (II), and gas barrier coating film (II) are provided on a base film in advance is prepared. The laminated film can be produced by laminating the gas barrier coating film (II) or the base film side of the laminated film and the heat seal layer or the surface olefin resin layer so as to face each other and bonding them through a laminating adhesive. When the gas barrier laminate film is commercially available, a commercially available product can also be used. Either the surface olefin-based resin layer or the heat seal layer may be laminated on the gas barrier laminate film first. In the present invention, when any film or layer is laminated, if necessary, pretreatment such as corona treatment or ozone treatment can be applied to the film as described above.

  Also, instead of bonding with a laminating adhesive, an anchor coat layer is laminated on the gas barrier coating film (II) of the gas barrier laminated film or the base film, and heat sealing is performed via an extruded molten resin layer on the anchor coat layer. It can also be produced by laminating a layer or a surface olefin resin layer. By adhering with an extruded molten resin layer, the flexibility of the tube laminate can be improved, and the moldability into a tube form can be improved.

  In the present invention, for example, a gravure printing method, an offset printing method, a relief printing method, a silk screen printing method, a flexographic printing method, etc. are used for any of the substrates constituting the laminate for a tube before the lamination. Thus, a desired printed pattern can be formed. Specifically, a desired printed pattern or the like can be formed on a substrate constituting the surface olefin-based resin layer or a substrate film having a vapor-deposited film of an organic silicate compound.

  For example, a desired printed pattern is provided on either one and / or both sides of the front and back surfaces of the surface olefin-based resin layer, and then a barrier laminate film and a heat seal layer are laminated to laminate the tube according to the present invention. A body is manufactured, and thereafter, the laminate tube according to the present invention, a packaged product using the same, and the like can be manufactured in the same manner as described above.

(11) Method for Producing Laminate Tube To give an example of producing a laminate tube according to the present invention using the tube laminate of the present invention, first, the tube laminate is cut into a predetermined size, and the tube The surface olefin-based resin layer surface and the heat seal layer surface at both ends of the laminate for the laminate are laminated, and then heat-sealed to produce a cylindrical body, and one cylindrical opening of the tubular body is For example, a laminated tube can be manufactured by forming a head having a shoulder and an opening by a normal method such as an extrusion molding method, and screwing a cap into the opening of the head. After filling the contents such as toothpaste and others from the other open end of the cylindrical body of this laminate tube, the open end is heat welded to form a bottom seal portion, and the contents are filled and packaged. A packaged product made of a laminated tube can be manufactured.

  In addition to the high-density polyethylene as described above, the ethylene-polymerized by using the metallocene catalyst described above as a material constituting the head portion composed of the shoulder portion, opening portion and the like of the laminated tube according to the present invention An α-olefin copolymer or the like can also be used.

  As a method of heat-sealing when manufacturing the cylindrical body part, known methods such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal, and a flame seal can be used.

  On the other hand, the manufacturing method of a laminate tube is not limited to the above. For example, using the above laminate for tubes, using the gravure printing method, flexographic printing method, etc. on the surface of the tube laminate, using gravure ink, flexographic ink, etc., letters, figures, symbols, designs, etc. A printed picture layer composed of, etc. is printed and formed, and then the tube laminate on which the printed pattern layer is formed is rolled and its polymer end is welded to produce a cylindrical body part constituting the laminated tube, The upper part of the cylindrical body is formed of, for example, a high-density polyethylene, and the head made of a shoulder and an opening is formed and welded by, for example, an injection molding method, a compression molding method, or other molding methods. Then, a cap manufactured by separately molding, for example, an injection molding method using polypropylene resin or the like is attached to the opening constituting the head, and the laminate tube according to the present invention is attached. It can be produced. Next, the contents to be filled and packaged may be filled from the open end of the lower end portion of the laminate tube, and then the open end may be heat sealed to form the bottom welded portion.

  Flexographic printing is a type of letterpress printing, using a flexible resin or rubber letterpress, and using a solvent-dried flexographic ink to print a desired printed pattern layer consisting of letters, figures, symbols, patterns, etc. To form. As the flexographic ink, it is possible to use an evaporation-drying ink mainly composed of an alcohol-based or aqueous vehicle, an ultraviolet curable ink, or the like that does not relatively invade rubber letterpress.

  In the present invention, a tube laminate is produced in a plain state by using a flexographic printing method or the like, and directly printed on the surface of the plain tube laminate or the plain cylindrical same part to obtain a desired print. Since a pattern layer can be formed, it is possible to produce a batch of raw fabric, increase its production efficiency, reduce manufacturing loss, etc., and to print only the required quantity according to orders. Manufacturing loss can be reduced and delivery time can be shortened. That is, usually, a desired printed picture layer is formed by printing on a raw film such as a plastic film, and then another plastic film or the like is laminated thereon to produce a laminated material with a printed picture. For this reason, the lead time from receiving an order becomes longer, and the raw fabric lot is known for each pattern, which makes the manufacturing process and manufacturing cost extremely disadvantageous. However, the present invention eliminates such problems. It has the advantage of obtaining.

  Examples of the contents filled and packaged in the laminate tube of the present invention include toothpaste, cosmetics, glue, paste, kneaded wasabi, creams, paints, ointments, pharmaceuticals, and the like.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.
Production Example 1
Using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and corona-treated on one side, this was mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and then on the corona-treated surface of the above biaxially stretched polyethylene terephthalate film, Hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organosilicon compound, was supplied to form a vapor-deposited film having a thickness of 200 mm, and plasma treatment was performed on the surface of the vapor-deposited film. Then, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixture of polyvinyl alcohol aqueous solution, silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

前記プラズマ処理面に、上記で製造したガスバリア性組成物をコーティングして厚さ０．４ｇ／ｍ²（乾操状態）のガスバリア性塗布膜を形成し、ガスバリア性積層フィルム（Ｉ）を製造した。

The plasma-treated surface was coated with the gas barrier composition produced above to form a gas barrier coating film having a thickness of 0.4 g / m ² (in the dry operation state) to produce a gas barrier laminated film (I). .

Production Example 2
On the surface of the gas barrier coating film of the gas barrier laminate (I) produced in Production Example 1, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organosilicon compound, is supplied using the plasma chemical vapor deposition apparatus. Then, a vapor-deposited film having a thickness of 200 mm was formed, and a gas-barrier coating film was formed on the vapor-deposited film in the same manner as described above to produce a gas-barrier laminated film (II).

Production Example 3
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which has been corona-treated on one side, is mounted on a feed roll of a take-up vacuum deposition apparatus, and then fed, and then corona treatment of the above biaxially stretched polyethylene terephthalate film Aluminum oxide was supplied to the surface to form an aluminum oxide vapor-deposited film having a thickness of 200 mm, and plasma treatment was performed on the aluminum oxide vapor-deposited film surface to produce a gas barrier laminate film (III).

Example 1
A laminating adhesive (trade name “LX703VL / KR90” manufactured by Dainippon Ink & Chemicals, Inc.) is applied to the PET side of the gas barrier laminate film produced in Production Example 2 to a thickness of 3 μm, and LLDPE having a thickness of 150 μm. (Tamapoly Co., Ltd., trade name “UB-IT”) and bonded. Next, a UV-curing flexographic ink was applied to the LLDPE surface laminated first, and dried. Next, a laminating adhesive (manufactured by Dainippon Ink & Chemicals, Inc., trade name “LX703VL / KR90”) is applied to the gel sol barrier coat of the gas barrier laminate film (II) to a thickness of 3 μm, and the thickness is 150 μm. LLDPE (manufactured by Tamapoly Co., Ltd., trade name “UB-IT”) was laminated to produce a laminate (I) for a tube of the present invention. The layer structure of this laminated body for tubes is UV-cured flexographic ink / LLDPE ¹⁵⁰ / DL / PET ¹² / CVD-SiOx / sol-gel barrier coat / CVD-SiOx / sol-gel barrier coat / DL / LLDPE ¹⁵⁰ .

The oxygen permeability and water vapor permeability of the laminate for tube (I) were measured. The results are shown in Table 2.
Next, a tube having a diameter of 35 mm and a height of 160 mm was formed using the tube laminate (I), and a head made of HDPE was attached to the opening by compression molding. This tube was filled with 150 g of kneaded wasabi and the oxygen permeability and water vapor permeability were measured.

Next, a hand biting test was performed on the tube, and the oxygen permeability and water vapor permeability after the hand biting were measured. The results are shown in Table 3.
Example 2
The gravure ink was applied to the gas barrier coating film surface of the gas barrier laminate film produced in Production Example 2. Next, an anchor coating agent (trade name “A3210 / A3075” manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) is applied to the biaxially stretched terephthalate film surface of the gas barrier laminate film to a thickness of 0.2 μm, and then the anchor coat is applied. Polyethylene was melt-extruded to a thickness of 15 μm on the agent-coated surface, and an unstretched polypropylene film (trade name “FCMN”, manufactured by Futamura Chemical Co., Ltd.) having a thickness of 80 μm was laminated. Next, an anchor coating agent (trade name “A32101 / A3075” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) is applied to the gas barrier coating film surface of the gas barrier laminate film (II) to a thickness of 0.2 μm, and then this anchor coating is applied. Polyethylene is melt-extruded to a thickness of 15 μm on the surface to which the agent is applied, and an unstretched polypropylene film having a thickness of 80 μm (trade name “FCMN”, manufactured by Futamura Chemical Co., Ltd.) is laminated to obtain the laminate for tubes of the present invention (II ) Was manufactured. The layer structure of this laminate for tubes is CPP ⁸⁰ / PE ¹⁵ / AC / PET ¹² / CVD-SiOx / sol-gel barrier coat / CVD-SiOx / sol-gel barrier coat / gravure ink / AC / PE ¹⁵ / CPP ⁸⁰ is there.

About this laminated body (II) for tubes, it carried out similarly to Example 1, and performed oxygen permeability and water vapor permeability. The results are shown in Table 2.
Next, a tube having a diameter of 35 mm and a height of 160 mm was formed using the tube laminate (II), and a head made of PP was attached to the opening by compression molding. This tube was operated in the same manner as in Example 1, and the oxygen permeability and water vapor permeability after hand-kneading were measured. The results are shown in Table 3.

Comparative Example 1
In place of the gas barrier laminate film (II) of Example 1, the gas barrier laminate film (III) produced in Production Example 3 was used, except that the gas barrier laminate film (III) was used. I) was produced. The layer structure of this laminated body for tubes is UV curable flexographic ink / milk white LLDPE ¹⁵⁰ / DL / PET ¹² / AlOx / DL / LLDPE ¹⁵⁰ .

Subsequently, oxygen permeability and water vapor permeability were performed on the comparative tube laminate (I) in the same manner as in Example 1. The results are shown in Table 2.
Further, a tube was produced in the same manner as in Example 1, and this tube was operated in the same manner as in Example 1 to measure the oxygen permeability and water vapor permeability after manual handling. The results are shown in Table 3.

Comparative Example 2
In place of the gas barrier laminate film (II) of Example 2, the gas barrier laminate film (I) produced in Production Example 1 was used except that the gas barrier laminate film (I) was used. II) was prepared. The layer structure of this laminated body for tubes is CPP ⁸⁰ / PE ¹⁵ / AC / PET ¹² / CVD-SiOx / sol-gel barrier coat / gravure ink / AC / PE ¹⁵ / CPP ⁸⁰ .

Subsequently, oxygen permeability and water vapor permeability were performed on the comparative tube laminate (II) in the same manner as in Example 1. The results are shown in Table 2.
Further, a tube was produced in the same manner as in Example 1, and this tube was operated in the same manner as in Example 1 to measure the oxygen permeability and water vapor permeability after manual handling. The results are shown in Table 3.

(Measuring method)
(1) Measurement of oxygen permeability Measurement was carried out with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.

(2) Measurement of water vapor permeability Measurement was performed with a measuring instrument (model name, Permatran 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH.

  The laminated body for tubes of the present invention is excellent in gas barrier properties and transparency, excellent in resistance to handling, and can maintain high gas barrier properties in actual use.

FIG. 1 is a diagram for explaining the layer structure of a laminate for a tube according to the present invention, in which a heat seal layer (10) is bonded to a gas barrier laminate film (30) by an adhesive layer (20) for lamination. The gas barrier laminated film (30) is formed by depositing a base film (31), a vapor deposition layer (33) obtained by vapor-depositing an organic silicon compound, a gas barrier coating film (35), and an organic silicon compound. The embodiment is a laminated film having excellent gas barrier properties in which a vapor deposition layer (37) and a gas barrier coating film (39) are laminated in this order. FIG. 2 is a diagram for explaining the layer structure of the laminate for a tube of the present invention, and after the anchor coat layer (60) is formed on the gas barrier laminate film (30), the extruded resin layer (25) is interposed therebetween. A heat seal layer (15) is laminated, wherein the gas barrier laminate film (30) comprises a base film (31), a vapor deposition layer (33) formed by vapor-depositing an organic silicon compound, and a gas barrier coating film. (35) An embodiment in which a vapor deposition layer (37) obtained by vapor-depositing an organosilicon compound and a gas barrier coating film (39) are laminated films in this order are laminated films having excellent gas barrier properties. 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 ... heat seal layer,
20: Adhesive resin layer,
25 ... melt-extruded resin layer,
30 ... Gas barrier laminate film,
31 ... Base film,
33 ... Vapor deposition layer formed by vapor-depositing an organosilicon compound,
35 ... gas barrier coating film,
37 ... Vapor deposition layer formed by vapor-depositing an organosilicon compound,
39: Gas barrier coating film,
40 ... surface olefin resin layer,
50 ... printing layer,
60: Anchor coat layer,
100: Plasma chemical vapor deposition apparatus,
101 ... substrate film,
110 ... Base film supply chamber,
111 ... unwinding roll,
120 ... first film forming chamber,
121, 123, 131, 133, 141, 143 ... auxiliary rolls,
122, 132, 142 ... cooling / electrode drum,
124, 134, 144 ... Raw material volatilization supply device,
125, 135, 145 ... gas supply device,
127, 137, 147 ... raw material supply nozzles 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 (2)

A laminated body for a tube formed by laminating a surface olefin-based resin layer, a gas barrier laminate film, and a heat seal layer in this order,
The gas barrier laminate film is provided with a vapor deposition film (I) formed by supplying an organic silicon compound by chemical vapor deposition on one surface of a base film, and the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1 or more) N + m represents the valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a sol A vapor deposition film in which a gas barrier coating film (I) made of a gas barrier composition obtained by polycondensation by a gel method is provided, and an organosilicon compound is supplied to the gas barrier coating film (I) by chemical vapor deposition (II) is provided on the deposited film (II). General formula _{^{R 1 n M (OR 2)}} m ( where in the formula, R ^1, R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n is an integer of 0 or more M represents an integer of 1 or more, and n + m represents a valence of M.), and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. And a gas barrier laminate film provided with a gas barrier coating film (II) made of a gas barrier composition obtained by polycondensation by a sol-gel method.   A laminate tube comprising the laminate for a tube according to claim 1.

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