JP2013035187A - Laminate having deodorization performance, and packaging body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having excellent deodorization performance without impairing heat sealing properties, and to provide a packaging body using the same.SOLUTION: The laminate 10 having deodorization performance includes at least a heat seal layer 4. The heat seal layer 4 is composed of a resin containing 0.01-50 mass% of a deodorizer composed of a tetravalent metal phosphate. The content of the deodorizing agent including the tetravalent metal phosphate is preferably 0.5-35 mass%. As the tetravalent metal phosphate, a compound is used represented by the following formula (1): HMO(PO).nHO (1), where M is a tetravalent metal, each of a, b, c and d is a positive number satisfying the following equation: a+4b=2c+3d (c may be 0), and n is 0 or a positive number.

Description

  The present invention relates to a laminate having deodorant performance (hereinafter, also simply referred to as “laminate”) and a package using the laminate, and in particular, has excellent deodorization performance without impairing heat sealability. The present invention relates to a laminate and a package using the same.

  2. Description of the Related Art Conventionally, packaging bodies that contain contents in a bag body that is molded by heat-sealing the peripheral edge of a laminate having heat-sealing properties have been distributed. For example, when filling and wrapping contents such as various foods and drinks in the package, it is excellent in heat sealability and sufficient sealability from the request of protecting the quality of the contents, extending the storage period, etc. In addition to being satisfactory, for example, it is required to have gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., or to have fragrance retention properties that protect the odor and the like of the contents.

  In recent years, packaging materials having various layer structures using various materials and materials have been developed, and various forms of packaging bags, packaging products, and the like have been proposed. For example, Patent Documents 1 and 2 have heat-sealing properties and oxygen-absorbing properties without changing the flavor of the contents, and can be heated in a microwave oven as a heating cooker. An oxygen-absorbing laminate useful as a material has been proposed.

JP 2010-099875 A JP 2010-082873 A

  Some foods and beverages and the like packaged with such packaging products emit malodorous substances such as ammonia from the contents themselves during storage. When a package filled with such contents is opened, malodorous substances diffuse and a sense of discomfort may be felt. As a technique for solving such a problem, it is conceivable to coat the innermost layer of the package with a substance having a deodorizing ability. However, in this case, since the coating agent inhibits heat sealing, there arises a problem that sufficient heat sealing properties cannot be obtained.

  Then, the objective of this invention is providing the laminated body which has the outstanding deodorizing performance, and a package using the same, without impairing heat-sealing property.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by adding a deodorant substance to the heat seal layer corresponding to the innermost layer of the package. It came to complete.

That is, the laminate having the deodorizing performance of the present invention is a laminate having the deodorizing performance including at least a heat seal layer.
The heat seal layer is made of a resin containing 0.01 to 50% by mass of a deodorant composed of a tetravalent metal phosphate.

In this invention, it is preferable that content of the deodorizer which consists of a tetravalent metal phosphate of the said heat seal layer is 0.5-35 mass%. In the present invention, the tetravalent metal phosphate is represented by the following formula (1),
H _{a Mb} O _c (PO ₄ ) _d · nH ₂ O (1)
(Where M is a tetravalent metal, a, b, c and d are positive numbers satisfying the following formula: a + 4b = 2c + 3d (where c may be 0), and n is 0 or It is a positive number). Furthermore, in the present invention, the base resin of the heat seal layer is preferably a polyolefin resin.

  The package of the present invention is characterized in that the laminate having the deodorizing performance of the present invention is formed into a bag.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has the outstanding deodorizing performance, and a package using the same can be provided, without impairing heat-sealability.

It is a schematic sectional drawing which shows an example of the laminated constitution of the laminated body of this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
The laminate of the present invention includes at least a heat seal layer and has deodorizing performance. FIG. 1 is a schematic cross-sectional view of a preferred embodiment of a laminate 10 of the present invention. In the illustrated example, a gas barrier layer 1, a laminating adhesive layer 2a, and a base resin are arranged from the outer layer toward the inner layer. The layer 3, the laminating adhesive layer 2b, and the heat seal layer 4 are sequentially laminated.

  In the present invention, it is important that the heat seal layer 4 is made of a resin containing 0.01 to 50% by mass, preferably 0.5 to 35% by mass of a deodorant composed of a tetravalent metal phosphate. is there. By containing the deodorant applied to the heat seal layer 4, it becomes possible to remove the odor generated from the food or drink, etc., but if this content is less than 0.01% by mass, sufficient deodorization is possible. Unable to get performance. On the other hand, if it exceeds 50% by mass, not only a great difference in deodorization performance is observed, but also the film-forming suitability deteriorates. In addition, since the laminated body 10 of this invention does not coat the deodorizing substance on the surface of the heat seal layer 4, it can ensure sufficient sealing performance.

In the present invention, the tetravalent metal phosphate has the following formula (1),
H _{a Mb} O _c (PO ₄ ) _d · nH ₂ O (1)
(Where M is a tetravalent metal, a, b, c and d are positive numbers satisfying the formula (a + 4b = 2c + 3d) (where c may be 0), and n is 0 or Or a compound represented by the following formula (2),
H _a A _b B _c M _d O _e (PO ₄ ) _f · nH ₂ O (2)
(A is a monovalent metal, B is a divalent metal, M is a tetravalent metal, a, b, c, e and n are 0 or a positive number, and b and c are Both are not 0, d and f are positive numbers, and a, b, c, d, e and f are preferably compounds represented by the formula (a + b + 2c + 4d = 2e + 3f). The compounds represented by the formulas (1) and (2) are characterized by exhibiting sufficient deodorizing performance and extremely low toxicity to the human body.

  The tetravalent metal phosphate represented by the formula (1) is a compound having hydrogen that is insoluble or hardly soluble in water, and is used as an amine compound such as trimethylamine, triethylamine and pyridine and a basic gas such as ammonia. Excellent deodorant performance is exhibited. Preferable specific examples of M in the above formula (1) include zirconium, titanium, tin, cerium, hafnium, etc., preferably zirconium and titanium.

  The tetravalent metal phosphate represented by a = b = c = d = 1 in the formula (1) is a compound that can be easily obtained as amorphous fine particles having an average particle diameter of 1 μm or less. The tetravalent metal phosphate represented by a = 1, b = 2, c = 0, d = 3 is a NASICON crystalline compound or an amorphous compound. The tetravalent metal phosphate represented by a = 2, b = 1, c = 0, and d = 2 is an α-type crystal that is a monohydrate, a β-type crystal that is an anhydrous salt, and a γ that is a dihydrate. It is a crystalline or amorphous compound having a layered structure such as a type crystal. Since the tetravalent metal phosphate represented by the formula (1) has the largest crystal interlayer distance and the highest deodorization speed, in the present invention, a = 2, b = 1, c = 0, A γ-type crystal having a coefficient of d = 2 can be preferably used.

Specific examples of the compound represented by the formula (1) include HTiO (PO ₄ ), HZrO (PO ₄ ), H ₂ Zr (PO ₄ ) ₂ , HZr ₂ (PO ₄ ) ₃ .H ₂ O, and HTi. ₂ (PO ₄ ) ₃ · H ₂ O, H ₂ Sn (PO ₄ ) ₂ · H ₂ O, H ₂ Ti (PO ₄ ) ₂ · 2H ₂ O, HSn ₂ (PO ₄ ) ₃ · 3H ₂ O, Can be mentioned.

  Further, the tetravalent metal phosphate represented by the formula (2) is a compound that is insoluble or flame retardant with respect to water, and has a monovalent metal and / or a divalent metal. The tetravalent metal phosphate represented by the formula (2) exhibits excellent deodorizing performance for sulfur-containing gases such as hydrogen sulfide and methyl mercaptan, and lower fatty acids such as acetic acid, valeric acid and butyric acid. . Preferable specific examples of M in the formula (2) include zirconium, titanium, tin, cerium, hafnium and the like, and zirconium and titanium are preferable. Preferred specific examples of the monovalent or divalent metal in the deodorant represented by the formula (2) include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, copper, iron, zinc, nickel, manganese, and Cobalt etc. can be mentioned. Among these, sodium, potassium, copper, zinc and manganese are preferable in the present invention.

The coefficients of a, b, c, d, e and f in the tetravalent metal phosphate represented by the formula (2) are represented by the following formulas (i) to (iii),
(I) a + b + c = 1, d = 1, e = 1, f = 1
(Ii) a + b + c = 1, d = 2, e = 0, f = 3
(Iii) a + b + c = 2, d = 1, e = 0, f = 2
It is preferable that either of these is satisfied. Here, in the formulas (i) to (iii), a, b and c may be 0, and b and c are not 0 at the same time. The tetravalent metal phosphate represented by the formula (2) is a compound having a structure in which part or all of hydrogen of the compound represented by the formula (1) is substituted with a monovalent or divalent metal. In the present invention, a crystalline compound having a γ-type layered structure represented by (iii) is particularly preferable.

  In the present invention, all of the tetravalent metal phosphates are usually obtained in a powder form, and the preferable average particle diameter is 0.01 to 20 μm, more preferably 0.01 to 10 μm, still more preferably. Is 0.01-5 μm. If the average particle size is less than 0.01 μm, reaggregation tends to occur and handling is difficult. On the other hand, if the average particle diameter is larger than 20 μm, it is difficult to uniformly disperse the resin in the resin, and problems such as difficulty in forming a thin film-like molded product such as a film are not preferable.

  In the present invention, as the base resin constituting the heat seal layer 4, polyolefin resins having various heat seal properties that can be melted by heat and fused to each other can be suitably used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resin, a poly (meth) acrylic resin, resins such as polyvinyl chloride resin. In the present invention, one or more kinds of these films, sheets or coating films can be used as the heat seal layer 4.

  In the present invention, among the above resins, polyolefin resins are preferable. In particular, a polypropylene random copolymer using a single site metallocene catalyst is suitable. Specific examples include a polypropylene random copolymer composed of a block or random copolymer of propylene and ethylene or propylene and 1-octene. This is because these copolymers are excellent in adhesiveness.

  In the present invention, when an inflation method is used as a film forming method for the heat seal layer 4, the melt flow rate (MFR) of the resin constituting the heat seal layer 4 is 0.2 to 4.0 g / min. And more preferably 0.2 to 2.0 g / min. It is. MFR is 0.2 g / min. Or 4.0 g / min. Exceeding this is disadvantageous in terms of processability. Here, the MFR is a value measured by a method based on JIS K6921, and the density is a value measured by a method based on JIS K7112.

  In the present invention, the layer thickness of the heat seal layer 4 is preferably 5 to 100 μm, and more preferably 10 to 60 μm. The heat seal layer 4 may be a single layer made of one of the above resins or a multilayer of two or more layers. For example, the heat seal layer 4 has two layers (not shown), one layer contains the tetravalent metal phosphate, and the other layer does not contain the tetravalent metal phosphate. can do. In this case, the layer containing the tetravalent metal phosphate is the innermost layer. By setting it as such a structure, it can be set as the laminated body excellent in the initial deodorizing performance. The other layer may contain other functional fillers. In the present invention, the heat seal layer 4 may be separated into a colored layer containing a pigment or dye and a layer not containing a pigment or dye. In this case, for example, a white pigment or dye is kneaded as the colored layer. Thus, a white resin layer having excellent light shielding properties may be used.

  As the white colorant, one type or a mixture of two or more colorants such as various white type inorganic or organic pigments and dyes can be used. For example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatase titanium oxide, rutile titanium oxide, calcium carbonate, zinc oxide, barium sulfate white One type or two or more types of pigments can be used. These can prevent or block the transmission of the sun, fluorescent lamps, etc. without impairing the cosmetics of the packaging container, and prevent light deterioration such as decomposition or alteration of the contents filled and packaged in the packaging bag, fading, etc. it can. In the colored layer, the blending amount of the colorant is 0.1 to 30% by mass, preferably 0.5 to 20% by mass with respect to the resin constituting the heat seal layer 4.

  The colorant is not limited to a white dye or a white pigment, and a colored layer may be formed using a pigment or dye of another color. In this case, the thickness of the colored layer is preferably 5 to 60 [mu] m, more preferably 10 to 40 [mu] m, in order to obtain the desired coloring effect.

  When the colored layer is formed, the heat seal layer 4 is formed as the innermost layer with a resin that does not contain a colorant. When inorganic titanium or the like is kneaded as a pigment or dye, the heat-sealability is lowered. However, as in the case of the addition of the tetravalent metal phosphate, a layer that does not contain a pigment or dye is formed in the innermost layer. , Heat sealability can be ensured. In this case, the thickness of the layer containing no pigment or dye is 5 to 60 μm, preferably 10 to 30 μm. If it is this range, sufficient heat-sealing property is securable.

  So far, the heat seal layer 4 of the laminate 10 of the present invention has been described, but the other structures are not particularly limited. For example, as shown in FIG. 1, the laminate 10 of the present invention may have a gas barrier layer 1 in addition to the base resin layer 3. Further, although not shown, the laminate 10 has a printing layer and the like. Also good. Furthermore, in order to laminate each layer, the laminating adhesive layers 2a and 2b made of a laminating adhesive can also be formed.

  In the present invention, as the base resin layer 3, various materials can be applied depending on the use as long as the contents to be packaged and mechanical strength, chemical resistance, solvent resistance, manufacturability, etc. during distribution are available. . The base resin layer 3 includes polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS). Resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, Polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It may be a resin. In the present invention, a polypropylene resin, a polyester resin, or a polyamide resin is particularly preferable.

  As the base resin layer 3, one or more of the above resins are used, and a single layer is formed using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like Film-formed, multi-layered by co-extrusion using two or more types of resin, or formed by mixing two or more types of resin, and the tenter method or tubular method 1 Various resin films formed by stretching in the axial or biaxial direction can be used.

  In the present invention, the thickness of the base resin layer 3 is preferably 6 to 100 μm, more preferably 9 to 50 μm. The base resin layer 3 according to the present invention has film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties. Various plastic compounding agents, additives, and the like can be added for the purpose of improving and modifying properties, electrical characteristics, strength, and the like. In this case, these additives may be arbitrarily added to the heat seal layer 4 from a very small amount to several tens of mass% according to the purpose. In the present invention, general additives include lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, colorants such as dyes and pigments. Etc. can be arbitrarily used, and further, a modifying resin or the like may be used.

  Moreover, in this invention, when using the laminated body 10 for the package for food-drinks, as shown in FIG. 1, various gas barrier films which can prevent permeation | transmission of oxygen and water vapor | steam may be provided as the gas barrier layer 1. FIG. Good. As the gas barrier film, it is preferable to use polyvinyl alcohol or ethylene / vinyl alcohol copolymer. When polyvinyl alcohol is used as a gas barrier film, the layer thickness is preferably 15 to 25 μm, and when an ethylene / vinyl alcohol copolymer is used, the layer thickness is preferably 10 to 30 μm. In addition to these, an aluminum foil may be used as the gas barrier layer. In this case, the thickness of the aluminum foil is preferably about 5 to 30 μm.

  When polyvinyl alcohol is used as the gas barrier layer 1, it may be used as a single layer, but since it is a water-soluble polymer, it is a laminated film in which a coating film made of polyvinyl alcohol is formed on a base film having excellent water resistance. There may be. As such a base film, the base film described in the section of a gas barrier laminate film described later can be suitably used. Thereby, water resistance is securable. 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 (saponification degree = 99%, polymerization degree = 1,400) ”manufactured by Nippon Synthetic Chemical Industry Co., Ltd. it can.

  When an ethylene / vinyl alcohol copolymer is used as the gas barrier layer 1, it may be used as a single layer film, but it is a laminated film in which a coating film made of an ethylene / vinyl alcohol copolymer is formed on a base film. May be. As such a base film, the base film described in the section of the gas barrier laminate film described later can be preferably used. Thereby, the various characteristics according to a base film, such as a mechanical characteristic, can be improved. 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.

A vapor deposition film formed by vapor-depositing an organosilicon compound, a metal, or a metal oxide is provided on one surface of the base film constituting the gas barrier layer 1, and the general formula R ¹ _n M (OR ² ) _m ( Here, R ¹ and R ² in the formula represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M A gas barrier property obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by the formula (1) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier laminate film provided with a gas barrier coating film of the composition may be used. In this case, 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 and has excellent gas barrier properties that prevent permeation of oxygen, water vapor, etc., and excellent hot water resistance.

  The base film resin constituting the gas barrier layer 1 includes polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene. Copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polyimide resin, polyamideimide resin Various resins such as polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins, polyurethane resins, acetal resins, and cellulose resins. It is possible to use. In particular, a polyester resin or a polyamide resin is suitable. The film thickness of the base resin is preferably 6 to 100 μm, and preferably 9 to 50 μm.

  In the present invention, it is preferable to form a vapor-deposited film formed by vapor-depositing an organosilicon compound, metal or metal oxide on one surface of the base film, but the base film may be surface-treated in advance. As a result, the adhesion to the vapor deposition film or the gas barrier coating film can be improved. Examples of such surface treatment include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, pretreatment such as oxidation treatment using chemicals and the like. .

  In this invention, as above-mentioned, the gas barrier layer 1 can be manufactured by forming the vapor deposition film formed by vapor-depositing a metal or a metal oxide on a base film. The vapor deposition film is, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination thereof, and a single layer or two or more layers of a vapor deposition film formed by vapor-depositing an organic silicon compound, metal, or metal oxide. Can be produced by forming a multilayer or composite layer comprising

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, on one surface of the base film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and further, as an oxygen supply gas In addition, a vapor deposition film such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using oxygen gas or the like and using a low temperature plasma generator or the like.

  As a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

  An example of a method for forming a deposited film by a low temperature plasma chemical vapor deposition method will be described with reference to FIG. 2 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus. In the illustrated example, the base film 101 is unwound from an unwinding roll 123 disposed in the vacuum chamber 122 of the plasma chemical vapor deposition apparatus 121, and further, the base film 101 is fed at a predetermined speed via an auxiliary roll 124. Cooling / conveying on electrode drum 125 circumferential surface. On the other hand, a vapor deposition monomer gas such as oxygen gas, inert gas, or organosilicon compound is supplied from the gas supply devices 126 and 127 and the raw material volatilization supply device 128 to prepare a mixed gas composition for vapor deposition, and this is supplied as a raw material. It introduces into the vacuum chamber 122 through the nozzle 129. The vapor deposition mixed gas composition is supplied onto the substrate film 101 conveyed on the circumferential surface of the cooling / electrode drum 125, and plasma is generated and irradiated by the glow discharge plasma 130 to form a vapor deposition film. Next, when the base film 101 on which the vapor deposition film is formed is wound around the take-up roll 134 via the auxiliary roll 133, a vapor deposition film formed by vapor-depositing an organic silicon compound can be formed. A predetermined power is applied to the cooling / electrode drum 125 from a power supply 131 disposed outside the vacuum chamber 122, and a magnet 132 is disposed in the vicinity of the cooling / electrode drum 125 to promote plasma generation. Has been. 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. The glow discharge plasma is derived from one or more gas components in the mixed gas. When the base film is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum surface to be A deposited film formed by depositing an organosilicon compound can be formed on the base film. Note that reference numeral 135 in the figure denotes a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump, and the degree of vacuum is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably, the degree of vacuum is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr. It is preferable to adjust.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and puts the obtained mixed gas into the vacuum chamber via the raw material supply nozzle Introduce. At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, inert gas, oxygen gas, or the like is preferably 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, more preferably 1 × 10. ⁻¹ to 1 × 10 ⁻² Torr. Moreover, the conveyance speed of a base film becomes like this. Preferably it is 10-300 m / min. More preferably, it is 50-150 m / min. And The vapor deposition film formed by vapor-depositing the organosilicon compound thus obtained is formed into a thin film in the form of SiO _X while oxidizing the plasma-formed source gas with oxygen gas on the base film, It is a continuous layer that is dense and has few gaps and is highly flexible. Therefore, the barrier property of the deposited film is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness. . Moreover, since the surface of the base film is cleaned by SiO _X plasma and polar groups, free radicals, etc. are generated on the surface of the base film, the tight adhesion between the deposited film and the base film becomes high. . Furthermore, the degree of vacuum at the time of forming the deposited film is compared with the degree of vacuum at the time of forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method, 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr. Since the degree of vacuum is low, the vacuum state setting time at the time of exchanging the base film can be shortened, the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

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 produced on one side of the base film. Is a continuous thin film mainly composed of silicon oxide represented by the general formula SiO _X (where X is a number from 0 to 2). It is. The silicon oxide vapor deposition film is mainly composed of a silicon oxide vapor deposition film represented by the general formula SiO _X (where X is a number from 1.3 to 1.9) in terms of transparency and barrier properties. The thin film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It is good also as what to do. For example, a compound having a C—H bond, a compound having a Si—H bond, a compound having a carbon unit in the form of graphite, diamond, fullerene, or the like, an organic silicon compound as a raw material, or a derivative thereof You may contain by a chemical bond etc. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to these, the type, amount, etc. of the compound contained in the deposited film can be changed by changing the conditions of the deposition process. Under the present circumstances, as content which said compound contains in a vapor deposition film, it is 0.1 to 50%, Preferably it is 5 to 20%. If the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the vapor-deposited film will be insufficient, and scratches, cracks, etc. will easily occur due to bending, etc., and high barrier properties will be stabilized. It can be difficult to maintain. On the other hand, if it exceeds 50%, the barrier property may be lowered.

  Furthermore, in the present invention, in the vapor deposition film formed by vapor-depositing an organosilicon compound, it is preferable that the content of the above compound decreases from the surface of the vapor deposition film in the depth direction. As a result, the impact resistance and the like are improved by the above compound on the surface of the deposited film, and the adhesiveness between the base film and the deposited film is low at the interface with the base film because the content of the above compound is small. Will be strong.

  In the present invention, the deposited film is formed in the depth direction using a surface analyzer such as an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above physical properties can be confirmed by analyzing by ion etching or the like and conducting elemental analysis of the deposited film.

  In this invention, it is preferable that the film thickness of the said vapor deposition film is 50 to 4000 mm, More preferably, it is 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 50 mm, it may be difficult to obtain 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. The film thickness of the vapor deposition film may be changed 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, a method of slowing the vapor deposition rate, or the like.

  In the present invention, the vapor deposition film formed by vapor-depositing an organic silicon compound, metal or metal oxide may be a multilayer film in which not only one vapor deposition film but also two or more layers are laminated, and the material to be used Also, it may be a vapor deposition film that is used in one kind or a mixture of two or more kinds and mixed with different materials.

  In the present invention, examples of monomer gases for vapor deposition of organic silicon compounds include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, and methylsilane. , Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. Can be mentioned. In particular, 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane are preferable from the viewpoint of handling properties, characteristics of the formed continuous film, and the like. As the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, a vapor deposition film formed by vapor-depositing an organosilicon compound, a metal, or a metal oxide can also be formed by physical vapor deposition. Examples of such physical vapor deposition include physical vapor deposition (Physical Vapor Deposition, PVD) such as vacuum deposition, sputtering, ion plating, and ion cluster beam. .

  Specifically, an organic silicon compound, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the base films, and a metal or metal oxidation is used as a raw material. It is possible to use an oxidation reaction deposition method in which oxygen is introduced and oxidized to deposit on one side of the base film, and a plasma assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma. . In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method of forming a vapor deposition film by physical vapor deposition will be described with reference to FIG. 3 showing a schematic configuration diagram showing an example of a take-up vacuum vapor deposition apparatus.

  First, the base film 101 fed out from the unwinding roll 143 is introduced into the cooled coating drum 146 through the guide rolls 144 and 145 in the vacuum chamber 142 of the wind-up type vacuum vapor deposition apparatus 141. On the substrate film 101 introduced onto the cooled coating drum 146, the evaporation source 148 heated by the crucible 147, for example, metal aluminum or aluminum oxide is evaporated, and if necessary, oxygen gas blowing is performed. While the oxygen gas or the like is jetted from the outlet 149 and supplied, an evaporated film formed by depositing aluminum oxide or the like is formed through the masks 150 and 150, and then the base film 101 on which the evaporated film is formed. Is fed through the guide rolls 151 and 152 and wound on the take-up roll 153, a deposited film can be formed by physical vapor deposition. In addition, first, a vapor deposition film of the first layer is formed using a roll-up type vacuum vapor deposition apparatus, and then a vapor deposition film is further formed thereon, or two or more roll-up vacuum vapor deposition apparatuses are connected continuously. Alternatively, a vapor deposition film may be formed to form a vapor deposition film composed of a multilayer film of two or more layers.

The deposited film formed by depositing a metal or metal oxide may be a thin film deposited with a metal oxide, for example, silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium. A vapor-deposited film of a metal oxide such as yttrium can be used. Preferably, a vapor-deposited film of an oxide of a metal such as silicon or aluminum can be used. The notation is expressed by MO _X (wherein, M represents a metal element, and the value of X varies depending on the metal element) such as SiO _X , AlO _X , MgO _{X and} the like.

  As the range of the value of X, silicon is more than 0 and less than 2, aluminum is more than 0 and less than 1.5, magnesium is more than 0 and less than 1, calcium is more than 0 and less than 1, potassium is more than 0 and less than 0. 5 or less, tin more than 0 and 2 or less, sodium more than 0 and 0.5 or less, boron more than 0 and 1, 5 or less, titanium more than 0 and 2 or less, lead more than 0 and 1 or less, zirconium 0 Exceeds 2 and yttrium ranges from 0 to 1.5. In this case, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. In general, examples other than silicon and aluminum are poor. For this reason, in this invention, silicon and aluminum are preferable as M, and the value of these X is 1.0-2.0 for silicon and 0.5-1.5 for aluminum. In addition, although the film thickness of a vapor deposition film changes with kinds etc. of the metal to be used or a metal oxide, it can be arbitrarily selected within the range of 50 to 2000 mm, preferably 100 to 1000 mm, for example. In addition, the deposited film formed by depositing a metal or metal oxide may be one kind or a mixture of two or more kinds as a metal or metal oxide to be used, or a mixture of different materials. May be.

  Furthermore, in the present invention, for example, a composite film composed of two or more different kinds of vapor deposition films may be formed by using both physical vapor deposition and chemical vapor deposition. As a composite film composed of two or more layers of different kinds of vapor-deposited films, first, an organic silicon that is dense and flexible and can relatively prevent the occurrence of cracks on a base film by chemical vapor deposition. A composite film composed of two or more layers is formed by forming a vapor deposition film formed by vapor deposition of a compound, and then forming a vapor deposition film formed by vapor deposition of a metal or metal oxide by physical vapor deposition on the vapor deposition film. A vapor deposition film made of a film can be formed. On the contrary, on the base film, first, a vapor deposition film formed by vapor-depositing a metal or metal oxide is formed by physical vapor deposition, and then dense by chemical vapor deposition. A vapor-deposited film formed by vapor-depositing an organosilicon compound that is highly flexible and can relatively prevent the occurrence of cracks may be formed to form a vapor-deposited film composed of a composite film composed of two or more layers.

In the present invention, the gas barrier layer 1 can also be produced by forming a gas barrier coating film on the surface of the base film. In the present invention, the gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M is a metal atom) N is an integer of 0 or more, m is an integer of 1 or more, and n + m is a valence of M.), a polyvinyl alcohol resin and / or ethylene. A coating film comprising a gas barrier composition comprising a vinyl alcohol copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. An object is coated on a vapor deposition film on a base film to form a coating film, and is formed by heat treatment at a temperature of 20 ° C. to 180 ° C. and below the melting point of the base film for 10 seconds to 10 minutes. it can. Further, the gas barrier composition is applied onto the vapor deposition film on the base film, and two or more coating films are laminated, and the temperature is 20 ° C. to 180 ° C. and the temperature below the melting point of the base film for 10 seconds to You may heat-process for 10 minutes and may form the composite polymer layer which laminated | stacked two or more gas barrier coating films.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The decomposition product 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, and a mixture thereof. Furthermore, as the hydrolysis condensate, A dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

The general formula ^{R ₁} n M ^R ₁ of ^(OR ₂₎ in _m, branched carbon atoms having 1 to 8 have a, preferably 1-5, more preferably 1-4 alkyl groups, Examples include 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, and n-octyl group. it can.

R ² in the general formula R ¹ _n M (OR ² ) _m is an alkyl group having 1 to 8, more preferably 1 to 5, particularly preferably 1 to 4 carbon atoms which may have a branch. Examples thereof include 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, and aluminum, with silicon being preferred. 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 the number of carbon atoms) 1 to 5 alkyl groups). In this case, as Ra, methyl group, ethyl group, n-propyl group, n-butyl group, etc. are used. Specific examples of such alkoxysilanes 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 ) _{4 and the} like.

When n is 1 or more, the general formula Rb _n Si (ORc) _4-m (where m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, , N-propyl group, n-butyl group, etc.). 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) can be used ₂ or the like. In the present invention, 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 specific examples include polytetramethoxysilane and polytetraemethoxysilane.

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 nbutoxyzirconium Zr (OC ₄ H ₉ ) ₄ etc. can be mentioned.

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 also be suitably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxy Examples thereof include titanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra nbutoxytitanium Ti (OC ₄ H ₉ ) ₄ , and others.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can also be used. 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} can be used 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 and heat resistance of the gas barrier layer are improved, and a decrease in the retort resistance of the film during stretching can be avoided. At this time, the amount of zirconium alkoxide used is preferably 10 parts by mass or less with respect to 100 parts by mass of alkoxysilane. If it exceeds 10 parts by mass, the gas barrier coating film is easily gelled. Moreover, since the brittleness of the film becomes large, the gas barrier coating film tends to be easily peeled when the base film is coated.

  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. At this time, the amount of titanium alkoxide used is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film is coated.

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

  When a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is, as a mass ratio, polyvinyl alcohol-based resin: ethylene / vinyl alcohol copolymer = 10: 0.05. It is preferable that it is -10: 6.

  The content of the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer is preferably in the range of 5 to 500 parts by mass, and preferably 20 to 200 parts per 100 parts by mass of the total amount of alkoxide. Part by mass. 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 deteriorate.

  In the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol-based resin, those 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 acetic acid groups remain, completely saponified polyvinyl alcohols in which no acetic acid groups remain, or 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 (saponification degree = 99%, polymerization degree = 1,400) ”manufactured by Nippon Synthetic Chemical Industry Co., Ltd. it can.

  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, including 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, the preferable saponification degree from the viewpoint of gas barrier properties is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. 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 a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M is a metal atom) N is an integer of 0 or more, m is an integer of 1 or more, and n + m is a valence of M.), a polyvinyl alcohol-based resin as described above, and And / or a gas barrier composition obtained by polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

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

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Examples thereof include N, N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. 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 alkoxide, silane coupling agent and the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid can be used. The amount of the acid used is preferably 0.001 to 0.05 mol% with respect to the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent.

  Furthermore, water in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, can be used with respect to 1 mol of the total molar amount of alkoxide. When the amount of water exceeds 100 mol, the polymer obtained from alkoxysilane and metal alkoxide becomes spherical particles. Furthermore, the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density. With such a porous polymer, the gas barrier property of the gas barrier laminate film cannot be improved. On the other hand, if the amount of water is less than 0.1 mol, the hydrolysis reaction may not proceed easily.

  Examples of the organic solvent used in the gas barrier composition include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butanol. The polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer is preferably handled in a dissolved state in a coating solution containing an alkoxide, a silane coupling agent, or the like, and is appropriately selected from organic solvents. be able to. For example, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, n-butanol is preferably used. 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 to 500 parts by mass relative to 100 parts by mass of the total amount of alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. is there.

  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 catalyst, an acid, water, an organic solvent, and, if necessary, a metal alkoxide, etc. Mix to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, a gas barrier composition is applied onto the deposited film on the base film by a conventional method and dried. By this drying step, polycondensation of 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. A plurality of coating films composed of two or more layers may be formed on the first coating film by further repeating the coating operation. Thereafter, the base film coated with the gas barrier composition is subjected to heat treatment at 20 to 180 ° C. and a temperature not higher than the melting point of the base film, preferably 50 to 160 ° C. for 10 seconds to 10 minutes. As a result, a gas barrier film in which one or more gas barrier coating films of the gas barrier composition are formed on the vapor deposition film can be produced.

  A gas barrier film obtained using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a gas barrier 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, On the coating film, a gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied to form a second coating film, and when these composite layers are formed, the gas barrier properties after hydrothermal treatment It is possible to produce a gas barrier film with improved resistance.

  Further, a coating film is formed from a gas barrier composition containing an ethylene / vinyl alcohol copolymer, or a coating film is formed from a gas barrier composition containing a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. It is also an effective means for improving the gas barrier property of the gas barrier film.

  The manufacturing method of the gas barrier layer 1 is demonstrated in detail using alkoxysilane as an 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 catalyst. Next, protons are deprived from the hydroxyl groups generated by the hydrolysis by the action of the sol-gel method catalyst, and the hydrolyzed products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be produced contains, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and an organic part resulting from a silane coupling agent. It is a composite polymer. In such a reaction, for example, a linear polymer having a partial structural formula represented by the following formula (I) and further having a portion derived from a silane coupling agent is first formed.

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

  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 is formed. A transparent coating film is formed on the top. In addition, when laminating | stacking two or more coating films, the composite polymer in the coating film of an interlayer is condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the surface of the vapor deposition film in which the organic reactive group of the silane coupling agent or the hydroxyl group generated by hydrolysis vaporizes the organic silicon compound, metal or metal oxide on the base film. Since it bonds to the hydroxyl group of the base material, the adhesion between the surface of the substrate film or the deposited film and the coating film is also good. Thus, in the present invention, the vapor deposition film formed by vapor-depositing an organosilicon compound, a metal or a metal oxide and the gas barrier coating film are, for example, a chemical bond, a hydrogen bond, or a hydrolytic or co-condensation reaction. Since a coordination bond or the like is formed, the adhesion between the deposited film and the gas barrier coating film is improved, and a better gas barrier effect can be obtained by the synergistic effect of the two layers.

In the present invention, when the amount of water added is 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.). Further, the hydroxyl group can be chemically bonded to the adhesive resin layer to form a strong laminated structure.

  In the present invention, the method for applying the gas barrier composition is, for example, once or plural times by application means such as roll coating such as a gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator and the like. A method of forming a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm by coating once, and 50 to 300 ° C. in a normal environment, preferably Can be condensed at a temperature of 70 to 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, to form a gas barrier coating film. The thickness of such a gas barrier laminate film is preferably 12 to 30 μm.

  In the present invention, although not shown, a printing layer can be provided. Such a printing layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, Add one or more additives such as cross-linking agents, lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and use solvents, diluents, etc. An ink composition obtained by adjusting the ink composition by kneading 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, aminoalkyd resin, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber, or the like can be used in combination. In addition to gravure printing, printing methods such as letterpress printing, screen printing, transfer printing, flexographic printing, and the like may be adopted as the printing method.

  In the present invention, when the heat seal layer 4 and the base resin layer 3 and the gas barrier layer 1 and the like are laminated according to the purpose, the laminating adhesive layers 2a and 2b may be formed using the laminating adhesive. Good. As an adhesive for laminating, for example, a polyvinyl acetate adhesive, a homopolymer such as ethyl, butyl, 2-ethylhexyl ester of acrylic acid, or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylic acid ester adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose Adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, reactive type (Meth) acrylic adhesive, chloroprene rubber, nitrile rubber Styrene - rubber adhesive comprising a butadiene rubber, a silicone-based adhesive, an alkali metal silicate, may be mentioned inorganic adhesive or the like made of a low-melting-point glass or the like.

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

In the present invention, the laminating adhesive layers 2a and 2b can be formed by, for example, a roll coating method, a gravure roll coating method, a coating method such as a kiss coating method, a printing method, or the like. .1 to 10.0 g / m ² (dry explosion state) is desirable.

Next, the manufacturing method of the laminated body of this invention is demonstrated.
As a laminate according to one preferred embodiment of the present invention, a resin constituting the gas barrier layer 1, the base resin layer 3, and the heat seal layer 4 is prepared, and these are used as a T-die coextrusion machine and an inflation coextrusion machine. Etc. are used to form a laminate comprising a three-layer coextrusion film-forming film laminated in the order of the gas barrier layer 1, the base resin layer 3, and the resin layer constituting the heat seal layer 4. Can be mentioned. In the illustrated example, these layers are laminated via the adhesive layers for laminating 2a and 2b. In these cases, the gas barrier layer 1 and the base resin layer are laminated via the laminating adhesive resin according to a conventional method. 3 and the heat seal layer 4 may be laminated.

  In addition, as a laminate of another preferred embodiment, although not shown, a resin constituting a gas barrier layer and a heat seal layer is prepared, and these are used in a T-die coextrusion machine, an inflation coextrusion machine, or the like. By coextrusion molding, a two-layer coextrusion film-forming film in which a gas barrier layer and a heat seal layer are sequentially laminated can be exemplified.

Next, the package of the present invention will be described.
The package of the present invention is formed by bag-making the laminate of the present invention. For example, the surfaces of the heat seal layer 4 of the laminate of the present invention are opposed to each other, and the peripheral edge thereof is heat sealed. Thus, the seal portion can be formed and manufactured. As the manufacturing method, the laminate of the present invention is folded or overlapped so that the inner layer faces each other, and the peripheral edge thereof is, for example, a side seal type, a two-side seal type, a three-side seal type, The package of the present invention is heat-sealed in a heat-sealing form such as a four-sided seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a square bottom seal type, a gusset type, etc. The body can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) is also possible.

  In the present invention, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  In the present invention, if, for example, the contents are filled from the opening of the package, and then vacuum-packed while depressurizing the air in the package and reducing the pressure, the oxidation due to oxygen remaining in the package in particular Can be efficiently prevented.

  Since the laminate of the present invention has a deodorizing performance while sufficiently ensuring heat sealability, the odor generated from the contents can be removed when used as a package. . Moreover, the laminated body of this invention can be used also as a cover material etc. of the packaging container which consists of a container main body and a cover material. The container body is a saddle-shaped or boat-shaped container made of polypropylene, and the laminated body of the present invention is used as a cover material through the fringe of the opening, and the cover material is heat-sealed after storing the contents to form a packaging container. Can do. Since the packaging body of the present invention can be provided with a gas barrier layer or the like according to the purpose, in this case, the gas barrier layer can prevent the permeation of oxygen and water vapor, and the storage stability of the contents is excellent.

Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
A kneaded resin in which 1% by mass of H ₂ Zr (PO ₄ ) ₂ .H ₂ O as a tetravalent metal phosphate is added to polyethylene (SP2020: Prime Polymer Co., Ltd.) is 50 μm, and the set temperature is 170. The film was formed at a temperature of 0 ° C. to produce a heat seal layer film.

<Example 2>
A film for a heat seal layer was produced in the same procedure as in Example 1 except that the tetravalent metal phosphate was HTiO (PO ₄ ).

<Example 3>
A heat seal layer film was produced in the same manner as in Example 1 except that the amount of H ₂ Zr (PO ₄ ) ₂ .H ₂ O added was 30% by mass.

<Example 4>
A heat seal layer film was produced in the same procedure as in Example 1 except that the amount of H ₂ Zr (PO ₄ ) ₂ .H ₂ O added was 0.05 mass%.

<Comparative Example 1>
A heat seal layer film was produced in the same procedure as in Example 1 except that the amount of H ₂ Zr (PO ₄ ) ₂ .H ₂ O added was 0.005 mass%.

<Comparative Example 2>
A heat seal layer film was produced in the same procedure as in Example 1 except that the amount of H ₂ Zr (PO ₄ ) ₂ .H ₂ O added was 60 mass%.

<Conventional example>
A film for heat seal layer was prepared in the same procedure as in Example 1 except that no tetravalent metal phosphate was added.

<Deodorization performance>
The heat seal layer films of Examples 1 to 4 and Comparative Examples 1 and 2 and the conventional example were cut into a size of 100 mm × 100 mm, sealed in a 1 L Tedlar bag, and then ammonia gas was injected. 24 hours after injecting the ammonia gas, the ammonia gas concentration in the Tedlar bag was measured with a detector tube (manufactured by Gastec Corporation). The initial concentration of ammonia gas was 200 ppm. The results are shown in Table 1.

<Sensory evaluation>
After corona treatment was applied to one side of the sealant films of Examples 1 to 4 and Comparative Examples 1 and 2 and the conventional example, a 12 μm thick silica-deposited polyethylene terephthalate (PET) film and a two-component curable urethane adhesive Dry lamination was performed to prepare a laminate of transparent barrier PET (12 μm) / adhesive / deodorant sealant (50 μm). Two pieces were cut into a size of 90 mm × 90 mm using this laminate, and a three-way flat pouch was produced with a seal width of 10 mm. One piece of shrimp was put in this flat pouch, the remaining one side was sealed and sealed, and the presence or absence of ammonia odor after storage at room temperature for 2 months was subjected to sensory evaluation. The case where the odor was not felt was marked with ○, and the case where the odor was felt was marked with ×. The obtained results are shown in Table 1.

<Heat sealability>
After corona treatment was applied to one side of the sealant films of Examples 1 to 4 and Comparative Examples 1 and 2 and the conventional example, a 12 μm thick silica-deposited polyethylene terephthalate (PET) film and a two-component curable urethane adhesive Dry lamination was performed to prepare a laminate of transparent barrier PET (12 μm) / adhesive / deodorant sealant (50 μm). Two pieces having a width of 15 mm were cut out from the obtained laminate, and 2 were stacked, and heat sealed by heating and pressurizing at 200 ° C. and 0.1 MPa for 1 second. The heat seal strength at which the two pieces of the obtained film for heat seal layer having a width of 15 mm were peeled at a peeling angle of 90 ° (T peel) and a peeling speed of 300 mm / min was measured. The evaluation results are shown in Table 1.

  From Table 1, the resin for the heat seal layer according to the laminate of the present invention is excellent in deodorizing performance. When the laminate of the present invention is heat sealed to produce a package, the resulting package is also erased. It can be seen that the odor performance is excellent.

DESCRIPTION OF SYMBOLS 1 Gas barrier layer 2a, 2b Laminate adhesive layer 3 Base resin layer 4 Heat seal layer 10 Laminate

Claims (5)

In a laminate having deodorant performance including at least a heat seal layer,
A laminate having deodorizing performance, wherein the heat seal layer is made of a resin containing 0.01 to 50% by mass of a deodorant comprising a tetravalent metal phosphate.   The laminate having a deodorizing performance according to claim 1, wherein the heat seal layer has a deodorant content of 0.5 to 35% by mass comprising a tetravalent metal phosphate. The tetravalent metal phosphate is represented by the following formula (1),
H _{a Mb} O _c (PO ₄ ) _d · nH ₂ O (1)
(Where M is a tetravalent metal, a, b, c and d are positive numbers satisfying the following formula: a + 4b = 2c + 3d (where c may be 0), and n is 0 or The laminate having a deodorizing performance according to claim 1 or 2, wherein the laminate is a compound represented by the formula:   The laminate having deodorant performance according to any one of claims 1 to 3, wherein the base resin of the heat seal layer is a polyolefin resin.   A package comprising the laminated body having a deodorizing performance according to any one of claims 1 to 4 formed into a bag.

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