JP2005161584A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film composed of a molded layer comprising a mixture of a specific poly(meth)acrylic acid polymer and polyalcohols and the metal compound-containing layer adjacent to the molded layer as the outermost layer and preventing the mutual blocking of the outermost layers due to heat-sealing when formed into a bag. <P>SOLUTION: This gas barrier laminated film is composed of a polymer film layer (A), the molded layer comprising a mixture of at least one kind of the poly(meth)acrylic acid polymer selected from the group consisting of poly(meth)acrylic acid and partially neutralized poly(meth)acrylic acid and polyalcohols and the layer, which contains a metal compound and an antiblocking agent (AB), adjacent thereto. The layer (C) forms the outermost layer of the laminated film and the mean particle size of the antiblocking agent (AB) is 0.1-5 μm and the ratio [mean particle size/thickness of layer (C)] of the mean particle size of the antiblocking agent (AB) and the thickness of the layer (C) is 0.5-15. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a gas barrier laminate film comprising a layer made of a polymer film, a molded product layer made of a specific polymer, and a layer containing a metal compound. More specifically, the present invention relates to a gas barrier laminated film in which a layer containing a metal compound forming one outermost layer further has an antiblocking agent, and self-adhesion in a sealing operation during bag making is suppressed.

As for the film having gas barrier properties, various gas barrier films are provided in accordance with the use depending on the diversification of polymers as materials and the kind and property of the object requiring gas barrier properties. With the development of various uses of gas barrier films, there is an increasing demand for other properties associated with gas barrier films.
Patent Document 1 discloses a molding made of a mixture of at least one poly (meth) acrylic acid polymer selected from the group consisting of poly (meth) acrylic acid and poly (meth) acrylic acid partially neutralized products and polyalcohols. An invention relating to a gas barrier film formed by coating a layer containing a metal compound on the surface of a physical layer is disclosed. When the film containing the metal compound layer of the film is used as an outer layer and the film is stacked and stored after bag making, when the layers are blocked by their own weight, or when making a bag in a standing pouch shape, the bottom part is between the layers. May be blocked due to heat sealing.
According to Patent Document 2, it is proposed to add inorganic and / or organic fine particles (anti-blocking agent) for the purpose of imparting anti-blocking properties to at least one outer layer of a laminated film made of a polyethylene-based unstretched film. Yes.
However, there is a need for a gas barrier laminate film that sufficiently considers the material and thickness of the film, the physical properties of the antiblocking agent, etc., and that effectively exhibits an antiblocking effect.

JP 2000-931 A Japanese Patent Application Laid-Open No. 08-300581

  The present invention relates to a molded article comprising a mixture of at least one poly (meth) acrylic acid polymer selected from the group consisting of poly (meth) acrylic acid and partially neutralized poly (meth) acrylic acid and a polyalcohol. Provided is a gas barrier laminate film in which blocking by heat sealing between the outermost layers does not occur when a bag is formed using a gas barrier laminate film having an outermost layer comprising a layer and a layer containing a metal compound adjacent thereto. For the purpose.

The present inventors comprise a mixture of at least one poly (meth) acrylic acid polymer selected from the group consisting of poly (meth) acrylic acid and poly (meth) acrylic acid partially neutralized products and polyalcohols. In a gas barrier laminate film having a molded product layer and a layer containing a metal compound adjacent thereto as an outermost layer, an antiblocking agent is added to the layer containing the metal compound, and the average particle size of the antiblocking agent having an average particle size in the specific range The inventors have found that the above problem can be solved by setting the ratio of the diameter and the thickness of the layer containing the metal compound and the antiblocking agent to a specific range, and have completed the present invention.
That is, the first of the present invention is at least one poly (meth) acrylic acid selected from the group consisting of a polymer film layer (A), poly (meth) acrylic acid, and a partially neutralized poly (meth) acrylic acid. A laminated film comprising a molded layer (B) comprising a mixture of a polymer and a polyalcohol and a layer (C) comprising a metal compound and an antiblocking agent adjacent thereto, wherein the layer (C) is a laminated film An outermost layer is formed, the average particle size of the antiblocking agent is 0.1 μm or more and 5 μm or less, and the ratio of the average particle size of the antiblocking agent to the thickness of the layer (C) (average particle size / The thickness (thickness of a layer (C)) provides the gas barrier laminated film whose range is 0.5-15.

  The second of the present invention has a vapor deposition layer (D) on one side of the polymer film layer (A), and a molded layer on the other side of the layer (A) or on the surface of the vapor deposition layer (D). The gas barrier laminate film of the first invention, in which (B) and a layer (C) adjacent thereto are arranged, is provided. A third aspect of the present invention provides the gas barrier laminate film of the first or second aspect, wherein at least the molded product layer (B) is heat-treated. According to a fourth aspect of the present invention, the metal compound constituting the layer (C) is at least one selected from the group consisting of magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide and zinc hydroxide. A gas barrier laminate film according to any one of the third to third aspects is provided. According to a fifth aspect of the present invention, the gas barrier according to any one of the second to fourth aspects, wherein the compound constituting the vapor deposition layer (D) is at least one selected from the group consisting of silicon oxide, aluminum oxide, aluminum, and silicon nitride. An adhesive laminated film is provided. 6th of this invention has the transparent primer layer (E) from at least 1 sort (s) of polymeric materials chosen from the group of a polyester resin, a polyurethane resin, and a nitrocellulose resin in any surface of a vapor deposition layer (D). A gas barrier laminate film according to any one of the second to fifth inventions is provided. A seventh aspect of the present invention provides the gas barrier laminate film according to any one of the first to sixth inventions, wherein a plastic film layer (F) is laminated on the outermost side opposite to the outermost layer (C). .

  According to the present invention, at least one poly (meth) acrylic acid polymer and polyalcohol selected from the group consisting of a polymer film layer (A), poly (meth) acrylic acid and a partially neutralized poly (meth) acrylic acid Gas barrier laminate film comprising a molded product layer (B) composed of a mixture with a metal and a layer (C) containing a metal compound and an antiblocking agent adjacent thereto, wherein the layer (C) forms the outermost layer of the laminate film The blocking strength of the layer (C) was extremely low, and even when the layer (C) was folded and heat sealed, blocking between the layers (C) was not recognized.

Hereinafter, the present invention will be described in detail.
The material of the polymer film layer (A) (also referred to as a base material) constituting the gas barrier laminate film of the present invention is not particularly limited, but polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene Polyester resin such as naphthalate (PEN), nylon 6, nylon 66, nylon 12, nylon 6,66 copolymer, nylon 6,12 copolymer, metaxylylene adipamide / nylon 6 copolymer, amorphous Polyamide such as reactive nylon, low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene / vinyl acetate copolymer, polypropylene, ethylene / propylene copolymer, ethylene / acrylic acid copolymer, ethylene`acrylic acid Salt copolymer, ethylene / ethyl acrylate copolymer, polymethyl It is selected from among plastic films such as polyolefins such as rupentene, polyvinylidene chloride, polyphenylene sulfide and the like according to the heat treatment temperature and intended use (for example, for sterilization). Moreover, you may apply an anchor agent to a base material layer, in order to improve adhesiveness with a molding layer (B). The thickness of the layer (A) is not particularly limited, but is preferably 1 to 200 μm, more preferably 1 to 100 μm, and most preferably 5 to 50 μm.

  Moreover, as a material which comprises the vapor deposition layer (D) provided in the single side | surface of the said polymer film layer (A), the thin film which consists of metal compounds, such as inorganic compounds, such as silicon oxide, aluminum oxide, aluminum, and silicon nitride, is mentioned. Those formed by vapor deposition or sputtering or ion plating can also be used. The thickness of the vapor deposition layer (D) is usually preferably 5 to 600 nm, more preferably 10 to 400 nm.

  Furthermore, for the purpose of protecting the vapor deposition layer (D) made of an inorganic compound or a metal compound, a transparent primer layer (made of a polymer material of polyester resin, polyurethane resin, or nitrocellulose resin having a glass transition point of 60 to 80 ° C. ( E) can also be applied. The thickness of the transparent primer layer (E) is usually 0.05 to 10 μm, more preferably 0.1 to 5 μm.

The molded product layer (B) according to the present invention comprises at least one poly (meth) acrylic acid polymer selected from the group consisting of poly (meth) acrylic acid and partially neutralized poly (meth) acrylic acid and poly (meth) acrylic acid. It consists of a mixture with alcohols.
The poly (meth) acrylic acid polymer is a copolymer of acrylic acid and methacrylic acid, containing two or more carboxyl groups, and a partially neutralized product of the carboxylic acid polymer and the carboxylic acid polymer. It is a generic name including
Specifically, poly (meth) acrylic acid is polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and methacrylic acid, or a mixture of two or more thereof. In addition, a homopolymer of acrylic acid or methacrylic acid or a copolymer of both is preferable as long as it is soluble in water, and a homopolymer of acrylic acid or a copolymer of methacrylic acid in which acrylic acid is a dominant amount is an oxygen gas barrier. It is particularly suitable in terms of sex.
The number average molecular weight of the poly (meth) acrylic acid polymer is not particularly limited, but is preferably in the range of 1,000 to 4,000,000, and more preferably in the range of 2,000 to 250,000, due to handling problems. It is.

  The partially neutralized product of poly (meth) acrylic acid can be obtained by partially neutralizing the carboxyl group of poly (meth) acrylic acid with an alkali (that is, forming a carboxylate). Examples of the alkali include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide, and ammonium hydroxide. This alkali metal salt is contained in the molded product layer (B) as a monovalent metal or ammonium ion. When a partially neutralized product of poly (meth) acrylic acid is used, it is possible to suppress coloring of the molded product layer (B) due to heat.

A desired degree of neutralization can be achieved by adjusting the amount ratio of poly (meth) acrylic acid and alkali. The degree of neutralization of the partially neutralized poly (meth) acrylic acid is preferably selected based on the degree of oxygen gas barrier properties of the resulting film. The degree of neutralization can be determined by defining the formula: degree of neutralization (%) = (N / N ₀ ) × 100. Here, N is the number of moles of neutralized carboxyl groups in 1 g of partially neutralized poly (meth) acrylic acid, and N 2 _O is the number of moles of carboxyl groups in 1 g of polymethacrylic acid before partial neutralization. It is.
Here, from the viewpoint of oxygen gas barrier properties, it is generally desirable to use an unneutralized product or a partially neutralized product having a neutralization degree of 20% or less. More preferably, it is desirable to use an unneutralized product or a partially neutralized product having a neutralization degree of 15% or less.

The polyalcohol includes a low molecular compound having two or more hydroxyl groups in the molecule to an alcohol polymer, and includes polyvinyl alcohol (PVA), sugars and starches. Specifically, in addition to low molecular weight compounds such as glycerin, ethylene glycol, and propylene glycol, PVA has a saponification degree of usually 95% or more, preferably 98% or more, and an average polymerization degree of usually 300 to 1500.
As the saccharide, monosaccharide, oligosaccharide and polysaccharide are used. These saccharides include sugar alcohols such as sorbitol, mannitol, dulcitol, xylitol, erythritol, and various substitutes and derivatives. These saccharides are preferably soluble in water and alcohol or a mixed solvent of water and alcohol.

The mixing ratio (mass ratio) of the poly (meth) acrylic acid polymer and the polyalcohol is preferably 99: from the viewpoint of obtaining a molded layer (B) having excellent oxygen gas barrier properties even under high humidity conditions. 1-20: 80, more preferably 95: 5-40: 60, most preferably 95: 5-50: 50.
In addition, when heat-treating the molded product layer (B) for the purpose of imparting water resistance and further gas barrier properties, a water-soluble inorganic acid or Metal salts of organic acids can be added as appropriate. Specific examples of inorganic or organic acid metal salts include phosphinic acid metal salts (hypophosphite metal salts) such as sodium phosphinate (sodium hypophosphite) and calcium phosphinate (calcium hypophosphite). Can be mentioned. The addition amount of the metal salt of the inorganic acid and organic acid is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the poly (meth) acrylic acid polymer solid content. .
In this way, a mixture solution for forming the molded product layer (B) is obtained.

The method for forming the molded product layer (B) on the polymer film layer (A) is as follows. A mixture solution of a poly (meth) acrylic acid polymer and a polyalcohol, an apparatus such as an air knife coater, kiss roll coater, metering bar coater, grapier roll coater, reverse roll coater, dip coater, die coater, or the like, Using a device combining them, the polymer film layer (A) as a base material is coated to a desired thickness, and then an apparatus such as an arch dryer, straight bath dryer, tower dryer, floating dryer, drum dryer, Alternatively, the film (molded product layer) is formed by drying by using an apparatus combining them, or by evaporating moisture by blowing hot air or irradiating infrared rays.
Further, in order to improve the coating property of the aqueous mixture and to increase the uniformity of the thickness of the molded product, it may be diluted with water, or alcohol may be added.

  For the purpose of improving the water resistance and gas barrier properties of the molded product layer (B) fixed on the surface of the polymer film layer (A), at least the molded product layer (B) can be heat-treated. A laminate coated with a layer (C) containing a metal compound and an antiblocking agent adjacent to the surface of the molding layer (B) may be heat-treated under specific conditions, or after the molding layer (B) is heat-treated. A layer (C) containing a metal compound and an antiblocking agent may be formed on the surface of the molded product layer (B).

  The heat treatment is performed using the heat treatment conditions described in JP-A-7-165742. That is, when a saccharide is used as the polyalcohol, the molded layer (B) is preferably subjected to a condition satisfying the relationship between the heat treatment temperature and the heat treatment time defined by the following relational expressions (a) and (b). Heat treatment.

(A) logt ≧ −0.0622 × T + 28.48
(B) 373 ≦ T ≦ 573
(Where t is the heat treatment time (minutes) and T is the heat treatment temperature (K).)

By adopting this heat treatment condition, the formed molded layer (B) has water resistance, and the thickness of the molded layer (B) measured at 30 ° C. and a relative humidity of 80% is 3 μm. The molded article layer (B) having an excellent oxygen gas barrier property having an oxygen permeability of 2.0 × 10 ⁻¹² mol / m · s · Pa (400 cm ³ / m ² · 24 h · atm) or less can be obtained. .

This heat treatment can be performed by placing the heat treatment product containing the molded product layer (B) in an oven kept at a predetermined temperature for a predetermined time. Further, the heat treatment may be performed continuously by passing through an oven maintained at a predetermined temperature within a predetermined time, or by contacting with a hot roll. By this heat treatment, the obtained molded layer (B) becomes a molded layer (B) which has water resistance and superior oxygen gas barrier properties even under high humidity conditions. Moreover, this molded product layer (B) is inactive against water and boiling water and has water resistance as defined below. Here, the water resistance means that the laminated film containing the molded product layer (B) is immersed in boiling water for 30 minutes and then dried, and the thickness of the molded product layer (B) is 50% of the thickness before immersion. When it is above, this molded product layer (B) is said to be water resistant.
In the case of a laminated film without a vapor deposition layer (D), the thickness of the molded product layer (B) governs the oxygen permeability of the entire laminated film, so it is shaped according to the degree of oxygen permeability required for the package. The thickness of the material layer (B) can be arbitrarily determined. Usually, it is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm, and most preferably 0.1 to 1 μm, thereby exhibiting an excellent oxygen gas barrier effect.

The layer (C) containing a metal compound and an antiblocking agent is composed of a metal compound, an antiblocking agent, a resin, and the like, and it is essential to be adjacent to the molded product layer (B).
As the metal of the metal compound related to the layer (C), an alkaline earth metal such as beryllium, magnesium, calcium, strontium and barium, and a transition metal having an acid valence of +2 such as zinc are effective. The types of metal compounds used include simple metals, inorganic salts such as oxides, hydroxides, halides and carbonates, organic salts such as carboxylates and sulfonates, and poly (meth) acrylic acid. Examples thereof include polyacid salts such as salts.
Among these, alkaline earth metals, oxides, hydroxides, and carbonates of transition metals having an acid value of +2 are preferable, and magnesium oxide, calcium oxide, and more preferably from the viewpoints of adhesion to a molded product and handling properties. At least one metal compound selected from the group consisting of zinc oxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, magnesium carbonate, and calcium carbonate is most preferably magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, At least one metal compound selected from the group consisting of calcium hydroxide and zinc hydroxide is used. The shape of the metal compound is preferably particulate. The particle size is 0.01 to 0.5 μm, more preferably 0.01 to 0.3 μm, from the viewpoint of the oxygen gas barrier property expression effect and transparency.

The anti-blocking agent constituting the layer (C) is not particularly limited, but inorganic and / or organic fine particles are preferable. Specifically, the organic fine particles include, for example, polymethyl methacrylate, polystyrene, polyamide, and the like that are made of a polymer that does not substantially deform and are obtained by emulsion polymerization or suspension polymerization. Examples of inorganic fine particles include silica, zeolite, diatomaceous earth, talc, force orinite, and amorphous aluminosilicate. From the viewpoint of transparency of the film, organic fine particle-based polymethyl methacrylate is preferable, and from the viewpoint of cost, inorganic fine particle-based silica, zeolite and diatomaceous earth are preferable. The average particle size of the anti-blocking agent is in the range of 0.1 or more and 5 μm or less in view of appearance, transparency and blocking properties. As will be described later, the average particle size of the antiblocking agent is limited to the thickness of the metal compound layer and the layer (C) containing the antiblocking agent, and the ratio between them (average particle size / layer (C) thickness) is 0. .5-15, preferably 1-10.
The amount of the anti-blocking agent to be used is not particularly limited and can be freely used as long as the film properties, appearance, transparency and the like are not impaired, but 0.2 to 10 mass with respect to 100 parts by mass of the layer (C). Part, further 1 to 5 parts by mass is preferable.

  A resin may be added to the layer (C) as necessary in order to impart adhesion of the metal compound and the antiblocking agent to the binder or the molded product layer (B) when forming the layer (C). As the resin, it is possible to use at least one resin selected from the group of alkyd resin, melamine resin, acrylic resin, urethane resin, nitrocellulose, epoxy resin, polyester resin, phenol resin, amino resin, fluororesin, and isocyanate. preferable. Although the usage-amount of resin is not specifically limited, Preferably it is 20-200 mass parts with respect to 100 mass parts of metal compounds, More preferably, it is 20-100 mass parts, Most preferably, it is 50-100 mass parts. The mixture of the metal compound, the antiblocking agent and the resin is dissolved or dispersed in the organic solvent of the resin. Although it does not restrict | limit especially as an organic solvent, Alcohol, an aliphatic hydrocarbon cable, aromatic hydrocarbon, ester, ketones are mentioned.

  A dispersion or suspension composed of the metal compound, the antiblocking agent, and a resin and solvent used as necessary is applied to the molded product layer (B) and dried to form the layer (C). As a method for applying the dispersion or suspension, the dispersion is applied to the surface of the molding layer (B) with a gravure roll coater, reverse roll coater, dip coater or die coater. The coating thickness of the layer (C) containing a metal compound and an antiblocking agent is preferably 0.1 to 3 μm, more preferably 0.2 to 2 μm, and most preferably 0.2 to 1 μm after drying.

The gas barrier laminate film of the present invention is further laminated with a plastic film layer (F) which is the outer layer on the opposite side to the layer (C) which forms the outermost layer in order to impart strength and sealing properties, and oxygen barrier properties. It can be set as a laminated film. The plastic film layer (F) is the innermost layer when it is formed into a bag, and is therefore referred to as the innermost layer.
Examples of the resin constituting the plastic film layer (F) include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene copolymer obtained using a metallocene catalyst. Polymer, propylene copolymer obtained by using metallocene catalyst, unstretched ethylene-propylene copolymer, unstretched polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-ethyl Examples thereof include polyolefins such as acrylate copolymers, nylon copolymers such as nylon 6/66 copolymers, nylon 6/12 copolymers, and the like. Examples of the resin capable of high frequency sealing include polyvinyl chloride, polyvinylidene chloride, nylon 6, nylon 66, and the like. Examples of the sealing method include a four-way seal, a three-way seal, a joint seal, and an envelope seal. Although the thickness of a plastic film layer (F) is not specifically limited, It is 10-200 micrometers, Furthermore, it is 20-150 micrometers, Most preferably, it is the range of 20-100 micrometers.

  The laminated film is not particularly limited, but layer (C) / molded layer (B) / polymer film layer (A) (polyethylene terephthalate layer) / plastic film layer (F) (unstretched polypropylene layer) ), Layer (C) / molded product layer (B) / polymer film layer (A) (polyethylene terephthalate layer) / plastic film layer (F) (linear low density polyethylene layer), layer (C) / molded product Layer (B) / Polymer film layer (A) (Polyethylene terephthalate layer) / Plastic film layer (F) (Low density polyethylene layer), Layer (C) / Molded product layer (B) / Polymer film layer (A) (Polyethylene terephthalate) / plastic film layer (F) (ethylene copolymer obtained using a metallocene catalyst), layer (C) / molded layer (B) / high Molecular film layer (A) (stretched nylon) / plastic film layer (F) (unstretched polypropylene layer), layer (C) / molded layer (B) / polymer film layer (A) (stretched nylon) / plastic film Layer (F) (linear low density polyethylene layer), layer (C) / molded layer (B) / polymer film layer (A) (stretched nylon layer) / plastic film layer (F) (low density polyethylene layer) ), Layer (C) / molded layer (B) / polymer film layer (A) (stretched nylon) / plastic film layer (F) (ethylene copolymer obtained using metallocene catalyst), layer (C) / molded product layer (B) / polymer film layer (A) (stretched nylon) / plastic film layer (F) (propylene copolymer obtained using a metallocene catalyst), transparent primer Layer (E) / deposition layer (D) / polymer film layer (A) (nylon or polyethylene terephthalate) / molded layer (B) / layer (C), layer (C) / molded layer (B) / high Molecular film layer (A) (stretched nylon or polyethylene terephthalate) / deposition layer (D), layer (C) / molded layer (B) / deposition layer (D) / polymer film layer (A) (nylon or polyethylene terephthalate) And the like.

In order to obtain the laminated film as described above, a plastic film layer formed from a thermoplastic resin by a known laminating method such as a coating method, a dry laminating method, and an extrusion coating method with or without an adhesive layer ( F) is laminated on the polymer film (A) or other film layer added as necessary so as to be the innermost layer opposite to the layer (C) forming the outermost layer of the laminated film of the present invention. . Thus, a gas barrier in which the polymer film layer (A), the molded product layer (B) and the layer (C) adjacent thereto are laminated films, and the layer (C) forms the outermost layer of the laminated film. Can be obtained.
In the dry laminating method, a layer (B) that is fixed to one surface of the polymer film layer (A) and a layer (C) that includes a metal compound and an antiblocking agent adjacent to the formed layer (B) ( A plastic film layer (F) or a sheet can be bonded to the innermost layer opposite to C).
In the extrusion coating method, a polymer film layer (A) of a gas barrier laminate film comprising a molded product layer (B) fixed on one side of a polymer film layer (A) of a base material and a layer (C) formed adjacent thereto. ) The other side of the thermoplastic resin is melt-extruded, and the plastic film layer (F) is laminated to form a gas barrier laminated film.

  The plastic film layer (F) constituting the gas barrier laminate film of the present invention is the innermost layer opposite to the layer (C) which is the outermost layer of the laminate film. When manufacturing a bag etc. from a laminated film, it is preferable to use the material (sealant) which can be heat sealed, a high frequency seal, or an ultrasonic seal in consideration of the case where films are heat-bonded.

In the gas barrier laminate film of the present invention thus obtained, the blocking strength of the outermost layer (C) is preferably in the range of 0 to 100 gf / 15 mm width, more preferably 0 to 70 gf / 15 mm width. Thereby, blocking at the time of preservation | save of a layer (C) or heat sealing can be prevented. The oxygen permeability of the gas barrier laminate film is preferably 0.1 to 20 cm ³ / m ² · day · atm (30 ° C., 80% RH), more preferably 0.1 to 10 cm ³ / m ² · day ·. atm, most preferably 0.1 to ⁵ cm ³ / m ² · day · atm. The water vapor permeability is preferably 0.1 to 4 g / m ² · day (40 ° C., 90% RH), more preferably 0.1 to 3 g / m ² · day, and most preferably 0.1 to ² g / m ^2. -Day.

  The gas barrier laminate film of the present invention is excellent in oxygen gas barrier properties in a high humidity atmosphere, such as bonito, shaving, seaweed, kelp, taro, miso, pickles, side dish, boiled, smoked salmon, peanut, almond, raw meat , Processed meat, fresh fish, processed fish products, yakitori, grilled meat, grilled fish, staff, beans, seaweed, dried fish, wiener, hamburger, cooked food, vegetables, bread, sandwiches, rice balls, fluo (fruit), instant ramen, ramen Attached soup, spicy vinegar miso, miso with dashi, fried egg, corn, sweet corn, konjac, wild vegetables, bamboo shoots, mayonnaise, ketchup, soy sauce, sauce, dashi soup, powdered soup, mirin, sprinkle, rice cracker, milk, skim milk powder, fermentation Milk, condensed milk, cream soup, corn soup, Japanese tea, oolong tea, tea, coffee Juice, cocoa, water, soy milk, carbonated drink, soft drink, lactic acid bacteria drink, smoked, salted, soup, western liquor, sake, wine, rice cake, beer, snack confectionery, fried confectionery, rice confectionery, bean confectionery, raw vegetable paste, gum , Candy, caramel, refreshing confectionery, ice cream, rice, rice, red rice, fried chicken, yellow powder, powdered product, Western confectionery, Japanese confectionery, candy natto, natto, tofu, green tea, shiitake, paste, biscuit, balm kuchen, castella, waffle, pie , Sliced ham, sliced bacon, sausage, salami sausage, corn beef, salmon, chikuwa, fresh bonito, chili oil, milk powder, fragrance, baby food, cream, cake, sponge cake, cheese, butter, raisin butter, curry, stew, Boiled crab, Sakiika pickle, pudding, jelly, yogurt, mousse, sheep crab, ja , Margarine, chocolate, marmalade, peanut butter, ann, dressing,

  Sugar, salted vinegar, cooking oil, sauce, soy sauce, tomato pyule, mustard, wasabi, spices, dried fruit, dried food, fruit sauce, potato salad, tuna flakes, udon, soba, raw noodles, food for microwave oven, oven Toaster-compatible foods, potion packs, bag-in-boxes, dietary supplements, nourishing tonics, frozen foods and other foods that are susceptible to deterioration by oxygen, infusion bags, heat insulating materials, heat-resistant agents, static eliminators, electromagnetic shielding materials, thinners , Essential oil, oil refining, deodorant, fragrance, pesticide, toothpaste, cosmetics, engine oil, gasoline, industrial chemicals, industrial solvents, petroleum additives, fragranced products, cooler, warmer, deodorant, insecticide, dehumidifier Agent, insect repellent, preservative, rust preventive agent, photographic developer, plant health care agent, powder, granule, tablet-shaped pharmaceutical, sheampoo, rinse, body saw , Soap, detergent, bath preparation, eye drops, adhesives, lacquers, herbal medicine, pet food, fertilizer, feed, textile products, leather products, hospital nutrition, medical equipment, warmers, cigarettes, equipment, cassettes, videotapes, MD, Suitable for packaging materials such as CDs, DVDs, CD-Rs, electronic parts, toiletries, miscellaneous goods and stationery. Also included are boil and retort applications for these foods and articles. Examples of forms when using these films and laminated films include bags, casings, pouches, lids, and the like.

(Example)
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these projecting examples. In addition, the measuring method of a physical property is as follows.
(1) Oxygen permeability According to JIS K7126, the oxygen permeability tester OX-TRAN 2/20 type manufactured by Modern Control was used and measured under conditions of 30 ° C. and 80% RH (relative humidity).
The unit is cm ³ / m ² · day · atm.
(2) Water vapor permeability According to JIS K-7129, the water vapor permeability tester PERMATRAN-W 3/31 type manufactured by Modern Control was used and measured at 40 ° C. and 90% RH.
The unit is g / m ² · day.
(3) Blocking strength Two layers (C) each containing a metal compound and an antiblocking agent are stacked on a 10 cm × 20 cm long and horizontal film, and a heat seal tester manufactured by Tester Sangyo Co., Ltd. is used. It was heated under pressure at 67 g / cm ² for 5 seconds (sealing part 2 cm × 15 cm, sealing pressure 2 kgf). This was measured as peel strength (gf / 15 mm) with a tensile tester in accordance with ASTM D-1893 under conditions of 23 ° C. and 60% RH. When this value is small, the anti-blocking property is good.

(Example 1)
As polyacrylic acid (PAA), a 25% by weight aqueous solution of polyacrylic acid (number average molecular maximum of 150,000) manufactured by Wako Pure Chemical Industries, Ltd. was used. 17.5 parts by mass of sodium phosphinate monohydrate manufactured by Wako Pure Chemical Industries, Ltd. was added to 100 parts by mass of the solid content of the PAA aqueous solution.
On the other hand, glycerin special grade manufactured by Wako Pure Chemical Industries, Ltd. was used as the polyalcohol. Both were diluted with water to prepare 10 mass% each. Subsequently, using a sodium phosphinate-added PAA aqueous solution and a glycerin aqueous solution, a mixed aqueous solution (concentration: 10% by mass) of sodium phosphinate-added PAA: glycerin = 60: 40 (mass ratio) was prepared.
Polyester film P-60 (thickness: 12 μm) manufactured by Toray Industries, Inc. (base film: may be abbreviated as PET) layer (A), the above aqueous mixture is applied to a table coater (K303 PROFERR manufactured by RK Print-Coat Instruments). ) And coated with a Meyer bar, and then water was evaporated using a dryer to obtain a molded layer (B) having a thickness of 0.4 μm. The molded product layer (B) was heat-treated with hot air at 220 ° C. for 10 seconds.

  Next, a layer (C) containing a metal compound and an antiblocking agent was prepared as follows. Zinc oxide fine particles (manufactured by Sakai Chemical Co., Ltd.) were mixed with polyester polyol resin (manufactured by Dainichi Seika Co., Ltd., NB-300) to prepare a zinc polyol fine particle-containing polyester polyol resin solution. At this time, the mass ratio of the zinc oxide fine particles and the polyester polyol resin solid content was set to 1.5: 1. Furthermore, 5 mass parts of isocyanate-based curing agent Ramic B Hardener (manufactured by Dainichi Seika Co., Ltd.) was added to 100 mass parts of resin solids to prepare a zinc oxide-containing paint. Further, silicone fine particles (Tospearl 120 (particle size: 2 μm) manufactured by GE Toshiba Silicone Co., Ltd.) as an anti-blocking agent are added to the zinc oxide-containing paint with respect to 100 parts by mass of the solid content of zinc oxide paint (resin + zinc oxide). 1.5 parts by mass were added. This paint was applied to the molded product layer (B) and dried with hot air at 100 ° C. for 1 to 2 seconds to form a 0.2 μm layer (C) to obtain a laminated film. The evaluation results of the laminated films obtained in Examples and Comparative Examples are shown in Table 1.

(Example 2)
The same operation as in Example 1 was performed except that the particle size of the anti-blocking agent was 3 μm (GE Toshiba Silicone Co., Ltd., Tospearl 130).
(Example 3)
The same procedure as in Example 1 was performed except that the thickness of the molded product layer (B) was 0.3 μm after drying.
Example 4
The same procedure as in Example 2 was performed except that the thickness of the molded product layer (B) was 0.3 μm after drying.

(Example 5)
The same procedure as in Example 3 was performed except that the antiblocking agent had a particle size of 5 μm (Tospearl 145 manufactured by GE Toshiba Silicone Co., Ltd.) and the thickness of the molded product layer (B) was 0.4 μm after drying.
(Example 6)
The same procedure as in Example 1 was conducted except that the thickness of the molded product layer (B) was 0.7 μm after drying.
(Example 7)
The same procedure as in Example 4 was performed except that the thickness of the molded product layer (B) was 0.7 μm after drying.
(Example 8)
The same procedure as in Example 5 was performed except that the thickness of the molded product layer (B) was 0.7 μm after drying.
Example 9
The same procedure as in Example 3 was performed except that an aluminum oxide-deposited PET film (manufactured by Toyo Metallizing Co., Ltd., 1011HG-CR (thickness 12 μm)) (PET-vm) was used as the substrate. However, the layer of the molded product layer (B), the layer containing the metal compound and the antiblocking agent (C) was formed in this order on the surface opposite to the vapor deposition layer (D) (thickness, 20 nm) of the substrate.

(Example 10)
The same procedure as in Example 4 was performed except that a biaxially stretched nylon film (manufactured by Unitika Ltd., Emblem ONBC (thickness 15 μm)) (abbreviated as Ny) was used as the substrate.
(Example 11)
The same procedure as in Example 4 was performed except that silicon oxide-deposited nylon (manufactured by Mitsubishi Plastics, Techbarrier NR (thickness 15 μm) (abbreviated as Ny-vm)) was used as the substrate. However, a layer (C) containing a metal compound and an antiblocking agent was formed on the surface of the molded product layer (B) on the surface opposite to the vapor deposition layer (D) of the substrate.
(Example 12)
The same procedure as in Example 4 was performed except that the amount of the antiblocking agent added was 0.8 parts by mass with respect to 100 parts by mass of the solid content of zinc oxide paint (resin + zinc oxide).
(Example 13)
The same procedure as in Example 4 was performed except that the addition amount of the antiblocking agent was changed to 3.0 parts by mass with respect to 100 parts by mass of zinc oxide paint solids (resin + zinc oxide).

(Comparative Example 1)
The same operation as in Example 1 was conducted except that the antiblocking agent was changed to an average particle size of 5 μm (manufactured by GE Toshiba Silicone Co., Ltd., Tospearl 145).
(Comparative Example 2)
The same procedure as in Example 3 was performed except that the antiblocking agent was changed to an average particle size of 10 μm (manufactured by Nippon Shokubai Co., Ltd., Eposta MA1010).
(Comparative Example 3)
The same procedure as in Example 6 was conducted, except that the antiblocking agent had an average particle size of 10 μm (manufactured by Hioki Catalyst Co., Ltd., Eposter MA1010) and the thickness of the molded product layer (B) was 0.5 μm after drying.
(Comparative Example 4)
The same procedure as in Example 1 was performed except that no antiblocking agent was added.

Claims (7)

  A mixture of at least one poly (meth) acrylic acid polymer selected from the group consisting of a polymer film layer (A), poly (meth) acrylic acid and a partially neutralized poly (meth) acrylic acid and a polyalcohol A laminated film comprising a molded product layer (B) and a layer (C) containing a metal compound and an antiblocking agent adjacent thereto, wherein the layer (C) forms the outermost layer of the laminated film, The average particle size of the blocking agent is 0.1 μm or more and 5 μm or less, and the ratio of the average particle size of the anti-blocking agent to the thickness of the layer (C) (average particle size / thickness of the layer (C)) A gas barrier laminate film having a range of 0.5 to 15.   It has a vapor deposition layer (D) on one side of the polymer film layer (A), and is adjacent to the molding layer (B) on the other side of the layer (A) or on the surface of the vapor deposition layer (D). The gas barrier laminate film according to claim 1, wherein the layer (C) is disposed.   The gas barrier laminate film according to claim 1 or 2, wherein at least the molded product layer (B) is heat-treated.   The metal compound constituting the layer (C) is at least one selected from the group consisting of magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide and zinc hydroxide. The gas barrier laminate film according to any one of the above.   The gas barrier laminate film according to any one of claims 2 to 4, wherein the compound constituting the vapor deposition layer (D) is at least one selected from the group consisting of silicon oxide, aluminum oxide, aluminum, and silicon nitride. .   The transparent primer layer (E) made of at least one polymer material selected from the group of polyester resin, polyurethane resin, and nitrocellulose resin is provided on any surface of the vapor deposition layer (D). 6. The gas barrier laminate film according to any one of 5 above.   The gas barrier laminate film according to any one of claims 1 to 6, wherein a plastic film layer (F) is laminated on the outermost side opposite to the outermost layer (C).