JP2003191400A - Gas barrier film laminated body and method for manufacturing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier packaging material in which transparency is excellent, the content is visible, a metal detector can be used, any source substance destroying environment is not used, and high gas barrier properties under a condition of high temperature and high humidity is avoidable, while the material is the most suitably usable as a boiling and retort sterilization material. <P>SOLUTION: At least a gas barrier coating film layer 2 is laminated on one face or both faces of a base material 1 comprising a plastic material and the coating film layer 2 is a gas barrier coating film layer in which at least one kind of metal alkoxides or a hydrolyzate thereof, a hydroxyl group- containing water-soluble polymer and a poly(meth)acrylic acid are mixed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for packaging used in the field of packaging non-food products such as foods and pharmaceuticals, electronic components, and the like. Deterioration by blocking the contents from water vapor
The present invention relates to a plastic film laminate that suppresses deterioration and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging non-food products such as foods and pharmaceuticals and electronic components are permeated through packaging materials in order to suppress alteration of contents and maintain their functions and properties. It is necessary to prevent the influence of oxygen, water vapor, and other gases that alter the contents, and it is required to have a gas barrier property of blocking these gases.

Therefore, as a conventional gas barrier layer,
Mainly used are metal foils made of metals such as aluminum and vapor deposited films thereof, resin films such as polyvinyl alcohol and ethylene vinyl copolymer, polyvinylidene chloride, polyacrylonitrile, or plastic films coated with these resins. Came.

[0004]

However, although the metal foil and the metal vapor deposition film have excellent gas barrier properties, the contents cannot be confirmed through the packaging material, the metal detector cannot be used during inspection, and There is a problem that it must be treated as an incombustible material when it is discarded. In addition, gas barrier resin films and films coated with them have a high temperature-humidity dependency and cannot maintain a high level of gas barrier properties.In addition, vinylidene chloride, polyacrylonitrile, etc. can be raw materials of harmful substances when they are discarded or incinerated. There is a problem that there is a property. That is, it can be said that the gas barrier packaging materials that are mainly used at present have merits and demerits and have various problems.

As a technique for solving such problems, a metal alkoxide or a metal alkoxide hydrolyzate,
A gas barrier packaging material provided with a composite coating with a water-soluble polymer having a hydroxyl group has been proposed (JP-A-6-1924).
54). Since this gas barrier packaging material has a certain degree of flexibility, is environmentally friendly, and is manufactured by coating, it can be manufactured at low cost.

However, the film of the gas barrier packaging material is composed of a hydrogen bond between a metal alkoxide hydrolyzate and a water-soluble polymer having a hydroxyl group, has low water resistance, and requires a treatment such as boil and retort sterilization. When used as a material, the coating layer cannot be used after swelling and melting.

The present invention is intended to solve the above-mentioned problems of the prior art, and since it is excellent in transparency, the contents can be seen through and a metal detector can be used, which causes environmental damage. Of course not to use causative substances,
An object of the present invention is to provide a gas barrier packaging material having a high gas barrier property under high temperature and high humidity, which can be used as a sterilization packaging material for boil and retort, and which is optimum as a packaging material.

[0008]

The invention according to claim 1 of the present invention is a water-soluble high-molecular compound having one or more kinds of metal alkoxide or its hydrolyzate and a hydroxyl group on one or both surfaces of a substrate made of a plastic material. Molecule, poly (meta)
A gas barrier film laminate, comprising a gas barrier coating layer mixed with acrylic acid.

The invention according to claim 2 of the present invention is the gas barrier film laminate according to claim 1, wherein the metal alkoxide is tetraethoxysilane.

The invention according to claim 3 of the present invention is the gas barrier film laminate according to claim 1 or 2, wherein the water-soluble polymer having a hydroxyl group is polyvinyl alcohol. It is a laminated body.

According to a fourth aspect of the present invention, in the gas barrier film laminate according to any one of the first to third aspects, the addition amount (weight ratio) of the poly (meth) acrylic acid is When the metal alkoxide or the hydrolyzate of the metal alkoxide is converted to a metal oxide, the weight ratio of poly (meth) acrylic acid to 100 of the metal oxide is 1 to 20, which is a gas barrier film laminate. Is.

The invention according to claim 5 of the present invention is characterized in that, in the gas barrier film laminate according to any one of claims 1 to 4, a heat seal layer is provided on the gas barrier coating layer side. And a gas barrier film laminate.

The invention according to claim 6 of the present invention is a water-soluble polymer having one or more kinds of metal alkoxide or its hydrolyzate and a hydroxyl group on one or both surfaces of a base material made of a plastic material, and poly (meth). A method for producing a gas barrier film laminate, which comprises applying a coating agent prepared by mixing acrylic acid and heating and drying the coating agent to form a gas barrier film layer.

The invention according to claim 7 of the present invention is the method for producing a gas barrier film laminate according to claim 6, wherein the heating and drying is performed at a high temperature of 200 ° C. or higher. It is a body manufacturing method.

The invention according to claim 8 of the present invention is the method for producing a gas barrier film laminate according to claim 6 or 7, wherein the addition amount (weight ratio) of the poly (meth) acrylic acid is all The method for producing a gas barrier film laminate is characterized in that it is 0.5 to 20 with respect to 100 solids in the coating agent.

[0016]

According to the present invention, one or more metal alkoxides or hydrolysates thereof and a water-soluble polymer having a hydroxyl group, poly (meth) acrylic acid, are mixed on one or both sides of a substrate made of a plastic material. By providing the gas barrier coating layer, gas barrier properties are exhibited, and when tetraethoxysilane is used as the metal alkoxide and polyvinyl alcohol is used as the polymer having a hydroxyl group, even higher gas barrier properties are exhibited.

Further, when the addition amount (weight ratio) of the poly (meth) acrylic acid is converted to a metal alkoxide or a hydrolyzate of the metal alkoxide into a metal oxide, the poly (meth) acrylic is based on 100 metal oxides. When the weight ratio of the acid is from 1 to 20, stable barrier properties and adhesion are exhibited, and when the gas barrier coating layer is produced by heating and drying, particularly when the heating and drying temperature is 200 ° C. or higher. , Moisture resistance and water resistance are improved.

Even if a heat seal layer is provided on the gas barrier coating layer side and evaluated as a more practical packaging material, the gas barrier property and the adhesiveness do not deteriorate even under severe conditions such as retort sterilization. In addition, it is possible to provide a highly practical packaging material having excellent flexibility and suitability, and having no problem with transparency.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the drawings. FIG. 1 is a sectional view for explaining a gas barrier film laminate of the present invention.

First, as shown in the figure, the gas barrier film laminate of the present invention shown in FIG. 1 comprises a substrate 1 and a gas barrier coating layer 2, and the substrate 1 is a substrate made of a plastic material. The gas barrier coating layer 2 is laminated on top.

The above-mentioned substrate 1 is made of a plastic material and is preferably transparent. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films such as 66-nylon, polycarbonate films, polyacrylonitrile films, engineering plastic films such as polyimide films. Etc. are used, and may be stretched or unstretched, and those having mechanical strength and dimensional stability are preferable. These are processed into a film and used. In particular, a film arbitrarily stretched biaxially among these is preferably used,
Further, when used as a packaging material, a biaxially stretched polyamide film or a polyester film is preferable in consideration of price, moisture resistance, filling suitability, texture, and disposability, but a polyester film such as a polyethylene terephthalate film (PET) is more preferable. preferable.

On the surface of the base material 1, various well-known additives and stabilizers such as antistatic agents, plasticizers, lubricants,
Antioxidants may be used, and in order to improve the adhesion with various films, corona treatment, plasma treatment, ozone treatment, etc. may be performed as pretreatment, and further chemical treatment, solvent treatment May be applied.

Further, in consideration of the wettability, the adhesiveness, and the uniform film forming property of the gas barrier coating layer 2 provided on the base material 1, the coating layer may be formed on the surface of the base material 1 depending on the packaging material application. An anchor coat layer may be provided by coating the anchor coat agent adapted to No. 2 with a wet coating method or the like.

As the anchor coating agent, various materials suitable for the gas barrier coating layer 2 can be used. For example, polyethyleneimine or its derivative, silane coupling agent, organic titanate, polyacrylic type, polyester type, polyurethane type. There are anchor coating agents containing epoxy resin, isocyanate resin, polyamide resin, or polyolefin emulsion or surfactant.

Further, on the surface of the substrate 1, silicon oxide,
Providing a ceramic vapor deposition layer of an inorganic compound such as aluminum oxide (alumina) or a gas barrier vapor deposition layer of a non-conductive (insulating) inorganic compound such as zinc oxide, calcium oxide, barium oxide is a gas barrier coating layer. It improves the wettability and adhesion of the base material 1 when forming 2.

Furthermore, providing the above-mentioned gas barrier vapor deposition layer of a non-conductive (insulating) inorganic compound on the surface of the base material 1 may improve the gas barrier property of the base material 1 as a packaging material by using a metal foil or a metal foil. It occurs when a gas barrier layer with a metal vapor deposition layer is provided, for example, the contents cannot be seen through the packaging material, the metal detector cannot be used during inspection, and it is treated as an incombustible material when discarded after use. The gas barrier function is improved by the synergistic effect of the gas barrier coating layer 2 and the non-conductive (insulating) vapor deposition layer while eliminating the inconveniences such as the necessity.

The thickness of the substrate 1 is not particularly limited, but considering the suitability as a packaging material, the case where other layers are laminated, and the workability when forming the gas barrier coating layer 2, In a practical range of 3 to 200 μm,
Generally, the thickness is more preferably 6 to 30 μm.

The gas barrier coating layer 2 in the laminate of the present invention comprises a water-soluble polymer having one or more kinds of metal alkoxide or its hydrolyzate and a hydroxyl group on one or both sides of a base material 1 made of a plastic material, and a poly. The coating layer must be formed of a resin mixed with (meth) acrylic acid.

The metal alkoxide is condensed after hydrolysis,
It is a well-known fact to form ceramic membranes such as glass. However, since metal oxides are hard and cracks easily occur due to strain due to volume reduction during condensation, it is very difficult to form a thin, transparent and uniform condensate film on the film. Therefore, by adding a polymer, it is possible to impart flexibility to the structure, prevent cracks, and form a film.

However, even if the addition of the polymer is visually uniform,
Microscopically, it is often separated into a metal oxide and a polymer portion, and a barrier packaging material is likely to be a hole in a barrier. Therefore, by adding a polymer having a hydroxyl group, it is possible to use the strong hydrogen bond between the hydroxyl group of the polymer and the hydroxyl group of the hydrolyzate of the metal alkoxide, so that the metal oxide can be successfully linked to the polymer during condensation. Disperses and develops a high barrier property close to that of ceramics.

When the metal alkoxide or the hydrolyzate of the metal alkoxide is converted into the metal oxide, the weight ratio of the metal oxide and the water-soluble polymer is 20:80 in consideration of the film forming property and the gas barrier property. It is preferably ˜95: 5. When the amount of the metal oxide is less than 20:80, the water-soluble polymer has strong properties, and the metal oxide does not exhibit the barrier property. Conversely, the water-soluble polymer is 95: 5
If it is less, the metal oxide does not form a film and cracks.

The metal alkoxide (metal oxide) used in the coating solution for forming the gas barrier coating layer 2 of the laminate of the present invention is a compound represented by the general formula M (OR) n (M) such as tetraethoxysilane and triisopropoxyaluminum. ;
Metals such as Si, Ti, Al, and Zr; R; alkyl groups such as CH ₃ and CH ₅ ). Among them, tetraethoxysilane is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

The water-soluble polymer having a hydroxyl group used in the coating liquid is preferably polyvinyl alcohol, starch or cellulose. Particularly, when polyvinyl alcohol (hereinafter PVA) is used as a coating agent for forming the gas barrier coating layer 2 of the laminate of the present invention, the gas barrier property is most excellent. Because PVA is a polymer containing the largest number of hydroxyl groups in the monomer unit, it forms a very strong hydrogen bond with the hydroxyl groups of the metal alkoxide after hydrolysis. PVA referred to here is generally obtained by saponifying polyvinyl acetate, and is a complete saponification in which only a few percent of acetic acid groups remain from a so-called partially saponified PVA in which an acetic acid group remains of several tens percent. Including PVA. The molecular weight of PVA varies from 300 to several thousand, but there is no problem in the effect regardless of the molecular weight. However, in general, a high molecular weight PVA having a high degree of saponification and a high degree of polymerization has high water resistance and is therefore preferable.

When tetraethoxysilane is used as the metal alkoxide and PVA is used as the water-soluble polymer, the metal alkoxide or a metal oxide obtained by converting the hydrolyzate of the metal alkoxide into a metal oxide (for example, SiO ₂ ),
The weight ratio with the water-soluble polymer is more preferably SiO ₂ / PVA of 50/50 to 70/30. This mixing ratio (weight ratio) is 4/6 to 6/4 when converted to the molar ratio of SiO ₂ and PVA, and the mixing ratio of hydrogen bonds in which one SiO ₂ corresponds to one molecule for each hydroxyl group of PVA. It is presumed that it exhibits very good dispersibility and exhibits a high gas barrier property.

The above-mentioned metal alkoxide or its hydrolyzate and a water-soluble polymer having a hydroxyl group have excellent gas barrier properties, but since the gas barrier coating layer 2 is formed by hydrogen bonding, the moisture resistance and water resistance are low, and the envelope is low. There is a limit to the use in wood. Poly (meth) acrylic acid (hereinafter PAA)
Are mixed for the purpose of improving their moisture resistance and water resistance.

PAA is an acidic polymer having a carboxylic acid in its skeleton. Therefore, when a carboxylic acid in PAA is used as a catalyst for hydrolysis of a metal alkoxide, the hydroxyl group of the metal alkoxide after hydrolysis and the carboxylic acid in PAA have a weak hydrogen bond, so that the metal oxide is comparatively stable. It can be dispersed and does not easily become a barrier hole. Further, by heating, a hydroxyl group in the metal oxide and an ester bond are also formed. In addition to having a hydrogen bond with the polymer having a hydroxyl group, an ester bond is formed by heating, so that the carboxylic acid in PAA can impart water resistance to the gas barrier coating layer 2.

The mixing method of the coating solution is a water-soluble polymer having a hydrolyzed metal alkoxide and a hydroxyl group, P
The effect is exhibited even if the AA aqueous solution is mixed in any order.
In particular, the method of hydrolyzing a metal alkoxide with a PAA aqueous solution and adding it to a water-soluble polymer is desirable in consideration of fine dispersion of the metal oxide. In this case, the same effect can be obtained by using an aqueous solution of PAA as the acid catalyst or adding an ordinary acid to increase the concentration of the acid catalyst to accelerate the hydrolysis rate.

When PAA is mixed, when the metal alkoxide or the hydrolyzate of the metal alkoxide is converted into metal oxide, the weight ratio of PAA to 100 metal oxide is:
It is preferably from 1 to 20. When it is 1 or less, the water resistance of the ester bond is not sufficiently exhibited, and when it is 20 or more, the barrier property due to the blending of the above-mentioned metal oxide and the water-soluble polymer having a hydroxyl group is impeded, and the barrier pores are This is because Further, when the mixing amount is 5 to 10, since the respective compounding ratios are combined in the most balanced manner, the optimum compounding ratio is achieved in gas barrier property, water resistance and flexibility.

Further, in consideration of the adhesiveness with the substrate, the wettability, and the prevention of cracking due to shrinkage, the coating solution of the gas barrier coating is subjected to isocyanate compound, silane coupling agent, titanium coupling agent, colloidal silica, Clay minerals such as smectite, stabilizers, colorants,
Known additives such as viscosity modifiers can be added within a range that does not impair gas barrier properties and water resistance.

The thickness of the gas barrier coating layer 2 after drying is not particularly limited, but if the thickness exceeds 50 μm, cracks may easily occur, so 0.01 to 50 is required.
It is desirable that the thickness is μm.

As a method for forming the gas barrier coating layer 2, a usual coating method can be used. For example, dipping method, roll coating, gravure coating,
Reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset method and the like can be used. Coating is performed on one side or both sides of the substrate 1 using these coating methods.

The gas barrier coating layer 2 must be formed by heating and drying. The drying method is hot air drying, hot roll drying, high-frequency irradiation, infrared irradiation, UV irradiation, or the like, as long as heat is applied to the gas-barrier coating layer 2 to remove water molecules, or two of them. The above may be combined.

When the heat applied to the surface of the gas barrier coating layer 2 in the laminate of the present invention by heating and drying is at a high temperature of 200 ° C. or higher, the barrier property is further improved, and the moisture resistance,
Water resistance is also improved. By performing the heat treatment at 200 ° C. or higher, it is possible to maintain the high barrier property and the adhesiveness without deteriorating the gas barrier coating layer 2 even in the boiling and retort sterilization treatments.

In the condensation of the hydrolyzed metal alkoxide contained in the gas barrier coating layer 2, intermolecular dehydration proceeds at 150 ° C., and P represented by a water-soluble polymer having a hydroxyl group.
Intermolecular dehydration of VA proceeds at 170 ° C. Further, the hydroxyl group of the water-soluble polymer and the carbonyl group of the poly (meth) acrylic acid are heated at high temperature to promote the ester bond. These comprehensive effects are realized by high-temperature heating and drying at 200 ° C. or higher, and impart sufficient moisture resistance and water resistance to the gas barrier coating. 230 ° C, which is close to the melting point of PET, is more preferable.
It is heating at 240 ° C. When heating and drying at 230 ° C. or higher, the time required for the effect is significantly shortened, but when it exceeds 240 ° C., it is difficult to process the PET base material because of its melting point.

As a method of high temperature heat treatment at 200 ° C. or higher, a general hot air drying method or a hot roll drying method can be used. A flame treatment method in which the surface of the gas barrier coating layer 2 is heat-treated with a flame of several thousands of degrees also has the same effect. Further, even when the heat setting temperature of the stretched film is 200 ° C. or higher, the effect of the stretch coating method in which the coating liquid for forming the gas barrier coating is applied during the biaxial stretching of the film is also effective. According to this method, one step can be omitted and there is an economical merit, which is preferable.

In the gas barrier film laminate of the present invention, by providing a heat seal layer (not shown) on the gas barrier coating layer 2 side, a packaging material with higher practicality can be provided. The heat-sealing layer is a layer serving as an inner surface of a packaging body such as a bag-shaped packaging body, and is used for an adhesive portion (sealing portion) when forming the bag-shaped packaging body or the like, for example, polyethylene, polypropylene, Heating of ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and metal cross-linked products thereof. A fusible resin is used. The thickness of the heat seal layer is determined according to the purpose, but is generally in the range of 15 to 200 μm. Also,
Depending on the shape of the package, a heat seal layer may be provided on the base material 1 side of the gas barrier film laminate.

As a method for forming the heat-sealing layer on the gas barrier film laminate of the present invention, a film-like material made of the above-mentioned resin (heat-fusible resin) is used by using a two-component curing type urethane adhesive. Dry laminating method for laminating to the gas barrier film layer 2 side or substrate 1 side of the gas barrier film laminate, non-solvent dry laminating method for laminating in the same manner using a solventless adhesive, and heating and melting the above-mentioned resin into a curtain shape. Any of the extrusion lamination method such as extrusion and laminating in the same manner can be formed by a known lamination method.

A print layer (not shown) may be laminated on the gas barrier coating layer 2 if necessary,
It is also possible to laminate a plurality of resins via an adhesive.
Further, it is also possible to stack a plurality of resins via a printing layer, a heat seal layer, and an adhesive on the surface of the substrate 1 opposite to the gas barrier coating layer 2.

[0049]

EXAMPLES The gas barrier film laminate of the present invention and the method for producing the same will be further described below with reference to specific examples.

First, as a coating for forming the gas barrier coating layer 2 on the upper surface of the substrate 1 of the gas barrier film laminate of the present invention, one kind of metal alkoxide, a water-soluble polymer having a hydroxyl group, and polyacrylic acid are used. A coating agent for a gas barrier film made of a resin obtained by mixing the above was prepared by combining the following components and mixing and adjusting them at a predetermined ratio.

(Component of coating agent) Metal alkoxide: tetraethoxysilane (Si (O
C ₂ H ₅ ) ₄ ; hereinafter referred to as TEOS) ・ Water-soluble polymer having a hydroxyl group: polyvinyl alcohol (PVA124 manufactured by Kuraray Co., Ltd., polymerization degree 2400) ・ Polyacrylic acid (PAA): polyacrylic acid aqueous solution (Wako Pure Chemical Industries, Ltd. (Mfd. Co., Ltd., molecular weight 25000) -hydrochloric acid (0.1N) / isopropyl alcohol = 1/1
(Weight ratio)

(Mixing and Preparation of Coating Agent) The above polyacrylic acid (PAA) aqueous solution and a mixed solution of hydrochloric acid (0.1N) / isopropyl alcohol = 1/1 were mixed, and then the mixed solution was mixed with a metal alkoxide. Was added to the above tetraethoxysilane (TEOS) and stirred for 30 minutes for hydrolysis. However, the amount of hydrochloric acid (0.1N) added to TEOS was set so that the molar ratio of TEOS to be mixed and the water component in hydrochloric acid was 1:16.

Subsequently, the hydrolyzed mixed solution was diluted with water so that the total solid content (total solid content of PAA and TEOS) of the solution was 5% by weight based on 100% by weight of the entire mixed solution. did.

Then, the diluted mixture is diluted with water / methanol alcohol = 95/5 (weight ratio) of the polyvinyl alcohol as a water-soluble polymer having a hydroxyl group to obtain a total solid content (PAA and PAA) of the mixture. The mixture was mixed with an aqueous polyvinyl alcohol solution prepared so that the total solid content of TEOS and PVA was 5% by weight with respect to 100% by weight of the entire mixture, and the mixture was stirred for 30 minutes to obtain a coating agent for forming a gas barrier film. .

A: SiO ₂ solid content (converted value) of TEOS, B: PVA solid content, C: PAA solid content, and the mixing ratio (solid content weight ratio) of A, B and C is adjusted. Using the prepared coating agent, gas barrier film laminates were prepared based on the following Examples 1 to 5.

Example 1 A corona-treated polyethylene terephthalate (PET) film having a thickness of 12 μm was used as a substrate 1, and the composition ratio of the coating agent was A / B on the upper surface of the substrate 1. = 60/40 A / C = 100/20, the coating agent for the gas barrier film is applied by a bar coater and dried in an oven at 200 ° C. for 2 minutes to form a gas barrier having a film thickness of about 0.5 μm. The gas barrier film laminated body of Example 1 was obtained by forming the hydrophilic coating layer 2.

<Example 2> The above was used except that the coating agent for gas barrier film was prepared by setting the compounding ratio of the coating agent to A / B = 60/40 A / C = 100/10. In the same manner as in Example 1, a gas barrier film laminate of Example 2 was obtained.

Example 3 The above was used except that the coating agent for gas barrier coating was prepared by setting the compounding ratio of the coating agent to A / B = 60/40 A / C = 100/5. A gas barrier film laminate of Example 3 was obtained in the same manner as in Example 1.

<Example 4> The above was used except that the coating agent for gas barrier film was prepared by setting the compounding ratio of the coating agent to A / B = 60/40 A / C = 100/2. In the same manner as in Example 1, a gas barrier film laminate of Example 4 was obtained.

<Example 5> The above-mentioned conditions were used except that the gas-barrier coating agent prepared by setting the compounding ratio of the coating agent to A / B = 40/60 A / C = 100/5. In the same manner as in Example 1, a gas barrier film laminate of Example 4 was obtained.

Example 6 A corona-treated polyethylene terephthalate (PET) film having a thickness of 12 μm was used as the base material 1, and the composition ratio of the coating agent on the top surface of the base material 1 was changed to the above-mentioned embodiment. In the same manner as in 2, the coating agent for the gas barrier film prepared by setting A / B = 60/40 A / C = 100/20 is applied by a bar coater, and dried in an oven at 240 ° C. for 2 minutes, A gas barrier coating layer 2 having a film thickness of about 0.5 μm was formed.

Subsequently, an unstretched polypropylene film having a thickness of 70 μm was laminated on the upper surface of the gas barrier coating layer 2 by a laminating machine using a urethane adhesive (A515 / A50 manufactured by Takeda Pharmaceutical Co., Ltd.),
A gas barrier film laminate of Example 6 was obtained.

<Example 7> The coating composition for the gas barrier film was prepared by setting the compounding ratio of the coating agent to A / B = 60/40 A / C = 100/5 in the same manner as in Example 3 above. Was prepared in the same manner as in Example 6 except that the agent was used,
A gas barrier film laminate of Example 7 was obtained.

Comparative Example 1 A coating agent prepared without mixing polyacrylic acid (PAA) by setting the compounding ratio of the coating agent to A / B = 60/40 A / C = 100/0. A gas barrier film laminate of Comparative Example 1 was obtained in the same manner as in Example 3 except that was used.

Comparative Example 2 The composition ratio of the coating agent was set to A / B = 0/40 A / C = 0/5 B / C = 40/5, and tetraethoxysilane (TEOS) of metal alkoxide was used. A gas barrier film laminate of Comparative Example 2 was obtained in the same manner as in Example 3 except that the coating agent prepared without mixing the above) was used.

<Comparative Example 3> The composition ratio of the coating agent is set to A / B = 60/0 A / C = 100/5, and polyvinyl alcohol (PVA) which is a water-soluble polymer having a hydroxyl group is mixed. A gas barrier film laminate of Comparative Example 3 was obtained in the same manner as in Example 3 except that the coating agent prepared without the above was used.

<Comparative Example 4> The compounding ratio of the coating agent was A / B = 60/40 A /, as in Comparative Example 1 above.
Gas barrier film laminate of Comparative Example 4 prepared in the same manner as in Example 6 except that C = 100/0 was used and the coating agent prepared without mixing polyacrylic acid (PAA) was used. Got

Comparative Example 5 The composition ratio of the coating agent was set to A / B = 0/40 A / C = 0/5 B / C = 40/5 as in Comparative Example 2 above. A gas barrier film laminate of Comparative Example 5 was prepared in the same manner as in Example 6 except that the coating agent prepared without mixing the metal alkoxide tetraethoxysilane (TEOS) was used.

<Comparative Example 6> The composition ratio of the coating agent was set to A / B = 60/0 A / C = 100/5 in the same manner as in Comparative Example 3, and the water-soluble polymer having a hydroxyl group was used. A gas barrier film laminate of Comparative Example 6 was obtained in the same manner as in Example 6 except that the coating agent prepared without mixing the polyvinyl alcohol (PVA) was used.

<Comparative Measurement 1> The oxygen permeability of each of the gas barrier film laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was measured by an oxygen permeability measuring device (OXTRAN-10 manufactured by Modern Control Co., Ltd.). / 50A) at 30 ° C
The measurement was performed in an atmosphere of 100% relative humidity.

On the surface of the gas barrier coating layer of each gas barrier film laminate used in the measurement, 3 with an oil-based pen (black).
A square of 3 cm × 3 cm was written and filled in, fixed with the surface of the coating layer facing upward, and then retort-treated at 121 ° C. for 30 minutes. The state of the oil-based pen (black) on the surface of the coating layer after the treatment was visually observed to evaluate the water resistance of the coating. The results of the comparative measurement 1 are shown in Table 1 below.

(Water resistance evaluation of gas barrier coating layer) 1: The coating melted and no ink remained 2: Some ink remains 3: Ink remains in perfect condition

[0073]

[Table 1]

<Comparison Result by Comparison Measurement 1> Comparison Measurement 1
As a result, as shown in Table 1, the laminates of Examples 1 to 5 showed low oxygen permeability. Also, in the water resistance evaluation, the gas barrier coating layer was not melted and showed high water resistance. On the other hand, in the laminate of Comparative Example 1 in which polyacrylic acid (PAA) was not mixed, the oxygen permeability was low at 0.77, but the water resistance was low at evaluation 1, and the gas barrier coating layer was dissolved after the retort treatment. Oops. The laminate of Comparative Example 2 in which the metal alkoxide tetraethoxysilane (TEOS) was not mixed had a high oxygen permeability of 32.5 and a low gas barrier property. Furthermore, in the laminate of Comparative Example 3 in which the water-soluble polymer PVA having a hydroxyl group was not mixed, a film was not formed because the gas barrier coating layer had no film-forming property,
The gas barrier property was low.

<Comparative Measurement 2> The gas barrier film laminates obtained in Examples 6 to 7 and Comparative Examples 4 to 6 were retort treated at 121 ° C. for 30 minutes, and the oxygen permeability after the retort treatment was measured. 3 using an oxygen permeability measuring device (Modern Control Co., OXTRAN-10 / 50A)
It was measured in an atmosphere of 0 ° C. and 100% relative humidity. Also,
1 of the unstretched polypropylene film laminated on the upper surface of the gas barrier coating layer of each gas barrier film laminate
90 mm from the coating layer of the film, cut in 5 mm width
Degree peeling test was performed using a tensile tester (Tensilon, manufactured by Orientec Co., Ltd.), and the peeling strength (strength required for peeling, force, laminate strength) at that time was determined. The peeling test was carried out at a peeling speed of 300 mm / min, 23 ° C. and a relative humidity of 65.
% Atmosphere. The results of the comparative measurement 2 are shown in Table 2 below.

[0076]

[Table 2]

<Comparison result by comparison measurement 2> Comparison measurement 2
As a result, as shown in Table 2, it was revealed that the laminates of Examples 6 to 7 showed low oxygen permeability even after the retort treatment, maintained high laminate strength, and had retort resistance. On the other hand, the laminates of Comparative Examples 4 to 6 showed high oxygen permeability and low laminate strength after being subjected to the retort treatment, and were found to have no retort resistance.

[0078]

As described above, the gas barrier film laminate of the present invention is a barrier film having high oxygen barrier properties and good adhesion, and using the gas barrier film laminate of the present invention, By performing post-processing such as printing, dry lamination, melt extrusion lamination, thermocompression lamination, etc., we provide packaging materials with a wide range of practical use for packaging foods and retort foods, or non-foods such as pharmaceuticals and electronic components. It is possible to do

[Brief description of drawings]

FIG. 1 is a side sectional view illustrating an example of a gas barrier film laminate of the present invention.

[Explanation of symbols]

1 ... Substrate 2 ... Gas barrier coating layer

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 3/10 C09K 3/10 EG Z // C08L 101: 00 C08L 101: 00 (72) Inventor Takeshi Kanetaka Tokyo capital Taito Taito 1-chome fifth No. 1 Toppan printing Co., Ltd. in the F-term (reference) 4D075 AE19 AE24 BB24Z BB26Z BB93Z CA03 CA13 CA38 CA42 CB06 DA04 DB36 DB37 DB48 DB53 DC36 EA07 EB07 EB13 EB19 EB20 EB22 EB35 EB38 EB43 EB47 EB56 4F006 AA12 AA15 AA35 AA38 AB24 AB64 BA05 CA07 DA04 EA05 4F100 AH08B AK01A AK01B AK21B AK25B AL05B AT00A BA02 BA03 BA07 BA10A BA10C GB15 GB23 JB09B JD02B JL12C JN01 YY00B 4H017 AD06 AC05 AB01 AB01 AB01 AB04 AB01 AB01

Claims (8)

[Claims] 1. A gas-barrier coating layer in which one or more metal alkoxides or hydrolysates thereof and a water-soluble polymer having a hydroxyl group and poly (meth) acrylic acid are mixed on one or both sides of a substrate made of a plastic material. A gas barrier film laminate, wherein the gas barrier film laminate is formed. 2. The gas barrier film laminate according to claim 1, wherein the metal alkoxide is tetraethoxysilane. 3. The gas barrier film laminate according to claim 1 or 2, wherein the water-soluble polymer having a hydroxyl group is polyvinyl alcohol. 4. When the addition amount (weight ratio) of the poly (meth) acrylic acid is calculated by converting a metal alkoxide or a hydrolyzate of the metal alkoxide into a metal oxide, poly (meth) is based on 100 metal oxides. 1 to 20 acrylic acid
The gas barrier film laminate according to any one of claims 1 to 3, wherein 5. The gas barrier film laminate according to any one of claims 1 to 4, wherein a heat seal layer is provided on the gas barrier coating layer side. 6. A coating agent obtained by mixing one or more metal alkoxides or hydrolysates thereof with a water-soluble polymer having a hydroxyl group and poly (meth) acrylic acid on one or both sides of a substrate made of a plastic material. A method for producing a gas barrier film laminate, which comprises: 7. The method for producing a gas barrier film laminate according to claim 6, wherein the heat drying is performed at a high temperature of 200 ° C. or higher. 8. The method according to claim 6, wherein the added amount (weight ratio) of the poly (meth) acrylic acid is 0.5 to 20 with respect to 100 of the solid content in all the coating agents. 7. The method for producing the gas barrier film laminate according to 7.