JP2003266461A - Method for manufacturing molding body, molded body and use application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a molding body representing remarkably excellent barrier properties, especially barrier properties excellent under highly humid environments, a molded body by employing the manufacturing method and its use application. <P>SOLUTION: A resin composition made of a PVA-based polymer and an inorganic laminar compound is molded with an electrical field impressed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl alcohol polymer (hereinafter sometimes abbreviated as PVA polymer).
The present invention relates to a method for producing a molded article having excellent barrier properties by treating a resin composition comprising an inorganic layered compound under specific conditions, a molded article obtained by the production method, and its use.

[0002]

2. Description of the Related Art Although the functions required of packaging materials are diverse, the barrier property against various gases (gas barrier property) is an important function that determines the storability of packaged contents. The gas barrier property is becoming more and more important due to the diversification of packaging technology, the regulation of additives and the change of taste. The deterioration factors of the packaged contents, particularly the food, include oxygen, light, heat, moisture, etc. Among them, oxygen is the main deterioration factor. In addition, barrier materials having barrier properties against not only oxygen gas but also various gases, organic solvent vapors, fragrances, etc. are effective for rust prevention, deodorization, and sublimation prevention, and are useful in many fields such as food, cosmetics, agricultural chemicals, and medical treatment. Are used in confectionery bags, skipjack packs, retort pouches, carbon dioxide beverage containers, and the like. However, the gas barrier properties of resins generally used for packaging materials are low, and the performance as a barrier material used for the above purpose was not sufficient.

On the other hand, a technique for dispersing a filler, particularly a layered inorganic compound in a resin for the purpose of improving the gas barrier property of the resin is widely known, and is disclosed in, for example, JP-A-64-43554. Is a saponified ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVOH)
Describes a method of dispersing mica and talc.
However, the resin composition obtained by such a method has a drawback that the dispersibility of the inorganic layered compound in the resin is poor and the transparency of the resin is significantly deteriorated.

In order to overcome this drawback, various attempts have been made to use an inorganic layered compound such as a layered silicate having a property of swelling or cleaving in a dispersion medium, particularly in water, as an inorganic layered compound. As a method for dispersing an inorganic layered compound in a polyamide, JP-A-62-74957 discloses a method of swelling an inorganic layered compound with a monomer and then polymerizing the monomer. Also, EVOH
As a method of dispersing the inorganic layered compound in the composition
In 39392, JP-A-5-86241, and JP-A-6-57066, an inorganic layered compound is mixed and dispersed in EVOH in a state where it is swollen and cleaved in an aqueous solvent (water-methanol solvent). The method is shown.
However, the method of polymerizing after swelling the inorganic layered compound with a monomer of polyamide is a very excellent method in improving the dispersibility of the inorganic layered compound, on the other hand, in the method, the viscosity is obtained by dispersing the inorganic layered compound. Therefore, it is practically limited to those containing an extremely low concentration of the inorganic layered compound. In addition, since the polyamide itself is not so excellent in the barrier property, the polyamide-based barrier material obtained by dispersing the inorganic layered compound by the method has a problem that the barrier property is inferior to that of EVOH alone. There is. In addition, when the inorganic layered compound is swollen and cleaved in an aqueous solvent, E
Regarding the method of mixing and dispersing in VOH, it is very difficult to secure sufficient dispersibility and it is difficult to stably exhibit the performance when montmorillonite or the like which has been conventionally used as an inorganic layered compound is used. I have a problem.

In addition to the above, Japanese Unexamined Patent Publication No. 7-70357 discloses a method of compounding a hydrophobic resin with an inorganic layered compound having a specific particle size and an aspect ratio.
Since the hydrophobic resin itself is not so excellent in the barrier property, there is a problem that the barrier property of the composite obtained by the method is still insufficient. Furthermore, as a method of improving the barrier properties of a resin by compounding a water-soluble resin such as a PVA-based polymer with an inorganic layered compound, a method of applying the compound to a film having a specific surface composition (JP-A-9- 1
11017) and a method using a specific inorganic layered compound (JP 2001-105543 A, JP 2001-114966 A, JP 2001-214 A).
No. 020) has been proposed. However, although the barrier property of the resin is improved by this method, the barrier property may be insufficient unless heat treatment at high temperature is performed, and a material that is easy to manufacture and has a high gas barrier property is desired. .

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and uses a method for producing a molded article having remarkably excellent barrier properties, particularly excellent barrier properties in a high-humidity environment, and a method for producing the same. The object of the present invention is to provide a molded product obtained by the method and its use.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly found that an electric field is applied to a resin composition comprising a PVA polymer and an inorganic layered compound. It was found that by molding the resin composition in an applied state, a molded article having remarkably excellent barrier properties, particularly excellent barrier properties in a high humidity environment, can be obtained, and the object of the present invention can be achieved. Has reached the present invention.

That is, the first invention of the present invention is a molded article characterized by molding a resin composition comprising the PVA-based polymer (A) and the inorganic layered compound (B) in a state where an electric field is applied. It is a manufacturing method.

The second invention of the present invention is a molded product obtained by the above-mentioned manufacturing method.

Further, a third invention of the present invention is a film, a laminate and a container having at least one layer consisting of the molded product obtained by the above-mentioned production method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The PVA-based polymer (A) used in the present invention is
It refers to a polymer obtained by saponifying a polymer containing 40 mol% or more of vinyl ester units represented by vinyl acetate as a constituent of the main chain. In this case, a vinyl ester other than vinyl acetate, for example, a vinyl ester such as vinyl propionate or vinyl pivalate may be used in place of vinyl acetate.

Further, the degree of saponification of the PVA-based polymer (A) in the present invention allows the resin composition comprising the PVA-based polymer (A) and the inorganic layered compound (B) to exhibit a higher barrier property. The molar ratio of the saponified ester group to the ester group existing before saponification is preferably 90% or more, more preferably 95% or more, still more preferably 97% or more, most preferably 98% or more.

Other than the vinyl ester, examples of the comonomer component used in an amount of 60 mol% or less include various compounds having a double bond in the molecule such as ethylene, propylene, butylene and unsaturated carboxylic acid. Of these, α-olefins having 4 or less carbon atoms are preferable, and PVA
Ethylene is particularly preferably used because it improves the moisture resistance and moldability of the resin composition comprising the polymer (A) and the inorganic layered compound (B) and gives a resin composition having excellent properties. PVA-based polymers obtained by copolymerizing ethylene in the range of 0.5 to 60 mol% are preferable because they stably exhibit good barrier properties in a wide humidity range, and ethylene in the range of 3 to 5 is preferable.
A PVA-based polymer copolymerized in the range of 0 mol% is more preferable, and since it can be used by dissolving it in a solvent mainly composed of water, a PVA-based polymer in which ethylene is copolymerized in the range of 4.5 to 15 mol%. Most preferred are polymers.

Further, in the present invention, another kind of polymer,
For example, polyamide, polyester, polyethylene, polypropylene, a copolymer of ethylene and propylene, polystyrene, polyisoprene, polymethylmethacrylate, polyethylene glycol and the like may be blended with the PVA polymer (A) within a range not hindering the object of the present invention. it can.

The viscosity average degree of polymerization (hereinafter abbreviated as the degree of polymerization) of the PVA-based polymer (A) in the present invention is not particularly limited, but a resin composition comprising the PVA-based polymer (A) is used. From the viewpoint of mechanical properties and workability in molding the composition, the degree of polymerization after saponification is 200 to 240.
The range of 0 is preferable, the range of 300 to 2000 is more preferable, and the range of 400 to 1500 is most preferable.

When the PVA polymer (A) is water-soluble, its polymerization degree P is measured according to JIS-K6726.
That is, after re-saponifying and purifying the PVA-based polymer,
It is determined by the following formula from the intrinsic viscosity [η] measured in water at 30 ° C. P = ([η] × 10 ³ /8.29) ^{(1 / 0.62)}

The PVA polymer (A) in the present invention is
It is preferable to contain an alkali metal. The content ratio of the alkali metal based on 100 parts by weight of the PVA polymer (A) is 0.0003 in terms of sodium of the alkali metal.
1 part by weight, preferably 0.0003 to 0.8 part by weight, more preferably 0.0005 to 0.6 part by weight, and 0.1.
001-0.5 weight part is especially preferable. Examples of the alkali metal include potassium and sodium,
They exist mainly as salts of lower fatty acids such as acetic acid and propionic acid. In addition, the alkali metal is PV
Also included are the alkali metals present in the additives of the A-based polymer (A). When the content ratio of the alkali metal to 100 parts by weight of the PVA polymer (A) is less than 0.0003 parts by weight, the water solubility of the PVA polymer (A) when used as an aqueous solution Tends to decrease.
On the other hand, if the amount exceeds 1 part by weight, the crystallinity of the PVA-based polymer may be lowered, and the molded article obtained by the production method of the present invention tends to be lowered in the barrier property against gas and water vapor.

Next, the inorganic layered compound (B) used in the present invention will be described. The inorganic layered compound (B) is an inorganic compound having a structure in which sheets, in which atoms are strongly bonded by covalent bonds or the like and are densely arranged, are stacked substantially in parallel by a weak force such as van der Waals force or electrostatic force. . Examples of the inorganic layered compound include mica, talc, montmorillonite, smectite, kaolinite, vermiculite, and the like.
These may be naturally produced or synthetic.

Among these inorganic layered compounds, those capable of swelling or cleaving by being immersed in an organic solvent or an inorganic solvent (collectively referred to as swellable inorganic compounds in the present specification) have excellent barrier properties and water resistance. It is preferably used for expressing Here, swelling means that when the inorganic layered compound is dipped in a large excess of an organic solvent or an inorganic solvent, the distance between layers as seen by an X-ray diffraction method is widened, and cleaving is a case where the same operation is performed. , The peak showing the distance between layers is
It is one that behaves as it becomes smaller or disappears. Examples of the swelling inorganic compound include vermiculite, montmorillonite, smectite, swelling synthetic fluoromica-based minerals in which lithium, sodium and the like are intercalated between layers. In addition, when mixed with a water-soluble resin, among such swellable inorganic compounds, a swellable inorganic compound having a property of swelling or cleaving with water (hereinafter referred to as water swelling property) is most preferably used. Examples of such water-swellable inorganic compounds include water-swellable vermiculite, water-swellable montmorillonite, water-swellable synthetic fluoromica minerals, and water-swellable synthetic smectites.

The water-swellable montmorillonite used in the present invention has 0.15 sodium atoms per 4 Si atoms.
Or more, preferably 0.2 or more, more preferably 0.
The ratio is 25 or more, and optimally 0.3 or more. Such montmorillonite can be obtained, for example, by dispersing the raw material montmorillonite in an aqueous solution of sodium oxalate, sodium carbonate, etc., collecting only the supernatant of the dispersion, and drying.

The swellable fluoromica-based mineral used in the present invention is typically obtained by heat-treating a mixture of talc and sodium and / or lithium silicofluoride or fluoride. As a specific method thereof, for example, the method disclosed in Japanese Patent Laid-Open No. 2-149415 can be mentioned. That is, it is a method in which talc is used as a starting material and sodium ions and / or lithium ions are intercalated into the starting material to obtain a swellable fluoromica-based mineral. In this method, a swellable fluoromica-based mineral is obtained by mixing talc with sodium and / or lithium silicofluoride or fluoride and heat-treating in a magnetic crucible at about 700 to 1200 ° C for a short time. As the swellable fluoromica-based mineral used in the present invention, those produced by this method are particularly preferable.

Further, in the present invention, the addition of a crosslinking agent to the PVA polymer (A) also has favorable results such as improvement in water resistance and mechanical properties of the molded article obtained by the production method of the present invention. It is preferably performed because it can be obtained. As such a cross-linking agent, any known cross-linking agent used for PVA-based polymers is preferably used, and a boron compound such as boric acid, a zirconium salt, a titanium compound such as titanium tetralactate, an epoxy group and / or Examples thereof include compounds having a plurality of isocyanate groups. The cross-linking agent is added to the resin or the resin solution in the saponification step before saponification of the vinyl ester polymer and the saponification step of the PVA polymer, or to the inorganic layered compound or its dispersion. , PVA-based polymer and inorganic layered compound are added at the time of mixing in an extruder, and are used at any process step in the production process of the resin composition comprising the PVA-based polymer and the inorganic layered compound. In addition, the cross-linking agent can be used in any process step in the manufacturing process of the film, the laminate and the container, such as coating and impregnating the film, the laminate and the container after molding.

The compounding amount of the inorganic layered compound (B) with respect to the PVA polymer (A) in the present invention is not particularly limited, but is 0.01 to 100 relative to 100 parts by weight of the PVA polymer (A). Part by weight is preferred, 0.5-8
0 parts by weight is more preferable, 1 to 70 parts by weight is further preferable, and 3 to 50 parts by weight is particularly preferable. If the amount is less than 0.01 part by weight, the effect of improving the barrier property which is the object of the present invention is not sufficient, and if it exceeds 100 parts by weight, a resin composition comprising the PVA polymer (A) and the inorganic layered compound (B). Because the toughness of the resin composition is large, the viscosity of the solution or dispersion of the resin composition becomes large, film formation becomes difficult, and pinholes are easily generated in the molded product of the resin composition. Not preferable.

In the present invention, as a method for producing a resin composition comprising a PVA polymer (A) and an inorganic layered compound (B) and a solution or dispersion thereof, a known method is to disperse an inorganic compound in a PVA polymer. Any of the above methods can be applied. For example, after polymerizing a vinyl ester-based monomer and optionally other monomers, the inorganic layered compound (B) is added, and then saponification, concentration and drying are carried out to produce PV.
Method for obtaining a resin composition comprising A-based polymer (A) and inorganic layered compound (B), or supplying saponified PVA-based polymer (A) and inorganic layered compound (B) to an extruder all at once Then, the inorganic layered compound (B) is dispersed in the PVA-based polymer (A) by the shearing force of the extruder to obtain a resin composition, and further, the solvent and the PVA-based polymer (A).
And a method in which the inorganic layered compound (B) is collectively charged and kneaded with a homogenizer to obtain a solution or dispersion of the resin composition.

In the present invention, the PVA polymer (A)
It is an essential condition that the resin composition comprising the inorganic layered compound (B) is molded while the electric field is applied. As a method of molding the resin composition in a state where an electric field is applied to the resin composition, the electrodes and the resin composition are arranged so that the resin composition exists between one or more electrodes, and the resin composition is Any known method such as applying an electric field to the resin composition by energizing the electrodes in a fluid state can be applied. At this time, it is preferable that the resin composition comprising the PVA-based polymer (A) and the inorganic layered compound (B) is in a solution or dispersion state from the viewpoint of enhancing the effect of the present invention. As the solvent of the solution or the dispersion medium of the dispersion, water, an organic solvent, a mixed solvent of water and an organic solvent, or the like is used.

As a method of applying an electric field to the resin composition when the resin composition is molded, for example, a device composed of a moving belt and electrodes arranged so as to sandwich the belt surface, or the moving belt itself. Is the electrode,
Using an apparatus in which electrodes are arranged so as to face the belt surface, a casting method, a dipping method, a gravure coating method, a resin composition or a solution or dispersion of the resin composition on the belt surface,
Examples thereof include a method of applying by a blade coating method, a calendar coating method, a spray coating method and the like, and applying an electric field. In the above method, a rotating roll may be used instead of the moving belt. Further, in the case of producing a molded article by removing the solvent or dispersion medium after applying the solution or dispersion liquid of the resin composition, or after pouring the solution or dispersion liquid of the resin composition into the mold, the solvent or dispersion medium In the case of producing a molded product by removing it, a drying device in which electrodes are arranged so that an electric field can be applied inside is used, and an electric field is applied while the solution or dispersion liquid of the resin composition has fluidity. It is also possible to perform drying while applying.

The electric field applied to the resin composition comprising the vinyl alcohol polymer (A) and the inorganic layered compound (B) is not particularly limited, but 0.01 V / cm to 1
A DC electric field of 000 V / cm is preferred, and 0.05 V / c
A DC electric field of m to 800 V / cm is more preferable, and 0.1
A DC electric field of V / cm to 500 V / cm is more preferable, and a DC electric field of 0.3 V / cm to 300 V / cm is particularly preferable. When the electric field applied to the resin composition is out of the above range, the effect of improving the barrier property is small. The application of the electric field can be adjusted by the applied voltage and the distance between the electrodes.

The molded product obtained by the production method of the present invention is used as it is, or after undergoing various molding processing steps, as a film, a laminate and a container having a barrier property. The molded product obtained by the production method of the present invention is used as it is as a single-layer molded product, and is separately provided for imparting functions such as heat welding, protecting against mechanical action from the outside, and improving handleability. It is used as a film, a laminate and a container having at least one layer consisting of the molded product obtained by the production method of the present invention by laminating the film and other materials such as paper. Further, it is also preferable to provide a printing layer on the molded article for improving the design.

In the present invention, the substrate used for the film, laminate and container is not particularly limited, but is a polyolefin resin such as polyethylene or polypropylene; polyethylene terephthalate (hereinafter sometimes abbreviated as PET), polyethylene. Polyester resins represented by isophthalate, polyethylene 2,6-naphthalate, polybutylene terephthalate and their copolymers; polyether resins represented by polyoxymethylene; nylon-6, nylon-6,6, Polyamide-based resin typified by polymethaxylene adipamide; polystyrene, poly (meth) acrylic acid ester,
Vinyl-based resins other than polyolefin-based resins typified by polyacrylonitrile, polyvinyl acetate, and copolymers thereof; polycarbonate-based resins; cellulosic resins typified by cellophane, acetate, etc .; and further polyimide, polyetherimide, polyphenylene Examples of the molded article include a simple substance, a copolymer, a mixture or a complex of various resins such as sulfide, polyether sulfone, polysulfone, polyether ketone, and a fluorine-containing polymer.

The substrate used for the film, laminate and container in the present invention is an unstretched film made of a simple substance, a copolymer, a mixture or a complex of the various resins described above, or a uniaxial direction or an orthogonal direction. An oriented film stretched in the biaxial direction is preferably used. Among them, biaxially stretched films of polypropylene, polyester, polyamide and the like are preferable in terms of heat-resistant dimensional stability and mechanical strength, as well as moldability and economic efficiency, and further, transparency, heat resistance and mechanical strength. From this point, a polyester film containing polyethylene terephthalate as a main component is particularly preferable.

The thickness of the above-mentioned film is not particularly limited, but is usually 1 to 250 μm, and is 3 as a packaging material.
It is particularly preferable that the thickness is ˜50 μm. Further, the base film may be a simple substance or a composite multilayer film, and the composite method and the number of layers in the multilayer film are arbitrary.

Further, the film having at least one layer of the molded product obtained by the production method of the present invention can be improved in various properties such as its barrier property and mechanical strength by adding a stretching operation. Examples of the stretching operation include uniaxial stretching, sequential or simultaneous biaxial stretching, and the like. The stretching ratio in such stretching operation depends on the blending ratio of the PVA-based polymer and the inorganic layered compound in the molded product, but is 1.1 to 12 times the film area after stretching with respect to the film area before stretching, Preferably 1.2
10 times is recommended.

Paper is also included in the laminate having at least one layer of the molded product obtained by the production method of the present invention. When the laminate having at least one layer of the molded body obtained by the production method of the present invention is paper, the base paper used as the base material is not particularly limited, and depending on the purpose, it is possible to use materials that are generally paper. Both can be preferably used. It is preferable to use glassine paper and semi-glassine paper as the base paper which is the base material, because it exhibits high barrier properties and recyclability even when the layer formed of the molded product obtained by the production method of the present invention is thin. The thickness of the base paper for a base material is not particularly limited, and may be appropriately selected in the range of 0.1 to 1000 μm, preferably 1 to 500 μm, and most preferably 3 to 300 μm as necessary.

Further, various materials conventionally used by being laminated on paper can be further laminated on the above-mentioned paper to be used as processed paper. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, etc. may be used to impart heat sealability to the above paper, and thermosetting resin or biaxially stretched PET may be used to impart scratch resistance.
A polyamide or the like can be laminated to impart pinhole resistance, and a water-soluble polymer compound can be laminated to impart water sticking property. In addition, polypropylene or vapor-deposited PE can be used to impart high moisture resistance.
It is effective to stack T and the like. Furthermore, it is also preferable to provide a plurality of the above layers, if necessary.

In the above various films and laminates, the thickness of the layer formed of the molded product obtained by the production method of the present invention is not particularly limited, but the average thickness is 0.1 to 0.1.
100 μm is preferable, 0.3 to 50 μm is preferable,
0.5 to 30 μm is particularly preferable. If the thickness is 0.1 μm or less, the barrier property may be insufficient even in a film or laminate having a layer formed of the molded product obtained by the production method of the present invention, and if it exceeds 100 μm, the elastic modulus becomes high, The handleability of the laminate is poor.

In producing a film, a laminate and a container having at least one layer of the molded article obtained by the production method of the present invention, when the molded article obtained by the production method of the present invention is laminated on a substrate. A known method for improving the adhesiveness to the substrate is appropriately adopted, such as corona treatment or other surface activation treatment on the substrate, or anchor treatment using a known anchor treatment agent.

When a container is manufactured by molding a paper having at least one layer of the molded body obtained by the manufacturing method of the present invention, the final shape of the paper container is not particularly limited, and various existing forms can be used. , For example, gable top containers, pillow bags,
Standing pouches, paper drums, boxes, trays, etc. are exemplified. In this case, the entire container does not have to be a container using a paper having at least one layer of the molded body obtained by the production method of the present invention, and the contents can be visually confirmed or the design is improved. For various reasons, for example, other materials may be partially used.

[0038]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In the text,% means% by weight unless otherwise specified, and each property was measured by the following method. The resins and the inorganic layered compounds in the following examples were vacuum dried at 80 ° C. for 12 hours or more and used, unless otherwise specified.

[Oxygen permeability] MODERN CONTR
OLS INC. Oxygen transmission rate measuring device MOCONOX
-TRAN2 / 20 type was used according to the method described in JIS K7126 (isobaric method) under the conditions of 20 ° C and 85% RH. In the present invention, the oxygen permeability of the film is the amount of oxygen permeation (ml / m ² · day · atm) measured at an arbitrary film thickness for a film composed of a single layer
Is converted to the amount of oxygen permeation at a film thickness of 1 μm (ml ・ μ
m / m ² · day · atm). In the case of laminated paper, the amount of oxygen permeation measured with the laminated paper (ml /
m ² · day · atm), and in the case of a container, it is represented by the amount of oxygen permeation per container (ml / container · day · atm) measured in the form of the sample container.

[Bending Resistance Test] Using a Gelbo flex tester (manufactured by Rigaku Kogyo Co., Ltd.), a test piece of 12 inches × 8 inches was formed into a cylindrical shape having a diameter of 3.5 inches, and both ends were gripped to obtain an initial state. Gripping interval 7 inches, gripping interval 1 at maximum bending
Inch, the first 3.5 inch of the stroke adds a twist of 440 degrees, and the subsequent 2.5 inch is a reciprocating reciprocating motion of linear horizontal motion at a speed of 40 times / minute,
After repeating this reciprocating motion 100 times under the conditions of 20 ° C. and 65% RH, the oxygen permeability was measured.

[Haze] A part of the sample film was cut off, silicone oil was applied, and the haze value was measured according to ASTM D1003-6 using HR-100 manufactured by Murakami Color Research Laboratory.

Example 1 1) Preparation of resin solution Ethylene-containing PVA (PVA-1) having a saponification degree of 99.0 mol%, ethylene content of 8 mol%, polymerization degree of 580, and sodium content of 0.05% was dissolved in warm water. Then, a 15% solution was prepared. This is called resin solution A.

2) Preparation of Inorganic Layered Compound Dispersion As an inorganic layered compound (B), a swellable fluoromica-based mineral (manufactured by Coop Chemical Co .; Somasif ME-100)
Was dispersed in water to have a concentration of 6% and stirred for 30 minutes using a household mixer to prepare an inorganic layered compound dispersion. This is referred to as an inorganic layered compound dispersion liquid B.

3) Preparation of coat film 100 parts by weight of resin solution A and inorganic layered compound dispersion B3
7.5 parts by weight and 35 parts by weight of water were mixed, and stirred for 3 minutes using a household mixer to prepare a coating liquid having a solid content concentration of 10%. The weight ratio of the PVA polymer (A) to the inorganic layered compound (B) in the coating liquid is 100/15. OPP film (manufactured by Tokyo Cellophane Paper Co., Ltd .; film thickness 2)
(0 μm) on the primer-treated surface of urethane anchor coating agent (manufactured by Toyo Morton Co., Ltd .; AD335A / CAT1)
The coating liquid was coated on the coating liquid of (0) using a bar coater, the distance between electrodes was 1 cm, and the applied voltage was 20 cm.
After passing through the DC electric field application zone set to V, it was immediately dried at 70 ° C. for 5 minutes. Then, heat treatment was performed at 100 ° C. for 2 minutes to obtain a coated film. The thickness of the coat layer of the obtained film was 5.7 μm.

4) Measurement The oxygen permeability of the film obtained above was measured and found to be 2.7 ml · μm / m ² · day · atm and the internal haze was 2.3%. The oxygen permeability after the bending resistance test was 2.8 ml · μm / m ² · day · atm.

Example 2 A film was prepared in the same manner as in Example 1 except that the distance between the electrodes was changed to 4 cm, and various performances similar to those in Example 1 were measured. The measurement results are shown in Table 1.

Example 3 As a PVA-based polymer (A), an ethylene-containing PVA having a saponification degree of 98.9%, an ethylene content of 5.5 mol%, a polymerization degree of 1200 and a sodium content of 0.0015% (PVA-).
2), and using natural montmorillonite (Kunimine Industries Co., Ltd .; Kunipia F) shown in Table 1 as the inorganic layered compound (B), the weight ratio of the PVA polymer (A) and the inorganic layered compound (B). And the same test as in Example 1 was conducted except that the applied electric field was changed as shown in Table 1. The measurement results are shown in Table 1.

Example 4 PVA polymer (A) having a saponification degree of 99.8 mol%,
Ethylene-containing PVA with an ethylene content of 2.5 mol%, a degree of polymerization of 1800, and a sodium content of 0.005% (PVA-
3) is used as the inorganic layered compound (B), and a mixture of the swellable fluoromica-based mineral (Somasif ME-100) and natural montmorillonite (Kunipia F) shown in Table 1 (ME-100 / Kunipia F = 2 /) on a weight basis. Use 1),
The same test as in Example 1 was performed except that the weight ratio of the PVA polymer (A) and the inorganic layered compound (B) and the applied electric field were changed as shown in Table 1. The measurement results are shown in Table 1.

Example 5 PVA polymer (A) having a saponification degree of 97.8 mol%,
Ethylene-containing PVA with an ethylene content of 11.5 mol%, a degree of polymerization of 380, and a sodium content of 0.14% (PVA-
4) was used, and the same test as in Example 1 was performed except that the weight ratio of the PVA polymer (A) and the inorganic layered compound (B) and the applied electric field were changed as shown in Table 1. The measurement results are shown in Table 1.

Example 6 PVA polymer (A) solution as saponification degree 99.5 mol%, ethylene content 44 mol%, sodium content 0.0
An inorganic layered compound ((PVA-5, manufactured by Kuraray Co., Ltd .; Eval EP-E105) (03%) containing ethylene was dissolved in a water / n-propanol mixed solvent (n-propanol 70%) to prepare an inorganic layered compound ( As a dispersion of B), a water / n-propanol mixed solvent (n-propanol 70
%) Is used as a dispersion medium, and the weight ratio of the PVA polymer (A) and the inorganic layered compound (B) and the applied electric field are shown in Table 1 using a dispersion liquid of a swelling fluoromica-based mineral (Somasif ME-100). The same test as in Example 1 was performed except that the conditions were changed. The measurement results are shown in Table 1.

Example 7 PVA polymer (A) having a saponification degree of 98.6 mol%,
PVA with 550 degree of polymerization and 0.05% sodium content
(PVA-6) as an inorganic layered compound (B) as a synthetic smectite (manufactured by Kunimine Industry Co., Ltd .; Smecton S)
The same test as in Example 1 was conducted except that the weight ratio of the PVA polymer (A) and the inorganic layered compound (B) and the applied electric field were changed as shown in Table 1 using A). The measurement results are shown in Table 1.

Comparative Example 1 A film was prepared in the same manner as in Example 1 except that the applied voltage was changed to 0 V, and various performances similar to those in Example 1 were measured. The measurement results are shown in Table 1.

Comparative Examples 2 and 3 Films were prepared in the same manner as in Examples 3 and 7 except that the applied voltage was changed to 0 V, and various performances similar to those in Examples 3 and 7 were obtained. It was measured. Table 1 shows the measurement results
Shown in. When the electric field is not applied (Comparative Examples 1 to 3), the oxygen barrier property is largely reduced as compared with the case where the electric field of the present invention is applied (Example 1, Example 3 and Example 7). I understand.

Comparative Example 4 A film was prepared in the same manner as in Example 1 except that the swellable fluoromica mineral (Somasif ME-100) used as the inorganic layered compound (B) in Example 1 was not used. Various performances similar to 1 were measured. The measurement results are shown in Table 1.

Comparative Example 5 A film was prepared in the same manner as in Example 4 except that the inorganic layered compound (B) was not used, and various performances similar to those in Example 4 were measured. The measurement results are shown in Table 1.

Comparative Example 6 The same test as in Example 5 was carried out except that an inorganic non-layered compound, silica (Mizawa Chemical Co .; Mizukasil) was used instead of the swellable fluoromica-based mineral, which was an inorganic layered compound, as the inorganic compound. went. The measurement results are shown in Table 1. When the inorganic layered compound (B) was not used (Comparative Examples 4 to 6), the inorganic layered compound (B) of the present invention was used (Example 1, Example 4 and Example 5). It can be seen that the oxygen barrier property is significantly reduced in comparison.

Example 8 Rosin size (manufactured by Arakawa Kagaku Kogyo; Size Pine E (TM) as a sizing agent for absolutely dry pulp in 230 ml of Canadian Standard Freeness consisting of 80 parts of NBK and 20 parts of LBK )) 0.
After adding 4% and sulfuric acid band 2.4% and fixing, papermaking was carried out by a Fourdrinier paper machine to obtain a base paper having a basis weight of 200 g / m ² and a water content of 12%. The coating liquid used in Example 1 was coated on one side of the base paper using a bar coater, and the distance between the electrodes was 1 c.
Immediately after passing through a DC electric field application zone set to m and applied voltage of 20 V, it was immediately dried at 70 ° C. for 5 minutes. Then 7
After drying at 0 ° C for 5 minutes, heat treatment was performed at 100 ° C for 2 minutes to obtain a coated paper. At this time, the coating amount of the coating liquid was 3.8 g / m ² in terms of solid content. The oxygen permeability of this laminated paper was 1.3 ml / m ² · day · atm.

Comparative Example 7 Example 8 was repeated except that the applied voltage was changed to 0 V in Example 8.
2. Prepare coated paper in the same manner as above, and apply coating liquid 3.
8 g / m ² of laminated paper was obtained. The oxygen permeability measured in the same manner as in Example 8 was 6.4 ml / m ² · day · atm, and the oxygen barrier property was reduced to about 1/5 as compared with Example 8.

Example 9 A high density polyethylene (HDPE) film having a thickness of 60 μm was laminated on the coated surface of the laminated paper obtained in Example 8 using an isocyanate adhesive. The four sides of the paper are heat-sealed and the HDPE layer is the innermost layer 30 ×
A 30 cm rectangular container was obtained. The oxygen permeability of this container was measured to be 1.5 ml / container.da.
It was y • atm.

Comparative Example 8 A container was prepared in the same manner as in Example 9 except that the laminated paper obtained in Comparative Example 7 was used. Oxygen permeability of the container is 10 ml
/ Container · day · atm, and the oxygen barrier property was significantly inferior to the container of Example 9.

[0061]

[Table 1]

[0062]

According to the production method of the present invention, it is possible to obtain a molded article having excellent barrier properties against various substances represented by oxygen gas, especially in a high humidity environment. In addition, the film, laminate and container having at least one layer of the molded product obtained by the production method of the present invention have excellent flex resistance and excellent barrier properties in many fields such as foods, cosmetics, agricultural chemicals and medicine. It can be preferably used as a packaging material and a container, and can prevent alteration of the contents for a much longer period than conventional products.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B65D 65/40 BRH B65D 65/40 BRHD C08J 5/18 CEX C08J 5/18 CEX C08K 3/34 C08K 3 / 34 C08L 29/04 C08L 29/04 A // B29K 29:00 B29K 29:00 105: 06 105: 06 F term (reference) 3E086 AC22 AD01 AD02 AD05 AD08 BA02 BA04 BA14 BA24 BA33 BA35 BB01 BB05 BB22 BB85 CA01 CA28 CA29 DA08 4F071 AA15X AA20X AA21X AA29 AA29X AB30 AE17 AH05 BA06 BB02 BC02 BC04 4F100 AA01B AC05 AK01A AK07 AK21B AK69B AL05B AT00A BA02 DA01 GA02 DJ01 GA02B16A02B16A02B16A02B16A02B16A02B16A02B16A16B

Claims (8)

[Claims] 1. A method for producing a molded article, which comprises molding a resin composition comprising a vinyl alcohol polymer (A) and an inorganic layered compound (B) while applying an electric field. 2. The electric field applied to the resin composition comprising the vinyl alcohol polymer (A) and the inorganic layered compound (B) is a direct current electric field of 0.01 V / cm to 1000 V / cm. The method for producing the molded article according to claim 1. 3. The resin composition comprising the vinyl alcohol-based polymer (A) and the inorganic layered compound (B) applies an electric field in the state of a solution or dispersion. Molded body manufacturing method. 4. A molded body obtained by the manufacturing method according to claim 1. 5. The molded article according to claim 4, wherein the vinyl alcohol polymer (A) is a vinyl alcohol polymer containing 0.5 to 60 mol% of an α-olefin unit having 4 or less carbon atoms. 6. A film having at least one layer comprising the molded article according to claim 4 or 5. 7. A laminate having at least one layer comprising the molded article according to claim 4 or 5. 8. A container having at least one layer composed of the molded article according to claim 4 or 5.