JP2003231789A - Dispersion composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersion composition which can form a film excellent in transparency and a gas barrier property even under high humidity, and to provide a film fabricated from this dispersion composition. <P>SOLUTION: In the dispersion composition, a compound in an inorganic layer is dispersed with a dispersing machine into a solution of an ethylene-vinyl alcohol copolymer, that the dispersion of the compound in the inorganic layer is conducted with a peripheral speed of 10 m/s or more with the dispersing machine, and that the viscosity of the dispersion composition obtained by the dispersion is 0.1-1.0 Pa*s. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dispersion composition in which an inorganic layered compound is dispersed in an ethylene-vinyl alcohol copolymer solution, and an excellent gas barrier property even under high humidity prepared from the dispersion composition. Regarding the film.

[0002]

2. Description of the Related Art Films containing an inorganic layered compound have hitherto been used for gases such as oxygen, carbon dioxide and nitrogen oxides,
It is known to have a high barrier property against low molecular weight compounds. For example, in JP-A-8-282112, when an inorganic layered compound having a large aspect ratio is contained in an intermediate layer and / or an undercoat layer of a multicolor heat-sensitive recording material, the transparency of each layer is reduced with a thin film thickness. It is disclosed that the barrier property against a substance can be enhanced without deteriorating.

Further, in JP-A-10-90828, in a photographic element such as a silver halide photographic light-sensitive material, it is controlled that a photographically useful compound such as a dye added to each layer of the photographic element is diffused between layers. It is disclosed that it is preferable to contain a swellable inorganic layered compound in the layer for the purpose of preventing the diffusion of the gas contained in the atmosphere into the photographic element layer.

In particular, synthetic mica is preferable as the swellable inorganic layered compound, and as the binder used in the layer to which the inorganic layered compound is added, a hydrophilic colloid such as gelatin or a synthetic hydrophilic polymer substance such as polyvinyl alcohol is used. It is preferably used.

However, when a hydrophilic colloid such as gelatin or a synthetic hydrophilic polymer such as polyvinyl alcohol is used as a binder for a layer or film to which the inorganic layered compound is added, it is used under low humidity, that is, in a dry environment. Shows high barrier properties against gas and low molecular weight compounds, and shows excellent performance, but under high humidity (80
% RH or more), the barrier property is remarkably lowered, and there is a problem that the performance as a layer (film) for controlling the diffusion of substances and the like cannot be sufficiently exhibited.

Therefore, even under high humidity (80% RH or more), the dispersion composition containing the inorganic layered compound capable of controlling the diffusion of the substance without lowering the barrier property against gas and low molecular weight compounds, and At present, it is desired to provide a film made of the dispersion composition.

It is known that the ethylene-vinyl alcohol copolymer has an excellent gas barrier property even under high humidity, as compared with the hydrophilic colloid and polyvinyl alcohol. For example, in JP-A No. 11-315222, in order to obtain a film having a high gas barrier property, a coating material in which an inorganic layered compound and polyvinyl alcohol or an ethylene-vinyl alcohol copolymer solution are dispersed is coated on the film material. Is described. And
In the examples of the publications, there is described a preparation example of a coating solution in which a natural montmorillonite as an inorganic layered compound is dispersed in a polyvinyl alcohol aqueous solution with a stirring device at a peripheral speed of 8.47 m / min.

However, since the dispersability of the inorganic layered compound is insufficient in the coating material described in the above publication, the inorganic layered compound aggregates, and the film made from this has insufficient transparency and also has a gas barrier property. It is still insufficient.

[0009]

The present invention has been made in view of the above problems, and an object thereof is to form a film excellent in transparency and gas barrier property even under high humidity. It is to provide possible dispersion compositions and films made from the dispersible compositions.

[0010]

The above-mentioned problems can be solved by providing the following dispersion composition and film. (1) A dispersion composition in which an inorganic layered compound is dispersed in a solution of an ethylene-vinyl alcohol copolymer by a disperser, wherein the inorganic layered compound is dispersed at a peripheral speed of 10
Dispersion composition characterized in that the viscosity of the dispersion composition obtained by the dispersion is 0.1 to 1.0 Pa · s. (2) The dispersion composition as described in (1) above, wherein the solvent used for the ethylene-vinyl alcohol copolymer solution is a mixed solvent containing water and n-propyl alcohol. (3) The dispersion composition as described in (1) or (2) above, wherein the mixing ratio (mass ratio) of water and n-propyl alcohol in the mixed solvent is 30:70 to 70:30. . (4) The method according to any one of (1) to (3) above.
A film produced from the dispersion composition according to any one of claims 1 to 3, wherein the solvent is substantially removed from the film. (5) The film as described in (4) above, wherein the film is provided on a norbornene resin film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The dispersion composition of the present invention is a dispersion composition in which an inorganic layered compound is dispersed in a solution of an ethylene-vinyl alcohol copolymer by a disperser. It is characterized in that the peripheral speed of the disperser is 10 m / s or more and the viscosity of the dispersion composition obtained by dispersion is 0.1 to 1.0 Pa · s. A film having excellent transparency and gas barrier properties can be formed from this dispersion composition. The peripheral speed of the disperser is less than 10 m / s, or the viscosity is 0.1-1.
If it deviates from 0 Pa · s, the dispersibility becomes insufficient. The upper limit of the peripheral speed depends on the disperser used, but is about 70 m / s in terms of heat generation. The viscosity is measured using a B-type viscosity meter, and the measurement conditions are a temperature of 25 ° C. and a rotor rotation speed of 60 rpm. The film produced from the dispersion composition has a high barrier property against gas and low molecular weight compounds even under high humidity (80% RH or more) and has excellent transparency.

1. Dispersion Composition (1) Inorganic Layered Compound Next, the inorganic layered compound contained in the inorganic matrix in the dispersion composition of the present invention will be described.
In the dispersion composition of the present invention, the inorganic layered compound contained in the inorganic matrix is preferably a swellable inorganic layered compound, and among them, for example, natural smectite, synthetic smectite, and swellable synthetic mica are more preferable. In particular, swellable synthetic mica is preferable.

The smectite is a tetrahedral sheet in which a Si-O tetrahedron containing Si atoms in the center spreads in a plane.
And an octahedral sheet having metal atoms such as Al and Mg in the center has a 2: 1 structure. In the smectite, in the tetrahedron, Si atoms are Al
Atom or the octahedral Al atom is M
By substitution with g atoms, the crystal layer lacks positive charge and the surface charge becomes negative.

In the tetrahedron, when Si atoms are replaced by Al atoms, tetrahedral substitution type (tetrahedral charged type)
Examples of smectites having such a structure include beidellite, nontronite, volkonskoite, saponite, and the like. Further, a case where Al atoms in the octahedron are replaced with Mg atoms is referred to as an octahedral substitution type (octahedral charged type), and smectites having such a structure include, for example, montmorillonite, hectorite, and steven. The site etc. are mentioned.

Among the above smectites, montmorillonite, saponite, and hectorite are preferable as natural smectites. Further, as the synthetic smectite, saponite, hectorite, and stevensite are preferable.

Examples of the swelling synthetic mica include Na tetrasic mica NaMg _2,5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (NaLi) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Na or Li Hectorite (NaLi) ₁ / 3Mg ₂ / 3Li _1/3 (Si ₄ O ₁₀ ) F ₂ and the like are preferable.

The above-mentioned inorganic layered compound has a laminated structure composed of unit crystal lattice layers having a thickness of 10 to 15 angstroms, and the substitution of metal atoms in the lattice is significantly larger than that of other clay minerals. As a result, the lattice layer is deficient in positive charge, and cations such as Na ⁺ , Ca ²⁺ and Mg ²⁺ are adsorbed between the layers to compensate for it. The cations existing between these layers are called exchangeable cations and can be exchanged with various cations. In particular, the cations between the layers are Li ⁺ , N
In the case of a ⁺ , since the ionic radius is small, the bond between the layered crystal lattices is weak, and it swells largely with water. When shear is applied in that state, it is easily cleaved to form a stable sol in water. The swelling synthetic mica has a strong tendency and is particularly preferably used.

Since the surface of the inorganic layered compound is hydrophilic, it is easily swelled in water and easily dispersed by shearing. At this time, a water-miscible organic solvent,
For example, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol; dimethyl sulfoxide, dimethylformamide, acetone and the like can be added.
Among them, ethanol, propanol, isopropanol and acetone are more preferable.

The surface of the inorganic layered compound is hydrophilic as described above, but it is negatively charged.
By using a quaternary salt compound and / or a quaternary salt compound, the surface can be hydrophobized, and the hydrophobized inorganic layered compound can be contained in the inorganic matrix in the dispersion composition of the present invention.

Specific examples of the tertiary salt compound and the quaternary salt compound include, for example, laurylamine hydrochloride (Pionine B-201), stearylamine hydrochloride (Pionine B-801) and oleylamine acetate (Pionine B-201).
709), stearylamine acetate (Pionine B-8)
09), stearylaminopropylamine acetate (Pionin B-104-DA) [trade names in parentheses; Pionin B series; manufactured by Takemoto Yushi Co., Ltd.], laurylpyridinium chloride (Pionin B-).
251), myristylpyridinium chloride (Pionine B-451), cetylpyridinium chloride (Pionine B-651) [trade names in parentheses: Pionine B
Series; manufactured by Takemoto Yushi Co., Ltd.] and the like, lauryl trimethyl ammonium chloride (Pionine B-211), cetyl trimethyl ammonium chloride (Pionine B-611), stearyl trimethyl ammonium chloride (Pionine B-81).
1), dilauryl dimethyl ammonium chloride (Pionine B-2211), distearyl dimethyl ammonium chloride (Pionine B-8811), lauryl dihydroxyethyl methyl ammonium chloride (Pionine B-221-B), oleyl bis polyoxyethylene methyl ammonium chloride (Pionine B-721-E), Stearyl hydroxyethyl dimethyl ammonium chloride (Pionine B-821-
A), lauryldimethylbenzylammonium chloride (Pionine B-231), lauroylaminopropyldimethylethylammonium ethosulfate (Pionine B-276), lauroylaminopropyldimethylhydroxyethylammonium perchlorate (Pionine B-277) [Products in parentheses are Suitable examples thereof include quaternary ammonium salt compounds such as Pionin B series; manufactured by Takemoto Yushi Co., Ltd.].

The quaternary ammonium salt compound having the following polyoxyethylene group is also preferred, for example, polyoxyethylene / trialkylammonium chloride polyoxyethylene / trialkylammonium bromide polyoxyethylene / dialkylammonium chloride polyoxyethylene.・ Dialkylammonium acetate polyoxyethylene ・ benzyl ・ dialkylammonium chloride polyoxyethylene ・ benzyl ・ dialkylammonium bromide di (polyoxyethylene) ・ alkylammonium chloride di (polyoxyethylene)
-Alkylammonium acetate di (polyoxyethylene) -benzyl-alkylammonium chloride di (polyoxyethylene) -benzyl-alkylammonium acetate di (polyoxyethylene) -dialkylammonium chloride di (polyoxyethylene) -dialkylammonium bromide tri ( Preferable examples include polyoxyethylene) / alkylammonium chloride tri (polyoxyethylene) / alkylammonium bromide tri (polyoxyethylene) / alkylammonium acetate.

A fourth group having the following polypropylene group
Suitable examples thereof include secondary ammonium salt compounds. For example, polyoxypropylene / trialkylammonium chloride polyoxypropylene / trialkylammonium bromide di (polyoxypropylene) / dialkylammonium chloride di (polyoxypropylene) / dialkylammonium bromide tri ( Polyoxypropylene)
-Alkyl ammonium chloride tri (polyoxypropylene) -alkyl ammonium bromide etc. are mentioned suitably.

Further, the cationic surfactants listed in Tables 1 to 4 below are also preferably used as the tertiary salt compound or the quaternary salt compound used for making the inorganic layered compound hydrophobic.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

Among the above-mentioned preferred tertiary salt compounds and quaternary salt compounds, N, N-dipolyoxyethylene-N-stearyl-N-methylammonium chloride and dodecyltrimethyl are used for making the inorganic layered compound hydrophobic. Ammonium chloride, polyoxyisopropylenetriethylammonium chloride and the like are more preferable.

To make the inorganic layered compound hydrophobic by using the tertiary salt compound and / or the quaternary salt compound, one kind may be used alone, or two or more kinds may be used in combination.
Making the inorganic layered compound hydrophobic by using the tertiary salt compound and / or the quaternary salt compound means that the inorganic layered compound is subjected to cation exchange with these compounds. Specifically, it can be performed by the following method. However, the present invention is not limited to this method.

First, in the first step, the inorganic layered compound is dispersed in water to obtain a suspension. The solid dispersion concentration in the suspension is preferably 1 to 15% by mass, but can be set freely as long as the concentration of the inorganic layered compound is sufficient. In this case, it is preferable to use an inorganic layered compound which has been previously freeze-dried. next,
In the second step, a solution of the tertiary salt compound or the quaternary salt compound is added to the inorganic layered compound suspension, or the inorganic layered compound suspension is added to the solution to perform cation exchange. To make the inorganic layered compound hydrophobic. Further, in the third step, the solid-liquid is separated and the hydrophobized inorganic layered compound is washed with water to sufficiently remove the by-product electrolyte.
This is dried and, if necessary, pulverized to obtain the desired product.

The above reaction proceeds sufficiently at room temperature, but may be heated. The maximum temperature for heating is the tertiary salt compound used or 4
It is governed by the heat resistance of the graded salt compound, and can be arbitrarily set as long as it is below its decomposition point.

The amount of the tertiary salt compound and / or the quaternary salt compound added is preferably equivalent to the cation exchange capacity of the inorganic layered compound when converted to ions, but a smaller amount is also used. Is possible. Further, an excess amount may be added to the cation exchange capacity. Specifically, the added amount is preferably 0.5 to 1.5 times (milliequivalent) of the cation exchange capacity of the inorganic layered compound, and more preferably 0.8 to 1.4 times.

Regarding the method for hydrophobizing the inorganic layered compound, JP-A-6-287014 and JP-A-9-17 are cited.
It is described in detail in each publication of No. 5817.

The aspect ratio of the inorganic layered compound is preferably 20 or more, more preferably 30 or more, still more preferably 100 or more, and particularly preferably 200 or more, from the viewpoint of the barrier property of the coating film. When the inorganic layered compound is smectite, the aspect ratio is 30 to 10
The range of 0 is particularly preferable. The aspect ratio is the ratio of thickness to major axis of particles.

From the viewpoint of the barrier property and the smoothness of the coating film, the average particle diameter of the inorganic layered compound is preferably 0.3 to 20 μm, and 0.5 to 10 is preferable.
More preferably, it is 1 μm to 5 μm. The average thickness of the particles in the inorganic layered compound is preferably 0.1 μm or less, and 0.0
It is more preferably 5 μm or less, particularly preferably 0.01 μm or less.

(2) Ethylene-Vinyl Alcohol Copolymer The ethylene-vinyl alcohol copolymer (hereinafter referred to as "EVOH") in the present invention means ethylene-
A saponification product of a vinyl ester copolymer, and vinyl alcohol is 40 to 8% in the copolymer from the viewpoint of gas barrier property.
Those containing 0 mol% are preferable, and more preferably 45
.About.75 mol%.

(3) Content of Each Component in Dispersion Composition The EVOH content in the dispersion composition is preferably 5 to 2
It is 5% by mass, more preferably 10 to 20% by mass. E
By setting the VOH content to 5 to 25% by mass, the gas barrier property and transparency of the film and the dispersion stability of the inorganic layered compound can be improved. The content of the inorganic layered compound in the dispersion composition is preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass. 0.5-5
By adjusting the content to be% by mass, the gas barrier properties and transparency of the film can be improved. Also, EV
The ratio of the inorganic layered compound to OH is 0.005-1.
It is preferably 0.01 to 0.5. The ratio is 0.0
By setting it in the range of 05 to 1, the gas barrier property and transparency of the film will be good.

(4) The aspect ratio of the inorganic layered compound in the dispersion composition and the aspect ratio of the inorganic layered compound dispersed in the particle size dispersion composition are preferably 20 or more, more preferably 30 or more, and even more preferably 100 or more. 200 or more is particularly preferable. Further, when the inorganic layered compound is smectite, the aspect ratio is particularly preferably in the range of 30 to 100. The particle diameter of the inorganic layered compound is preferably 0.3 to 20 μm in average major axis,
It is more preferably 0.5 to 10 μm, and 1 to 5 μm.
More preferably m. The average thickness of the particles in the inorganic layered compound is preferably 0.1 μm or less, more preferably 0.05 μm or less, and 0.01 μm.
The following are particularly preferred.

2. Preparation of Dispersion Composition Containing EVOH and Inorganic Layered Compound (1) To prepare the dispersion composition, E
It can be prepared by mixing a VOH solution and a dispersion liquid of an inorganic layered compound. 1) Preparation of EVOH solution EVOH is obtained by dissolving in an appropriate solvent,
As the solvent for dissolving EVOH, other than water / n-propanol mixed solvent, dimethyl sulfoxide, dimethylformamide, and a mixed solvent of these and water are used, but the water / n-propanol mixed solvent is It is preferable in terms of manufacturing suitability (dryability, safety, dispersibility). The mixing ratio (mass ratio) of water and n-propyl alcohol is preferably 30:70 to 70:30, more preferably 2
5:75 to 70:30, particularly preferably 25:75 to 6
It is preferably 0:40 from the viewpoint of the stability of the dispersion composition and the transparency of the film obtained therefrom.
When importance is attached to transparency, it is also preferable to increase the fraction of n-propyl alcohol or add about 5 to 20 mass% of n-butyl alcohol. From the viewpoint of viscosity and dispersibility, the concentration of the EVOH solution used is preferably 2 to 20% by mass of EVOH content, particularly preferably 3 to 1
It is 5% by mass. 2) Preparation of Dispersion Liquid of Inorganic Layered Compound For the preparation of the inorganic layered compound, water or a demulsifier (for example, polyphosphate) is appropriately added as a dispersion medium, and a media mill (Viscomil, manufactured by AIMEX) is used. It can be obtained by dispersing by a dispersing method such as The concentration of the inorganic layered compound in the dispersion liquid of the inorganic layered compound is preferably 1 to 10% by mass, and particularly preferably 2 to 8% by mass from the viewpoint of dispersibility, handleability and production suitability.

3) Mixing of EVOH Solution and Dispersion of Inorganic Layered Compound The mixing of the above two solutions was carried out at a peripheral speed of a dispersing machine of 10 m.
/ S or more, and the dispersion composition obtained by dispersion is dispersed so that the viscosity is 0.1 to 1.0 Pa · s. As a method for adjusting the viscosity of the obtained dispersion composition to be 0.1 to 1.0 Pa · s, for example, the solid content concentration of EVOH, the inorganic layered compound, etc., the degree of polymerization of EVOH, the solvent composition, etc. are appropriately selected. It is done by changing. The viscosity increases as the solid content concentration and the degree of polymerization increase, and the viscosity also increases by increasing the solvent composition, for example, the ratio of water to the mixed solvent of water / n-propyl alcohol. The viscosity of the dispersion composition is measured using a B-type viscometer, and the measurement temperature is 25 ° C.
Viscosity when measured under the measurement conditions of a rotor rotation speed of 60 rpm.

In order to carry out such dispersion, a thin film swirling mixer or the like is used as a disperser, the particle size of the inorganic layered compound in the obtained dispersion is uniform, and the stability of the dispersion is good. It is preferable from a certain point of view. In particular, according to this method, even when a dispersion in which the compound is highly cleaved is used as the dispersion of the inorganic layered compound, the resulting dispersion is stable and does not aggregate, and thus a film from the dispersion is formed. Excellent in both transparency and gas barrier properties. The thin film swirl type mixer is a mixer of a type in which the dispersion liquid is stirred while rotating (swirling) into a cylindrical film shape. An example of a thin film swirl type mixer is shown in FIG. In FIG. 1, 10 is a thin film swirl type mixer, 11 is a stirring tank, 12 is a rotary blade,
13 is a ring-shaped dam plate, 14 is a rotating shaft, 15 is a motor,
Reference numeral 16 is a lid, 17a and 17b are raw material supply pipes, 19 is an outlet pipe, 20 is a pressure transmitter, and 20a is a signal transmission circuit from the pressure transmitter.
21 represents a cylindrical film of the dispersion liquid. The outer diameter of the rotary blade is slightly smaller than the inner diameter of the container, and the gap between them is about several millimeters (for example, 3 mm).

When the dispersion liquid of the raw material is supplied into the container from 17a and 17b and the rotary blade 12 is rotated, the dispersion liquid is rotated (swirl) into a cylindrical film due to the rotational force and centrifugal force generated in the dispersion liquid. Then, the liquid that has been stirred is discharged from the outflow pipe 19 (continuous processing). In the case of batch processing, the inner diameter of the ring-shaped dam plate 13 is made small so that the gap between the rotating shaft and the dam plate is almost eliminated, and the liquid after the treatment is discharged from the raw material supply pipes 17a or 17b. The peripheral speed is 1
It is set to 0 m / sec or more, preferably about 20 to 70 m / sec, more preferably about 30 to 50 m / sec. The pressure transmitter 20 is for detecting the pressure of the liquid to be treated (depending on the liquid film thickness and the peripheral speed), and by keeping this pressure constant, a substantially constant particle diameter can be obtained. This mixer is disclosed in JP-A-11-333275.
The technical matters which are described in detail in the publication, and described in paragraphs 0006 to 0030 and FIGS. 1 to 5 can be utilized for the preparation of the dispersion liquid of the present invention.

Further, a more preferable example of the thin film swirl type mixer is shown as a conceptual diagram in FIGS. 2 (A) and 2 (B). Figure 2
In (A), 30 is a thin film swirl type mixer, 31 is a stirring tank,
32 is a perforated cylinder, 32a is a small hole provided in the perforated cylinder, 33
Is a ring-shaped dam plate, 34 is a rotary shaft, 35 is a motor, 36
Is a lid, 37a and 37b are raw material supply pipes, 39 is an outflow pipe, and 40 is a cylindrical film of the pigment dispersion liquid. Further, FIG. 2B shows a porous cylinder. The outer diameter of the perforated cylinder 32 is slightly smaller than the inner diameter of the container 31, and the gap between the two is about several millimeters (for example, 3 mm). The diameter of the small holes can be several millimeters, for example 3 millimeters.

When the raw material dispersion liquid is supplied into the container from 37a and 37b and the perforated cylinder 32 is rotated, the dispersion liquid is rotated (swirled) along with the inner and outer peripheral surfaces of the perforated cylinder.
Then, while maintaining the thin film cylindrical shape by centrifugal force, it is subjected to the stirring action due to the speed difference between the container and the perforated cylinder. Further, the dispersion liquid flowing into the small holes receives a strong centrifugal force and is radially ejected into the dispersion liquid between the perforated cylinder and the inner surface of the container to promote the stirring action. The liquid subjected to the stirring process is discharged from the outflow pipe 39 (continuous process). In case of batch processing, ring-shaped dam plate 3
The inner diameter of 3 is reduced to almost eliminate the gap between the rotary shaft and the dam plate, and the treated liquid is discharged from the raw material supply pipe 37a or 37b. The peripheral speed is 10 m / sec or more, preferably about 20 to 70 m / sec, more preferably about 30 to 50 m / sec. This thin film swirl type mixer is described in detail in JP-A No. 11-347388, and the technical matters described in paragraphs 0005 to 0018 and FIGS. 1 to 5 can be used for the preparation of the dispersion liquid of the present invention. it can.

Further, a thin film swirl type mixer (high speed stirring device) as described in JP-A-2001-300281.
Can be used. This mixer is based on
An inner tank made of a hard synthetic resin having high wear resistance is tightly fitted into the stirring tank of the mixer described in JP-A-1-347388, and a dam plate and a perforated cylinder are made of the same material as the inner tank. Thus, it is a mixer in which the metal component is prevented from being mixed in the liquid after the treatment which has been atomized.

To prepare a dispersion composition in which an inorganic layered compound is dispersed in a solution of EVOH, for example, using the thin film swirling mixer shown in FIGS. 2 (A) and 2 (B),
In the case of the batch method, the EVOH solution is placed in a stirring tank in advance, and then the dispersion liquid of the powder of the inorganic layered compound is gradually added and stirred. In case of continuous type, EVOH
The solution and the dispersion of the inorganic layered compound are stirred while continuously being supplied at a specific ratio. As described above, the mixing ratio of the EVOH solution and the dispersion of the inorganic layered compound is such that the ratio of the inorganic layered compound to EVOH in the resulting dispersion composition is preferably 0.005 to 1, particularly preferably 0.01 to
Mix to 0.5.

(2) It is also preferable from the viewpoint of dispersibility to use an annular gap type disperser for preparing a dispersion composition containing EVOH and an inorganic layered compound.
The annular gap type disperser used in the present invention is
With a wet disperser using beads or the like as a dispersion medium, pulverization,
A rotor that rotates at high speed in contact with a liquid to be dispersed and a liquid containing a dispersion medium (hereinafter, also referred to as “suspension”), and a position with a distance from the rotor and a liquid contact surface of the rotor. And a crushing chamber formed between the casing and a casing (Casing; stator). The crushing chamber is narrowed to increase the crushing energy density, thereby significantly improving the crushing efficiency. With this type of disperser, it is possible to pulverize and disperse easily and in a short time.

FIG. 3 shows an example of the annular gap type disperser. In the annular gap type dispersing machine 40, the rotating rotor 41 is provided with a rotating cylindrical body 41a in a concentric circle at the tip of a shaft member having the rotating shaft A as its axis. The surface of the rotating cylinder 41a comes into contact with the suspension S (a liquid containing an inorganic layered compound, EVOH and a dispersion medium) supplied from the inlet 43, and the suspension S rotates on the rotating cylinder 41a.
The rotational force from a is given. Casing (stator)
42 are provided facing each other along the surface of the rotary cylinder 41a with a constant gap B from the surface of the rotary cylinder 41a, and the suspension S can be inserted between the rotary cylinder 41a and the casing 42. A narrow dispersion chamber 45 is formed.

When the suspension S is introduced from the introduction port 43, the suspension S is inserted along the inner wall surface of the rotary cylinder 41a and the wall surface of the casing 42, and is folded at the end of the cylinder to the outer wall surface of the cylindrical body portion. Along the wall surface of the casing 42 is inserted. The suspension S is a rotating cylindrical body 41a that rotates concentrically while being inserted through the dispersion chamber 45 in a certain direction.
It receives a rotational force from the surface, is crushed and dispersed through a dispersion medium, and is then discharged from the discharge port 46. Here, the sample and the dispersion medium can be easily separated by discharging in the direction opposite to the vertical direction. Further, a gap separator, a slit separator, or the like may be provided at the discharge port for separation.
The gap B is 0.5 to 5 mm, preferably 1 to 3 mm. Further, the peripheral speed of the rotating roller 41 is 10 m / se.
c or more, preferably about 15 to 40 m / sec.

FIG. 4 shows another example of the annular gap type disperser. In the annular gap type disperser 50, the tip of the rotary rotor 50 having the rotation axis C as the center of rotation has a rotation chamber 50 in which a cooling liquid (refrigerant) circulates.
a, a casing 54 is provided around the rotation chamber 50a with a substantially constant gap D therebetween.
The gap between a and the casing 54 forms a narrow dispersion chamber 55. The suspension S is from the inlet 53 to the dispersion chamber 55.
In the dispersion chamber 55, the rotational force from the rotation chamber 50a is received through the dispersion medium and the particles are pulverized and dispersed by the grinding force of the dispersion medium. After the inorganic layered compound has been ground, the grinding media is removed from the suspension by the screen 56,
The dispersion liquid of the inorganic layered compound is discharged from the discharge port 57.
Reference numeral 51 is a refrigerant flow path for circulating the refrigerant in the rotary chamber 50a, 52 is the inside of the rotary chamber 50a in which the refrigerant circulates, 59 is a refrigerant circulation path provided inside the casing 54,
Controls suspension temperature rise. Reference numeral 59a is a refrigerant inlet, and 59b is a refrigerant outlet. The gap D is 0.5 to
It is 5 mm, preferably 1-3 mm. Further, the peripheral speed of the rotating rotor 51 is 10 m / sec or more, preferably 1
It is set to about 5 to 40 m / sec.

Known beads can be appropriately selected and used as the medium. The particle size of the medium depends on the desired particle size to be obtained, but in the present invention, it is preferably 0.3 to 2 mm, more preferably 0.5 to 1 mm. Specific examples of the above-mentioned annular gap type media mill include OB mill (O
B-0.5 type, OB-2 type, OB-5 type, OB-10 type),
Diamond Fine Mill MD- manufactured by Mitsubishi Heavy Industries, Ltd.
1, etc.

Preparation of the suspension used in the annular gap type dispersing machine shown in FIGS.
First, an EVOH solution is prepared, and the inorganic layered compound is added to the EVOH solution adjusted to have the intended composition of the dispersion liquid, and a dispersion medium is further added to the EVOH solution. The viscosity is adjusted in the same manner as in the case of using the thin film swirling mixer.

Further, in the dispersion method according to the above (1) and (2), coarse dispersion can be carried out before dispersion using a thin film swirl type mixer or an annular gap type disperser. Coarse dispersion is carried out by an ordinary stirring device, such as a stirring device having stirring blades.

3. Film The film of the present invention may be a film alone from the dispersion composition or a composite film obtained by coating and drying the dispersion composition on at least one surface of another film. The film made from the dispersion composition of the present invention has a high barrier property against gas and low-molecular compounds even under high humidity (80% RH or more) and has excellent transparency, and therefore is transparent to other films. The gas barrier property can be improved without impairing the property. Examples of other films include, but are not limited to, norbornene resin film and other polyolefin films. Among them, the norbornene resin film is a film suitable for medical devices and the like because it has a small permeation and absorption of water and is excellent in gas barrier property, chemical resistance, heat resistance and transparency. The norbornene resin film can be coated with a gas barrier film from the dispersion composition of the present invention to further improve the gas barrier property of the norbornene resin. As the norbornene resin, known ones can be appropriately used, and for example, Japanese Patent Laid-Open No.
The resin described in JP-A-139865 can be used. The coating amount of the inorganic layered compound in the composite film is 0.05 to 1 g / m ² in solid content, preferably 0.1.
It is about 1 to 0.5 g / m ² . By setting the amount to 0.05 to 1 g / m ² , it is possible to achieve both barrier properties and transparency. Further, before applying the dispersion composition of the present invention to a film such as a norbornene resin film, activation treatment such as glow discharge treatment or corona discharge treatment, or / and application of an anchor coating agent may be performed on the surface of the film. It is preferable in terms of film adhesion. As the anchor coating agent, a polyurethane resin type coating agent is preferable.

[0055]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively. Example 1 (1) Dispersion composition <Preparation of 8% aqueous dispersion of synthetic mica> Synthetic mica (ME-10
0, manufactured by Co-op Chemical Co., Ltd., and 80 parts of water, and 920 parts of water are stirred by a stirring blade to coarsely disperse, and then dispersed for 3 cycles with Viscomil (manufactured by AIMEX Co., Ltd.) to synthesize 8% A mica water dispersion was obtained. <Preparation of Synthetic Mica Water / n-Propyl Alcohol Mixed Solvent Dispersion> In a mixed solvent consisting of 60 parts of n-propyl alcohol and 8.8 parts of water, the synthetic mica aqueous dispersion (8%) was added.
Add 31.3 parts with stirring to give 2.5% of synthetic mica.
A water / n-propyl alcohol mixed solvent dispersion was obtained. <Preparation of EVOH Solution> EVOH (EP-E was added to a mixed solvent consisting of 60 parts of n-propyl alcohol and 40 parts of water.
105A, Kuraray Co., Ltd.) (15 parts) are added with stirring, the temperature is raised to 60 ° C., and the mixture is stirred until it is dissolved and 13% E
A VOH solution was prepared. <Preparation of synthetic mica / EVOH-containing dispersion composition> EV
A water / n-propyl alcohol mixed solvent dispersion 5 of the synthetic mica while stirring 100 parts of an OH solution with a stirring blade.
Two parts were added to prepare a synthetic mica / EVOH water / n-propyl alcohol mixed solvent dispersion. For this dispersion liquid, further, using a FILMIX FM-80-50 (rotation body of the type shown in FIG. 2 (B)), a peripheral speed of 50 m / s, treatment for 30 seconds / stop for 1 minute and cooling. A mica / EVOH
A dispersion composition containing was obtained. As a result of measuring the viscosity of the obtained dispersion composition with a B-type viscometer, it was 300 mPa · sec.

(2) A 100 μm thick norbornene resin film (Zeonor 1600, manufactured by Nippon Zeon Co., Ltd.) whose surface is corona-treated.
Anchor coating agent (Adcoat AD335 / CAT
10 (mass ratio 12/1) manufactured by Toyo Morton Co., Ltd. was applied to a thickness of 0.05 μm. On top of this, the synthetic mica / EVOH-containing dispersion composition was dried to a film thickness of 2 μm.
m to give a norbornene resin film provided with a synthetic mica / EVOH film.

Comparative Example 1 (1) Dispersion Composition A dispersion composition was prepared in the same manner as in Example 1 except that the following procedure was used in <Preparation of synthetic mica / EVOH-containing dispersion composition>. Obtained. <Preparation of Synthetic Mica / EVOH-containing Dispersion Composition> Example 1
52 parts of the water-n-propyl alcohol mixed solvent dispersion of the synthetic mica prepared in Example 1 while stirring 100 parts of the EVOH solution prepared in 1 above with a stirring device (Despa MH-L, manufactured by Asada Iron Works Co., Ltd.). Was added and the mixture was stirred for 90 minutes at a peripheral speed of 8.5 m / min to obtain a dispersion composition containing synthetic mica / EVOH. As a result of measuring the viscosity of the obtained dispersion composition with a B-type viscometer, it was 210 mPa · sec. (2) Film Using the dispersion composition obtained in (1) above, a norbornene resin film provided with a synthetic mica / EVOH film was produced in the same manner as in Example 1.

Comparative Example 2 (1) Dispersion Composition Example 1 except that <Preparation of EVOH solution> and <Preparation of synthetic mica / EVOH-containing dispersion composition> in Example 1 were changed as follows. A dispersion composition was obtained in the same manner. <Preparation of EVOH Solution> EVOH (EP-E was added to a mixed solvent consisting of 60 parts of n-propyl alcohol and 40 parts of water.
5 parts of 105A, manufactured by Kuraray Co., Ltd.) was added with stirring, the temperature was raised to 60 ° C., and the mixture was stirred until dissolved to prepare an EVOH solution. <Preparation of synthetic mica / EVOH-containing dispersion composition> EV
While stirring 100 parts of the OH solution with a stirring blade, 20 parts of the synthetic mica water / n-propyl alcohol mixed solvent dispersion prepared in Example 1 was added to mix the synthetic mica / EVOH water / n-propyl alcohol. A solvent dispersion was prepared.
Further to this dispersion, Filmix FM-80
-50 (using a rotating body of the type shown in FIG. 2B) was subjected to a dispersion treatment in which a cycle consisting of a treatment for 30 seconds at a peripheral speed of 50 m / s and a cooling for 1 minute was performed 10 times, A dispersion composition containing synthetic mica / EVOH was obtained. As a result of measuring the viscosity of the obtained dispersion composition with a B-type viscometer, 80 mP
It was a sec. (2) Film Using the dispersion composition obtained in (1) above, a norbornene resin film provided with a synthetic mica / EVOH film was produced in the same manner as in Example 1.

[Evaluation] (1) Measurement of haze Synthetic mica / EV prepared in Example 1 and Comparative Examples 1 and 2
The haze of the norbornene resin film provided with the OH film was measured with a haze meter. The results are shown in Table 1. (2) Measurement of oxygen permeability Synthetic mica / EV prepared in Example 1 and Comparative Examples 1 and 2
The oxygen permeability of the norbornene resin film provided with the OH film was measured by a gas permeability measuring device (OX-T manufactured by MOCON).
RAN ML). Measurement conditions are 25 ℃ and 20%
It was RH and 25 degreeC * 80% RH.

[0060]

[Table 5]

[0061]

EFFECTS OF THE INVENTION The dispersion composition of the present invention is used under high humidity (8
Even at 0% RH or more), a film having a high barrier property against gas and low molecular weight compounds and having high transparency can be formed.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an example of a thin film swirling mixer for preparing a dispersion composition of the present invention.

FIG. 2 is a conceptual diagram showing another example of a thin film swirling mixer for preparing the dispersion composition of the present invention.

FIG. 3 is a conceptual diagram showing an example of an annular gap type disperser for preparing the dispersion composition of the present invention.

FIG. 4 is a conceptual diagram showing another example of an annular gap type disperser for preparing the dispersion composition of the present invention.

[Explanation of symbols]

10, 30 Thin film swivel mixer 11, 31 stirring tank 12 rotating blades 13, 33 Ring-shaped dam plate 14, 34 rotation axis, 32 perforated cylinder 40, 50 Annular Gap Disperser 41a rotating cylinder 50a rotating room 42, 54 casing 45, 55 dispersion chamber

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C08J 7/04 C08J 7/04 P C08K 3/20 C08K 3/20 3/34 3/34 5/05 5 / 05 F term (reference) 4F006 AA12 AA31 AB20 AB72 BA05 CA07 4F070 AA13 AA26 AC12 AC22 AC27 AC36 AC39 AC47 AC50 AD01 AD06 AE28 AE30 CA03 CA04 CB11 CB12 4F071 AA15X AA29XAB26 AC30 AC05 AC07 AC12 AC04 BA22 AD22 AE20 AD22 AE22 AC22 AD02 AE22 AD22 AE22 AE22 AE22 AE22 AE22 AE AE AA01A AC05 AK02B AK69A AL05A BA02 CC00A DE10A JA06A JD02 JN01 4J002 BB221 BE031 DE027 DJ006 DJ056 EC037 EC047 EE037 EP017 EV207 FA016 FB088 FD206 GG00 GG02 HA06

Claims (5)

[Claims] 1. A dispersion composition in which an inorganic layered compound is dispersed in a solution of an ethylene-vinyl alcohol copolymer by a disperser, wherein the inorganic layered compound is dispersed at a peripheral speed of 10 m / s or more. And a viscosity of the dispersion composition obtained by the dispersion is 0.1 to 1.0 Pa · s. 2. The dispersion composition according to claim 1, wherein the solvent used in the ethylene-vinyl alcohol copolymer solution is a mixed solvent containing water and n-propyl alcohol. 3. The mixing ratio (mass ratio) of water and n-propyl alcohol of the mixed solvent is 30:70 to 70:30.
The dispersion composition according to claim 1 or 2, wherein 4. A film made from the dispersion composition according to any one of claims 1 to 3, comprising:
A film, wherein the solvent is substantially removed from the film. 5. The film according to claim 4, wherein the film is provided on a norbornene resin film.