JPH11246728A - Composition containing inorganic layered compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which is excellent in dispersion state and stability and gives a film, etc., excellent in gas barrier properties by treating a saponified ethylene-vinyl ester copolymer, an inorg. layered compd., and a solvent contg. a specified amt. of water with a high-pressure dispersion apparatus. SOLUTION: A saponified ethylene-vinyl ester copolymer, an inorg. layered compd. pref. having an aspect ratio of 50-5,000 and/or a particle size of 1 μm or lower (e.g. montmorillonite), and a solvent contg. at least 10 wt.% water (pref. a mixture of water and an alcohol) is subjected to dispersion treatment, pref. under a pressure of 100 kgf/cm<2> or higher, with a high-pressure dispersion apparatus. Pref., the compounding ratio (by vol.) of the inorg. layered compd. to the saponified ethylene-vinyl ester copolymer is (10/1)-(1/100). The compsn. is applied to a substrate and dried to give a laminate excellent in barrier properties against O2 . N2 , CO2 , water, low-molecular perfume components, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composition containing an inorganic layered compound.

[0002]

2. Description of the Related Art Saponified ethylene-vinyl ester copolymer (hereinafter sometimes referred to as EVOH) has a high gas barrier property among resins, and has been used for packaging materials and the like. For the purpose of further improving gas barrier properties, a composition in which EVOH and an inorganic powder are combined is used, for example, in JP-A-6-57066 and JP-A-1-3086.
27 and JP-A-5-39392.

[0003]

However, in the prior art, a composition obtained by kneading an EVOH obtained by kneading with a mixer or an extruder and an inorganic powder is an E.V.
Since the dispersion of the inorganic powder in VOH is not sufficient, the gas barrier property of the obtained composition is not sufficient, and when the mixing ratio of the inorganic powder is increased to enhance the gas barrier property, the melt viscosity during kneading increases. There was a problem.
Also, the method of mixing the EVOH solution and the aqueous dispersion of the inorganic powder and the method of adding the inorganic powder to the EVOH solution and mixing them are not a composition having good dispersibility of the inorganic powder. The gas barrier properties of the resulting films and the like have not been satisfactory yet.

An object of the present invention is to solve the above-mentioned problems and to provide a composition containing EVOH and an inorganic layer compound which is excellent in stability to maintain a good dispersion state.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides an inorganic layered product obtained by treating a saponified ethylene-vinyl ester copolymer, an inorganic layered compound and a solvent containing water at a weight ratio of 1/10 or more with a high-pressure dispersing apparatus. It is to provide a compound-containing composition.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The saponified ethylene-vinyl ester copolymer used in the present invention is obtained by saponifying an ethylene-vinyl ester copolymer, and examples of the vinyl ester include vinyl acetate and vinyl trifluoroacetate. From the viewpoint of gas barrier properties of the obtained resin composition, the number of ethylene units based on the total number of monomer units is 20 to 60 in percentage.
%, Preferably 20-45%, more preferably 25-4%
0%. The degree of saponification of the vinyl ester unit is
90% or more, preferably 95% or more, more preferably 9% or more.
8% or more. Here, the saponification degree of the vinyl ester unit means a percentage of the number of the saponified vinyl ester units to the total number of the vinyl ester units and the saponified vinyl ester units existing in the EVOH. More specifically, commercially available brand names such as EVAL (Kuraray Co., Ltd.) and Soarnol (Nippon Synthetic Chemical Co., Ltd.) may be mentioned.

In the present invention, EVOH includes:
A so-called EVOH derivative having a functional group other than a hydroxyl group can also be used. Examples of the functional group other than the hydroxyl group include an amino group, a thiol group, a carboxyl group, a sulfone group, a phosphate group, a carboxylate group, a sulfonate ion group, and a phosphate ion group. , Ammonium group, phosphonium group, silyl group,
Examples include a siloxane group, an alkyl group, an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, and a halogen group. Some or all of the hydroxyl groups in EVOH may be replaced by one or more of these functional groups.

[0008] The inorganic layered compound used in the present invention is a compound or a substance having a layered structure in which unit crystal layers are stacked on each other. Here, the layered structure means that atoms are strongly bonded by a covalent bond or the like to form a dense structure. The surface arranged in
It refers to a structure that is stacked almost in parallel by weak coupling force such as van der Waals force.

Specific examples of the inorganic layered compound include graphite, phosphate derivative type compounds (zirconium phosphate type compounds, etc.), chalcogenides, hydrotalcite compounds, lithium aluminum composite hydroxides, clay minerals, etc. Can be mentioned. Here, “chalcogenide” refers to group IV (Ti, Zr, Hf) and group V (V, N
b, Ta) and / or a dichalcogenide of a group VI (Mo, W) element, which is represented by the formula MX ₂ (M is the above element, and X is chalcogen (S, Se, Te)). Say. From the viewpoint of dispersibility, an inorganic layered compound having the property of swelling and cleaving in a solvent as described below is preferable, and a clay mineral having swelling and cleaving property in a solvent is particularly preferable.

The degree of "swelling / cleaving" of the inorganic layered compound in a solvent can be evaluated by the following "swelling / cleaving" test. The swellability of the inorganic stratiform compound is preferably about 5 or more (more preferably about 20 or more) in the swellability test described below. On the other hand, the cleavage property of the inorganic layered compound is preferably about 5 or more (more preferably about 20 or more) in the following cleavage test. In these cases, a solvent having a density smaller than the density of the inorganic layered compound is used as the solvent. When the inorganic stratiform compound is a natural swellable clay mineral, it is preferable to use water as the solvent.

<Swellability test> 2 g of the inorganic layered compound is slowly added to 100 mL of a solvent (a 100 mL graduated cylinder is used as a container). After standing, the volume of the former (inorganic layered compound dispersed layer) is read from the scale at the interface between the inorganic layered compound dispersed layer and the supernatant after 24 hours at 23 ° C. The larger the value, the higher the swelling property.

<Cleaving test> 30 g of an inorganic layered compound was slowly added to 1500 mL of a solvent, and a dispersing machine (Despar MH-L, manufactured by Asada Tekko Co., Ltd., blade diameter 52 mm, rotation speed 3100 rpm, container capacity 3 L, bottom-blade distance) Distance 2
(8 mm) at a peripheral speed of 8.5 m / sec for 90 minutes (23 ° C.), take 100 mL of the dispersion, put it in a graduated cylinder and let it stand for 60 minutes, then, from the interface with the supernatant, the volume of the inorganic layered compound dispersion layer I Read.

The clay mineral generally has a two-layer structure having an octahedral layer made of aluminum, magnesium or the like as a central metal on a silica tetrahedral layer; and a silica tetrahedral layer comprising aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedral layer having magnesium or the like as a central metal is narrowed from both sides. The former two-layer structure type includes kaolinite group and antigolite group, and the latter three-layer structure type includes smectite group, vermiculite group and mica group depending on the number of interlayer cations. Can be.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, Examples include muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, and chlorite. In addition, reference can be made to literatures such as Haruo Shimizu, "Clay Mineralogy", 1988, Asakura Shoten Co., Ltd.

The solvent used in the present invention contains water at a ratio of 1/10 or more by weight. Examples of the solvent other than water include methanol, ethanol, 2-propanol, 1-butanol, pentanol, and the like. Alcohols such as octanol and 1,3-pentanediol, ketones such as acetone and methyl ethyl ketone, methyl acetate,
Esters such as ethyl acetate and ethers such as n-butyl cellosolve and ethylene glycol can be exemplified. These solvents may be used alone or in combination of two or more. When the content of water is less than 1/10 by weight, the stability of the inorganic layered compound in the obtained inorganic layered compound-containing composition is not sufficient, and precipitation and the like are likely to occur.

From the viewpoint of the solubility of EVOH, a mixed solvent of water and an alcohol is preferably used. Preferred examples of the alcohol include methanol, ethanol, 2-propanol, 1-propanol and 1-butanol. In the case of a water / alcohol mixed solvent, the mixing ratio of water / alcohol is usually 1/10 to 10/1, preferably 2/8 to 8/2. Alcohol may be one kind,
Two or more types may be used.

When the obtained composition containing an EVOH, an inorganic layer compound and a solvent is used as a coating liquid or the like, the solvent is a liquid at around room temperature and evaporates when the composition is dried. It is preferable to use a solvent which has a boiling point of 20.
Those having a temperature of 0 ° C. or lower (more preferably 140 ° C. or lower) are preferable.

When EVOH is mixed with an inorganic stratiform compound, it is preferable to add the inorganic stratiform compound to the EVOH solution, and it is more preferable to stir by heating, in terms of dispersibility, and that the boiling point of the solvent is 50 ° C. or higher ( (80 ° C. or more). From the viewpoint of the boiling point and the melting point, the solvent may be water, methanol, ethanol, 1-
Butanol, 2-propanol, 1-propanol and the like are particularly preferred. An EVOH dispersion in the form of an emulsion may be used as the EVOH, and the dispersion medium of the EVOH dispersion is preferably a mixed water / alcohol dispersion medium.

The composition containing an inorganic layered compound according to the present invention may be an EV
OH, inorganic layered compound and water in a weight ratio of at least 1
By treating a solvent containing / 10 with a high-pressure dispersion device, a composition having more excellent dispersibility of the inorganic layered compound can be obtained. When processing in a high-pressure dispersing apparatus, the EVOH and the inorganic layered compound may be separately processed and then mixed,
After both are mixed in advance, treatment may be performed, but at least one of EVOH and the inorganic layered compound is 1/1.
Treated with a solvent containing zero or more water. For example, a method in which an EVOH solution and a dispersion containing an inorganic layered compound are separately treated in a high-pressure dispersing apparatus and then mixed, a method in which EVOH, an inorganic layered compound and a solvent are mixed and then treated, and a method in which the inorganic layered compound is treated. There is a method of treating a dispersion containing a compound with a high-pressure dispersing device, mixing EVOH with the dispersion, and treating again with a high-pressure dispersing device. However, EVOH and an inorganic layered compound are separately separated by a high-pressure dispersing device. In the case where both are mixed after the treatment, the solvent after the mixing is water 1/1 from the viewpoint of the stability of the inorganic layered compound.
It is preferable to contain 0 or more.

Before and after the treatment in the high-pressure dispersion device, the EV
Some operation may be performed on the OH, the inorganic layered compound, and the composition thereof. The operations include mixing, separation, stirring, dissolving, dispersing, heating, cooling, drying, defoaming, extraction, and standing. For example, EVOH is dissolved in a solvent,
The inorganic layered compound is dispersed in water, and the mixture thereof is treated with a high-pressure dispersing apparatus to obtain an inorganic layered compound-containing composition, and an additive such as a surfactant is added to the obtained liquid composition. The composition obtained by stirring under the above conditions can be suitably used as a coating liquid as described below.

When the inorganic layered compound and EVOH are mixed beforehand in the high-pressure dispersing apparatus, the mixing method is not particularly limited. For example, when an EVOH solution is used as the EVOH, for example, water is contained at least 1/10. First, EVOH is added to and dissolved in a water / alcohol mixed solvent to be dissolved, and then an inorganic layered compound is added and dispersed. In addition, a method of adding an inorganic layered compound and EVOH in this order, a dispersion of an inorganic layered compound and an EVOH solution There are a plurality of methods, such as a method of mixing, but any method may be used.

The container used for mixing is preferably provided with a jacket on the outer wall through which a heat medium such as hot water or steam can be passed for temperature control. In addition, from the viewpoint of uniformity of bubble entrapment and dispersion, a container with a baffle or the like is used. For the same reason, it is preferable that the position of the dispersion blade is slightly shifted (eccentric) instead of the center of the pot. . Also, in order to have a relatively high solid content and good dispersion, as it is difficult to chew bubbles,
The inside of the kettle with the internal pressure reduced to 200 mmHg or less
The method of high-speed stirring at 7000 rpm easily obtains the effect of high shearing force.

The high-pressure dispersing apparatus of the present invention refers to a high-pressure dispersing device such as a high-shearing or high-pressure state, in which a composition in which particles to be dispersed and a medium such as a solvent are mixed and passed through a plurality of thin tubes at a high speed so as to collide. A device that creates conditions.
For example, the composition is preferably passed through a thin tube having a diameter of 1 to 1000 μm, and the composition has a maximum pressure condition of 1 μm.
It is preferable to 00kgf / cm ² or more pressure is applied, 500 kgf / cm ² or more is more preferable. Further, when the composition passes through the high-pressure dispersion device, it is preferable that the maximum arrival speed of the composition reaches 100 m / sec or more,
Further, the heat transfer rate is preferably 100 kcal / hr or more.

In FIG. 1, the high
The principle of the high pressure processing unit in the pressure dispersion processing device is schematically shown.
Was. In FIG. 1, the pumps shown in FIG.
High pressure is applied to the processed sample in the tube section. And momentarily
The flow velocity at the point where the maximum velocity is reached is, for example, 300 m / sec.
In the case of c, the volume is 1 × 10^-3m^Three1 / (3 ×
10^Five) Pass in sec, sample temperature rises by 35 ° C
Energy transfer to the sample due to pressure loss
It is. The specific gravity of the sample is 1g / cm ^Three,specific heat
3.8 × 10 4 kcal / h at 1 cal / g ° C.
r.

As such a high-pressure dispersion device, for example, Mi
ultra high pressure homogenizer (trade name: Microfluidizer) manufactured by crofluidics Corporation
Alternatively, there is a Nanomizer manufactured by Nanomizer, and a Menton-Gaulin-type high-pressure dispersing apparatus, such as a homogenizer manufactured by Izumi Food Machinery, may be used. When a microfluidizer is used as the high-pressure dispersion device, the object to be treated preferably has fluidity at the temperature at which the treatment is performed, and it is preferable to use an EVOH solution in which EVOH is dissolved in a solvent.

When the composition containing an inorganic layered compound of the present invention is used by coating, from the viewpoint of drying after coating, the total solid content concentration is preferably as high as possible.
It is preferable that the concentration of both EVOH and the inorganic layered compound is as high as possible.

The composition ratio (volume ratio) between the inorganic layered compound and EVOH is not particularly limited, but the inorganic layered compound / EVO
The volume ratio of H (the ratio at the time of “preparation”) is usually 10/1.
From the viewpoint of gas barrier properties,
5 or more is preferable, and 90/10 or less is preferable from a moldability viewpoint. Further, from the viewpoint of the flexibility of the obtained molded product, the volume ratio is preferably from 5/95 to 30/70, and from 10/90 to
30/70 is particularly preferred. When used as a film or a laminate, the volume ratio is preferably 7/93 or more from the viewpoint of suppressing deterioration in physical properties due to bending, and from the viewpoint of suppressing flexibility or peeling from the substrate. Is preferably 17/83 or less.

The above volume ratio is determined based on the “charge” of these components.
In this case, the values of the numerator (weight of the inorganic layered compound) and the denominator (weight of EVOH) of the weight ratio can be obtained by dividing by the respective densities.

The composition containing an inorganic layered compound of the present invention includes:
Various solvents can be blended for the purpose of improving coating properties and adjusting viscosity, and additives can be blended as necessary. Examples of additives include pigments, surfactants, fungicides, preservatives, crosslinking agents, defoamers, antioxidants, and the like.

Examples of the pigment include a rust preventive pigment for a primer, a coloring pigment, a metal foil pigment, a brilliant pigment, an extender pigment and the like. Examples of the rust preventive pigment for a primer include strontium chromate, zinc chromate, zinc phosphate, lead red, zinc white, basic sulfate, and basic carbonate. Examples of the coloring pigment include phthalocyanine blue, phthalocyanine green, quinacdrine, indanthrone, isoindolinone, berylene, anthrapyrimidine, benzimidazolone, carbon black, titanium dioxide, graphite, yellow iron oxide, and red iron oxide.

As the metal foil pigment, aluminum foil, bronze foil, tin foil, gold foil, silver foil, copper foil, titanium metal foil, stainless steel foil, nickel foil, chromium foil, alloy foil of the above metals, and metal coated with plastic Foil and the like.

The glitter pigments include mica foil and foil-like phthalocyanine blue, and the extender pigments include calcium carbonate, gypsum, clay and talc.

As the surfactant, for example, nonionic,
It can be appropriately selected and used from any surfactants such as anionic, cationic and amphoteric surfactants in consideration of workability such as stability of processing solution, foaming property and coating property.

Examples of the nonionic surfactant include polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxyethylene alkyl phenyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, and pentaerythritol fatty acid. Partial esters, polyoxyethylene sorbitan acid fatty partial esters, and polyoxyethylene alkyl ethers are exemplified.

Examples of the anionic surfactant include dialkyl sulfosuccinate, alkane sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene alkyl sulfophenyl ether salt,
Examples thereof include alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, fatty acid alkyl ester sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, and fatty acid monoglyceride sulfates. Examples of the cationic activator include an alkylamine salt and a dialkylamine salt, and examples of the amphoteric system include N, N, N-trialkyl-N-sulfoalkylene ammonium betaine.

The fungicides and preservatives include the fourth
Grade ammonium salts, nitrogen-containing sulfur compounds, halogen-containing nitrogen-sulfur compounds, organic iodine-based compounds, benzimidazole-based compounds, and the like can be used. Specific examples of the fungicide include 2-thiazol-4-ylbenzimidazole, methylbenzimidazol-2-ylcarbamate, N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfamide, Methylthiuram disulfide, N- (trichloromethylthio)-
4-cyclohexene-1,2-dicarboximide,
2,4,5,6-tetrachloro-1,3-isophthalonitrile, and 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, bis (2-pyridylthio)
-Zinc-1,1-dioxide, etc., but considering heat resistance, 2-thiazol-4-ylbenzimidazole, methylbenzimidazol-2-ylcarbamate and 2,4,5,6-tetrachloro- 1,3-isophthalonitrile, bis (2-pyridylthio) -zinc-1,
1-dioxide is preferred.

Specific examples of the antibacterial agent include 1,2-benzisothiazolin-3-one (BIT),
2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 10,10'-oxybisphenoxyarsine and the like are used.

Examples of the crosslinking agent include a titanium-based coupling agent, a silane-based coupling agent, a melamine-based coupling agent, an epoxy-based coupling agent, an isocyanate-based coupling agent, a copper compound, and a zirconium compound. From the viewpoint of improving water resistance, a zirconium compound is particularly preferably used. Specific examples of the zirconium compound include, for example, zirconium halides such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride, and zirconium bromide; zirconium sulfate;
Zirconium salts of mineral acids such as basic zirconium sulfate and zirconium nitrate; zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate and zirconium stearate; zirconium ammonium carbonate, sodium zirconium sulfate and zirconium acetate Zirconium complex salts such as ammonium, sodium zirconium oxalate, sodium zirconium citrate and ammonium zirconium citrate; The amount of the crosslinking agent to be added is not particularly limited, but the ratio (K = CN / H) of the number of moles of the crosslinking group (CN) of the crosslinking agent to the number of moles of the hydrogen bonding group (HN) of the resin
N) is preferably used so as to be in the range of 0.001 or more and 10 or less. More preferably, the molar ratio K is in the range of 0.01 or more and 1 or less.

When the composition containing an inorganic layered compound of the present invention is used for coating, a solvent can be added in order to further improve the wettability at the time of coating.
As the solvent, a solvent which is a liquid at around room temperature and which evaporates when applied to a substrate and dried is preferably used.
Examples thereof include alcohols such as methanol, ethanol, 2-propanol, 1-butanol, pentanol, octanol and the like, acetone, methyl ethyl ketone, ethyl acetate and the like. A plurality of types of solvents may be used.
The liquid thus prepared can be used by coating, dip coating, or brush.

The following are examples of indicators for evaluating the dispersibility of the inorganic layered compound in the composition containing an inorganic layered compound of the present invention. In the case of a liquid composition dispersed in a solvent, a method of thinly casting the composition on a smooth base material (for example, a glass plate) and judging by comparing the appearance (if the dispersion is poor, agglomeration The average particle size of the inorganic layered compound when dispersed in an EVOH solution or dispersion (based on the average particle size (R0) of the inorganic layered compound when dispersed alone in the dispersion medium). R) is close to the value of R0.

The average particle size of the inorganic layered compound in the composition can be determined by a method based on a diffraction / scattering method, a method based on a dynamic light scattering method, a method based on a change in electric resistance, a method based on image processing after photographing with a microscope, and the like. It is. In the method by the diffraction / scattering method, when the composition has substantially no scattering (being transparent) and the scattering derived from the inorganic layered compound is dominant, only the particle size distribution of the inorganic layered compound regardless of the presence or absence of the resin Is relatively preferably used.

In the particle size distribution and average particle size measurement by the diffraction / scattering method, a diffraction / scattering pattern obtained when light is passed through a dispersion liquid is used to calculate the particle size distribution having the most consistent pattern using Mie scattering theory or the like. This is done by doing Commercially available devices include a laser diffraction / light scattering particle size analyzer LS230, LS200, LS10 manufactured by Coulter Inc.
0, laser diffraction particle size distribution analyzer S manufactured by Shimadzu Corporation
ALD2000, SALD2000A, SALD300
0, laser diffraction / scattering type particle size distribution analyzer LA910, LA700, LA500 manufactured by Horiba, Nikkiso Microtrac SPA and Microtrac FRA.

When measuring the particle size distribution, it is preferable to measure without dilution. In the case of a liquid that is too scattered and has low light transmittance, the liquid can be measured without dilution by shortening the optical path length (for example, in the case of LA910 manufactured by HORIBA, Ltd., the optical path length is remarkably measured by a batch type cell, a paste cell, or the like). Can be shortened). However, when diluted with a solvent having the same composition as the liquid solvent composition, the dispersibility often does not change. In such a case, the dispersibility may be evaluated by measuring the diluent.

In this measuring method, if the distance between the particles is smaller than the wavelength of the light source, the particles cannot be separated and identified.
A plurality of particles close to each other (with a resin or the like therebetween) are recognized as one particle. For this reason, not only poor dispersion due to aggregation of particles but also poor dispersion caused by the presence of a resin can be evaluated by the present method.

The inorganic layered compound used in the present invention has an aspect ratio of 50 from the viewpoint of gas barrier properties.
It is preferable that the number is at least 5,000. Here, the aspect ratio (Z) is a ratio obtained from the relationship of Z = L / a. Here, L is the particle size (volume-based median diameter) of the inorganic layered compound in the dispersion obtained by the particle size measurement method by the diffraction / scattering method described above, and a is the unit thickness of the inorganic layered compound. is there. The “unit thickness a” is a value determined based on the measurement of the inorganic stratiform compound alone by a powder X-ray diffraction method or the like described later. More specifically, as shown schematically in the graph of FIG. 1 in which the horizontal axis indicates 2θ and the vertical axis indicates the intensity of the X-ray diffraction peak, it corresponds to the lowest angle peak among the observed diffraction peaks. From the angle θ
Equation of g (nλ = 2D sin θ, n = 1, 2, 3,...)
Is defined as “unit thickness a” (for details of the powder X-ray diffraction method, see, for example, Jiro Shiokawa, “Guidance on Instrumental Analysis (a)”, p. 69 (1985))
(Chemistry Doujinsha can be referred to.)

When the resin composition obtained by removing the solvent from the dispersion is subjected to powder X-ray diffraction, it is usually possible to determine the interplanar spacing d of the inorganic layered compound in the resin composition. More specifically, as shown in the graph of FIG. 2 in which the horizontal axis indicates 2θ and the vertical axis indicates the intensity of the X-ray diffraction peak,
Of the diffraction peaks observed on the lower angle (larger interval) side than the diffraction peak position corresponding to the above “unit thickness a”, the interval corresponding to the peak at the lowest angle side is referred to as “plane interval d” ( a <d). As schematically shown in the graph of FIG. 3, when it is difficult to detect the peak corresponding to the “surface distance d” by overlapping with a halo (or background), the baseline on the lower angle side than 2θd is detected. The area of the portion excluding is set as a peak corresponding to the “surface distance d”. Here, “θd” is “(unit length a) +
(The width of a single resin chain) "(for details of the method of determining the spacing d, see, for example, Shuichi Iwami et al.," Encyclopedia of Clay ", p. 35 or less and p. 271 or less,
1985, Asakura Shoten Co., Ltd. can be referred to).

As described above, the "integrated intensity" of the diffraction peak (corresponding to the plane distance d) observed in the powder X-ray diffraction of the resin composition is the same as that of the reference diffraction peak (corresponding to "plane distance a"). The relative ratio to the integrated intensity is preferably 2 or more (more preferably 10 or more). Usually, the above-mentioned surface distance d
And the value of “unit thickness a”, that is, the value of k = (da) (when converted to “length”) is equal to or less than the width of a single resin chain constituting the resin composition. Large (k = (d
-A) ≧ resin single-chain width). Such “width of single resin chain” can be determined by simulation calculation or the like (for example, “Introduction to Polymer Chemistry”, 103-1)
10, page 1981, Kagaku Doujin), and in the case of polyvinyl alcohol, it is 4 to 5 angstroms (2 to 3 angstroms for water molecules).

The above aspect ratio Z = L / a is appropriate for approximating the “true aspect ratio” with the aspect ratio Z for the following reason. That is, it is extremely difficult to directly measure the “true aspect ratio” of the inorganic layered compound in the resin composition. On the other hand, there is a relationship of a <d between the spacing d obtained by the powder X-ray diffraction method of the resin composition and the “unit thickness a” obtained by the powder X-ray diffraction measurement of the inorganic layered compound alone. When the value of (da) is equal to or greater than the width of a single resin chain in the composition, the resin is inserted between the layers of the inorganic layered compound in the resin composition. Therefore,
The thickness of the inorganic layered compound in the resin composition is approximated by the “unit thickness a”, that is, the “true aspect ratio” in the resin composition is referred to as the “aspect ratio” in the dispersion of the inorganic layered compound. Approximating with "Z" is of sufficient relevance.

As described above, it is extremely difficult to measure the true particle size in the resin composition. However, the particle size of the inorganic stratiform compound in the resin is determined in the dispersion (resin / inorganic stratiform compound / solvent). Can be considered to be quite close to the particle size of the inorganic layered compound. However, since the particle diameter L in the dispersion obtained by the diffraction / scattering method is considered to be very unlikely to exceed the major axis Lmax of the inorganic layered compound, the true aspect ratio (Lmax / a) of the present invention is not so high. The probability of being lower than the “aspect ratio Z” used in (Lmax / a <Z) is theoretically quite low.

From the above two points, it is considered that the definition Z of the aspect ratio used in the present invention has sufficient validity. In the present specification, “aspect ratio” or “particle size” means “aspect ratio Z” defined above or “particle size L determined by a diffraction / scattering method”.

From the viewpoint of gas barrier properties, the inorganic layered compound used in the present invention preferably has an aspect ratio of 50 or more, more preferably 100 or more, still more preferably 200 or more, and particularly preferably 500 or more. From the viewpoint of productivity, the aspect ratio is preferably 5,000 or less, more preferably 3,000 or less, further preferably 2,000 or less, and particularly preferably 1500 or less.

The particle size of the inorganic layered compound used in the present invention measured by the method described above is 5 from the viewpoint of moldability.
μm or less, and from the viewpoint of transparency,
Preferably it is 3 μm or less. When used for applications where transparency is more important (for example, food packaging applications), the particle size is particularly preferably 2 μm or less.

The composition containing an inorganic layered compound of the present invention may further contain a resin other than EVOH. Other resins include, for example, polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer. Examples include polyolefin resins such as polymers, ethylene-methyl methacrylate copolymers, and ionomer resins.

The inorganic layered compound-containing composition of the present invention obtained as described above can be used as an inorganic layered compound-containing resin composition by removing the solvent by drying or the like. The same EV as described above was added to the obtained inorganic layered compound-containing resin composition.
A resin other than OH may be mixed. As the mixing method, a general method used for mixing resins can be exemplified.

The composition containing an inorganic layered compound of the present invention can be formed into a molded product by a cast film forming method or the like. Further, a laminate can be formed by coating and drying on a substrate as described later. As a method for producing a laminate, for example, a method in which an inorganic layered compound-containing composition is dried and formed into a film (a method such as cast film formation) and then bonded to a substrate, or the composition is applied to the substrate and dried A coating method is generally used, and the latter is particularly preferably used.

Examples of the coating method include a direct gravure method, a reverse gravure method, a microgravure method, a two-roll beat coating method, a roll coating method such as a bottom feed three-reverse coating method, a doctor knife method, a die coating method, and a dip coating method. Methods, bar coating methods, and coating methods combining these methods.

In the case of forming a laminate, the thickness of the layer formed from the composition containing an inorganic layered compound is preferably 30 μm or less, more preferably 10 μm or less in terms of dry thickness, depending on the intended properties of the laminate. Further, when the thickness is 1 μm or less, the layer formed of the composition has an advantage that the transparency is remarkably high. The lower limit is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 100 nm or more, in order to obtain an effect.

The substrate is not particularly limited, and the form is not particularly limited, such as a film, a sheet, a bottle, and a tray. The material is resin, paper, aluminum foil, wood,
Known or general materials such as cloth and nonwoven fabric can be used according to the purpose and application. In particular, when it is in the form of a film, it may be uniaxially or biaxially stretched in addition to non-stretched. Of course, well-known undercoating or corona treatment may be applied, and these surface treatments may be applied not only to the film form but also to other forms of the substrate as long as the object of the invention is not impaired.

The resins constituting the base material include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene , Ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin and other polyolefin resins; polyethylene terephthalate (PE
T), polyester-based resins such as polybutylene terephthalate and polyethylene naphthalate; amide-based resins such as nylon-6, nylon-6,6, methaxylenediamine-adipic acid condensation polymer, and polymethylmethacrylimide;
Acrylic resins such as polymethyl methacrylate; styrene or acrylonitrile resins such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, and polyacrylonitrile; hydrophobicized cellulose resins such as cellulose triacetate and cellulose diacetate Resins; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polytetrafluoroethylene (Teflon); hydrogen-bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and cellulose derivatives; polycarbonate resins; Engineering plus for polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene oxide resin, liquid crystal resin, etc. Click resins.

The above-mentioned resin composition containing an inorganic layered compound can also be formed into a molded article such as a film by an ordinary method, and can be laminated on the above-mentioned substrate by an ordinary method such as coating, laminating and co-extrusion. To form a laminate.

When the substrate is a transparent material, the composition containing an inorganic layered compound and the resin composition containing an inorganic layered compound preferably have transparency. This transparency is 80% or more (and further 85%) in total light transmittance at a wavelength of 500 nm.
% Or more, especially 90% or more).
Such transparency can be suitably measured with, for example, a commercially available spectrophotometer (manufactured by Hitachi, Ltd., self-recording spectrophotometer 330). Further, the haze (HAZE) is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.
% Or less, and a commercially available haze meter (manufactured by Suga Test Instruments) is used for the measurement.

The laminate obtained by forming or laminating the inorganic layered compound-containing composition and the inorganic layered compound-containing resin composition of the present invention is used for various applications. For example,
Used as a retardation film using the birefringence, a gas / low-molecular diffusion barrier film / molded product utilizing the low-molecular diffusion delay effect of a layered structure, a greenhouse for agricultural facilities, a facility for tunnels, etc. be able to. When used as a gas barrier film for packaging foods and pharmaceuticals, the film can be used as a molded product by printing or further laminating another film.

From the viewpoint of gas barrier properties, a film obtained by removing the solvent from the inorganic layered compound-containing composition of the present invention and a film made of the inorganic layered compound-containing resin composition having a thickness of 1 μm at 23 ° C. and 50% RH Oxygen permeability below 3
Preferably 0cc / m ² · day · atm or less, more preferably not more than ^{5cc / m 2 · day · atm} , more preferably not more than ^{1cc / m 2 · day · atm} . When used for applications requiring more gas barrier properties, 0.1 cc / m ² · day · a
tm or less, preferably 0.05 cc / m ² · day · a
tm or less, more preferably 0.02 cc / m ² · day
-Atm or less is particularly preferred.

[0064]

According to the present invention, a well-dispersed composition comprising EVOH and an inorganic layered compound can be obtained, and a film or sheet having excellent gas barrier properties can be obtained by molding the composition. be able to. Further, the laminate is not only excellent in oxygen barrier properties, but also remarkably excellent in barrier properties of other gas molecules, such as helium, nitrogen, carbon dioxide gas, water, limonene, menthol, and other low-molecular aroma components. . ,

[0065]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 As an inorganic layered compound, high-purity montmorillonite (trade name Kunipia G; Kunimine Industries)
1 part by weight was added to 100 parts by weight of water while stirring, and the mixture was dispersed and stirred until a uniform liquid was obtained, thereby preparing an aqueous dispersion of montmorillonite having a concentration of about 1% by weight. While vigorously stirring the dispersion, 350 parts by weight of 2-propanol and 25 parts by weight of 1-butanol were gradually added, and the weight ratio of the dispersion medium was water / 2-propanol / 1-butanol = 2/7. The dispersion was adjusted to be 5 / 0.5. This is designated as solution A.

Further, EP-F101 (EV manufactured by Kuraray Co., Ltd.)
OH, ethylene copolymerization rate; 32%, below, EVOH-
5 parts by weight) was added to 95 parts of a solvent mixed at a weight ratio of water / 2-propanol = 3/7, dissolved by heating to about 80 ° C. and stirring for 4 hours, and EV
An OH-F solution was obtained. This is designated as solution B. Here, 56 parts of the liquid A and 694 parts of the liquid B were mixed to obtain 750 parts of the liquid C. Solution C is a solvent of water / 2-propanol / 1-butanol, and the weight ratio is water / 2-propanol / 1-butanol =
On 21/74/5, the solid content concentration calculated was 0.5.
6% by weight.

The liquid C was dispersed in a high-pressure dispersing apparatus (trade name: ultrahigh-pressure homogenizer M110-E / H, Microfluidics Corporati)
and 1 time treatment at 1750 kgf / cm ² to obtain a uniform dispersion having good dispersibility. This is designated as solution D.
The particle size of the inorganic layered compound in the solution D was 0.440 μm when measured in the same solvent.

Example 2 The solution D prepared in Example 1 was applied to a 12 μm-thick biaxially stretched polyethylene terephthalate film (internal corona treated product, trade name: Spet T410)
2; manufactured by Toyobo Co., Ltd.), a microgravure coater, a line speed of 6 m / min, and a drying temperature of 100 ° C.
And dried so as to have a dry film thickness of 0.05 μm to obtain a laminate. In addition, a 40 μm-thick non-stretched LLDPE film (internal corona-treated product)
When TUS-FCS # 40 (manufactured by Tosello Co., Ltd.) was dry-laminated using a commercially available adhesive, a laminate having good transparency in appearance was obtained.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing the internal structure of a high-pressure dispersing apparatus and a mechanism for dispersing particles in a fine state by high-pressure, high-shear processing.

FIG. 2 shows an X-ray diffraction peak of an inorganic layered compound,
It is a graph which shows the relationship with the "unit thickness a" of this compound typically.

FIG. 3 is a graph showing X of a resin composition containing an inorganic layered compound;
4 is a graph schematically showing a relationship between a line diffraction peak and “plane spacing d” of the composition.

FIG. 4 is an X-ray diffraction peak of the resin composition when a peak corresponding to “plane spacing d” overlaps with a halo (or background) and is difficult to detect;
It is a graph which shows typically the relationship with the "plane spacing d" of this composition. In this figure, the area of the portion excluding the base line on the lower angle side than 2θd is set as the peak corresponding to “surface interval d”.

[Explanation of symbols]

 A: Sample injection B: Pump pressurization C: Channel branch D: Collision / shear E: Pressure release / processing completed

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08J 5/18 CER C08J 5/18 CER G02F 1/1333 505 G02F 1/1333 505

Claims (22)

[Claims] 1. An inorganic layered product obtained by treating a saponified ethylene-vinyl ester copolymer, an inorganic layered compound and a solvent containing water at a weight ratio of 1/10 or more in a high-pressure dispersing apparatus. Compound-containing composition. 2. The compounding ratio of the inorganic layered compound and the saponified ethylene-vinyl ester copolymer is a volume ratio (inorganic layered compound /
Saponified ethylene-vinyl ester copolymer)
The composition containing an inorganic layered compound according to claim 1, wherein the composition ratio is from 1/100. 3. The composition containing an inorganic layered compound according to claim 1, wherein the inorganic layered compound has an aspect ratio of 50 or more and 5000 or less. 4. The composition containing an inorganic layered compound according to claim 1, wherein the particle size of the inorganic layered compound is 1 μm or less. 5. The composition containing an inorganic layered compound according to claim 1, wherein the high-pressure dispersion apparatus performs the dispersion treatment under a pressure condition of 100 kgf / cm ² or more. 6. A solvent obtained by treating a solvent containing a saponified ethylene-vinyl ester copolymer, an inorganic layered compound and water at a weight ratio of 1/10 or more with a high-pressure dispersing apparatus and then removing the solvent. A resin composition containing an inorganic layered compound. 7. A composition comprising the composition containing an inorganic layered compound according to any one of claims 1 to 5 and another resin. 8. A resin composition comprising the resin composition containing an inorganic layered compound according to claim 6 and another resin. 9. The film obtained by removing the solvent has an oxygen permeability of 30 cc / m ² · day · atm or less at 23 ° C. and 95% RH (relative humidity) per 1 μm thickness. Item 6. The composition containing an inorganic layered compound according to any one of Items 1 to 5. 10. A film having a thickness of 23 per μm of the obtained film.
Oxygen permeability at 30 ° C. and 95% RH (relative humidity)
The resin composition containing an inorganic layered compound according to claim 6, wherein the resin composition is not more than cc / m ² · day · atm. 11. A laminate obtained by applying and drying a composition containing an inorganic layered compound according to any one of claims 1 to 5 on a substrate. 12. A laminate having at least one layer comprising the resin composition containing an inorganic layered compound according to claim 6. 13. A laminate obtained by applying and drying the composition according to claim 7 on a substrate. 14. A laminate having at least one layer comprising the resin composition according to claim 8. (15) A molded article comprising the resin composition containing an inorganic layered compound according to (6). 16. The molded article according to claim 15, wherein the molded article is a film. 17. The laminate according to claim 11, which is used for packaging. 18. The method according to claim 15, which is used for packaging.
The molded article as described. 19. The liquid crystal display device according to claim 11, which is used for a liquid crystal display device.
A laminate according to any one of the preceding claims. 20. The molded article according to claim 15, which is used for a liquid crystal display device. 21. The method according to claim 11, which is used for facility horticulture.
A laminate according to any one of the preceding claims. 22. The molded article according to claim 15, which is used for greenhouse horticulture.