JPH09157406A - Gas barrier resin composition and film - Google Patents

Abstract

(57) Abstract: To provide a resin composition and a film having excellent transparency and gas barrier properties. A resin composition containing an inorganic layered compound, wherein the total Haze (%) and the volume fraction of the inorganic layered compound [=
Inorganic layered compound / (inorganic layered compound + resin)] is in the range of the following formula: A resin composition or film. 5 <[(total Haze (%)) / (inorganic layered compound volume fraction)] <50.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, a film and a laminate having excellent gas barrier properties.

[0002]

BACKGROUND OF THE INVENTION Although various functions are required for packaging, various gas barrier properties for protecting contents are important properties that affect the storability of foods. Distribution forms, diversification of packaging technology, regulation of additives However, due to changes in tastes and the like, the need for it is increasing. The gas barrier property was also a weak point of general plastic materials. Oxygen, light, heat, water, etc.
Above all, oxygen is important as a substance causing it. The barrier material is a material that is indispensable for effectively blocking oxygen and at the same time controlling the deterioration of foods such as gas filling and vacuum packaging.In addition to oxygen gas, various gases, organic solvent vapors, fragrances, etc. By having a barrier function, it can be used for rust prevention, deodorization, and sublimation prevention, and food such as confectionery bags, skipjack packs, retort pouches, carbon dioxide beverage containers,
It is used in many fields such as cosmetics, pesticides, and medical care.

[0003] Among the films made of thermoplastic resin, oriented films such as polypropylene, polyester and polyamide have excellent mechanical properties, heat resistance and transparency and are widely used as packaging materials. I have. However, when these films are used for food packaging, the barrier properties against oxygen and other gases are insufficient,
Various problems such as oxidative deterioration and alteration of contents due to aerobic microbes, permeation of aroma components, loss of flavor, and moistening of contents by external moisture, resulting in poor mouthfeel. Tend to occur. Therefore, a method such as stacking another film layer having a good gas barrier property is usually adopted.

Conventionally, various transparent plastic materials having a high gas barrier property have been known. For example, although there are films made of polyvinyl alcohol, polyethylene vinyl alcohol copolymer and polyvinylidene chloride resin, they can be bottled and bottled. While the metal and glass materials used have almost zero oxygen permeability, these plastic materials are still permeable to oxygen that cannot be ignored. In addition, when aluminum foil is used for packaging, the gas barrier property is excellent, but the content cannot be seen.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a resin composition having excellent transparency and gas and water vapor barrier properties, a molded article such as a film, and a molded article such as a film laminate.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, arrived at the present invention. That is, the present invention is a resin composition containing an inorganic layered compound, wherein the total Haze (%) and the inorganic layered compound volume fraction [=
Inorganic layered compound / (inorganic layered compound + resin)] is in the range of the following formula: A resin composition or film. 5 <[(total Haze (%)) / (inorganic layered compound volume fraction)] <50.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The “inorganic layered compound” used in the present invention refers to an inorganic compound in which unit crystal layers are stacked on each other to form a layered structure. In other words, a “layered compound” is a compound or substance having a layered structure. A “layered structure” is defined as a surface in which atoms are strongly bonded by covalent bonds or the like and arranged densely, and van der Waals A structure that is stacked in parallel by a weak coupling force such as force. Examples of the "inorganic layered compound" used in the present invention include those having an "aspect ratio" measured by the method described below of usually 50 or more and 5,000 or less and a particle size of 5 µm or less.

From the viewpoint of gas barrier properties, the aspect ratio is preferably 100 or more, more preferably 200 or more. It is technically difficult to obtain an inorganic layered compound having an aspect ratio of more than 5000, and it is costly and economically expensive. In terms of easy manufacturing, the aspect ratio is 2000 or less (further 15
00 or less) is preferable. From the viewpoint of the balance between gas barrier properties and easiness of production, the aspect ratio is preferably in the range of 200 to 3000.

From the viewpoint of film formability or moldability when formed into a film, the "particle size" of the inorganic layered compound measured by the method described below is preferably 5 μm or less. If the particle size exceeds 5 μm, the film-forming property or moldability of the resin composition tends to deteriorate. From the viewpoint of the transparency of the resin composition, the particle size is more preferably 3 μm or less.

When the film of the present invention is used in applications where transparency is important (for example, food packaging applications), it is particularly preferable that the particle size be 1 μm or less. Also,
This transparency has a total light transmittance of 500 nm at a wavelength of 80
% Or more (further 85% or more) is desirable. Such transparency can be preferably measured by, for example, a commercially available spectrophotometer (manufactured by Hitachi, Ltd., self-recording spectrophotometer Model 330).

Specific examples of the inorganic layered compound used in the present invention include graphite, phosphate derivative type compounds (zirconium phosphate type compounds, etc.), clay minerals, chalcogenides [Group IV (Ti, Zr, Hf). ), V group (V,
Nb, Ta) and Group VI (Mo, W) dichalcogenides of the formula MX ₂ . Here, X represents chalcogen (S, Se, Te). ] Etc. can be mentioned.

The particle size of the inorganic layered compound used in the present invention means the particle size determined by the dynamic light scattering method in a solvent.
Although it is extremely difficult to measure the true particle size in the resin composition, when the resin is sufficiently swollen with the same kind of solvent as the solvent used in the dynamic light scattering method to be combined with the resin, the inorganic layered compound in the resin is used. Can be considered to be close to the particle size in the solvent.

The aspect ratio (Z) of the inorganic layered compound used in the present invention is represented by the relationship Z = L / a.
L is a particle size obtained by a dynamic light scattering method in a solvent,
a is a unit thickness of the inorganic layered compound (unit thickness a
Is a value determined by measurement of the inorganic layered compound alone by a powder X-ray diffraction method or the like. ). However, in Z = L / a, the interplanar spacing d of the inorganic layered compound obtained from the powder X-ray diffraction of the composition is present, and the relationship of a <d is satisfied. Here, the value of da is larger than the width of the resin single chain in the composition. The above Z is not necessarily the true aspect ratio of the inorganic layered compound in the resin composition, but for the following reasons,
It is quite valid.

It is extremely difficult to directly measure the aspect ratio of the inorganic layered compound in the resin composition. Composition powder X
There is a relationship of a <d between the interplanar spacing d of the inorganic layered compound obtained by the line diffraction method and the unit thickness a determined by the powder X-ray diffraction measurement of the inorganic layered compound alone, and the value of da is the composition. If the width is equal to or more than the width of the resin single chain in the product, the resin is inserted between the layers of the inorganic layered compound in the resin composition, and thus the thickness of the inorganic layered compound is the unit thickness a. it is conceivable that. In addition, it is extremely difficult to measure the true particle size in the resin composition, but in the case of swelling sufficiently with a solvent of the same kind as the solvent used in the dynamic light scattering method to form a composite with the resin, The particle size of the inorganic layered compound in can be considered to be quite close to that in the solvent (however,
Since it is considered that the particle size L determined by the dynamic light scattering method does not exceed the major axis Lmax of the inorganic layered compound, the true aspect ratio Lmax / a should be less than the definition Z of the aspect ratio in the present invention. Is theoretically impossible. ). From the above two points, the definition of the aspect ratio of the present invention is considered to be relatively valid. The aspect ratio or particle size used in the present invention means the aspect ratio and particle size defined above.

From the viewpoint of easily giving a large aspect ratio, an inorganic layered compound having a property of swelling and cleaving in a solvent is preferably used. The degree of "swelling / cleavage" of the inorganic layered compound used in the present invention in a solvent can be evaluated by the following "swelling / cleavage" test. The swelling property of the inorganic layered compound is about 5 in the following swelling test.
It is preferable that it is above (further more than about 20). 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 layered compound is a natural swellable clay mineral, it is preferable to use water as the solvent.

<Swellability Test> 100 mL of a solvent is placed in a 100 mL graduated cylinder, and 2 g of the inorganic layered compound is slowly added thereto. 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 the 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 larger this value, the higher the cleavage.

As the inorganic layered compound which swells and cleaves in the solvent used in the present invention, clay minerals which have a swelling and cleaving property in the solvent are particularly preferably used. Clay-based minerals generally have an octahedral layer with a central metal such as aluminum or magnesium on top of a tetrahedral layer of silica.
It is classified into a type having a layered structure and a type having a three-layered structure in which a tetrahedral layer of silica has an octahedral layer having aluminum, magnesium or the like as a central metal narrowed from both sides. Examples of the former include kaolinite group and antigolite group, and examples of the latter include smectite group, vermiculite group and mica group depending on the number of interlayer cations. Specifically, kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilylic mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite. , Xanthophyllite, chlorite and the like.

The solvent for swelling the present inorganic layered compound is not particularly limited. For example, in the case of a natural swelling clay mineral, water, alcohols such as methanol, dimethylformamide, dimethylsulfoxide, acetone and the like can be mentioned, preferably. , And alcohols such as water and methanol.

The resin used in the present invention is not particularly limited, but for example, polyvinyl alcohol (PV
A), ethylene-vinyl alcohol copolymer (EVO
H), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), polysaccharides, polyacrylic acid and its esters, and the like.

An example of a preferred resin has a weight percentage of hydrogen-bonding groups or ionic groups of 2 per unit weight of resin.
A high hydrogen bonding resin satisfying a ratio of 0% to 60% is exemplified. More preferred examples include those in which the weight percentage of the hydrogen bonding group or the ionic group per unit weight of the high hydrogen bonding resin satisfies the ratio of 30% to 50%. Examples of the hydrogen bonding group of the high hydrogen bonding resin include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like, and examples of the ionic group include a carboxylate group, a sulfonic acid ion group, and a phosphoric acid group. Examples include an ionic group, an ammonium group, and a phosphonium group. Among the hydrogen-bonding groups or ionic groups of the high hydrogen-bonding resin, more preferred are a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, and an ammonium group. Can be

Specific examples of the high hydrogen-bonding resin include, for example, polyvinyl alcohol and a vinyl alcohol fraction of 4
1 mol% or more of ethylene-vinyl alcohol copolymer,
Polysaccharides such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, cellulose, pullulan, chitosan, polyacrylic acid, sodium polyacrylate, polybenzenesulfonic acid, Examples thereof include sodium polybenzenesulfonate, polyethyleneimine, polyallylamine, ammonium salts thereof, polyvinylthiol, polyglycerin, and the like.

More preferable examples of the high hydrogen bond resin include polyvinyl alcohol and polysaccharides.
The polyvinyl alcohol used in the layer containing the inorganic layered compound of the present invention is a polymer having a monomer unit of vinyl alcohol as a main component. Examples of such polyvinyl alcohol include polymers obtained by hydrolyzing or transesterifying (saponifying) the acetic ester portion of a vinyl acetate polymer (that is, a copolymer of vinyl alcohol and vinyl acetate), , A polymer obtained by saponifying a trifluorovinyl acetate polymer, a vinyl formate polymer, a vinyl pivalate polymer, a t-butyl vinyl ether polymer, a trimethylsilyl vinyl ether polymer and the like. , "PVA World", 1992, Polymer Publishing Co., Ltd .; Nagano et al., "Poval", 1981, Polymer Publishing Co., Ltd.).

"Saponification" in polyvinyl alcohol
The degree is preferably 70% or more, more preferably 85% or more, and more preferably 98% or more so-called completely saponified product in terms of molar percentage. The degree of polymerization is 10
0 or more and 5000 or less are preferable, and 200 or more and 3000 or less are more preferable.

The above-mentioned polysaccharides are biopolymers synthesized in a biological system by polycondensation of various monosaccharides, and here, those chemically modified based on them are also included. Examples thereof include cellulose and cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin and chitosan.

When the resin used in the present invention is a highly hydrogen-bonding resin, a crosslinking agent for a hydrogen-bonding group may be used for the purpose of improving its water resistance (meaning the barrier property after a water-resistant environmental test). it can.

The crosslinking agent for hydrogen-bonding group is not particularly limited, but examples thereof include titanium coupling agents, silane coupling agents, melamine coupling agents, epoxy coupling agents, isocyanate coupling agents,
A copper compound, a zirconia compound, etc. are mentioned, More preferably, a zirconia compound is mentioned.

Specific examples of the zirconia compound include zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride, zirconium halides such as zirconium bromide, zirconium sulfate, basic zirconium sulfate, zirconium nitrate and other mineral acids. Salts, zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium salts of organic acids such as zirconium stearate, ammonium zirconium carbonate, sodium zirconium sulfate,
Examples thereof include zirconium ammonium acetate, zirconium sodium oxalate, sodium zirconium citrate, zirconium ammonium citrate, and other zirconium complex salts.

The amount of the cross-linking agent for hydrogen-bonding groups added is the ratio (K) of the number of moles of cross-linking groups (CN) of the cross-linking agent to the number of moles of hydrogen-bonding groups (HN) of the high hydrogen-bonding resin. (Ie K = C
N / HN) is not particularly limited as long as it is in the range of 0.001 to 10, but is preferably in the range of 0.01 to 1.

The volume fraction of the inorganic layered compound used in the present invention means the composition of the inorganic layered compound and the resin.
The volume fraction represented by the formula: [inorganic layered compound / (inorganic layered compound + resin)] is shown. The volume fraction of the inorganic layered compound is not particularly limited, but is generally in the range of 0.05 to 0.9, and 0.05 to 0.5.
Is preferably within the range. Also, 0.05 to 0.3
In the range of, the flexibility of the film is improved, and 0.07 to 0.1
In the range of 7, there is an advantage that the deterioration of the barrier property due to bending is small and the peel strength is strong.

The method of blending the composition comprising the inorganic layered compound and the resin is not particularly limited, but for example, a solution prepared by dissolving the resin in a solvent and a dispersion prepared by swelling and cleaving the inorganic layered compound in the solvent in advance are used. After mixing, the method of removing the solvent, the dispersion of the inorganic layered compound swollen and cleaved in the solvent is added to the resin, the method of removing the solvent, the inorganic layered compound is added to the liquid in which the resin is dissolved, and after swelling and cleavage , The method of removing the solvent,
Moreover, the method of heat-kneading a resin and an inorganic layered compound, etc. are mentioned. The former three methods are particularly preferably used as a method for easily obtaining a large aspect ratio.

In the former three methods described above, in order to improve the water resistance of the film (meaning the barrier property after the water resistance environment test), after removing the solvent from the system, 110 ° C. to 220 ° C.
It is preferable to heat-age at ° C. At this time, the aging time is not limited, but it is necessary for the film to reach at least the set temperature, and in the case of a method using a heating medium contact such as a hot air dryer, it is preferably 1 second or more and 100 minutes or less. There is no particular limitation on the heat source, and various methods such as heat roll contact, heat medium contact (air, oil, etc.), infrared heating, microwave heating, etc. can be applied. Further, the effect of the water resistance, when the resin is a high hydrogen bond resin,
It is remarkably excellent when the inorganic layered compound is a swelling clay mineral.

The total haze used in the present invention is JI.
As described in SK 7105 "Method for testing optical properties of plastics", the formula: [(scattered light transmittance /
The total light transmittance) × 100] is a value shown in%.

The resin composition of the present invention is molded into various forms for use. The form of the molded product is not particularly limited,
When used for packaging, such as films, sheets, containers (tray, bottles, etc.), the gas barrier property is sufficiently exhibited. Also, they are often used in stacked form.

The substrate on which the resin composition layer containing the inorganic layered compound of the present invention is laminated is not particularly limited, and may be resin, paper,
Examples include general base materials such as aluminum foil, wood, cloth, and non-woven fabric. As the resin used as the base material, polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene- Vinyl acetate copolymer, ethylene-methylmethacrylate copolymer, polyolefin resin such as ionomer resin, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6, nylon-
6,6, metaxylenediamine-adipic acid polycondensation polymer,
Amide resin such as polymethylmethacrylimide, acrylic resin such as polymethylmethacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene such as polyacrylonitrile, acrylonitrile resin, triacetic acid Hydrophobic cellulosic resins such as cellulose and cellulose diacetate, halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride and Teflon, hydrogen bonding properties such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer and cellulose derivatives Resin, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyphenylene oxide resin, polymethylene oxide resin, liquid crystal resin, etc. And engineering plastics resins and the like.

Of these, in the laminate in the form of a film, the outer layer is biaxially stretched polypropylene,
Polyethylene terephthalate, nylon, biaxially stretched polypropylene coated with polyvinylidene chloride called K coat, polyethylene terephthalate, nylon and the like are preferably arranged.

The non-stretched thermoplastic resin layer used as the sealant layer in the present invention is a film obtained by extrusion molding a thermoplastic resin by an inflation molding method, a T-die molding method or the like, and has substantially no resin orientation. It is a small film. The film thickness is not particularly limited, but it is 1 μm to obtain sufficient heat seal strength.
The thickness is preferably m or more.

The thermoplastic resin used in the non-stretched thermoplastic resin layer is not particularly limited, but polypropylene, polyethylene (low density, high density) is used because of heat seal strength, desorption of food scent, resin odor and the like. , Ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-4-methyl-1
-Pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer resin Polyolefin resins such as, and polyester resins such as polyethylene terephthalate and polybutylene terephthalate are preferably used.

The method for laminating the layer containing the inorganic layered compound on the non-stretched thermoplastic resin layer is not particularly limited, but for example, the resin composition containing the inorganic layered compound may be applied to the non-stretched thermoplastic resin layer. Apply the working fluid to the surface of the substrate, dry,
Preferred examples include a coating method of heat treatment, a method of laminating a layer containing an inorganic layered compound later, and a method of extruding and laminating a thermoplastic resin layer on a layer containing an inorganic layered compound. Further, the interface between the two may be treated with a corona treatment or an anchor coating agent.

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

The thickness of the coating film is not particularly limited, but the dry thickness is preferably 10 μm or less, more preferably 1 μm or less (if it is 1 μm or less, the transparency of the laminate is remarkably excellent, and thus the transparency is improved). Is more preferable for the required use of. The lower limit is not particularly limited, but 1n is required to obtain an effective gas barrier effect.
It is preferably m or more, and more preferably 10 nm or more.

Further, within a range that does not impair the effects of the present invention,
The resin composition and the film may be mixed with various additives such as an ultraviolet absorber, a colorant and an antioxidant. The present invention includes a laminated film or laminate having at least one film layer described above.

[0043]

INDUSTRIAL APPLICABILITY The resin composition of the present invention and the molded product or laminated product such as a film made of the resin composition have excellent transparency and excellent gas barrier property and water vapor barrier property, and therefore have various uses including food packaging. Can be used for

In order to reduce the value of Haze in the present invention, for example, by increasing the rotation speed ratio G / B between the G roll and the B roll of the reverse gravure coating method, Haze is lowered, and The total haze also decreases by increasing the speed difference (GB). Even if the total Haze is reduced, the internal Haze value is constant and the external Haze is reduced. Further, when the oxygen gas barrier property and the total Haze value are plotted, the oxygen gas barrier property exponentially improves as the total Haze value decreases. From this, it is assumed that the inorganic layered compound was oriented parallel to the substrate due to shearing during coating. Then, it is considered that the maze effect of the inorganic crystals was improved and the oxygen permeability was further lowered due to the inorganic layered compound being oriented horizontally on the substrate. In this way, the rotation speed ratio G / B of the reverse gravure coating method G /
Increase B or speed difference between G roll and B roll (G-
By increasing B), the transparency of the coating film can be improved and the oxygen permeability can be expected to decrease.

The resin composition of the present invention is excellent in transparency and has a high level of barrier properties that cannot be imagined from conventional materials. The resin composition of the present invention can be used for applications in which a metal such as aluminum foil or glass or an inorganic material is indispensable from the viewpoint of barrier properties, and is also excellent in transparency. It can be said that it is a material that breaks the common sense of the composition (needless to say, the present invention, which is a resin composition, is superior to them in regard to weaknesses such as opacity of metals and brittleness of ceramics).

The use of the molded product of the present invention as a packaging material is, as a film, miso, bonito flakes, confectionery, ramen,
Used for foods such as hams, sausages, tetra packs, packed rice, curry, stew, etc. for boiling and retort, bottles for squeeze bottles such as mayonnaise, juice, soy sauce, sauce, edible oil, etc. As a tray, a cup of yogurt or pudding,
Used in a wide range of applications in various shapes, such as trays for microwave oven foods, as well as infusion packs, semiconductor packaging, oxidizing chemical packaging, precision material packaging, and other medical, electronic, chemical, mechanical, and other industrial material packaging. It is what is done.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
The methods for measuring physical properties are described below.

[Haze]: Measured with a haze meter of Suga Test Instruments. [Thickness measurement]: The thickness of 0.5 μm or more was measured using a commercially available digital thickness meter (contact type thickness meter, trade name: ultra-high precision decimicro head MH-15M, manufactured by Nihon Kogaku Co., Ltd.). On the other hand, if the thickness is less than 0.5 μm, the weight analysis method (the weight measurement value of a film of a certain area is divided by
Furthermore, in the case of the laminate of the composition of the present invention and the substrate, the elemental analysis method (specific inorganic elemental analysis value of the laminate (derived from the composition layer) and the inorganic layered compound alone) The method of determining the ratio of the resin composition layer of the present invention to the base material) from the ratio of the specific element fractions. [Measurement of particle size]: Measured under the conditions of an ultrafine particle size analyzer (BI-90, manufactured by Brookhaven Co., Ltd.), temperature of 25 ° C., and water solvent. The central diameter determined by the photon correlation method by the dynamic light scattering method was defined as the particle diameter L. [Aspect ratio calculation]: X-ray diffractometer (XD-5A,
(Manufactured by Shimadzu Corporation), using an inorganic layered compound alone,
Diffraction measurement of the resin composition was performed by the powder method. Thus, the plane spacing (unit thickness) a of the inorganic layered compound was determined, and diffraction analysis of the resin composition confirmed that there was a portion where the plane spacing of the inorganic layered compound was widened. Using the particle size L obtained by the dynamic light scattering method described above, the aspect ratio Z was determined by the formula Z = L / a.

[Coating Liquid A] Polyvinyl alcohol (PV
A117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, degree of polymerization
1700 and PVA103; manufactured by Kuraray Co., Ltd., saponification degree: 9
Mix 8.5% and 300 degree of polymerization in equal amount with deionized water (0.7 μS)
/ cm) to 4.0 wt% and used as the resin solution (B). Natural montmorillonite (Kunipia F; manufactured by Kunimine Industries Co., Ltd.) was dispersed in the resin solution (B) as powder (C) at 6.0 wt% to obtain a resin composition (mixed composition liquid). Further, (B) and (C) were mixed such that the solid component ratio (volume ratio) of each of them was inorganic layered compound / resin = 2/8. Zirconium ammonium carbonate (manufactured by Daiichi Rare Element Industry Co., Ltd .; Zircosol AC7 (aqueous solution containing 15 wt% in terms of zirconium oxide)) was used as a cross-linking agent for hydrogen-bonding groups in the liquid mixture, based on 15 mol of hydroxyl groups of polyvinyl alcohol. Coating solution A was added to the mixture so that the ratio was 1 mol.

[Example 1] A coating solution A was prepared by using a surface-corona-treated biaxially stretched polyethylene terephthalate (OPET) film (Lumira-Q27; manufactured by Toray Industries, Inc.) having a thickness of 12 µm as a base material. Direct reverse coating (test coater; Inoue Metal Industry Test No. 3 machine, rotation speed ratio G / B between gravure roll (G roll) and backing roll (B roll) is 100%, gravure roll mesh diagonal line ( Number of markings per inch of roll) # 200, drying temperature 100 ° C), coating speed 20 m / min, speed difference (G-
B) Reverse gravure coating was performed at 40 m / min. The thickness of the obtained film was 224 nm, the total Haze was 8.3 and the external Haze was 7.3.

[Embodiment 2] The rotational speed ratio G / B is set to 150.
% And the speed difference (GB) was changed to 50 m / min. The thickness of the obtained film is 144
nm, total Haze is 6.6, external Haze is 5.
It was 6.

[Embodiment 3] The rotation speed ratio G / B is set to 200.
%, And the speed difference (GB) was changed to 60 m / min. The thickness of the obtained film is 96n
m, the total Haze is 5.3, and the external Haze is 4.3.
Met.

[Embodiment 4] The rotational speed ratio G / B is set to 250.
%, And the speed difference (GB) was changed to 70 m / min. The thickness of the obtained film is 48n
m, the total Haze is 4.4 and the external Haze is 3.4.
Met.

Example 5 Example 5 was repeated except that the coating speed was changed to 100 m / min and the speed difference (GB) was changed to 200 m / min. The thickness of the obtained film was 160 nm, the total Haze was 4.5 and the external Haze was 3.5.

[Embodiment 6] The rotation speed ratio G / B is set to 120.
%, Coating speed 100 m / min, speed difference (GB) 220
The same procedure as in Example 1 was repeated except that m / min was used instead. The thickness of the obtained film was 96 nm, and the total Haze was 3.
8, the external Haze was 2.8.

[Embodiment 7] The rotation speed ratio G / B is set to 250.
%, Coating speed 100 m / min, speed difference (GB) 350
The same procedure as in Example 1 was repeated except that m / min was used instead. The thickness of the obtained film was 38 nm, and the total Haze was 2.
7, the external Haze was 1.7.

[Example 8] A coating liquid A was prepared by using a surface-corona-treated biaxially stretched polyethylene terephthalate (OPET) film (Lumira-Q27; manufactured by Toray Industries, Inc.) having a thickness of 12 µm as a substrate. Direct reverse coating (test coater; Inoue Metal Industry Test No. 3 machine, rotation speed ratio G / B between gravure roll (G roll) and backing roll (B roll) is 100%, gravure roll mesh diagonal line # 80, drying temperature 100 ℃), coating speed 125m /
Reverse gravure coating was carried out for a minute (speed difference (GB) 250 m / min). The thickness of the obtained film is 401n
m, the total Haze is 9.2, and the external Haze is 8.2.
Met.

Example 9 The procedure of Example 8 was repeated except that the coating speed was changed to 175 m / min and the speed difference (GB) was changed to 350 m / min. The thickness of the obtained film was 337 nm, the total Haze was 7.5, and the external Haze was 6.5.

[Example 10] Example 8 except that the coating speed was changed to 300 m / min and the speed difference (GB) was changed to 600 m / min.
The same was done. The thickness of the obtained film is 350 nm
The total Haze was 7.2 and the external Haze was 6.2.

[Example 11] Example 8 except that the coating speed was changed to 400 m / min and the speed difference (GB) was changed to 800 m / min.
The same was done. The thickness of the obtained film is 320 nm
And the total haze was 7.1 and the external haze was 6.1.

Example 12 The procedure of Example 8 was repeated except that the coating speed was changed to 500 m / min and the speed difference (GB) was changed to 1000 m / min. The thickness of the obtained film is 295n
m, the total Haze is 5.8, and the external Haze is 4.8.
Met.

Comparative Example 1 A coating liquid A was prepared by using a surface-corona-treated biaxially stretched polyethylene terephthalate (OPET) film (Lumira-Q27; manufactured by Toray Industries, Inc.) having a thickness of 12 μm as a base material. Micro gravure coating (test coater; Yasui Seiki: micro gravure coating method, gravure roll (G roll) and backing roll (B roll)
The rotation speed ratio G / B to 200%, coating speed 3 m /
Min, speed difference (GB) of 9 m / min, gravure roll mesh diagonal line # 90, drying temperature 100 ° C.). The thickness of the obtained film was 976 nm, and the total Haze was 2
The external Haze was 3.0 and the external Haze was 22.0.

[Comparative Example 2] A coating liquid A was prepared by using a 12 μm thick biaxially stretched polyethylene terephthalate (OPET) film (Lumira-Q27; manufactured by Toray Industries, Inc.) as the base material and having the surface corona treated. Was hand coated by bar coating (drying temperature 100 ° C.). The thickness of the obtained film is 5
50 nm, total Haze is 24.2, external Haze
Was 23.2.

[Comparative Example 3] A biaxially oriented polypropylene (OPP) film (Pyrene P2102; manufactured by Toyobo Co., Ltd.) having a thickness of 20 μm, the surface of which was corona-treated, was used as a base material.
The coating liquid A was hand-coated by bar coating (drying temperature 100 ° C.). The thickness of the obtained film was 600 nm, the total Haze was 25.0 and the external Haze was 23.5.
Met.

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Claims (15)

[Claims] 1. A resin composition containing an inorganic layered compound, wherein the total Haze (%) and the volume fraction of the inorganic layered compound [=
Inorganic layered compound / (inorganic layered compound + resin)] is in the range of the following formula: A resin composition or film. 5 <[(total Haze (%)) / (inorganic layered compound volume fraction)] <50. 2. The resin composition or film according to claim 1, wherein the inorganic layered compound has a particle size of 5 μm or less and an aspect ratio of 50 to 5,000. 3. The resin composition or film according to claim 2, wherein the inorganic layered compound swells and cleaves in a solvent. 4. The resin composition or film according to claim 3, wherein the inorganic layered compound is a clay mineral. 5. The aspect ratio of the inorganic layered compound is 200.
It is -3000, The resin composition or film of Claim 2, 3 or 4 characterized by the above-mentioned. 6. An inorganic layered compound having a volume fraction of 0.05 to
The resin composition or film according to claim 1, wherein the resin composition or film is in the range of 0.9. 7. The resin composition or film according to claim 1, wherein the resin is a high hydrogen-bonding resin. 8. The high hydrogen-bonding resin has a weight percentage of hydrogen-bonding groups or ionic groups per unit weight of resin of 30% to.
It is 50%, The resin composition or film of Claim 7 characterized by the above-mentioned. 9. The resin composition according to claim 7, wherein the high hydrogen-bonding resin is polyvinyl alcohol or a polysaccharide, or a film comprising the same. 10. A laminated film or laminate having at least one layer of the film according to any one of claims 1 to 9. 11. A laminated film or a laminate having at least one layer of the film according to claim 1, wherein the film thickness is in the range of 1 nm to 10 μm. 12. At least one layer of the film according to claim 1 and biaxially oriented polypropylene, 2
A laminated film or laminate having at least one layer selected from axially stretched nylon and biaxially stretched polyethylene terephthalate. 13. The oxygen permeability at 31 ° C. and 61% RH per 1 μm thickness is ² cc / m ² · day · atm or less, according to any one of claims 1 to 12. The resin composition or film of. 14. The oxygen permeability at 31 ° C. and 61% RH per 1 μm of thickness is 0.2 cc / m ² · day · atm or less, according to any one of claims 1 to 12. The resin composition or film as described in 1. 15. The inorganic layered compound swollen and cleaved in a solvent is dispersed in a resin or a resin solution, and the solvent is removed from the system while maintaining the dispersed state. A method for producing the resin composition or film according to item 1.