JP2000318092A - Gas barrier laminated film and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated film having high oxygen and steam barrier properties by providing a layer made of a resin exhibiting optical anisotropy when melted and a layer made of a composition containing an inorganic layer compound and a resin. SOLUTION: The gas barrier laminated film is formed by providing a layer made of a resin exhibiting optical anisotropy when melted and a layer made of a composition containing an inorganic layer compound and a resin. The container is formed by using the laminated film. Then, as the resin exhibiting the anisotropy when melted, a liquid crystal polyester resin composition having a liquid crystal polyester as a continuous phase and a copolymer having a functional group including a reactivity with the polyester as a dispersing phase is preferably used. As the polyester, a polymer called a 'thermotropic liquid crystal polymer' is used. Specifically, a composition obtained by reacting an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a gas barrier laminated film and a container.

[0002]

2. Description of the Related Art Various functions are required for containers. Those
Gas barrier properties for long-term storage of contents
Is very important. Particularly in recent years, oxygen permeability <1c
c / m ^Two・ 1atm ・ 24hr, water vapor permeability <1
g / m^Two・ Gas burrs satisfying both 1atm ・ 24hr
Packaging materials are being demanded. In such applications
Generally, aluminum foil has been used.
And pinholes occur when mechanical stress is applied
In some cases, the gas barrier properties were significantly reduced. oxygen
Ethylene / vinyl alcohol copolymer for barrier properties
It is known that the body shows high barrier properties,
It is susceptible to effects and significantly reduces oxygen barrier properties under high humidity.
There were problems such as getting up. Also, JP-A-3-6153
0, JP-A-3-63127, JP-A-3-7
No. 6640 and the like, the surface of a thermoplastic resin silicon
A gas barrier material on which an oxide or the like is deposited is disclosed
However, due to mechanical stress during bending and processing,
Cracks occur in the oxide layer, reducing gas barrier properties
And other problems. In addition, it consists of liquid crystalline polymer
Films having excellent gas barrier properties have also been disclosed (Japanese Patent Application Laid-Open
JP-A-53-86798, JP-A-7-304936
Gazette, Japanese Patent Application Laid-Open No. 9-286907).
It is desirable to improve the barrier properties.

[0003]

SUMMARY OF THE INVENTION The present invention provides high oxygen,
It is an object of the present invention to provide a film and a container having a water vapor barrier property.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the use of a resin having optical anisotropy at the time of melting and a composition comprising an inorganic layered compound and a resin. The inventors have found that the above problems can be solved, and have completed the present invention. That is, the present invention provides a gas barrier laminate film having a layer made of a resin exhibiting optical anisotropy when melted, and a layer made of a composition composed of an inorganic layered compound and a resin, and a container made of the gas barrier laminate film. Such is the case.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Various resins that exhibit optical anisotropy when melted used in the present invention are known as liquid crystalline polymers, such as wholly aromatic or semi-aromatic polyesters, polyesterimides, polyesteramides, and the like. And the like. In the present invention, a liquid crystal polyester or a composition using a liquid crystal polyester as one component is preferably used as such a liquid crystalline polymer. However, from the viewpoint of moldability and the performance of the obtained film, (X) It is more preferable to use a liquid crystal polyester resin composition in which liquid crystal polyester is used as a continuous phase and a copolymer having a functional group reactive with the liquid crystal polyester (Y) is used as a dispersed phase.

[0006] The liquid crystal polyester referred to here is a polyester called a thermotropic liquid crystal polymer.
Specifically, (1) A compound obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. (2) Those obtained by reacting a combination of different aromatic hydroxycarboxylic acids. (3) Those obtained by reacting an aromatic dicarboxylic acid with a nucleus-substituted aromatic diol. (4) Those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate. And those forming an anisotropic melt at a temperature of 400 ° C. or less are preferred. In addition, instead of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, their ester derivatives may be used.

The repeating structural units of the liquid crystal polyester include the following repeating structural units derived from an aromatic dicarboxylic acid, the following repeating structural units derived from an aromatic diol,
Examples of the repeating structural unit derived from an aromatic hydroxycarboxylic acid include, but are not limited to, these.

A repeating structural unit derived from an aromatic dicarboxylic acid:

[0009]

A repeating structural unit derived from an aromatic diol:

[0011]

A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

A liquid crystal polyester which is particularly preferable from the balance of heat resistance, mechanical properties and workability is And more preferably at least 30 mol% of the entire repeating unit.
The above is included. Specifically, the combination of repeating structural units is preferably any one of the following (I) to (VI).

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

The production methods of the liquid crystal polyesters (I) to (VI) are described, for example, in JP-B-47-47870, JP-B-63-3888, JP-B-63-3891, and JP-B-56-18016. JP-A-2-515
No. 23, and the like. Of these, a combination of (I), (II) or (IV) is preferable, and a combination of (I) or (II) is more preferable.

In the field where high heat resistance is required, the following repeating unit (a ') is 30 to 80 mol%, the repeating unit (b') is 0 to 10 mol%, and the repeating unit (c ') is 10 mol%. ２５25 mol%, repeating unit (d ′) is 10 to 35
Liquid crystal polyesters consisting of mol% are preferably used.

[0022] (In the formula, Ar is a divalent aromatic group.)

In the field where the gas barrier laminate film or container of the present invention requires easy disposal such as incineration after use from the viewpoint of environmental problems, preferred combinations of the fields required in each of the above-mentioned fields are listed. Among them, a liquid crystal polyester formed of a combination of only carbon, hydrogen and oxygen is particularly preferably used.

The component (Y) used in the liquid crystal polyester resin composition is a copolymer having a functional group reactive with the liquid crystal polyester. The functional group reactive with the liquid crystal polyester is not particularly limited as long as it has reactivity with the liquid crystal polyester, and specific examples include an oxazolyl group, an epoxy group, and an amino group. Preferably, it is an epoxy group. The epoxy group or the like may be present as a part of another functional group, and such an example includes a glycidyl group.

In the copolymer (Y), the method for introducing such a functional group into the copolymer is not particularly limited, and it can be carried out by a known method. For example, at the stage of synthesizing the copolymer, it is possible to introduce the monomer having the functional group by copolymerization, or it is also possible to graft copolymerize the monomer having the functional group to the copolymer. It is.

As a monomer having a functional group reactive with the liquid crystal polyester, and particularly as a monomer having a glycidyl group, unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether are preferably used.

Specifically, the unsaturated carboxylic acid glycidyl ester includes, for example, glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconate, triglycidyl butenetricarboxylate,
Glycidyl p-styrenecarboxylate and the like can be mentioned. As unsaturated glycidyl ethers,
For example, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, styrene-p-glycidyl ether and the like are exemplified.

The unsaturated carboxylic acid glycidyl ester is preferably of the general formula Wherein R is a hydrocarbon group having an ethylenically unsaturated bond and having 2 to 13 carbon atoms. The unsaturated glycidyl ether is preferably a compound represented by the general formula: (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or It is. ).

The copolymer (Y) having a functional group reactive with the liquid crystal polyester preferably contains 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. It is a copolymer containing.

The copolymer (Y) having a functional group reactive with the liquid crystal polyester may be a thermoplastic resin or a rubber, or a mixture of a thermoplastic resin and a rubber. You may. A rubber having excellent thermal stability and flexibility of a molded product such as a film or sheet obtained by using the liquid crystal polyester resin composition is more preferable.

More preferably, the copolymer (Y) having a functional group reactive with the liquid crystal polyester is
A copolymer having a heat of fusion of crystal of less than 3 J / g. The copolymer (Y) preferably has a Mooney viscosity of 3 to 70, more preferably 3 to 30, and more preferably 4 to 30.
25 are particularly preferred. The Mooney viscosity here refers to a value measured using a large rotor at 100 ° C. according to JIS K6300. Outside these ranges, the thermal stability and flexibility of the composition may be undesirably reduced.

The rubber mentioned here corresponds to a polymer substance having rubber elasticity at room temperature according to a new edition of Polymer Dictionary (edited by the Society of Polymer Science, published in 1988, Asakura Shoten).
Specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (including random copolymer, block copolymer (including SEBS rubber or SBS rubber, etc.), and graft copolymer), or The hydrogenated product, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber,
Isobutylene-isoprene copolymer, acrylate-ethylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene-propylene-styrene copolymer rubber, styrene-isoprene copolymer Rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluoro rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-non-conjugated diene copolymer rubber, thiol rubber, polysulfide Examples include rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide, etc.), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and the like. Among them, an acrylate-ethylene copolymer is preferably used, and a (meth) acrylate-ethylene copolymer rubber is more preferred.

These rubber-like substances are produced by any production method (eg, emulsion polymerization method, solution polymerization method, etc.) and any catalyst (eg, peroxide, trialkylaluminum, lithium halide, nickel-based catalyst, etc.). It may be something.

The rubber as the copolymer (Y) is a rubber having a functional group reactive with the liquid crystal polyester in the above rubber. In such a rubber, a method for introducing a functional group reactive with the liquid crystal polyester into the rubber is not particularly limited, and can be performed by a known method. For example, it is possible to introduce the monomer having the functional group by copolymerization at the stage of synthesizing the rubber, or it is also possible to graft copolymerize the monomer having the functional group to the rubber.

As specific examples of the copolymer (Y) having a functional group reactive with the liquid crystal polyester, rubbers having an epoxy group include (meth) acrylate-ethylene- (unsaturated glycidyl carboxylate and And / or unsaturated glycidyl ether) copolymer rubber.

Here, the (meth) acrylic acid ester is
An ester obtained from acrylic acid or methacrylic acid and an alcohol. Alcohols have 1 carbon atom
~ 8 alcohols are preferred. Specific examples of (meth) acrylates include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, ter
Examples thereof include t-butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. As the (meth) acrylic acid ester, one kind thereof may be used alone, or two or more kinds may be used in combination.

Preferably, the (meth) acrylic acid ester unit is more than 40% by weight and less than 97% by weight, more preferably 45 to 70% by weight, and the ethylene unit is at least 3% by weight.
0% by weight, more preferably 10 to 49% by weight, 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ether unit and / or unsaturated glycidyl ether unit,
More preferably, it is 0.5 to 20% by weight. If it is out of the above range, the resulting film or sheet may have insufficient thermal stability or mechanical properties, and
Not preferred.

The copolymer rubber can be produced by a conventional method, for example, bulk polymerization, emulsion polymerization, solution polymerization or the like using a free radical initiator. Typical polymerization methods are described in JP-B-46-45085 and JP-B-6-45085.
No. 1-127709, pressure of 500 k in the presence of a polymerization initiator generating free radicals
g / cm ² or more and a temperature of 40 to 300 ° C.

Other rubbers that can be used in the copolymer (Y) of the present invention include acrylic rubber having a functional group reactive with liquid crystal polyester and vinyl aromatic having a functional group reactive with liquid crystal polyester. Hydrocarbon compounds
A conjugated diene compound block copolymer rubber can also be exemplified.

The acrylic rubber mentioned here is preferably represented by the general formula (1) (In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms or a cyanoalkyl group.), A general formula (2) (Wherein, R ² is an alkylene group having 1 to 12 carbon atoms, R ³
Represents an alkyl group having 1 to 12 carbon atoms. ) And general formula (3) (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ^{5 is} an alkylene group having 3 to 30 carbon atoms, R ⁶ is an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and n is an integer of 1 to 20) .)) At least one monomer selected from the compounds represented by formula (1).

Specific examples of the alkyl acrylate represented by the general formula (1) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Examples thereof include butyl acrylate, pentyl acrylate, hexyl acrylate, actyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, and cyanoethyl acrylate.

The alkoxyalkyl acrylate represented by the general formula (2) includes, for example, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate and the like. One or more of these can be used as the main component of the acrylic rubber.

As a constituent of the acrylic rubber, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the above general formulas (1) to (3), if necessary. Can be used. Examples of such unsaturated monomers include styrene, α-methylstyrene,
Acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinylnaphthalene, N-methylolacrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and the like. .

The preferred constituent ratio of the acrylic rubber having a functional group reactive with the liquid crystal polyester is at least one monomer selected from the compounds represented by the above general formulas (1) to (3). 0 to 99.9% by weight, 0.1 to 30.0% by weight of unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether, selected from the compounds represented by the above general formulas (1) to (3). Unsaturated monomer copolymerizable with at least one monomer 0.0
３30.0% by weight. When the constituent ratio of the acrylic rubber is within the above range, heat resistance and impact resistance of the composition,
The molding processability is good and preferable.

The method for producing the acrylic rubber is not particularly limited. For example, JP-A-59-113010, JP-A-62-64809, and JP-A-3-160008.
Or a well-known polymerization method described in WO95 / 04764 or the like, and can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization in the presence of a radical initiator. .

The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with the liquid crystal polyester is preferably (a)
Epoxidation of a rubber obtained by epoxidizing a block copolymer consisting of a sequence mainly composed of a vinyl aromatic hydrocarbon compound and (b) a sequence mainly composed of a conjugated diene compound, or epoxidation of a hydrogenated product of the block copolymer This is the rubber obtained.

The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or its hydrogenated product can be produced by a known method, for example, Japanese Patent Publication No. 40-23.
798 and JP-A-59-133203.

As the aromatic hydrocarbon compound, for example,
Styrene, vinyltoluene, divinylbenzene, α-methylstyrene, p-methylstyrene, vinylnaphthalene and the like can be mentioned, among which styrene is preferable.
Examples of the conjugated diene compound include butadiene, isoprene, pyrrylene, 1,3-pentadiene, 3-butyl-1,3-octadiene and the like, butadiene or isoprene is preferred.

The rubber used as the copolymer (Y) is preferably (meth) acrylate-ethylene-
(Unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is used.

The rubber used as the copolymer (Y) may be vulcanized as required and used as a vulcanized rubber. The above (meth) acrylic acid ester-ethylene-
Vulcanization of the (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is achieved by using a polyfunctional organic acid, a polyfunctional amine compound, an imidazole compound, and the like. It is not limited.

As a specific example of the copolymer (Y) having a functional group reactive with the liquid crystal polyester, the thermoplastic resin having an epoxy group includes (a) 50 to 99% by weight of ethylene units, (b) ) 0.1 to 30% by weight, preferably 0.5 to 20% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units.
% By weight, and (c) an epoxy group-containing ethylene copolymer having an ethylenically unsaturated ester compound unit of 0 to 50% by weight.

Examples of the ethylenically unsaturated ester compound (c) include vinyl carboxylate such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. Esters, α, β-unsaturated carboxylic acid alkyl esters, and the like. Particularly, vinyl acetate, methyl acrylate and ethyl acrylate are preferred.

Specific examples of the epoxy group-containing ethylene copolymer include, for example, a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units and glycidyl methacrylate units, and a methyl acrylate unit. Copolymers composed of glycidyl methacrylate units and ethyl acrylate units, and copolymers composed of ethylene units, glycidyl methacrylate units and vinyl acetate units are exemplified.

The melt index of the epoxy group-containing ethylene copolymer (hereinafter sometimes referred to as MFR. JI
SK6760, 190 ° C, 2.16 kg load) is preferably 0.5 to 100 g / 10 min, more preferably 2 to 50 g / 10 min. The melt index may be outside this range, but the melt index is 100
If it exceeds g / 10 minutes, it is not preferable in view of the mechanical properties of the composition, and if it is less than 0.5 g / 10 minutes, the component (A)
Is inferior in compatibility with the liquid crystal polyester.

[0055] Also, the epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2. If the flexural rigidity is outside this range, the molding processability and mechanical properties of the composition may be insufficient, which is not preferable.

The epoxy group-containing ethylene copolymer is usually prepared by reacting an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high-pressure radical polymerization method in which copolymerization is carried out in the presence. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt-grafted and copolymerized in an extruder.

The liquid crystal polyester resin composition which is a preferred specific example of the liquid crystal polymer used in the present invention is a copolymer having (X) a liquid crystal polyester as a continuous phase and (Y) a functional group reactive with the liquid crystal polyester. Is a resin composition having a dispersed phase. When the liquid crystal polyester is not a continuous phase, the gas barrier properties and heat resistance of a molded article such as a film or a sheet using the liquid crystal polyester resin composition are significantly reduced, which is not preferable.

In the resin composition of such a copolymer having a functional group and a liquid crystal polyester, although the details of the mechanism are not known, the reaction between component (X) and component (Y) of the composition is not clear. It is considered that a reaction occurs, and the component (X) forms a continuous phase and the component (Y) is finely dispersed, so that the moldability of the composition is improved.

It is preferable that the flow start temperature (FT1) of the liquid crystal polyester resin composition is higher than [flow start temperature (FT2) -10 of liquid crystal polyester of component (X) of the composition]. More preferably, FT1 is higher than FT2. When FT1 is higher than [FT2-10], the molding processability of the composition is improved, which is preferable. Here, the flow start temperature is measured using a capillary rheometer (for example, Shimadzu flow tester CFT-500 manufactured by Shimadzu Corporation), and the resin heated and melted at a heating rate of 4 ° C./min. / Cm ² , inner diameter 1 mm, length 10
When extruded from a 0.5 mm nozzle, the melt viscosity is 480.
A temperature (° C.) showing 00 poise.

One embodiment of the above liquid crystal polyester resin composition comprises (X) 56.0 to 99.9 of liquid crystal polyester.
44% by weight, preferably 65.0 to 99.9% by weight, more preferably 70 to 98% by weight, and (Y) a copolymer having a functional group reactive with a liquid crystal polyester.
The resin composition contains 0 to 0.1% by weight, preferably 35.0 to 0.1% by weight, and more preferably 30 to 2% by weight. If the content of the component (X) is less than 56.0% by weight, the gas barrier properties and heat resistance of a molded article such as a film or a sheet obtained from the composition may be undesirably reduced. On the other hand, when the component (X) exceeds 99.9% by weight, the molding processability of the composition may be reduced, and the cost is high, which is not preferable.

As a method for producing such a liquid crystal polyester resin composition, a known method can be used. For example, there is a method in which each component is mixed in a solution state and the solvent is evaporated or precipitated in the solvent. From an industrial point of view, a method of kneading each component having the above composition ratio in a molten state is preferable. For the melt kneading, kneading apparatuses such as a single-screw or twin-screw extruder and various kneaders which are generally used can be used. In particular, a biaxial high kneader is preferred. During melt-kneading, the cylinder set temperature of the kneading device is 2
The temperature is preferably in the range of 00 to 360 ° C, more preferably 2 to 360 ° C.
30-350 ° C.

At the time of kneading, the respective components may be previously mixed uniformly using a device such as a tumbler or a Henschel mixer, or if necessary, the mixing may be omitted, and each component may be separately supplied to the kneading device. Methods can also be used.

In the liquid crystalline polymer used in the present invention, if necessary, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an inorganic or organic colorant, a rust inhibitor Various additives such as a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a mold release improving agent such as a fluororesin can be added during the manufacturing process or in the subsequent processing process.

The water absorption of the liquid crystalline polymer used in the present invention is preferably 0.05% by weight or less. If it exceeds this, the surface of the obtained resin film is unfavorably roughened or foamed. Here, the water absorption is measured with respect to the liquid crystalline polymer pellets using a commercially available moisture meter, and the method is not particularly limited, and can be measured by a known method.

As the layer comprising such a liquid crystalline polymer in the laminated film of the present invention, a film or sheet obtained by molding such a liquid crystalline polymer can be used. In the present invention, a film and a sheet are distinguished mainly by a difference in thickness, and in this specification, only one of them may be described in a sense including the other.

As the film or sheet made of such a liquid crystalline polymer, for example, a T-die method for extruding and winding a molten resin from a T-die, or extruding a molten resin into a cylindrical shape from an extruder provided with an annular die, cooling and winding the same. The film or sheet obtained by the inflation film forming method, the film or sheet obtained by the hot pressing method or the solvent casting method, or the sheet obtained by the injection molding method or the extrusion method is further subjected to uniaxial stretching or biaxial stretching. A coated film or sheet can also be used.

Injection molding of the composition as a liquid crystalline polymer,
In the case of extrusion molding or the like, a film or a sheet can be obtained by dry blending the component pellets at the time of molding and melt-molding them without going through a kneading step in advance.

In the T-die method, a uniaxially stretched film or a biaxially stretched film obtained by winding a molten resin extruded through a T-die while stretching in a winder direction (longitudinal direction) is preferably used.

The conditions for setting the extruder during the formation of the uniaxially stretched film can be appropriately set according to the composition of the composition.
The cylinder set temperature is preferably in the range of 200 to 360 ° C, more preferably in the range of 230 to 350 ° C. If the ratio is outside this range, thermal decomposition of the composition may occur or film formation may be difficult, which is not preferable.

The slit interval of the T-die is 0.2 to 2.0.
mm is preferable, and 0.2 to 1.2 mm is more preferable.
The draft ratio of the uniaxially stretched film is preferably in the range of 1.1 to 40, more preferably 10 to 40, and particularly preferably 15 to 35.

The draft ratio mentioned here is a value obtained by dividing the cross-sectional area of the T-die slit by the cross-sectional area of the film perpendicular to the longitudinal direction. If the draft ratio is less than 1.1, the film strength is insufficient, and if the draft ratio exceeds 45, the surface smoothness of the film may be insufficient, which is not preferable. The draft ratio can be set by controlling the setting conditions of the extruder, the winding speed, and the like.

For the biaxially stretched film, the same extruder setting conditions as those for forming the uniaxially stretched film, that is, the cylinder set temperature is preferably in the range of 200 to 360 ° C., more preferably 230 to 350 ° C. The composition is melt-extruded at a slit interval of preferably 0.2 to 1.2 mm, and the melt sheet extruded from the T-die is simultaneously stretched in the longitudinal direction and the direction perpendicular to the longitudinal direction (lateral direction). First, the melt sheet extruded from the T-die is stretched in the longitudinal direction, and then the stretched sheet is stretched in a transverse direction from the tenter at a high temperature of 100 to 300 ° C. in the same step. Can be

When obtaining a biaxially stretched film, the stretching ratio is preferably in the range of 1.2 to 20 times in the longitudinal direction and 1.2 to 20 times in the transverse direction. If the stretching ratio is out of the above range, the strength of the composition film may be insufficient, or it may be difficult to obtain a film having a uniform thickness, which is not preferable.

An inflation film obtained by forming a melt extruded from an ordinary cylindrical die by inflation is also preferably used. further,
At that time, a double rotating die as disclosed in Japanese Patent Publication No. 4-506779 can also be used.

That is, the liquid crystalline polymer is supplied to a melt-kneading extruder equipped with a die having an annular slit, and is set at a cylinder set temperature of 200 to 360 ° C., preferably 230 to 350 ° C.
The molten resin is extruded from the annular slit of the extruder upward or downward from the annular slit of the extruder. The annular slit interval is usually 0.1 to 5 mm, preferably 0.2
~ 2mm, diameter of annular slit is usually 20 ~ 1000m
m, preferably 25 to 600 mm.

Draft is applied to the melt-extruded molten resin film in the longitudinal direction (MD), and air or an inert gas, for example, nitrogen gas, is blown from the inside of the cylindrical film so that a transverse direction perpendicular to the longitudinal direction is obtained. The film is expanded and stretched in (TD).

In inflation molding (film formation),
The preferred blow ratio is 1.5 to 10, and the preferred MD draw ratio is 1.5 to 40. If the setting conditions during the inflation film formation are outside the above range, it may be difficult to obtain a high-strength film having a uniform thickness and no wrinkles, which is not preferable.

The expanded film is usually air-cooled or water-cooled on its circumference, and then passed through a nip roll and taken up.

The thickness of the film is not particularly limited, but is preferably 3 to 1000 μm, more preferably 3 to 50 μm.
0 μm.

The inorganic layer compound in the layer comprising the composition comprising the inorganic layer compound and the resin constituting the laminated film of the present invention refers to an inorganic compound having a layer structure in which unit crystal layers are stacked on each other. A layered structure is a surface in which atoms are tightly arranged by strongly bonding atoms by covalent bonds, etc.
It refers to a structure that is stacked almost in parallel by a weak coupling force such as van der Waals force.

Specific examples of such an inorganic layered compound include:
Graphite, phosphate derivative type compound (zirconium phosphate compound), chalcogenide [Group IV (Ti,
Zr, Hf), a dichalcogen compound of group V (V, Nb, Ta) and Group VI (Mo, W), the formula MX _2. Here, M represents an atom belonging to the group IV, V or VI, and X represents a chalcogen (S, Se, Te). And clay-based minerals.

As the inorganic layered compound, the aspect ratio measured by the method described later is preferably 50 to 5000, more preferably 100 to 5000, from the viewpoint of gas barrier properties, economy and availability of the obtained laminated film. , 200 to 3000 are particularly preferred. In addition, from the viewpoint of moldability of a laminated film described below, the particle size measured by a method described below is preferably 5 μm or less,
3 μm or less is more preferable.

The aspect ratio (Z) of the inorganic layered compound used in the present invention is represented by the following relationship: Z = L / a.
Here, L is the particle size of the inorganic layered compound, which is the particle size determined by a dynamic light scattering method in a solvent, and a is the unit thickness of the inorganic layered compound.

The unit thickness a can be determined, for example, by preparing a film made of a composition with the dictated resin and then using a powder X-ray diffraction method or the like. For details of how to determine a, see, for example, Shuichi Iwami et al., Encyclopedia of Clay, pages 35 and below and pages 271 and below, 1985, Asakura Shoten Co., Ltd., JP-A-7-251487 and JP-A-6-251487. 93133
Can be referred to.

From the viewpoint of the aspect ratio as described above,
As the inorganic layered compound, an inorganic layered compound swelled and / or cleaved in a solvent and an inorganic layered compound swelled and / or cleaved in a solvent are preferably used. The degree of swelling or cleavage of the inorganic layered compound used in the present invention in a solvent can be evaluated by the following swelling test or cleavage test. The degree of swelling of the inorganic layered compound is preferably such that the swelling value in the following swelling test is 5 or more (more preferably 20 or more). On the other hand, the degree of cleavage of the inorganic layered compound is preferably such that the cleavage value in the following cleavage test is 5 or more (more preferably 20 or more).

<Swellability test>: 2 g of the inorganic layered compound was added to 100 mL of a solvent (for example, using a 100 mL graduated cylinder as a container), stirred, and allowed to stand at 23 ° C. for about one day. The volume (ml) of the former (inorganic layered compound dispersed layer) is read as the swelling value from the scale of the interface. It can be said that the larger the value is, the higher the swelling property is.

<Cleavage test>: 30 g of inorganic layered compound
Was slowly added to 1500 mL of a solvent, and sufficiently dispersed by a dispersing machine (23 ° C.). After 100 mL of the dispersion was taken and allowed to stand for about 1 hour, the inorganic layered compound dispersion layer was measured from the scale at the interface with the supernatant in the same manner as described above. The volume (ml) is read as the cleavage value. It can be said that the larger this value is, the higher the cleavage is.

In these tests, the solvent that swells or cleaves the inorganic layered compound is, for example, water,
Alcohols such as methanol, dimethylformamide,
Dimethyl sulfoxide, acetone and the like can be mentioned, and water or alcohols are more preferable.

As the inorganic layered compound which swells and / or cleaves in a solvent, a clay mineral which swells and / or cleaves in a solvent can be suitably used. Clay-based minerals generally have a two-layer structure having an octahedral layer with aluminum or magnesium as the central metal on top of a silica tetrahedral layer, and a silica tetrahedral layer containing aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedral layer serving as a central metal is sandwiched from both sides.
The former includes kaolinites and antigolites, and the latters include smectites, vermiculites and micas depending on the number of interlayer cations.

Particularly preferred as the inorganic layered compound used in the present invention are kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, and muscovite. , Margarite, talc, vermiculite, phlogopite, zansophyllite, or chlorite.

As the resin used in the composition comprising the inorganic layered compound and the resin of the present invention, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (E
VOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), polysaccharides, polyacrylic acid or esters thereof are preferred.

As a more preferred resin, a high hydrogen bonding resin in which the weight percentage of the hydrogen bonding group or the ionic group per unit weight of the resin satisfies the ratio of 20 to 60% is mentioned. 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. Sulfonate ion groups, phosphate ion groups, ammonium groups, phosphonium groups, and the like. More preferred as a hydrogen-bonding group or an ionic group of the high hydrogen-bonding resin is a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonate ion group, or an ammonium group, and particularly preferable. Is a hydroxyl group.

Specific examples of such a resin include polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of at least 41 mol%, hydroxymethylcellulose, hydroxyethylcellulose, and the like.
Polysaccharides such as carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, cellulose, pullulan, chitosan, polyacrylic acid, sodium polyacrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, Examples thereof include polyethyleneimine, polyallylamine, its ammonium salt, polyvinyl thiol, and polyglycerin.

More preferable examples of the high hydrogen bonding resin include polyvinyl alcohol and polysaccharide. Polyvinyl alcohol is obtained by hydrolyzing (saponifying) an acetic ester portion of a vinyl acetate polymer, and is usually a copolymer of vinyl alcohol and vinyl acetate. Here, the saponification ratio is preferably 70% or more in terms of mole percentage, and more preferably 85% or more. The degree of polymerization is preferably 100 or more and 5000 or less.

The polysaccharide is a biopolymer synthesized in a biological system by polycondensation of various monosaccharides, and herein includes those chemically modified based on them. For example, cellulose derivatives such as cellulose, hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan and the like can be mentioned.

In the present invention, the composition ratio (weight ratio) of the inorganic layered compound and the resin is (5/9) in terms of weight ratio (inorganic layered compound / resin) from the viewpoint of gas barrier properties and moldability.
The range of 5) to (90/10) is preferable, and (5/95)
More preferably, it is in the range of (50/50).

The method for producing the composition comprising the above-mentioned inorganic layered compound and resin is not particularly limited. From the viewpoint of the dispersibility of the inorganic layered compound in the obtained composition layer and the ease of operation, for example, a solution in which a resin is dissolved and a dispersion in which the inorganic layered compound is swollen and / or cleaved in advance in a solvent are used. After mixing, a method of removing the solvent (method 1), a method in which the resin is dissolved in a dispersion obtained by swelling and / or cleaving the inorganic layered compound in the solvent, and a method of removing the solvent (method 2), the method of removing the inorganic compound from the solution in which the resin is dissolved Examples of the method include a method of removing the solvent after adding the layered compound and swelling and / or cleaving (method 3), and a method of hot-kneading the resin and the inorganic layered compound (method 4). From the viewpoint that a large aspect ratio of the inorganic layered compound can be easily obtained, any one of the methods 1 to 3 is preferably used. That is, as the composition comprising the inorganic layered compound and the resin used in the present invention, a composition obtained by using the inorganic layered compound and the resin swelled and / or cleaved in a solvent is suitably used. Furthermore, within a range that does not impair the effects of the present invention, in the resin composition,
Various additives such as an ultraviolet absorber, a colorant, and an antioxidant may be mixed.

The gas barrier laminate film of the present invention is a gas barrier laminate film having a layer composed of a resin exhibiting optical anisotropy when melted and a layer composed of a composition composed of an inorganic layered compound and a resin. Other layers may be included as long as the object of the invention is not impaired. As other layers, a thermoplastic resin (excluding the liquid crystalline polymer)
A layer consisting of

The thermoplastic resin used herein is not particularly limited, but may be 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, polyolefin resin such as ionomer resin, polyethylene terephthalate, polybutylene terephthalate, polyester resin such as polyethylene naphthalate, nylon-6, Nylon-6,6, meta-xylenediamine-
Condensation polymers of adipic acid, amide resins such as polymethyl methacrylimide, acrylic resins such as polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene such as polyacrylonitrile, Acrylonitrile resins, cellulose triacetates, hydrophobic cellulose resins such as cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, halogen-containing resins such as Teflon, polyvinyl alcohol,
Ethylene-vinyl alcohol copolymer, hydrogen bonding resin such as cellulose derivative, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin,
Examples include engineering plastic resins such as polymethylene oxide resins and liquid crystal resins. Among them, biaxially stretched polypropylene, polyethylene terephthalate, biaxially stretched polypropylene coated with polyvinylidene chloride called nylon or K coat, polyethylene terephthalate, and nylon are preferably used. Among them, nylon is particularly preferably used in terms of maintaining piercing strength.

As the gas barrier laminate film of the present invention, the above-mentioned gas barrier laminate film further having a layer made of a heat-sealable resin as the outermost layer is preferable and preferable for use as a container.

The heat-sealable resin is not particularly limited as long as it can be heat-sealed, and is not particularly limited. However, polyethylene (low-density, high-density), 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,
Polyolefin-based resins such as ionomer resins are preferably used. Particularly preferably, linear low density polyethylene or polypropylene is used.

As the gas barrier laminate film of the present invention, the above-mentioned gas barrier laminate film further has a layer made of a heat sealable resin on one outermost layer and a thermoplastic resin (provided that the other outermost layer has a thermoplastic resin). A layer having a layer consisting of (excluding the liquid crystalline polymer) is suitable for use as a container and can protect the surface of the container. As the layer composed of the thermoplastic resin (excluding the liquid crystalline polymer) here, the layer composed of the thermoplastic resin (except the liquid crystalline polymer) already described as the other layer can be employed. .

The embodiment of the gas barrier laminate film of the present invention is as follows: a layer composed of a thermoplastic resin (excluding the liquid crystalline polymer), an A layer, a layer composed of a liquid crystalline polymer, a B layer, an inorganic layer compound and a resin. A layer composed of a composition consisting of a C layer and a layer composed of a heat-sealing resin as a D layer,
Specifically, a film laminated in the order of A layer / B layer / C layer / D layer. A film laminated in the order of A layer / A layer / B layer / C layer / D layer. A film laminated in the order of A layer / B layer / C layer / A layer / D layer. And the like, and these are particularly preferred as a laminated film. In addition, although there are two A layers in each of the above and in the above, these may be the same or different.

The method for laminating the layer (C layer in the above specific embodiment) comprising the composition comprising the inorganic layered compound and the resin of the present invention on another layer is not particularly limited. A coating method in which a coating liquid of the composition is applied to the surface of another layer and dried (solvent is removed) and then heat-treated, or a method of laminating a film made of the composition is preferable, and the coating method is particularly preferable. preferable. For example, taking the above specific embodiment as an example, the coating liquid for the C layer is used for the B layer and the A layer.
Layer or the D layer directly.
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, and a doctor knife method, a die coating method, a dip coating method, and a bar coating method. Examples of the method include a coating method and a coating method combining these methods. In addition, as the coating liquid here, it is preferable to use the one before the last removal of the solvent in each of the methods 1 to 3 exemplified for the method for producing the composition comprising the inorganic layered compound and the resin. That is, the coating liquid is preferably a mixture of a solution in which a resin is dissolved and a dispersion obtained by swelling and / or cleaving an inorganic layered compound in a solvent in advance (1 ′), and swelling the inorganic layered compound in a solvent. And (2 ') a resin obtained by dissolving a resin in a cleaved dispersion, or (3') obtained by adding an inorganic layered compound to a solution obtained by dissolving a resin and swelling and / or cleaving (3 ').

In laminating a layer comprising the composition comprising the inorganic layered compound of the present invention and a resin (layer C in the above specific embodiment) on another layer, an anchor coat layer may be provided. For example, polyethyleneimine-based, titanium-based,
Polybutadiene, urethane and the like are not particularly limited, but an anchor layer composed of an isocyanate compound and an active hydrogen compound is preferable from the viewpoint of water resistance.

Examples of the isocyanate compound include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), and 4,4′-methylenebiscyclohexyl isocyanate. H12MDI) and isophorone diisocyanate (IPDI). Examples of the active hydrogen compound include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol,
Low molecular weight polyols such as 6-hexanediol, neopentyl glycol, trimethylolpropane, polyether polyols such as polyethylene glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol, poly β methyl δ valero Lactones, polycaprolactones, polyester polyols such as polyesters from diols / dibasic acids, etc., where diols are ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, And dibasic acids such as adipic acid, azelaic acid, sebacic acid, isophthalic acid and terephthalic acid. Other polyols include castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol,
There are active hydrogen compounds such as neoprene.

The mixing ratio between the isocyanate compound and the active hydrogen compound is not particularly limited, but the amount to be added is determined in consideration of the equivalence relationship between the isocyanate group and the active hydrogen group (for example, -OH, -NH, -COOH). Is preferred. For example, the ratio of the number of moles of isocyanate groups (AN) to the number of moles of active hydrogen groups of the active hydrogen compound (BN) (R = AN /
BN) is preferably used in a range of 0.001 or more and 10 or less. The molar ratio R is 0.01
More preferably, it is in the range of 1 or less. When the molar ratio R is within this range, it is preferable in terms of adhesive strength, tackiness, and blocking.

When mixing the isocyanate compound and the active hydrogen compound, it is preferable to use a solvent. Such solvents are mainly organic solvents, alcohols,
Examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, halogenated hydrocarbons, and mixed solvents thereof.

The method for laminating the anchor coat layer is not particularly limited, but a coating method is preferred.
Roll coating methods such as direct gravure method, reverse gravure method, micro gravure method, two roll beat coating method, bottom feed three reverse coating method, and doctor knife method, die coating method, dip coating method, bar coating method and the like Methods such as a combined coating method can be mentioned.

The coating thickness of the anchor coating agent is not particularly limited, but the dry thickness is preferably 0.01 μm to 5 μm. The thicker the coating thickness, the better the heat seal strength, but sometimes the gelbo test resistance is poor. Therefore, more preferably 0.03 μm to 2.0 μm. More preferably, the thickness is 0.05 μm to 1.0 μm.

The thickness of the layer comprising the composition comprising the inorganic layered compound and the resin of the present invention (layer C in the above specific embodiment) is preferably 10 μm or less in terms of dry thickness, and more preferably 1 μm or less.
μm or less is more preferable. If the thickness exceeds the above range, the flexibility may be deteriorated. The lower limit is not particularly limited, but is 1 nm in order to obtain an effective gas barrier effect.
It is preferable that it is above.

In the present invention, as a method for laminating each layer other than the layer composed of the composition comprising the inorganic layered compound and the resin (the layer C in the above specific embodiment), a known method such as dry lamination or extrusion lamination may be used. Can be used. In addition, printing can be performed on the surface of any of the layers.

The method of laminating the layer made of the heat-sealing resin is not particularly limited, but includes, for example, a method of dissolving the above-mentioned heat-sealing resin in a solvent and coating, a method of extruding and laminating the heat-sealing resin, and a method of heat-sealing. Preferred examples include a method of dry laminating a film made of a conductive resin.
Further, the interface of the laminate may be subjected to a treatment such as a corona treatment, an ozone treatment, an electron beam treatment, or an anchor coating agent.

The container of the present invention is a container comprising such a gas-barrier laminated film. As the container of the present invention,
A container made of a gas-barrier laminated film having a layer made of a heat-sealing resin as the outermost layer is preferable because it is easy to manufacture. In this case, since it is preferable to manufacture a container from the gas barrier laminated film by heat sealing, it is preferable to use the gas barrier laminated film by configuring the layer made of the heat sealable resin to be the innermost. Is preferred. Further, the container of the present invention further has a layer made of a heat-sealing resin in one outermost layer and a layer made of a thermoplastic resin (excluding the liquid crystalline polymer) in the other outermost layer. A container made of the gas-barrier laminated film is easy to manufacture and can protect the container surface, which is preferable. In this case, it is preferable to manufacture a container from the gas barrier laminate film by heat sealing,
Moreover, since the surface of the container can be protected by using the layer made of the thermoplastic resin as the outermost layer of the container, the layer made of the heat-sealable resin is the innermost layer, and the layer made of the thermoplastic resin is the outermost layer. It is preferable to use the gas-barrier laminated film in such a manner as to be structured as described above.

In the present invention, the thickness of the gas barrier laminated film when used as a container is not particularly limited, but is preferably 30 to 300 μm. If the thickness is smaller than the lower limit, the protection of the contents may be inferior, and if the thickness is larger than the upper limit, the cost may be increased, which is not preferable.

[0117] Each material of the container of the present invention may be mixed with additives such as an ultraviolet absorber, a coloring agent and an antioxidant.

The shape of the container of the present invention is not particularly limited. The container of the present invention is preferably a bag, a standing pouch, a bag-in-drum, a retort container, a deep drawn container or a cart can. Specifically, for example, shapes such as a three-side seal packaging bag, a four-side seal packaging bag, a pillow packaging bag, a gusset packaging bag, and a standing pouch are preferably used. Above all, the shape of the standing pouch is more preferable because the effects of the present invention can be utilized. There is no particular limitation on the bag making method, and various commercially available bag making machines are used.

[0119]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The methods for measuring various physical properties are described below.

[Oxygen permeability]: An oxygen permeability measuring device (OX-TRAN) according to JIS K7126 (isobaric method).
10 / 50A, manufactured by MOCON), test gas: 99.99% oxygen, carrier gas: 98% nitrogen, hydrogen 2
%, A temperature of 23 ° C., a test gas side relative humidity of 60% and 90%, and a carrier gas side relative humidity of 60%. The unit is cc / m ² .1 atm.24 hr.

[Water vapor permeability]: JIS Z0208
According to the (cup method), the measurement was performed under two conditions of a temperature of 35 ° C. and a relative humidity of 60% and 95%. Unit is g / m ² · 1a
tm ・ 24hr.

[Measurement of Particle Size]: Using a laser diffraction / scattering type particle size distribution measuring apparatus (LA910, manufactured by Horiba, Ltd.), based on the volume basis of particles considered to be inorganic layered compounds present in the resin matrix of the medium. The median diameter L was measured. The undiluted dispersion liquid was applied to a paste cell at an optical path length of 50 μm.
m, and the diluent was measured with a flow cell method at an optical path length of 4 mm.

[Aspect ratio]: X-ray diffractometer (XD-
5A, manufactured by Shimadzu Corporation), and the diffraction measurement of the inorganic layered compound alone and the resin composition by the powder method was performed. Thereby, the interplanar spacing (unit thickness) a of the inorganic layered compound is obtained,
Using the particle diameter L obtained by the above method, the aspect ratio Z
Was determined by the equation of Z = L / a.

[Swellability test]: 100 ml of ion-exchanged water is placed in a 100 ml measuring cylinder, and 2 g of the inorganic layered compound is slowly added thereto. After standing at 23 ° C. for 24 hours, the volume (ml) of the inorganic layered compound dispersed layer was read from the scale at the interface between the inorganic layered compound dispersed layer (suspended portion) and the supernatant in the graduated cylinder, and the swelling value was obtained. .

[Cleaving test]: 30 g of inorganic layered compound
Was slowly added to 1,500 ml of ion-exchanged water, and a dispersion machine (manufactured by Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 m)
m, rotation speed 3,100 rpm, container capacity 3 L, distance between bottom and blade 28 mm), peripheral speed 8.5 m / min, 23 ° C.
, And 100 ml of the dispersion was collected in a measuring cylinder. After standing for 60 minutes, the volume (ml) of the inorganic layered compound dispersed layer was read from the scale at the interface between the inorganic layered compound dispersed layer and the supernatant in the graduated cylinder, and the value was determined as a cleavage value.

[Gelbo test]: Regarding the obtained film, GELBO FLEX TES manufactured by Instrument Marketing Service
Using TER MODEL 500ES, 500 gelbo tests were performed.

(1) Liquid Crystal Polyester of Component (X) (i) 8.3 kg (60 mol) of p-acetoxybenzoic acid, 2.49 kg (15 mol) of terephthalic acid, 0.83 kg (5 mol) of isophthalic acid and 4 5,45 kg (20.2 mol) of 4,4′-diacetoxydiphenyl was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was increased while stirring under a nitrogen gas atmosphere, and polymerization was performed at 330 ° C. for 1 hour. The acetic acid gas produced as a by-product during this period was polymerized under strong stirring while being liquefied and collected and removed by a cooling tube. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system.
The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This is further 280 in a rotary kiln under a nitrogen gas atmosphere.
C. for 3 hours so that the flow onset temperature is 32.
A wholly aromatic polyester comprising the following repeating structural units in the form of particles at 4 ° C. was obtained. Here, the flow start temperature refers to a resin heated and melted at a heating rate of 4 ° C./min using a Shimadzu Flow Tester Model CFT-500 manufactured by Shimadzu Corporation under a load of 100 kgf / cm ² and an inner diameter of 1 mm. , Length 10
When extruded from a 0.5 mm nozzle, the melt viscosity is 480.
A temperature (° C.) showing 00 poise. Hereinafter, the liquid crystal polyester is abbreviated as X-1. The polymer is 3
It exhibited optical anisotropy at 40 ° C. or higher. Liquid crystal polyester X
The repeating structural unit of -1 is as follows.

[0128]

(2) Component (Y) According to the method described in Example 5 of JP-A-61-127709, methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38.7 / 2.3. (Weight ratio), Mooney viscosity = 15, heat of fusion of crystal <1 J / g
Rubber was obtained. Hereinafter, the rubber may be abbreviated as Y-1. Here, the Mooney viscosity is a value measured using a large rotor at 100 ° C. according to JIS K6300. The heat of fusion of the crystal was determined by
It was determined by raising the temperature from 150 ° C. to 100 ° C. at a rate of 20 ° C./min.

Reference Example 1 (Liquid crystal polyester resin composition) 80% by weight of X-1 and 20% by weight of Y-1 were mixed with a TEX-30 type twin screw extruder manufactured by Nippon Steel Corporation at a cylinder set temperature of 350 ° C. Melt kneading was performed at a screw rotation speed of 200 rpm to obtain pellets of the composition. The composition pellets exhibited optical anisotropy at 340 ° C. or higher under pressure.
The flow start temperature of the composition pellets was 328 ° C.
The pellets of this composition were supplied to a 60 mmφ single screw extruder equipped with a cylindrical die, and a cylinder set temperature of 350 ° C.
Melt kneading is performed at a rotation speed of 60 rpm, and the molten resin is extruded upward from a cylindrical die having a diameter of 70 mm, a lip interval of 1.0 mm, and a die setting temperature of 355 ° C. The film is expanded, then cooled and then passed through a nip roll to take up 75m
/ Min to obtain a liquid crystal polyester resin composition film. At this time, the stretching ratio in the film MD direction is 20.
5, the blow ratio was 4.1, and the film thickness was about 12 μm. Hereinafter, the film may be abbreviated as g-1.
The oxygen permeability of g-1 is 7 cc / m ² .1 atm.24 h
r (60% relative humidity on the test gas side), and the water vapor permeability is 0.6 g / m ² .1 atm.24 hr (relative humidity 6
0%) and 0.7 g / m ² .1 atm.24 hr (relative humidity 95%).

Reference Example 2 (Coating liquid for layer C) Dispersion pot (trade name: Despa MH-L, manufactured by Asada Iron Works Co., Ltd.)
And ion-exchanged water (0.7 μS / cm or less)
g of polyvinyl alcohol (PVA117)
H; manufactured by Kuraray Co., Ltd., degree of saponification; 99.6%, degree of polymerization 1
700) and stirring under low speed (1500 rpm)
m, the peripheral speed is 4.10 m / min) and the temperature is raised to 95 ° C.
After stirring for a period of time to dissolve the mixture and lowering the temperature to 60 ° C. while stirring, a silicone surfactant S
H3746 (manufactured by Dow Corning Toray Co., Ltd.) at 0.2
The liquid to which 5 g had been added was added to obtain a mixed liquid (B). 196
0 g of the mixture (B) was charged into a stirring emulsifier (trade name: vacuum emulsifier PVQ-3UN, manufactured by Mizuho Industry Co., Ltd.). Montmorillonite (Kunipia F; manufactured by Kunimine Kogyo KK) as an inorganic layered compound such that the weight ratio of polyvinyl alcohol to the inorganic layered compound is 2: 1.
60. Cleavage value = 80. ) Is added as powder in 50g,
After confirming that the montmorillonite was substantially precipitated in the solution, the mixture was rapidly stirred at 600 mmHg and 5000 rpm for 10 minutes to obtain a resin composition mixed solution (C). At this time, the particle size was 1.483 μm. 2000 g of the resin composition mixture (C) was dispersed in a high-pressure dispersing apparatus (trade name: ultrahigh-pressure homogenizer M110-E / H, microfluidics)
Corporation), 1750kgf /
By treating once at cm ² , a uniform dispersion (D) having good dispersibility was obtained. The solid content concentration of the dispersion (D) was 7.5% by weight. The dispersion (D) was cast into a film and subjected to X-ray analysis to determine the bottom distance from the peak, which was 41.2 angstroms, and was sufficiently cleaved. At this time, the aspect ratio of the inorganic layered compound was 4
It was 61. Hydrochloric acid was added to the dispersion (D) with titanium acetylacetonate (TC100, manufactured by Matsumoto Pharmaceutical Co., Ltd.) under low-speed stirring (1500 rpm, peripheral speed 4.10 m / min) so that the pH of the solution was 3 or less. While adjusting the temperature, 5.33 g of titanium acetylacetonate was gradually added to obtain a coating liquid for the C layer.

Example 1 <Laminated Film> An anchor coat agent (Adcoat AD3) was formed on the film g-1.
35 / CAT10 = 15/1 (weight ratio): Toyo Morton Co., Ltd.) by gravure coating (test coater; Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m /
(Min., Drying temperature 80 ° C.). The dry thickness of the anchor coat layer was 0.05 μm. Further, a coating liquid for the C layer is gravure coated on the anchor coat layer (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m / min, drying temperature 100 ° C.), and coated. A film was obtained. The dry thickness of the coating layer was 0.5 μm. Then, the adhesive layer (Adcoat AD503 / CAT10 = 15/1 (weight ratio): manufactured by Toyo Morton Co., Ltd.) was applied to the coating layer of the coating film to form a linear low-density polyethylene (50 μm thick). TUX-FCS, manufactured by Tocelo Co., Ltd.)
Was dry-laminated to obtain a laminated film. Next, an adhesive (Adcoat AD503 / CAT10 = 15/1 (weight ratio): Toyo Morton Co., Ltd.) was used on the non-coated side of g-1 of the laminated film to form a biaxially oriented polypropylene (20 μm thick). OPP) film (Pyrene P210)
2: Laminated by surface corona treatment of Toyobo Co., Ltd.) to obtain a four-layer laminate (OPP / LCP composition / composition of inorganic layered compound and resin / LLDPE). The oxygen permeability of the four-layered laminate measured with the OPP layer on the test gas side and the LLDPE layer on the carrier gas side was <0.20 cc / m ² · 1 atm · 24 hr (test gas side relative humidity 60%) <0 30 cc / m ² .1 atm.24 hr (90% relative humidity on the test gas side). The water vapor permeability of this four-layer laminate measured with the OPP layer as the test gas side was <0.5 g / m ² .1 atm.24 hr (relative humidity 6
0%) <0.6 g / m ² .1 atm.24 hr (relative humidity 9
5%).

Example 2 In Example 1, the used biaxially oriented polypropylene (OPP) film having a thickness of 20 μm was replaced with a polyethylene terephthalate film having a thickness of 12 μm (Espet T410).
0, manufactured by Toyobo Co., Ltd.) to obtain a laminated film. The oxygen permeability of the four-layer laminate measured in the same manner as in Example 1 was <0.20 cc / m ² .1 atm.24 hr (test gas side relative humidity 60%) <0.30 cc / m ² .1 atm.24 hr. (90% relative humidity on the test gas side). The water vapor permeability of the four-layer laminate was <0.6 g / m ² .1 atm.24 hr (relative humidity 6
0%) <0.7 g / m ² .1 atm.24 hr (relative humidity 9
5%). A Gelbo test was performed on the obtained laminated film. When the oxygen permeability and the water vapor permeability of the laminated film after the test were measured in the same manner as above, there was no change from that before the gelbo test.

Comparative Example 1 The g-1 film used in Example 1 was replaced with 12 μm
Polyethylene terephthalate film (Espet T
A laminated film was obtained in the same manner as in Example 1, except that 4100, Toyobo Co., Ltd. was used. The oxygen permeability of the laminate increases with increasing humidity on the oxygen side,
At 90% relative humidity on the oxygen side, 10.0 cc / m ² .1 atm.24 hr (relative humidity
90%).

[0135]

According to the present invention, there is provided a film and a container which are hardly affected by environmental humidity, are resistant to mechanical stress, and have high oxygen and water vapor barrier properties. An excellent gas barrier laminated film and container can be obtained. As a use of the container of the present invention, confectionery,
Western confectionery, miso, pickles, konjac, chikuwa, kamaboko, other processed fishery products, meatballs, hamburgers, ham / sausage, pet food, pesticides / fertilizers, cosmetics, aromatics,
It is also used for medical, electronic, chemical, and mechanical applications such as infusion packs, semiconductor packaging, oxidizing chemical packaging, and precision material packaging.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Taiichi Sakatani 2-10-1 Tsukahara, Takatsuki-shi, Osaka Prefecture Inside Sumika Plastics Tech Co., Ltd. (72) Inventor Toshiya Kuroda 2-1-1 Tsukahara, Takatsuki-shi, Osaka No. Sumitomo Plastics Co., Ltd. F-term (reference) 4F100 AA00B AA00H AC10B AC10H AJ03B AK01A AK01B AK01J AK01K AK21B AK41A AK41K AK53A AK53J AK63C AK69B AK80A AL05A12 J01 BA03 J01 BA03 J02 BA03

Claims (18)

[Claims] 1. A gas barrier laminate film comprising a layer made of a resin exhibiting optical anisotropy when melted and a layer made of a composition made of an inorganic layer compound and a resin. 2. The gas barrier laminate film according to claim 1, further comprising a layer made of a heat-sealing resin as an outermost layer. Further, one outermost layer has a layer made of a heat-sealing resin, and the other outermost layer is made of a thermoplastic resin (excluding a resin exhibiting optical anisotropy when melted). The gas barrier laminate film according to claim 1, comprising a layer. 4. A resin exhibiting optical anisotropy at the time of melting, wherein (X)
The liquid crystal polyester resin composition according to any one of claims 1 to 3, wherein the liquid crystal polyester is a continuous phase and (Y) a copolymer having a functional group reactive with the liquid crystal polyester is a dispersed phase. The gas barrier laminate film according to the above. 5. A resin exhibiting optical anisotropy when melted,
Composition obtained by melt-kneading (X) 56.0 to 99.9% by weight of a liquid crystal polyester and (Y) 44.0 to 0.1% by weight of a copolymer having a functional group reactive with the liquid crystal polyester. The gas-barrier laminated film according to any one of claims 1 to 3, which is a product. 6. The gas barrier laminate film according to claim 4, wherein the functional group reactive with the liquid crystal polyester is an oxazolyl group, an epoxy group or an amino group. 7. A copolymer (Y) having a functional group reactive with a liquid crystal polyester, containing 0.1 to 30% by weight of an unsaturated glycidyl ester unit and / or an unsaturated glycidyl ether unit. The gas barrier laminate film according to claim 4, wherein the gas barrier laminate film is a polymer. 8. The gas barrier laminate film according to claim 4, wherein the copolymer (Y) having a functional group reactive with the liquid crystal polyester is a rubber having an epoxy group. 9. The gas barrier laminate film according to claim 4, wherein the copolymer (Y) having a functional group reactive with the liquid crystal polyester is a thermoplastic resin having an epoxy group. 10. The liquid crystal polyester (X) is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. The gas barrier laminate film according to the above. 11. The gas barrier laminated film according to claim 4, wherein the liquid crystal polyester (X) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids. . 12. A layer comprising a composition comprising an inorganic layer compound and a resin is a layer comprising a composition obtained by using an inorganic layer compound and a resin swelled and / or cleaved in a solvent. The gas barrier laminate film according to any one of claims 1 to 11, which is characterized in that: 13. An inorganic layered compound having an aspect ratio of 50.
The gas barrier laminate film according to any one of claims 1 to 12, wherein the thickness is from 5,000 to 5,000. 14. The gas barrier laminate according to claim 1, wherein the weight ratio of (inorganic layer compound / resin) is in the range of (5/95) to (90/10). the film. 15. The resin in a composition comprising an inorganic layered compound and a resin is a high hydrogen bonding resin having a weight percentage of hydrogen bonding groups or ionic groups per unit weight of the resin of 20 to 60%. 2. The method according to claim 1, wherein
15. The gas-barrier laminated film according to any one of items 14 to 14. 16. The gas barrier according to claim 1, wherein the resin in the composition comprising the inorganic layered compound and the resin is a polyvinyl alcohol, a polysaccharide, or an ethylene-vinyl alcohol copolymer. Laminated film. 17. A container comprising the gas-barrier laminated film according to any one of claims 1 to 16. 18. The container according to claim 17, wherein the container is a bag, a standing pouch, a bag-in-drum, a retort container, a deep drawn container, or a cart can.