JP2000334906A - Vapor deposited film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve gas barrier properties by incorporating a liquid crystal polyester resin composition layer having a liquid crystal polyester of a continuous phase and a polymer as a dispersed phase and a vapor deposited layer of an inorganic compound in a vapor deposited film. SOLUTION: The vapor deposited film is constituted by providing a liquid crystal polyester obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid as a continuous phase, a liquid crystal polyester resin composition layer using a copolymer made as a dispersed layer of a functional group such as an oxazolyl group having reactivity with the liquid crystal polyester of the continuous phase, an epoxy group, an amino group or the like, and a vapor deposited layer of an inorganic compound using a metal such as aluminum, aluminum oxide, silicon, silicon oxide or the like. Thus, gas barrier properties can be improved, and a post-treatment is facilitated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film having excellent heat resistance and gas barrier properties.

[0002]

2. Description of the Related Art Packaging materials made of plastic films are used in various fields of industry such as foods, beverages, pharmaceuticals, electric and electronic parts, but they do not always sufficiently satisfy the requirements of the market. There is no present. In some cases, baking treatment is performed on electric or electronic components in a packaged state, and the packaging material may be required to have sufficient heat resistance. Further, the easiness of the burning treatment of the used film is also demanded from the market.

[0003] In response to such demands from a wide variety of markets, for example, when aluminum foil is used as a component, the aluminum foil is heavy, expensive, or easily generates pinholes, and thus has insufficient gas barrier properties. However, various problems such as a large amount of ash remaining during incineration have been pointed out.

Further, even when a plastic film is used, olefin resins such as polyethylene and polypropylene have low heat resistance and poor gas barrier performance. Ethylene-vinyl acetate copolymers and the like have poor gas barrier properties especially under high humidity and insufficient heat resistance. Polyvinyl chloride and polyvinylidene chloride have low heat resistance, insufficient gas barrier properties, and have problems with combustion gas at the time of disposal, and in all cases, they do not sufficiently satisfy the various demands of the market as described above. Was.

Unlike general-purpose polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polymers, for example, liquid crystal polyesters, are not entangled even in a molten state due to their rigid molecules, and form polydomains having a liquid crystal state. The molecular chains were remarkably oriented in the flow direction even by a severe shearing, and the melt viscosity suddenly decreased. It is described that the liquid crystalline polymers described in JP-A-7-304936 and JP-A-9-286907 are excellent in molding processability and can easily obtain a film excellent in heat resistance, chemical resistance, gas barrier properties and the like. However, depending on the application, further gas barrier properties may be required.

[0006]

Under such circumstances, the problem to be solved by the present invention, that is, an object of the present invention, is to provide a film having excellent gas barrier properties.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such a problem and arrived at the present invention.
That is, the present invention provides a layer comprising a liquid crystal polyester resin composition having (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersion phase, and an inorganic vapor deposition layer. And a vapor deposition film having:

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The liquid crystal polyester resin composition used in the present invention is a liquid crystal polyester resin composition containing (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase. .

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, ester derivatives thereof 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:

[0012]

A repeating structural unit derived from an aromatic diol:

[0014]

A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

A liquid crystal polyester which is particularly preferred 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).

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

The method for producing the liquid crystal polyesters (I) to (VI) is 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 in the liquid crystal polyester resin composition of the present invention, the liquid crystal polyester of the component (A) contains 30 to 80 mol% of the following repeating unit (a '), A liquid crystal polyester in which b ′) is 0 to 10 mol%, the repeating unit (c ′) is 10 to 25 mol%, and the repeating unit (d ′) is 10 to 35 mol% is preferably used.

[0025] (In the formula, Ar is a divalent aromatic group.)

In the field of the film of the present invention, from the viewpoint of environmental problems, etc., the field in which easy disposal such as incineration after use is required is particularly preferable among the preferable combinations of the fields required in the above. , Hydrogen and oxygen are particularly preferably used.

The component (B) used in the liquid crystal polyester resin composition of the present invention 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 (B), 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 containing a glycidyl group, unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether are preferably used.

Specifically, examples of the unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester,
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 (B) 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 (B) 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 (B) 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 (B) 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 can be 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.

In the present invention, the copolymer (B)
Is a rubber having a functional group reactive with the liquid crystal polyester in the rubber as described above. 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 (B) 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) acrylate 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 3% by weight to 5% 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 usual 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 (B) 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 component 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 a hydrogenated product thereof can be produced by a known method.
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 (B) 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 (B) can 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 (B) 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 epoxy group-containing ethylene copolymer has a melt index (hereinafter sometimes referred to as MFR. JI.
SK6760, 190 ° C., 2.16 kg load) is preferably 0.5 to 100 F-10 minutes, more preferably 2 to 100 F-10 minutes.
~ 50F-10 minutes. The melt index may be outside this range, but the melt index is 100F
If it exceeds -10 minutes, it is not preferable from the viewpoint of mechanical properties of the composition, and if it is less than 0.5F-10 minutes, the compatibility with the liquid crystal polyester of the component (A) is inferior.

[0058] 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 used in the present invention is a resin composition having (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as 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.

The details of the mechanism of such a resin composition of a copolymer having a functional group and a liquid crystal polyester are not clear, but the composition between the component (A) and the component (B) of the composition is not clear. It is considered that a reaction occurs, and the component (A) forms a continuous phase, and the component (B) is finely dispersed, thereby improving the moldability of the composition.

One embodiment of such a liquid crystal polyester resin composition comprises (A) 56.0 to 99.9 liquid crystal polyester.
44% by weight, preferably 65.0 to 99.9% by weight, more preferably 70 to 98% by weight, and (B) 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 (A) is less than 56.0% by weight, the gas barrier properties and heat resistance of a molded article such as a film or sheet obtained from the composition may be undesirably reduced. On the other hand, if the content of the component (A) exceeds 99.9% by weight, the molding processability of the composition may be reduced, and the composition is expensive, 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 of the above composition in a molten state is preferred. 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 20
The temperature is preferably in the range of 0 to 360 ° C, more preferably 23 ° C.
0-350 ° 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 the components may be separately supplied to the kneading device. Methods can also be used.

In the liquid crystal polyester resin composition used in the present invention, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an inorganic or organic colorant, Various additives such as a rust agent, a cross-linking 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 a subsequent processing process. .

As the layer comprising the liquid crystal polyester resin composition used in the present invention, such a liquid crystal polyester resin composition is melted by, for example, a T-die method of extruding and winding a molten resin from a T-die, or an extruder provided with an annular die. Extruding the resin into a cylindrical shape, cooling and winding the film or sheet obtained by the inflation film forming method, the film or sheet obtained by the hot press method or the solvent casting method, or the sheet obtained by the injection molding method or the extrusion method Can be further used as a film or sheet obtained by uniaxially or biaxially stretching. In the case of injection molding, extrusion molding, or the like, a film or sheet can be obtained by dry blending and pelletizing the component pellets at the time of molding without going through a kneading step in advance.
In addition, a film and a sheet are distinguished mainly by a difference in thickness, and in this specification, there is a case where only one is described in a meaning including the other.

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 it in the winder direction (longitudinal direction) is preferably used.

The conditions for setting the extruder when forming a 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 referred to 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 a biaxially stretched film is obtained, the stretching ratio is preferably 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 sheet extruded from a cylindrical die by inflation is also preferably used.

That is, the liquid crystal polyester resin composition obtained by the above method was supplied to a melt kneading extruder equipped with a die having an annular slit, and was set at a cylinder set temperature of 20.
Melt kneading is performed at 0 to 360 ° C, preferably 230 to 350 ° C, and the molten resin is extruded upward or downward from the annular slit of the extruder. The interval between the annular slits is usually 0.1 to 5 mm, preferably 0.2 to 2 mm, and the diameter of the annular slit is usually 20 to 1000 mm, 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 to thereby obtain a transverse direction perpendicular to the longitudinal direction. The film is expanded and stretched in (TD).

In the 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 liquid crystal polyester resin composition 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 off.

In the case of inflation film formation, conditions can be selected according to the composition of the liquid crystal polyester resin composition such that the cylindrical melt film expands to a uniform thickness and a smooth surface state.

The thickness of the layer comprising the liquid crystal polyester resin composition in the present invention is not particularly limited, but is preferably 3 to 1000 μm, more preferably 5 to 50 μm.

The vapor-deposited film of the present invention is a vapor-deposited film having a layer composed of the above liquid crystal polyester resin composition and a vapor-deposited layer of an inorganic substance. Hereinafter, typical examples of the form of the film of the present invention will be described.

The first embodiment of the film according to the present invention comprises:
This is a vapor-deposited film obtained by vapor-depositing an inorganic substance on a film made of the liquid crystal polyester resin composition obtained by the above method. The inorganic substance here is preferably a metal or an inorganic oxide, and more preferable specific examples include aluminum, aluminum oxide, silicon, silicon oxide, and the like. A single substance or two or more of such inorganic substances are used. I can do it.

For example, in order to deposit aluminum on a film made of a liquid crystal polyester resin composition, it is generally carried out by vacuum deposition. That is, a roll-shaped unwinder and a winder equipped with a film made of a liquid crystal polyester resin composition are accommodated in a container, the inside of the container is sealed, and after evacuation, the inside of the evaporation source in the container is removed. This is a method in which aluminum is heated from above and vapor-deposited on a liquid crystal polyester resin composition which continuously travels from an unwinder to a winder to obtain a vapor-deposited film. At this time, the degree of vacuum in the container is usually maintained at about 10 ⁻² to 10 ⁻⁴ Pa, and the aluminum in the evaporation source is heated to about 1400 ° C. The thickness of the aluminum layer to be deposited depends on the running speed of the liquid crystal polyester resin composition film, the heating conditions for aluminum,
It can be controlled by the gas pressure of aluminum in the container, etc.
The thickness of the aluminum deposition layer is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.1 μm. Here, the film made of the liquid crystal polyester resin composition may be previously treated with an anchor coat agent.

In the present invention, aluminum oxide is
AlO, Al ₂ O ₃ , Al ₂ O _{2 and the} like.
₂ O ₃ is preferred. The silicon oxide in the present invention is generally represented by SiO _x (where X represents a number from 0.3 to 2.0).

In order to deposit aluminum oxide, silicon or silicon oxide on a film made of a liquid crystal polyester resin composition, aluminum oxide, silicon or silicon oxide is deposited in a vacuum vessel under almost the same conditions as in the case of aluminum described above. A method of heating and evaporating silicon oxide from an evaporation source onto a film made of a liquid crystal polyester resin composition can be used. As a heating method at that time, there are methods such as resistance heating, high-frequency induction heating, arc discharge, and electron beam evaporation, and a heating method can be appropriately selected.

A method of heating and evaporating aluminum, silicon, siloxane, metal alkoxide and the like onto a film made of a liquid crystal polyester resin composition in the presence of oxygen gas is also included. At this time, plasma can be used to promote the reaction with oxygen. The thickness of the deposited layer of aluminum oxide or silicon oxide obtained by this method can also be controlled by the running speed of the film made of the liquid crystal polyester resin composition, the heating conditions, the gas pressure in the container, and the like. Is 0.01 to 1 μm
Is preferable, and the range of 0.01 to 0.1 μm is more preferable.

The thus-obtained vapor-deposited film of the present invention is excellent in heat resistance, chemical resistance and gas barrier properties, and has good adhesiveness between the vapor-deposited layer and the layer comprising the liquid crystal polyester resin composition. .

The second embodiment of the vapor-deposited film of the present invention comprises a layer composed of the liquid crystal polyester resin composition described above, a layer composed of a thermoplastic resin (excluding the liquid crystal polyester resin composition), and a vapor-deposited layer of an inorganic substance. And a vapor-deposited film having: As a specific example, a vapor-deposited film obtained by laminating a film composed of a thermoplastic resin (excluding the liquid-crystalline polyester resin composition) on a vapor-deposited film obtained by vapor-depositing an inorganic substance on a film composed of the liquid crystal polyester resin composition described above. Further, a vapor deposition film obtained by laminating a film composed of a liquid crystal polyester resin composition on a vapor deposition film obtained by vapor-depositing an inorganic substance on a film composed of a thermoplastic resin (excluding the liquid crystal polyester resin composition) can also be used.

In the case of the former vapor-deposited film, a film made of a thermoplastic resin (excluding the liquid crystal polyester resin composition) may be laminated on the vapor deposition layer side or on the liquid crystal polyester resin composition side. It is preferable, but the lamination on the vapor deposition layer side is preferable because the vapor deposition layer can be protected by the thermoplastic resin. The same applies to the case of the latter deposited film.

The thermoplastic resin (excluding the liquid crystal polyester resin composition) used herein is not particularly limited, but may be polyolefin, polystyrene, polycarbonate, polyester, polyacetal, polyamide, polyphenylene ether, polyether sulfone. ,
It preferably contains at least one selected from ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, fluororesin, and acrylic resin.

The layer made of such a thermoplastic resin (excluding the liquid crystal polyester resin composition) may be formed in the same manner as in the method for producing a film or sheet made of the liquid crystal polyester resin composition described above, or by appropriately changing the method. A film or sheet obtained by the above method can be used.

The thickness of the layer made of the thermoplastic resin (excluding the liquid crystal polyester resin composition) is not particularly limited, but is preferably in the range of 1 to 1000 μm. The deposition surface of the film made of the thermoplastic resin can be treated in advance with an anchor coat agent.

Here, as the inorganic substance used for vapor deposition, the same inorganic substances as those described above can be used, and the vapor deposition method can be performed in the same manner as described above.

The form of the vapor-deposited film in the present invention can take various forms by combining them in addition to the forms described above. In the present invention,
The films constituting the laminate can be bonded to each other using thermocompression bonding, ultrasonic fusion, or an adhesive. When an adhesive layer is interposed between the films constituting the vapor-deposited film of the present invention, the films can be adhered to each other by various methods such as dry lamination and melt extrusion lamination using an adhesive resin. In this case, even if an inorganic vapor-deposited layer is present on any surface to be bonded, the bonding can be performed similarly. In some cases, the liquid crystal polyester resin composition, the thermoplastic resin, and, if necessary, the adhesive resin are coextruded to form a vapor-deposited film on the laminate.

Either one of the surfaces of the liquid crystal polyester resin composition or the thermoplastic resin, or both surfaces, may be subjected to a surface treatment in advance and then deposited or adhered. Examples of such a surface treatment method include corona discharge treatment, plasma treatment, flame treatment, sputtering treatment, solvent treatment, ultraviolet treatment, polishing treatment, infrared treatment, and ozone treatment.

[0095]

The present invention will be described below with reference to examples.

(1) Liquid Crystal Polyester of Component (A) (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 heated at 280 ° C. in a rotary kiln under a nitrogen gas atmosphere.
For 3 hours, the flow start temperature becomes 324.
A wholly aromatic polyester comprising the following repeating structural units in the form of particles at a temperature of ° C was obtained. Here, the flow start temperature is determined using a Shimadzu flow tester CFT-500 manufactured by Shimadzu Corporation.
The resin heated and melted at a heating rate of 4 ° C./min is loaded with a load of 10
Under 0kgf / cm ² , inner diameter 1mm, length 10mm
When extruded from the nozzle, the melt viscosity is 48000
A temperature (° C.) indicating poise. Hereinafter, the liquid crystal polyester is abbreviated as A-1. The polymer is 340 under pressure
It showed optical anisotropy at a temperature of at least ° C. Liquid crystal polyester A-1
Are as follows.

[0097]

(2) Component (B) (i) According to the method described in Example 5 of JP-A-61-227709, methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38.7 / 2.3
(Weight ratio), Mooney viscosity = 15, heat of fusion of crystal <1
A rubber of J / g was obtained. Hereinafter, the rubber may be abbreviated as B-1. Here, the Mooney viscosity is JIS K6300
It is a value measured using a large rotor at 100 ° C. according to The heat of fusion of the crystal was determined by using a DSC and heating the sample from -150 ° C to 100 ° C at a rate of 20 ° C / min.

(3) Method for measuring physical properties of laminate (i) Gas barrier property: The obtained film was measured in the following manner. Oxygen gas permeability: JIS K71
According to the 26A method (differential pressure method), it was measured at a temperature of 20 ° C. using oxygen gas. Unit is cc / m ² · 24hr · 1a
tm. Water vapor permeability: Measured at a temperature of 40 ° C. and a relative humidity of 90% according to JIS Z0208 (cup method). The unit is g / m ² · 24 hr · 1 atm.

(Ii) Flex test: Regarding the obtained film, MIT flex tester Foldin manufactured by Toyo Seiki Co., Ltd.
g Using an Endurance Tester MIT-D type, load 1K based on JIS-p-8115.
gf, bending angle 135 degrees, bending surface radius 1 mm,
A bending test was performed at a bending speed of 175 times / min, and the number of times of bending until the film was broken was determined.

Example 1 80% by weight of A-1 and 20% by weight of B-1 were melt-kneaded using a TEX-30 type twin screw extruder manufactured by Nippon Steel Corporation at a cylinder set temperature of 350 ° C. and a screw rotation speed of 200 rpm. Was performed to obtain a 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 fed to a 60 mmφ single screw extruder equipped with a cylindrical die, and the cylinder temperature was set to 350 ° C. and the number of rotations was set to 60.
melt kneading at rpm, diameter 50mm, lip interval 1.0
mm, the molten resin is extruded upward from a cylindrical die having a die set temperature of 355 ° C. At this time, dry air is pressed into the hollow portion of the cylindrical film to expand the cylindrical film, and then cooled and then passed through a nip roll. And taken off at a take-off speed of 40 m / min to obtain a liquid crystal polyester resin composition film.
At this time, the stretching ratio in the MD direction of the film was 8.6, the blow ratio was 4.5, and the film thickness was 17 μm. Hereinafter, the film may be abbreviated as F-1. The oxygen gas permeability of F-1 is 0.6 cc / m ² · 24 hr · 1 atm,
The water vapor transmission rate was 0.4 g / m ² · 24 hr · 1 atm. The bending test result was> 100,000 times.

F-1 was cut into a size of 25 cm × 20 cm, placed in a vacuum chamber, and aluminum was vapor-deposited on F-1 under a vacuum of 1 × 10 ⁻⁴ mmHg at about 500 °. The oxygen gas permeability of the deposited F-1 is 0.1 cc.
/ M ² · 24 hr · 1atm, water vapor permeability is 0.3g
/ M ² · 24 hr · 1 atm. After the cellophane tape was pressed onto the vapor-deposited layer, the cellophane tape was pulled off and peeled off, but almost no aluminum deposited on the cellophane tape was visually observed.

Example 2 FIG. 1 shows an example of a specific embodiment of the vapor deposition film of the present invention. F-1 film (1) placed in a evacuated container
1) A silicon oxide was vapor-deposited on a vacuum, and a vapor-deposited film (vapor-deposited layer: 12) and a polypropylene film 13 were obtained.
Are obtained by thermocompression bonding. The film obtained in this way has excellent gas barrier properties like the film obtained in Example 1, and the deposited layer can be protected by polypropylene.

Example 3 FIG. 2 shows another specific embodiment of the vapor deposition film of the present invention.
Here is an example. Aluminum oxide is vacuum-heat-deposited on the F-1 film (22) placed in the evacuated container, and an adhesive resin is formed between the obtained vapor-deposited film (deposited layer: 23) and the polyethylene terephthalate film 25. 24 is melt-extruded to bond the two, and then the non-deposited surface of the F-1 film and the low-density polyethylene 21 as a sealant are thermocompression-bonded. The film thus obtained is excellent in gas barrier properties like the film obtained in Example 1, and is easy to print while protecting the deposited layer with polyethylene terephthalate,
Furthermore, it can be easily processed into a bag by heat-sealing each other with the sealant inside.

[0105]

According to the present invention, a film having excellent gas barrier properties can be obtained. As this film, a film having excellent heat resistance and chemical resistance can be obtained. The vapor-deposited film of the present invention has excellent adhesiveness between the vapor-deposited layer and a layer composed of a liquid crystal polyester resin composition in particular, and is also excellent in maintaining gas barrier properties. Further, since the deposited film of the present invention can be easily post-processed after being used, it is provided as a film suitable as a packaging material for foods, beverages, medical care, medicines, electric parts, electronic parts, precision parts, and the like.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one example of a specific embodiment of the vapor deposition film of the present invention.

FIG. 2 is a cross-sectional view showing one example of a specific embodiment of the vapor deposition film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 ... F-1 film 12 ... Silicon oxide vapor deposition layer 13 ... Polypropylene film 21 ... Low density polyethylene film (sealant) 22 ... F-1 film 23 ... Aluminum oxide vapor deposition Layer 24: adhesive resin 25: polyethylene terephthalate film

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4F100 AA01B AA19B AA20B AB10B AB11B AK01A AK01C AK04 AK04J AK25 AK25J AK41A AK43A AK53A AK54 AK54J AL01 AL02A AL05A AN02 AN02A AN02BA10 BA03 BA03 BA03 BA02 BA10 BAB

Claims (10)

[Claims] 1. A layer comprising a liquid crystal polyester resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase, and an inorganic vapor-deposited layer. A vapor-deposited film comprising: 2. An inorganic substance is deposited on a film comprising a liquid crystal polyester resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase. A vapor-deposited film comprising: 3. A layer comprising a liquid crystal polyester resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase; However, a vapor-deposited film comprising a layer comprising a liquid crystal polyester resin composition) and a vapor-deposited layer of an inorganic substance. 4. The vapor-deposited film according to claim 1, wherein the inorganic substance is at least one of aluminum, aluminum oxide, silicon, and silicon oxide. 5. A liquid crystal polyester resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase, comprising: 0 to 99.9% by weight, and (B) 44.0 to 0.1% by weight of a copolymer having a functional group reactive with the liquid crystal polyester, which is a composition obtained by melt-kneading. Claim 1
5. The vapor-deposited film according to any one of items 4 to 4. 6. The vapor-deposited film according to claim 1, wherein the functional group reactive with the liquid crystal polyester is an oxazolyl group, an epoxy group or an amino group. 7. The vapor-deposited film according to claim 1, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a rubber having an epoxy group. 8. The vapor deposition according to claim 1, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a thermoplastic resin having an epoxy group. the film. 9. The liquid crystal polyester (A) according to claim 1, which is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. The vapor-deposited film as described. 10. The vapor-deposited film according to claim 1, wherein the liquid crystal polyester (A) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids.