JP3326480B2 - Container made of liquid crystal polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a container made of a liquid crystal polyester resin composition and having excellent mechanical strength, impact strength, heat resistance and gas barrier properties.

[0002]

2. Description of the Related Art Containers having gas barrier properties are widely used in the industrial world, but at present, existing gas barrier containers do not sufficiently satisfy the requirements of the market.
In other words, the required properties of the gas barrier container include not only excellent gas barrier properties, but also heat resistance that enables use in a microwave oven or heat treatment as a retort food packaging material, and facilitates the formation of a film that is the base material of the container. There are various demands in the market, such as moldability that can be performed easily, and ease of recycling and disposal after use, but the conventional gas barrier container has not sufficiently responded to these requirements.

[0003] For example, polypropylene has insufficient gas barrier properties, and ethylene-vinyl acetate copolymer has a remarkable decrease in gas barrier properties under moisture absorption, and also has insufficient heat resistance. Polyvinylidene chloride has low heat resistance, and has environmental problems at the time of disposal because it contains chlorine.

[0004] Polyethylene terephthalate (hereinafter PE)
T may be abbreviated as T) also has insufficient heat resistance and insufficient water vapor barrier properties. A gas barrier material obtained by depositing an inorganic substance such as silica or alumina on an ethylene-vinyl acetate copolymer or PET, or a gas barrier material obtained by laminating an aluminum foil or the like on a thermoplastic resin has insufficient heat resistance and is not suitable for film peeling. There is a problem,
There is also a problem that a material using a metal cannot be used in a microwave oven.

On the other hand, a liquid crystal polyester is generally called a melt-type liquid crystal (thermotropic liquid crystal) polymer, and is characterized in that molecules are oriented in a molten state by strong intermolecular interaction. Due to its strong intermolecular interaction and molecular orientation, it is expected to be industrialized as a film material with functions such as gas barrier properties in addition to the well-known high strength, high elastic modulus and high heat resistance properties of liquid crystal polyester. It has been.

However, unlike aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyesters are not entangled even in a molten state because the molecules are rigid, and the molecular chains are remarkably oriented in the flow direction. It exhibits such a behavior that the melt viscosity is suddenly lowered even by shearing, or that the melt viscosity is rapidly decreased by a rise in temperature and the melt tension during melting is extremely low. Therefore, it is very difficult to maintain the shape in the molten state, and it is difficult to balance the vertical and horizontal performance due to the orientation of the molecules, and in extreme cases, it will tear in the direction of molecular orientation, so sheets, There is a big problem that the practicality in the fields of film molding, containers molded by using them, blow molding and the like is poor, and the function of liquid crystal polyester has not been sufficiently put to practical use.

[0007] Such a liquid crystal polyester is disclosed in JP-A-52-109578 and JP-A-58-3171.
No. 8 discloses a laminate in which uniaxially oriented liquid crystal polyester films are laminated in a direction to cancel the anisotropy of strength, but the productivity is poor and there is a problem of film peeling.

US Pat. No. 4,975,312, WO
Japanese Patent No. 9015706 discloses a method for canceling the anisotropy of liquid crystal polyester by rotating a ring die.
JP-A-63-173620 discloses a device for canceling anisotropy by inflation film formation using a special slit. Further, JP-A-62-25513, JP-A-63-95930, and 63-24
No. 251 proposes a special device or the like in the T-die method. However, these methods all show a method of alleviating anisotropy due to molecular orientation by a very special molding method, and have disadvantages such as high cost, a limitation in thinning, and poor practicality.

Further, Japanese Patent Application Laid-Open No. 62-187,033,
JP-A-64-69323, JP-A-2-17801
6, JP-A-2-253919, JP-A-2-253919
JP-A-253920, JP-A-2-253949,
JP-A-2-253950 discloses a multilayer (laminated) sheet and a multilayer (laminated) of a liquid crystal polyester and a thermoplastic resin.
Films have been proposed, but there is a problem that peeling occurs due to the interposition of an adhesive layer between the layers, the inherent gas barrier properties of liquid crystal polyester, the performance such as heat resistance is reduced, and the production of thin films is difficult. .

[0010] Also, Japanese Patent Application Laid-Open No. 61-192762,
JP-A-1-288421, JP-B-6-92525
In this publication, a molded article of a composition obtained by mixing and kneading a liquid crystal polyester with a polyester such as PET is described, but its gas barrier properties are not sufficient.

Japanese Patent Application Laid-Open No. 4-166320 discloses a method for producing a container using a liquid crystal polyester having a specific structure. Specifically, a polycondensation reaction is carried out from polyethylene terephthalate and acetoxybenzoic acid by conducting an acidolysis reaction. It uses a polyester obtained in this way, and its gas barrier properties are not sufficient. Further, further improvement in sheet forming and anisotropy has been desired.

[0012] As described above, the above-mentioned method is devised in the processing of the liquid crystal polyester, but the liquid crystal polyester itself is difficult to form a film due to the anisotropic properties of the liquid crystal polyester and the rapid change in melt viscosity. It has not yet solved the essential problem. Further, in the method which enables the film formation of the liquid crystal polyester, the excellent gas barrier properties expected of the liquid crystal polyester cannot be sufficiently exhibited. Therefore, there has been a strong demand from the market for a liquid crystal polyester resin composition container which retains excellent functions such as gas barrier properties of liquid crystal polyester, has improved anisotropy in mechanical properties, and is easy to mold.

[0013]

DISCLOSURE OF THE INVENTION The present invention provides a liquid crystal polyester having excellent mechanical properties, heat resistance and gas barrier properties, and has a unique viscosity behavior upon melting, which was a disadvantage of the liquid crystal polyester. An object of the present invention is to provide a container comprising the improved liquid crystal polyester resin composition.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems and arrived at the present invention. That is, the present invention relates to (A) liquid crystal polyesters 56 to 99.
Thermoplastic resin 44% by weight and (B) epoxy group
The obtained that sheet materials obtained from the liquid crystal polyester resin composition containing 1 wt%, instrumentation into a mold having a container shape
From the starting temperature of minus 20 ℃ of the resin composition
A method for producing a container made of a liquid crystal polyester resin composition , characterized by being formed by applying heat at plus 50 ° C. , and a sheet or film made of the liquid crystal polyester resin composition as a lid material, and containing the contents therein. A method for producing a container made of a liquid crystal polyester resin composition, wherein the container is adhered to an opening of the container made of a liquid crystal polyester resin composition and sealed. Next, the present invention will be described in detail.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystal polyester as the component (A) of the liquid crystal polyester resin composition of the present invention is a polyester called a thermotropic liquid crystal polymer. Specifically, (1) a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, (2) a combination of different aromatic hydroxycarboxylic acids, and (3) an aromatic hydroxycarboxylic acid Examples thereof include those comprising a combination of a dicarboxylic acid and a nucleus-substituted aromatic diol, and (4) those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate. It forms an ionic melt. Incidentally, these aromatic dicarboxylic acids,
Instead of aromatic diols and aromatic hydroxycarboxylic acids, their ester-forming derivatives may be used. Examples of the repeating structural unit of the liquid crystal polyester include, but are not limited to, the following.

A repeating structural unit derived from an aromatic dicarboxylic acid:

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[0017]

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A repeating structural unit derived from an aromatic diol:

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[0019]

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A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

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A liquid crystal polyester which is particularly preferable from the balance of heat resistance, mechanical properties and workability is

Embedded image Is preferably 30 mol% or more,
Specifically, combinations of repeating structural units are as shown in (I) to (VI) below.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The production methods of the liquid crystal polyesters (I) to (VI) are described in, for example, JP-B-47-47870, JP-B-63-3888, and JP-B-63-389.
No. 1, JP-B-56-18016, JP-A-2-
No. 51523, and the like. Of these, a combination of (I), (II) and (IV) is preferable,
More preferred is a combination of (I) and (II).

In the field where high heat resistance is required in the container made of 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 '). Liquid crystal polyesters comprising 0 to 10 mol% of the unit (b '), 10 to 25 mol% of the repeating unit (c'), and 10 to 35 mol% of the repeating unit (d ') are preferably used.

[0030]

Embedded image (In the formula, Ar is a divalent aromatic group.)

In the container made of the liquid crystal polyester resin composition used in the present invention, the fields in which easy disposal such as incineration after use is required from the viewpoint of environmental issues include the fields required in each of the fields mentioned above. Among the preferred combinations, a liquid crystal polyester formed by a combination consisting of only carbon, hydrogen and oxygen is particularly preferably used.

Component (B) of the liquid crystal polyester resin composition used in the present invention is a thermoplastic resin having an epoxy group. In the liquid crystal polyester resin composition, the liquid crystal polyester of the component (A) forms a continuous phase, and the thermoplastic resin of the component (B) forms a dispersed phase. The reason why the liquid crystal polyester resin composition of the present invention has better moldability than the liquid crystal polyester alone is not necessarily clear, but the carboxylic acid at the terminal of the liquid crystal polyester reacts with the epoxy group of the component (B) to obtain a melt viscosity temperature. This is probably because the dependency was changed.

The functional group having an epoxy group is preferably a glycidyl group. As the monomer having a glycidyl group, unsaturated carboxylic acid glycidyl ester, unsaturated glycidyl ether and the like are preferably used. Preferably, the thermoplastic resin (B) is a copolymer containing 0.1 to 30% by weight of unsaturated glycidyl ester units and / or unsaturated glycidyl ether units.

Preferred examples of the thermoplastic resin (B) having an epoxy group include (a) 50 to 99.9% by weight of ethylene units, and (b) glycidyl ester units of unsaturated carboxylic acid and / or unsaturated units. Glycidyl ether unit is 0.1 to 30% by weight, preferably 1 to 30%
% By weight, and (c) an epoxy group-containing ethylene copolymer having an ethylenically unsaturated ester compound unit of 0 to 50% by weight. When the constituent components (a), (b) and (c) of the epoxy group-containing ethylene copolymer are within the above ranges, the resulting liquid crystal polyester resin composition is excellent in heat resistance, moldability, and the like, and is preferable. .

The epoxy group-containing ethylene copolymer (B)
In (b), the compound providing an unsaturated carboxylic acid glycidyl ester unit and an unsaturated glycidyl ether unit are represented by the following general formulas (18) and (19), respectively.

[0036]

Embedded image (R is a hydrocarbon group having 2 to 13 carbon atoms having an ethylenically unsaturated bond.)

[0037]

Embedded image (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ O-or

[0038]

Embedded image It is. )

Specifically, examples of the unsaturated glycidyl carboxylate include glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconate, triglycidyl butenetricarboxylate,
Glycidyl p-styrenecarboxylate and the like can be mentioned. As unsaturated glycidyl ethers,
Examples thereof include vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, and styrene-p-glycidyl ether.

The above-mentioned epoxy group-containing ethylene copolymer may be a tertiary or higher copolymer of unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether with ethylene and (c) an ethylenically unsaturated ester compound. Can also be used.

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

The epoxy group-containing ethylene copolymer may contain, in addition to the above-mentioned monomers, other monomers copolymerizable therewith. Examples of the monomer include isobutylene, styrene and derivatives thereof, and halogenated olefins such as tetrafluoroethylene and hexafluoropropylene.

Examples of the above-mentioned epoxy group-containing ethylene copolymer include a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units and glycidyl methacrylate units and methyl acrylate units, and a copolymer composed of ethylene units and glycidyl methacrylate units. Copolymers composed of methacrylate units and ethyl acrylate units, and copolymers composed of ethylene units, glycidyl methacrylate units, and vinyl acetate units are exemplified.

Further, the melt index of the epoxy group-containing ethylene copolymer [hereinafter may be referred to as MFR.
The measurement was performed according to JIS K6760 (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 out of this range, but if the melt index exceeds 100 g / 10 minutes, it is not preferable from the viewpoint of mechanical properties when the composition is formed.
If it is less than 10 minutes, the compatibility with the liquid crystal polyester of the component (A) is inferior, which is not preferable.

The epoxy group-containing ethylene copolymer has a flexural rigidity of preferably 10 to 1800 kg / cm ² , more preferably 20 to 1300 kg / cm ² . If the flexural rigidity is out of this range, the film forming processability of the composition may be insufficient or the mechanical properties of the film 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 ratio of component (A) to component (B) in the liquid crystal polyester resin composition used in the present invention is such that component (A) is 56 to 99% by weight, preferably 65 to 98% by weight, and component (B) Is 44 to 1% by weight, preferably 35 to 2% by weight.
% By weight. If the amount of the component (A) is less than 56% by weight, the film forming processability is insufficient, and the gas barrier properties and tensile strength of the film obtained from the composition are undesirably reduced. On the other hand, if the content of the component (A) exceeds 99% by weight, the effect of improving the anisotropy of the tensile strength of the film obtained from the composition may not be sufficient, which is not preferred.

Further, the combination of components (A) and (B) in the liquid crystal polyester resin composition used in the present invention can be freely changed within the above range depending on the use. However, from the viewpoint of environmental problems, carbon, oxygen, hydrogen Is preferably used.

In the liquid crystal polyester resin composition used in the present invention, an inorganic filler can be used if desired. Such inorganic fillers include talc, clay,
Examples include fillers for intercalation such as montmorillonite. Further, calcium carbonate, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flake, glass fiber, carbon fiber alumina fiber, silica alumina fiber, boric acid Examples thereof include aluminum whiskers and potassium titanate fibers.

The liquid crystal polyester resin composition used in the present invention may further contain, if necessary, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic compound. Various additives such as colorant, rust inhibitor, cross-linking agent, foaming agent, fluorescent agent, surface smoothing agent, surface gloss improving agent, release improver such as fluororesin, etc. in the manufacturing process or in the subsequent processing process Can be added.

The method for producing the liquid crystal polyester resin composition of the present invention is not particularly limited, and a known method can be used. For example, mixing each component in a solution state,
Examples of the method include evaporating the solvent or precipitating the solvent. From an industrial point of view, a method of kneading each component 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.

In the melt kneading, the cylinder set temperature of the kneading device is preferably in the range of 200 to 360 ° C, more preferably 230 to 340 ° 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 a method in which mixing is omitted and separately supplied to the kneading device separately may be used. it can.

The method for molding the liquid crystal polyester resin composition container of the present invention is not particularly limited, and it is molded by various molding methods. Specific examples of the molding method include ordinary injection molding and molding from pellets. Press molding, thermoforming in which a sheet-like molded body (hereinafter, a sheet or a film is collectively referred to as such) and then heating and deforming according to a mold are preferably used. In the case of injection molding or sheet-like molded body molding, the resin composition of the present invention is dry-blended at the time of molding and kneaded during the melt-processing operation without undergoing a kneading process in advance to obtain the resin composition of the present invention. You can also get

Injection molding of the liquid crystal polyester resin composition container of the present invention and press molding from the resin composition pellets are carried out within a temperature range from the flow initiation temperature of the resin composition to 70 ° C. of the flow initiation temperature. It is preferred to do so.
If the molding temperature is outside the temperature range, molding failure may occur, which is not preferable. Flow start temperature: Temperature at which the melt viscosity shows 48,000 poise when the resin heated at a heating rate of 4 ° C./min is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kgf / cm 2.

The liquid crystal polyester resin composition container of the present invention is preferably formed by thermoforming a sheet-like molded product of the resin composition, and the method of forming the sheet or film will be specifically described. The sheet-like molded body used as the material of the container and the lid member can be obtained by melt-kneading the liquid crystal polyester resin composition obtained by the above method with an extruder and taking out the molten resin extruded through a die. it can. As a base (die), a normal T-type die (hereinafter sometimes referred to as a T-die) can be used. The sheet-like molded product of the liquid crystal polyester resin composition, which is a material of the container of the present invention, can also be obtained by an inflation film forming method.

FIG. 1 is a schematic view showing an example of an apparatus for forming a sheet-like molded product of the liquid crystal polyester resin composition of the present invention. In FIG. 1, a liquid crystal polyester resin composition melt-kneaded by an extruder (1) passes through a downward T-die (2) to form a sheet-like melt (3), and then passes through a pressure roll (4) to form a longitudinal melt. Winded by the take-up device in the direction. On this occasion,
An air knife can be used instead of the pressure roll (4B).

The setting conditions of the extruder at the time of such film formation are appropriately selected according to the composition of the composition, and the setting temperature of the cylinder is in a range of from the flow start temperature of the resin to 70 ° C. of the flow start temperature. Is more preferable, and the flow start temperature plus 10 ° C to the flow start temperature plus 50 ° C is more preferable. If the ratio is out of this range, the composition may be thermally decomposed or film formation may be difficult, which is not preferable.

The slit gap of the T die (2) is 0.2 to
0.8 mm is preferred. The thickness of the liquid crystal polyester resin composition sheet-like molded article of the present invention can be controlled in the range of 1 to 1000 μm, but for use in molding the liquid crystal polyester resin composition container of the present invention, the thickness is preferably 10 to 500 μm. It is practically preferable. Further, from the viewpoint of ease of molding, those having a thickness of 30 μm to 300 μm are more preferable. The draft ratio of the sheet-like molded product of the liquid crystal polyester resin composition of the present invention is in the range of 1.1 to 40.0. Here, the draft ratio is a value obtained by dividing the cross-sectional area of the slit of the T-die by the cross-sectional area of the film in the longitudinal direction. When the draft ratio is less than 1.1, the sheet-like molded product is insufficient, and when the draft ratio exceeds 40.0, the surface smoothness of the film becomes 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.

In the liquid crystal polyester resin composition container of the present invention, the sheet-like molded product of the resin composition obtained as described above is mounted on a mold having the shape of a container, and the flow of the resin composition is carried out. It is obtained by applying a heat of −20 ° C. to + 50 ° C. of the starting temperature and thermoforming. More preferably, it is obtained by thermoforming in a temperature range from -10 ° C to 30 ° C of the flow start temperature. It can also be obtained by stamping and molding a sheet-like molded body into a container in the same temperature range. If the temperature range is out of this range, color unevenness may occur in the molded container, or molding may be difficult, which is not preferable.

The shape of the liquid crystal polyester resin composition container of the present invention is such that the ratio of the depth of the container to the diameter of the mouth of the container is 1/10 or more in the case of a circular container and the shape of the container in the case of a rectangular container. The ratio of the depth to the length of the longest diagonal line of the container opening is 1/10 or more. When each ratio is 1/10 or less, the capacity of the contents is insufficient, which is not preferable.

The method for molding the lid material of the container of the liquid crystal polyester resin composition of the present invention is not particularly limited, and it is molded by various molding methods. The specific molding method is as follows. A method of obtaining a sheet-like molded body by taking out the extruded molten resin and a method of obtaining the same by inflation film formation are preferably used.

The lid of the liquid crystal polyester resin composition container of the present invention is used by cutting a sheet-like molded body so as to conform to the shape of the opening of the container of the present invention. The lid material of the liquid crystal polyester resin composition container of the present invention is 10 μm to 500 μm.
A sheet-like molded body having a thickness of m is preferably used. More preferably, a sheet-shaped molded product having a thickness of 30 µm to 200 µm is used. If it is out of this range, the strength may be insufficient or the opening may be difficult, which is not preferable.

The method of bonding the lid material is not particularly limited, but a method using so-called heat bonding (heat sealing) using heat and pressure, a method using an adhesive, a method using ultrasonic waves, and the like are preferably used. Can be The thermal bonding is performed by overlapping the lid around the opening portion of the container of the present invention, and reducing the flow start temperature of the liquid crystal polyester resin composition of the present invention by -40.
It is performed by a method of applying pressure to the bonded portion in a range of from + 20 ° C to + 20 ° C.

[0065]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples, and the present invention is not limited to these examples.

(1) Method of measuring physical properties Melt tension: A 2.1 mmφ × 14.75 mm die was attached to a Capillograph manufactured by Toyo Seiki Co., Ltd., and extruded at an extrusion speed of 5 mm / min. Maximum take-off speed 150m / mi
The tension at the time when the strand broke was measured when the wire was taken up with the speed automatically changed until n.

Deflection temperature under load (TDUL): TDUL
Test piece for measurement (127 mm length x 12.7 mm width x 6.4
mm), and according to ASTM D648,
TDUL (load 18.6 kg) was measured.

Tensile strength anisotropy: A 100 μm-thick sheet-like molded article obtained by using a T-die was taken in the longitudinal direction of the test piece (MD direction) and the direction perpendicular thereto (TD direction). Punched into a No. 2 test piece according to JIS K7127, and pulled at a speed of 10 mm /
The tensile strength was measured in min. It can be said that the smaller the ratio between the tensile strength of the test piece punched in the MD direction and the tensile strength of the test piece punched in the TD direction, the smaller the anisotropy.

Oxygen gas permeability: JIS K7126
The measurement was performed at a temperature of 20 ° C. in accordance with the method A (differential pressure method). The unit is cc / m ² · 24 hr · 1 atm.

Water vapor permeability: Measured at a temperature of 40 ° C. and a relative humidity of 90% in accordance with JIS Z0208 (cup method). The unit is g / m ² · 24 hr · 1 atm. The oxygen gas transmission rate and the water vapor transmission rate were set to 25
It was calculated by converting to μm.

Drop impact: A container made of the composition is filled with water, sealed with a lid material, and then dropped from a height of 1.0 m.
The presence or absence of impact fracture was examined.

Microwave permeability: Water was placed in a sealed container made of the composition, and it was examined whether or not the water in the container was heated by a commercially available microwave oven.

(2) Liquid crystal polyester (A) (i) p-acetoxybenzoic acid 10.8 kg (60 mol), terephthalic acid 2.49 kg (15 mol), isophthalic acid 0.83 kg (5 mol) and 4,4 5.45 kg (20.2 mol) of '-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. During this time, the polymerization was carried out under vigorous stirring while removing acetic acid produced as a by-product. 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 having a size of 2.5 mm or less. This was further treated in a rotary kiln under a nitrogen gas atmosphere at 280 ° C. for 3 hours to obtain a particulate wholly aromatic polyester having a flow temperature of 324 ° C. and comprising the following repeating structural units. Hereinafter, the liquid crystal polyester is abbreviated as A-1. This liquid crystal polyester A
-1 showed optical anisotropy at 340 ° C. or more under pressure. The ratio of the repeating structural units of the liquid crystal polyester A-1 is as follows.

[0075]

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(Ii) p-hydroxybenzoic acid 16.6k
g (12.1 mol), 8.4 kg (4.5 mol) of 6-hydroxy-2-naphthoic acid and 18.6 kg of acetic anhydride
(18.2 mol) was charged into a polymerization tank equipped with a comb-shaped stirring blade,
The temperature was increased while stirring in a nitrogen gas atmosphere.
Time, and then 320 ° C. under a reduced pressure of 2.0 torr
For 1 hour. During this time, acetic acid produced as a by-product was continuously distilled out of the system. Thereafter, the system was gradually cooled, and the polymer obtained at 180 ° C. was taken out of the system.

The obtained polymer is pulverized in the same manner as in the above (i), and then treated in a rotary kiln under a nitrogen gas atmosphere at 240 ° C. for 5 hours to obtain the following particles having a flow temperature of 270 ° C. A wholly aromatic polyester consisting of repeating units was obtained. Hereinafter, the liquid crystal polyester is abbreviated as A-2. This liquid crystal polyester A-2 showed optical anisotropy at 280 ° C. or more under pressure. The ratio of the repeating structural units of the liquid crystal polyester A-2 is as follows.

[0078]

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(3) Thermoplastic resin having epoxy group (B) Composition of epoxy group-containing ethylene copolymer used, MF
R and flexural rigidity are as follows. Where M
FR measured at 190 ° C. under a load of 2.16 kg (unit:
g / 10 minutes) and the flexural rigidity is ASTM D747.
It is a value measured based on. B-1: Copolymer produced by high-pressure radical polymerization method Brand name Sumitomo Chemical Co., Ltd. Bondfast 7L Composition ethylene / glycidyl methacrylate / methyl acrylate = 67/3/30 (weight ratio) MFR = 9 Flexural rigidity = 60kg / cm ²

B-2: Copolymer produced by a high-pressure radical polymerization method Trade name Bondfast 20B manufactured by Sumitomo Chemical Co., Ltd. Composition: ethylene / glycidyl methacrylate / vinyl acetate = 83/12/5 (weight ratio) MFR = 20 bending Rigidity = 430 kg / cm ²

B-3: Copolymer produced by high-pressure radical polymerization method Trade name Bondfast E composition manufactured by Sumitomo Chemical Co., Ltd. Ethylene / glycidyl methacrylate = 88/1
2 (weight ratio) MFR = 3 Flexural rigidity = 700 kg / cm ²

B-4: Copolymer produced by high-pressure radical polymerization method Composition: ethylene / glycidyl methacrylate / methyl acrylate = 93.5 / 0.5 / 6.0 (weight ratio) MFR = 6 Flexural rigidity = 1380 kg / cm ²

B-5: Low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen F-101-1) 1
Glycidyl methacrylate (1.2 parts by weight) was blended with 00 parts by weight, and the mixture was melt-kneaded while being deaerated using a twin-screw extruder. The glycidyl methacrylate content of the obtained resin was 0.8% by weight. MFR = 6 Flexural rigidity = 1900 kg / cm ²

Examples 1 to 6 and Comparative Examples 1 to 5 After mixing the components with the composition shown in Table 1 using a Henschel mixer, the cylinder set temperature was adjusted using a twin screw extruder TEX-30 manufactured by Nippon Steel Corporation. The mixture was kneaded at a temperature 20 ° C. higher than the flow start temperature shown in Table 1 at a screw rotation speed of 200 rpm to obtain a resin composition pellet. The test piece for load deflection test was injection molded at a molding temperature of 20 ° C. higher than the flow start temperature shown in Table 1 and a mold temperature of 100 ° C. using a PS40E5ASE type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. It was prepared and subjected to TDUL measurement. The results are as shown in Table 2.

The sheet was formed by kneading the above resin composition pellets into a 20 mmφ single screw extruder equipped with a T die (VS20-20, manufactured by Tanabe Plastics Machinery Co., Ltd.) as schematically shown in FIG. Using a mold), the cylinder set temperature was set to a temperature 25 ° C. higher than the flow start temperature shown in Table 1, melt-kneaded at a screw rotation speed of 80 rpm, and a T-die having a die lip width of 100 mm and a die slit gap of 0.5 mm was used. It was extruded and wound at a speed of 2 to 8 m / min through two pressure rolls heated to a temperature 80 ° C. lower than the flow start temperature shown in Table 1, and the thickness was 100 μm.
m and 150 μm of the composition sheet having a thickness of 10
The 0 μm sheet was subjected to a gas permeation test. The evaluation results are as shown in Table 2.

For a 150 μm thick sheet of the above composition, the drawing ratio (circular container; container depth / container diameter, square container; container depth / container opening / diagonal length) is 1
/ 8 is set on the press machine, and the sheet is
After preheating at the flow start temperature of the composition, the temperature was increased to 10
℃ and heated press molding to obtain a molded container.

Further, with respect to the above composition, a drawing ratio of 1 /
Using a PS40E5ASE type injection molding machine manufactured by Nissei Plastics Co., Ltd., the square-shaped container No. 6 and the circular container having a drawing ratio of 3/2 were set at a molding temperature 20 ° C. higher than the flow start temperature shown in Table 1, and It was produced by injection molding at a temperature of 100 ° C.

In any case, when the container is covered with a lid, the lid is made of the same material as that used for molding the container.
Thermo-compression bonding (heat sealing) using a 00 μm thick sheet
did.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

The liquid crystal polyester resin composition used in the present invention has good moldability, and the deep drawn container obtained from the composition has excellent impact resistance and gas barrier properties. Moreover, the container is excellent in heat resistance and does not contain metal, so that it can be used in a microwave oven. The liquid crystal polyester resin composition container of the present invention can be used as individual packaging, interior packaging, and exterior packaging for various items to be packaged by utilizing such characteristics. Specifically, it can be widely used for food containers, retort food containers, microwave oven containers, chemical containers, cosmetic containers, electronic material containers, and the like.

[Brief description of the drawings]

FIG. 1 shows a schematic view of an example of a film forming apparatus.

[Explanation of symbols]

 1. Extruder 2. 2. T-die 3. Sheet-like melt of the resin composition Crimping roll (A, B)

Claims (12)

(57) [Claims] (A) 56 to 99% by weight of a liquid crystal polyester.
And (B) mounting a sheet-like molded product obtained from a liquid crystal polyester resin composition containing 44 to 1% by weight of a thermoplastic resin having an epoxy group in a mold having a shape of a container;
From the flow start temperature of the resin composition of minus 20 ° C to plus
A method for producing a container made of a liquid crystal polyester resin composition, wherein the container is formed by applying heat at 50 ° C. 2. A container made of the polyester resin composition according to claim 1, wherein a sheet-like molded product or a film-shaped molded product obtained from the liquid crystal polyester resin composition according to claim 1 is used as a cover material, and the contents are stored therein. A method for producing a container made of a liquid crystal polyester resin composition, characterized in that the container is adhered to an opening of the container and sealed. 3. The thermoplastic resin (B) is a copolymer containing 0.1 to 30% by weight of unsaturated glycidyl ester units and / or unsaturated glycidyl ether units. 3. The production method according to 1 or 2. 4. The thermoplastic resin (B) comprises (a) 50 to 99.9% by weight of ethylene units, and (b) 0.1 to 0.1% of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units. 3. The method according to claim 1, wherein the epoxy group-containing ethylene copolymer comprises 30% by weight and (c) 0 to 50% by weight of an ethylenically unsaturated ester unit. 5. The method according to claim 1, wherein the liquid crystal polyester (A) contains the following repeating unit in an amount of 30 mol% or more. Embedded image 6. The liquid crystal polyester (A) according to claim 1, wherein the polyester is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. The manufacturing method as described. 7. The method according to claim 1, wherein the liquid crystal polyester (A) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids. 8. A liquid crystal polyester (A) comprising the following repeating units:
4. The production method according to any one of 4. Embedded image 9. A liquid crystal polyester (A) comprising the following repeating units:
4. The production method according to any one of 4. Embedded image 10. A liquid crystal polyester (A) comprising the following repeating unit:
5. The production method according to any one of items 1 to 4. Embedded image 11. The liquid crystal polyester resin composition according to claim 1, wherein the composition comprises only carbon, hydrogen and oxygen.
5. The production method according to any one of items 1 to 4. 12. A container made of a liquid crystal polyester resin composition,
In a circular container, the ratio of the depth of the container to the diameter of the mouth of the container is 1/10 or more. In the case of a rectangular container, the ratio of the depth of the container to the length of the longest diagonal line of the opening of the container is 1 / 1
The method according to claim 1, wherein the number is 0 or more.