JPH09249798A - Container made from liquid crystal polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a container made from a liquid crystal polyester resin composition which retains the excellent performances (e.g. mechanical properties, heat resistance and gas barrier properties) of the constituent liquid crystal polyester and improved in its peculiar undesirable viscosity behavior in a molten state and to provide a process for producing the same. SOLUTION: This container is made from a liquid crystal polyester resin composition containing 56-99wt.% liquid crystal polyester and 44-1wt.% thermoplastic epoxy resin and is a cylindrical one having a ratio. of the depth to the diameter of the mouth of 1/10 or above or a square one having a ratio of the depth to the longest diagonal of 1/10 or above. Alternatively, it is prepared by using a sheet or film made from the composition as the cover and bonding this cover to the opening of a container made from the composition and holding contents to seal the container.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Although a container having a gas barrier property is widely used in the industrial world, it is the current situation that the existing container having a gas barrier property does not sufficiently satisfy the market demand.
In other words, the required properties for the gas barrier container are 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 easy formation of a film that is the original material of the container. Although there are various demands in the market such as molding processability that can be achieved, ease of recycling after use, disposal, etc., conventional gas barrier containers have not sufficiently met these demands.

For example, polypropylene has an insufficient gas barrier property, and the ethylene-vinyl acetate copolymer system has a remarkable decrease in the gas barrier property under moisture absorption and also has an insufficient heat resistance. Polyvinylidene chloride has low heat resistance, and since it contains chlorine, it poses an environmental problem at the time of disposal.

Polyethylene terephthalate (hereinafter PE
(Although it may be abbreviated to T), the heat resistance is still insufficient and the water vapor barrier property is also insufficient. A gas barrier material formed by vapor-depositing an inorganic substance such as silica or alumina on an ethylene-vinyl acetate copolymer or PET, or a gas barrier material obtained by adhering an aluminum foil or the like to a thermoplastic resin has insufficient heat resistance and may cause peeling of films. There is a problem,
Further, there is a problem that a material using metal cannot be used in a microwave oven.

On the other hand, the liquid crystal polyester is generally called a melt-type liquid crystal (thermotropic liquid crystal) polymer and is a polyester 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 having functions such as gas barrier properties in addition to the properties such as high strength, high elastic modulus and high heat resistance that are well known for liquid crystal polyesters. It has been.

However, unlike aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyesters do not become entangled even in a molten state because the molecules are rigid, and the molecular chains are remarkably oriented in the flow direction. It also exhibits a behavior in which the melt viscosity sharply decreases due to shearing, and a behavior in which the melt viscosity sharply decreases due to temperature rise and the melt tension during melting is extremely low. Therefore, it is very difficult to keep the shape in the molten state, and it is difficult to balance the performance in the vertical and horizontal directions due to the molecules being oriented, and in the extreme case, the sheet is torn in the molecular orientation direction, so that the sheet, There is a big problem that it is not practical in the fields of film molding, containers molded by using them, blow molding, etc., and the function of liquid crystal polyester has not been fully put into practical use.

Regarding such a liquid crystal polyester, JP-A-52-109578 and JP-A-58-3171
Japanese Unexamined Patent Publication No. 8 discloses a laminate in which uniaxially oriented liquid crystal polyester films are laminated in a direction in which the anisotropy of strength is canceled, but the productivity is poor and there is a problem of film peeling.

US Pat. No. 4,975,312, WO
No. 9015706 discloses a device for canceling the anisotropy of liquid crystal polyester by rotating a ring die.
Further, JP-A-63-173620 discloses a device for canceling anisotropy by an inflation film formation using a special slit, and further discloses JP-A-62-25513 and JP-A-63-95930. Kaisho 63-24
No. 251, gazette proposes a special device in the T-die method. However, all of them show a method of alleviating anisotropy due to molecular orientation by a very special molding method, and there is a drawback that the cost is high, there is a limit in thinning the film, and the practicality is poor.

Further, Japanese Patent Laid-Open No. 62-187033,
JP-A-64-69323, JP-A-2-17801
6, JP-A-2-253919, JP-A-2-
253920, JP-A-2-253949,
Japanese Unexamined Patent Publication (Kokai) No. 2-253950 discloses a multilayer (laminate) sheet of liquid crystal polyester and a thermoplastic resin, and a multilayer (laminate).
Films have been proposed, but peeling occurs due to the interposition of an adhesive layer between the layers, there is a problem that the performance such as gas barrier properties and heat resistance originally possessed by liquid crystal polyester is deteriorated, and it is difficult to manufacture a thin film. .

Further, Japanese Patent Application Laid-Open No. 61-192762,
Japanese Unexamined Patent Publication No. 1-288421, Japanese Patent Publication No. 6-92525
The publication describes a molded article of a composition obtained by mixing and kneading a polyester such as PET with a liquid crystal polyester, but its gas barrier property is not sufficient.

Further, Japanese Unexamined Patent Publication (Kokai) No. 4-166320 discloses a method for producing a container using a liquid crystal polyester having a specific structure. Specifically, an acidolysis reaction is performed from polyethylene terephthalate and acetoxybenzoic acid to cause polycondensation. The obtained polyester is used, and its gas barrier property is not sufficient. Further, further improvement in sheet molding and anisotropy has been desired.

As described above, in the above-described method, some contrivances are recognized in the processing of the liquid crystal polyester, but the anisotropy of the liquid crystal polyester and the difficulty of film formation due to the abrupt change of the melt viscosity cause the liquid crystal polyester itself. It has not solved the essential problems that it has. Further, in the method capable of forming a film of liquid crystal polyester, the excellent gas barrier properties expected of liquid crystal polyester have not been sufficiently exhibited. Therefore, there has been a strong demand from the market for a liquid crystal polyester resin composition container that 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 retains the excellent mechanical properties, heat resistance, gas barrier properties, and other functions of liquid crystal polyester, and exhibits the unique viscosity behavior during melting, which is a drawback of liquid crystal polyester. An object of the present invention is to provide a container made of the improved liquid crystal polyester resin composition.

[0014]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies in order 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 having wt% and (B) epoxy groups
In the case of 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, and in the case of a rectangular container, the depth of the container obtained from a liquid crystal polyester resin composition containing 1 to 1% by weight. A container made of a liquid crystal polyester resin composition in which the ratio of the lengths of the longest diagonal lines of the container is 1/10 or more, and a sheet or film made of the liquid crystal polyester resin composition as a lid material, The present invention relates to a container made of a liquid crystal polyester resin composition, which is adhered to an opening of the container made of the liquid crystal polyester resin composition and hermetically 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, (3) an aromatic Examples thereof include a combination of a dicarboxylic acid and a nucleus-substituted aromatic diol, and (4) a polyester obtained by reacting a polyester such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid. Anisotropic at a temperature of 400 ° C. or lower. To form a crystalline melt. Incidentally, these aromatic dicarboxylic acids,
Instead of aromatic diols and aromatic hydroxycarboxylic acids, their ester-forming derivatives may also be used. Examples of the repeating structural unit of the liquid crystal polyester include the following, but are not limited thereto.

Repeating structural unit derived from aromatic dicarboxylic acid:

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[0017]

[Chemical 6]

Repeating structural units derived from aromatic diols:

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[0019]

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Repeating structural unit derived from aromatic hydroxycarboxylic acid:

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Particularly preferred liquid crystal polyester from the viewpoint of balance between heat resistance, mechanical properties and processability 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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Regarding the production method of the liquid crystal polyesters (I) to (VI), for example, Japanese Patent Publication No. 47-47870, Japanese Patent Publication No. 63-3888, and Japanese Patent Publication No. 63-389.
No. 1, JP-B No. 56-18016, JP-A No. 2-
It is described in, for example, Japanese Patent No. 51523. Of these, a combination of (I), (II) and (IV) is preferable,
The combination of (I) and (II) is more preferable.

In the container of the liquid crystal polyester resin composition of the present invention, in the field where high heat resistance is required, the liquid crystal polyester of the component (A) contains 30 to 80 mol% of repeating units (a ') below. A liquid crystal polyester having a unit (b ') of 0 to 10 mol%, a repeating unit (c') of 10 to 25 mol% and a repeating unit (d ') of 10 to 35 mol% is 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, from the viewpoint of environmental problems, in the fields where ease of disposal such as incineration after use is required, the fields required for each of the above are Among the preferred combinations, a liquid crystal polyester composed of a combination of only elements of carbon, hydrogen and oxygen is particularly preferably used.

The 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. Although the reason why the moldability of the liquid crystal polyester resin composition of the present invention is better than that of the liquid crystal polyester alone, it is not always clear that the carboxylic acid at the terminal of the liquid crystal polyester and the epoxy group of the component (B) react and the temperature of the melt viscosity is increased. 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 carboxylic acid 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 unit, (b) unsaturated carboxylic acid glycidyl ester unit and / or unsaturated. 0.1-30% by weight of glycidyl ether unit, preferably 1-30
An epoxy group-containing ethylene copolymer composed of 0 to 50% by weight of the ethylenically unsaturated ester compound unit (c) is included. When the constituent components (a), (b) and (c) of the epoxy group-containing ethylene copolymer are within the above range, the resulting liquid crystal polyester resin composition is excellent in heat resistance and molding processability, which is preferable. .

The epoxy group-containing ethylene copolymer (B)
In (b), the compound giving the unsaturated carboxylic acid glycidyl ester unit and the 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 C2-C18 hydrocarbon group having an ethylenically unsaturated bond, and X is -CH ₂ O- or

[0038]

Embedded image It is. )

Specifically, as the unsaturated carboxylic acid glycidyl ester, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester,
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 epoxy group-containing ethylene copolymer may be a terpolymer or more terpolymer of unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether and ethylene and (c) ethylenic unsaturated ester compound. It 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-
Unsaturated carboxylic acid alkyl ester etc. are mentioned. Particularly, vinyl acetate, methyl acrylate and ethyl acrylate are preferred.

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

Examples of the above-mentioned epoxy group-containing ethylene copolymers include copolymers consisting of ethylene units and glycidyl methacrylate units, copolymers consisting of ethylene units and glycidyl methacrylate units and methyl acrylate units, ethylene units and glycidyl units. Examples thereof include a copolymer composed of a methacrylate unit and an ethyl acrylate unit, a copolymer composed of an ethylene unit, a glycidyl methacrylate unit and a vinyl acetate unit.

Further, the melt index of the epoxy group-containing ethylene copolymer [hereinafter sometimes referred to as MFR.
JIS K6760 (190 ° C, 2.16kg)
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 in terms of mechanical properties when the composition is prepared, and 0.5 g / 10
If it is less than minutes, the compatibility with the liquid crystal polyester of the component (A) is poor, which is not preferable.

The epoxy group-containing ethylene copolymer having a flexural rigidity of preferably 10 to 1800 kg / cm ² , more preferably 20 to 1300 kg / cm ² is used. 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 of mixing an unsaturated epoxy compound and a radical generator with polyethylene and performing melt graft copolymerization in an extruder.

The ratio of the component (A) to the component (B) in the liquid crystal polyester resin composition used in the present invention is such that the component (A) is 56 to 99% by weight, preferably 65 to 98% by weight, and the component (B). Is 44 to 1% by weight, preferably 35 to 2
% By weight. When the content of the component (A) is less than 56% by weight, the film forming processability is insufficient, and the gas barrier property and tensile strength of the film obtained from the composition are deteriorated, which is not preferable. On the other hand, when the content of the component (A) exceeds 99% by weight, the effect of improving the anisotropy of tensile strength of the film obtained by the composition may not be sufficient, which is not preferable.

Further, the combination of the 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, but from the viewpoint of environmental problems, carbon, oxygen, hydrogen are used. A combination consisting solely of is preferably used.

If desired, an inorganic filler can be used in the liquid crystal polyester resin composition used in the present invention. Such inorganic fillers include talc, clay,
Examples include fillers for intercalation such as montmorillonite, and further calcium carbonate, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flakes, 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 an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic compound, if necessary. Various additives such as colorants, rust preventives, cross-linking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss modifiers, release modifiers such as fluororesins, etc. It can be added.

The method for producing the liquid crystal polyester resin composition in the present invention is not particularly limited, and known methods 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 temperature of the kneading device is preferably in the range of 200 to 360 ° C, more preferably 230 to 340 ° C.

Upon kneading, the respective components may be uniformly mixed in advance with a device such as a tumbler or a Henschel mixer, or a method of omitting the mixing and separately supplying the respective amounts to the kneading device 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 may be molded by various molding methods. Specific examples of the molding method include ordinary injection molding and pellet molding. Press molding, thermoforming in which a sheet-shaped molded product (hereinafter, a sheet or a film is generically referred to as such) is heated and then deformed according to a mold is preferably used. In the case of injection molding or sheet-shaped molding, the resin composition of the present invention is directly kneaded without being subjected to a kneading process in advance, dry blending at the time of molding and kneading during a melt processing operation. 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 starting temperature of the resin composition to 70 ° C. of the flow starting temperature. It is preferable to carry out.
If the molding temperature is out of the temperature range, molding failure may occur, which is not preferable. Flow initiation temperature: A temperature at which the melt viscosity is 48,000 poise when a resin heated at a temperature rising 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 also preferably formed by thermoforming a sheet-shaped formed product of the resin composition. The sheet or film forming method will be specifically described. A sheet-shaped molded product that is a material for the container and the lid material 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 (die). it can. As the die, a T-type die (hereinafter sometimes referred to as a T-die) can be used. Further, the liquid crystal polyester resin composition sheet-shaped molded article which is the material of the container of the present invention can be obtained by an inflation film forming method.

FIG. 1 shows a schematic view of an example of an apparatus for molding a sheet-shaped molded product of the liquid crystal polyester resin composition of the present invention. In FIG. 1, the 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-bonding roll (4). It is taken up 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, but the setting temperature of the cylinder is in the range from the flow starting temperature of the resin to the flow starting temperature plus 70 ° C. Is preferable, and the range of 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 preferable. The thickness of the liquid crystal polyester resin composition sheet-shaped molded product of the present invention can be controlled in the range of 1 to 1000 μm, but when used for molding the liquid crystal polyester resin composition container of the present invention, the thickness is 10 to 500 μm. Practically preferable. Further, from the viewpoint of ease of molding, it is more preferable that the thickness is 30 μm to 300 μm. The draft ratio of the sheet-shaped molded product of the liquid crystal polyester resin composition of the present invention is in the range of 1.1 to 40.0. The draft ratio here means 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-shaped molded product is insufficient, and when the draft ratio exceeds 40.0, the surface smoothness of the film is 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-shaped molded product of the resin composition obtained as described above is mounted on a mold having a container shape, and the resin composition is flown. It is obtained by thermoforming by applying heat at a starting temperature of -20 ° C to + 50 ° C. More preferably, it is obtained by thermoforming in the temperature range of -10 ° C to + 30 ° C of the flow starting temperature. It can also be obtained by punching a sheet-shaped molded product into a container shape in the same temperature range. If the temperature range is out of this range, color irregularity may occur in the molded container and 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 that of the container in the case of a rectangular container. The ratio of the depth to the length of the longest diagonal of the container opening is 1/10 or more. When the ratio of each is 1/10 or less, the capacity of the content is insufficient, which is not preferable.

There are no particular restrictions on the method of molding the lid material of the liquid crystal polyester resin composition container of the present invention, and it may be molded by various molding methods. Specific molding methods include the above-mentioned die (die). A method of obtaining a sheet-shaped molded article by taking out the extruded molten resin and a method of obtaining it by inflation film formation are preferably used.

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

The method for adhering the lid material is not particularly limited, but a so-called heat-adhesion method using heat and pressure, a method using an adhesive, a method using ultrasonic waves, etc. are preferably used. To be The thermal bonding is performed by superposing the lid and the peripheral portion of the opening of the container of the present invention, and the liquid crystal polyester resin composition of the present invention has a flow starting temperature of minus 40.
It is carried out by a method in which a pressure is applied to the bonded portion in the range of ℃ to plus 20 ℃.

[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: Toyo Seiki Co., Ltd., 2.1 mmφ x 14.75 mm die attached to a capillograph, extruded at an extrusion speed of 5 mm / min., From which a minimum take-up speed of 5 m / min. Maximum take-up speed 150m / mi
The tension at the time of breaking the strand was measured when the speed was automatically changed to take up to n.

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

Anisotropy of tensile strength: A sheet-like molded article having a thickness of 100 μm obtained by using a T-die has the longitudinal direction of the test piece in the take-up direction (MD direction) and the direction perpendicular thereto (TD direction). Punched into the shape of No. 2 type test piece conforming to JIS K7127, and pulling speed 10 mm /
The tensile strength was measured at min. It can be said that the smaller the ratio of the tensile strength of the test piece punched in the MD direction to 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 under the condition of a temperature of 20 ° C. according to the method A (differential pressure method). The unit is cc / m ² · 24 hr · 1 atm.

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

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

Microwave transparency: Water was placed in a hermetically sealed container of the composition, and it was investigated whether the water in the microwave was heated in a commercial microwave oven.

(2) Liquid crystalline 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 raised with stirring under a nitrogen gas atmosphere to carry out polymerization at 330 ° C. for 1 hour. Polymerization was performed under strong stirring while removing acetic acid by-produced during this period. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system.

The obtained polymer was crushed with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles 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 repeating temperature of 324 ° C. and consisting of 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 higher under pressure. The ratio of repeating structural units of the liquid crystal polyester A-1 is as follows.

[0075]

[Chemical 21]

(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 with a comb-shaped stirring blade,
The temperature is raised with stirring under a nitrogen gas atmosphere, and the temperature is set to 1 at 320 ° C.
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 was pulverized in the same manner as in the above (i) and then treated in a rotary kiln in a nitrogen gas atmosphere at 240 ° C. for 5 hours to give the following particles in a flowing temperature of 270 ° C. A wholly aromatic polyester composed of repeating units was obtained. Hereinafter, the liquid crystal polyester is abbreviated as A-2. This liquid crystalline polyester A-2 exhibited optical anisotropy at 280 ° C. or higher under pressure. The ratio of the repeating structural units of the liquid crystal polyester A-2 is as follows.

[0078]

Embedded image

(3) Thermoplastic Resin Having Epoxy Group (B) Composition of Epoxy Group-Containing Ethylene Copolymer Used, MF
The R and flexural modulus are as follows. Where M
FR is a measured value at 190 ° C and a load of 2.16 kg (unit:
g / 10 min), and the flexural modulus is ASTM D747.
It is the value measured based on. B-1: Copolymer produced by high-pressure radical polymerization method Product name Sumitomo Chemical Co., Ltd. Bondfast 7L Composition ethylene / glycidyl methacrylate / methyl acrylate = 67/3/30 (weight ratio) MFR = 9 Flexural rigidity = 60 kg / cm ²

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

B-3: Copolymer produced by high-pressure radical polymerization method Product name: Bondfast E composition, manufactured by Sumitomo Chemical Co., Ltd. Ethylene / glycidyl methacrylate = 88/1
2 (weight ratio) MFR = 3 Bending 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 (Sumitomo Chemical Co., Ltd., trade name: Sumikasen F-101-1) 1
1.2 parts by weight of glycidyl methacrylate was mixed with 00 parts by weight and melt-kneaded while degassing using a twin-screw extruder. The glycidyl methacrylate content of the obtained resin was 0.8% by weight. MFR = 6 Bending rigidity = 1900 kg / cm ²

Examples 1 to 6 and Comparative Examples 1 to 5 After mixing the components in the composition shown in Table 1 with a Henschel mixer, a cylinder set temperature was set using a TEX-30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. Was kneaded at a temperature 20 ° C. higher than the flow starting temperature shown in Table 1 at a screw rotation speed of 200 rpm to obtain pellets of the resin composition. The test piece for load deflection test was injection molded at a molding temperature of 20 ° C higher than the flow starting 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 shown in Table 2.

The sheet was molded by kneading the above resin composition pellets, and as shown in FIG. 1, a 20 mmφ single screw extruder equipped with a T die (manufactured by Tanabe Plastics Machinery, VS20-20). Mold), the cylinder set temperature is set to be 25 ° C. higher than the flow starting temperature shown in Table 1, melt kneading is performed at a screw rotation speed of 80 rpm, and a die lip width of 100 mm and a die slit gap of 0.5 mm are obtained from a T die. It is 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 starting temperature shown in Table 1, and the thickness is 100 μm.
m and 150 μm of the composition sheet were obtained, and the thickness was 10
The 0 μm sheet was subjected to a gas permeation test. The evaluation results are shown in Table 2.

For the 150 μm thick sheet of the composition, the drawing ratio (circular container; container depth / container diameter, rectangular container; container depth / diagonal length of container opening) was 1
/ 8 mold is set in the press and the sheet is placed for 3 minutes.
After preheating at the flow start temperature of the composition, the temperature is raised to 10
The temperature was raised by 0 ° C. and a molded container was obtained by hot press molding.

Further, with respect to the above composition, the drawing ratio 1 /
Using a PS40E5ASE type injection molding machine manufactured by NISSEI PLASTIC INDUSTRIES CO., LTD., The square container of No. 6 and the circular container having a drawing ratio of 3/2 were heated to a temperature 20 ° C higher than the flow starting temperature shown in Table 1, and the mold was 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.
Thermocompression bonding (heat sealing) using a sheet with a thickness of 00 μm
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-drawing container obtained from the composition has excellent impact resistance and gas barrier property. Moreover, since the container has excellent heat resistance and contains no metal, it can be used in a microwave oven. The liquid crystal polyester resin composition container of the present invention can be used as an individual container, an inner container, or an outer container of 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 drawings]

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

[Explanation of symbols]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08J 5/00 CFD C08L 23/08 LCK C08L 23/08 LCK 29/10 LGZ 29/10 LGZ 33 / 14 LJE 33/14 LJE 67/03 67/03 B29C 51/00 // B29C 51/00 B65D 1/00 A B29K 67:00 B29L 22:00

Claims (11)

[Claims] 1. (A) 56 to 99% by weight of liquid crystal polyester
And (B) a circular container obtained from a liquid crystal polyester resin composition containing 44 to 1 wt% of a thermoplastic resin having an epoxy group, the ratio of the depth of the container to the diameter of the mouth of the container is 1/10 or more. Yes, and in a rectangular container, the ratio of the depth of the container to the length of the longest diagonal line of the container opening is 1
/ 10 or more, The container made from the liquid crystal polyester resin composition characterized by the above-mentioned. 2. A sheet or film made of the liquid crystal polyester resin composition according to claim 1 is used as a lid, and the lid is adhered to the opening of the container made of the liquid crystal polyester resin composition according to claim 1. A container made of a liquid crystal polyester resin composition, characterized in that it is hermetically sealed. 3. The thermoplastic resin (B) is a copolymer containing 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. A container made of the liquid crystal polyester resin composition according to 1 or 2. 4. The thermoplastic resin (B) comprises 0.1 to 50% by weight of (a) ethylene units and 0.1 to (b) unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units. The container made of a liquid crystal polyester resin composition according to claim 1 or 2, which is an epoxy group-containing ethylene copolymer comprising 30% by weight and (c) an ethylenically unsaturated ester unit of 0 to 50% by weight. 5. The liquid crystal polyester resin composition container according to any one of claims 1 to 4, wherein the liquid crystal polyester (A) contains 30 mol% or more of the following repeating units. Embedded image 6. The liquid crystal polyester (A) is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, and any one of claims 1 to 4 is provided. A container made of the liquid crystal polyester resin composition described. 7. The liquid crystal polyester resin composition according to any one of claims 1 to 4, wherein the liquid crystal polyester (A) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids. Product container. 8. A liquid crystal polyester (A) comprising the following repeating units:
4. A container made of the liquid crystal polyester resin composition according to any one of 4 above. Embedded image 9. The liquid crystal polyester (A) is composed of the following repeating units:
4. A container made of the liquid crystal polyester resin composition according to any one of 4 above. Embedded image 10. A liquid crystal polyester (A) comprising the following repeating unit:
A container made of the liquid crystal polyester resin composition according to any one of 1 to 4. Embedded image 11. A liquid crystal polyester resin composition comprising only elements of carbon, hydrogen and oxygen.
A container made of the liquid crystal polyester resin composition according to any one of 1 to 4.