JPH1017752A - Liquid crystal polyester resin composition and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive liquid crystal polyester resin composition excellent in tensile physical properties, improved in anisotropic property and having good film-forming property and gas barrier property and a film formed from the composition. SOLUTION: This liquid crystal polyester resin composition comprises (A) 0.1-99.9wt.% liquid crystal polyester and (B) 99.9wt.% to 0.1wt.% graft copolymer of a copolymer having epoxy group with a themoplastic resin. This film is obtained by forming the liquid crystal polyester resin composition into a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal polyester resin composition which can be used for molded articles by injection molding or extrusion molding, and a gas barrier film obtained by forming the composition into a film.

[0002]

2. Description of the Related Art Unlike crystalline polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyesters do not entangle even in a molten state because molecules are rigid, form polydomains having a liquid crystal state, and are formed by low shear. It exhibits a behavior in which molecular chains are remarkably oriented in the flow direction, and is generally called a molten liquid crystal (thermotropic liquid crystal) polymer. Due to this unique behavior, the melt fluidity is extremely excellent, and a thin molded product of about 0.2 to 0.5 mm can be easily obtained, and this molded product has high strength and high rigidity. Have. However, there is a disadvantage that the anisotropy is extremely large. Further, the vibration damping performance and impact resistance are not sufficient, and the molding temperature is high, so that the use thereof has been limited. Another problem is that liquid crystal polyesters are generally expensive.

[0003] An inexpensive liquid crystal polyester resin composition which retains excellent heat resistance and mechanical properties of liquid crystal polyester, improves moldability, impact resistance, anisotropy of molded products, and is inexpensive is strongly demanded from the market. I was JP-A-56-11535
No. 7 discloses a resin composition containing a melt-processable polymer and an anisotropic melt-forming polymer, and adding the anisotropic melt-forming polymer to the melt-processable polymer. It describes that the processability of a melt-processable polymer can be improved by this. For example, polyphenylene ether /
Examples are given in which a liquid crystal polyester is added to a polystyrene mixture. JP-A-2-97555 describes a resin composition in which liquid crystal polyester is mixed with various polyarylene oxides for the purpose of improving solder heat resistance. However, in general, a composition comprising a liquid crystal polyester having a high molding temperature and an amorphous polymer such as polyphenylene ether having a lower molding temperature is blended, even if the melt processability of the composition is improved, There has been a problem that the appearance of the molded product is poor due to the thermal decomposition of the compounded resin during the molding process. Further, there is a problem that the heat resistance, mechanical properties, impact resistance, and the like of the composition are insufficient.

Further, JP-A-57-40551 and JP-A-2-102257 disclose compositions comprising a liquid crystal polyester and an aromatic polycarbonate, but they have insufficient heat resistance and mechanical properties. It was not something. U.S. Pat. No. 5,216,073 discloses blends obtained by compounding an epoxidized rubber with a liquid crystal polymer, but their heat resistance and mechanical properties are not sufficient. Also, JP-A-2-6736
JP-A No. 6 discloses a thermoplastic resin composition comprising a resin having an aromatic vinyl and / or alkyl (meth) acrylate having a specific functional group as an essential component and a liquid crystal polymer. Properties are not sufficient, and there is no description about film formation. Also, JP-A-58-201850, JP-A-1-121357, JP-A-1-193351, and JP-A-7-30
No. 4936, EP67272 / A2, etc.
A composition comprising a thermoplastic resin mixed with a liquid crystalline polymer is described, but none of these compositions exhibit sufficient physical properties, particularly, tensile properties or heat resistance.

On the other hand, from the viewpoint of film raw materials, 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. Polyester, because of its strong intermolecular interaction, molecular orientation, high strength, well-known for liquid crystal polyester,
Industrialization as a film material having functions such as gas barrier properties in addition to performance such as high elastic modulus and high heat resistance has been expected. However, unlike aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyester does not entangle even in the molten state due to the rigidity of molecules, and the molecular chains are significantly oriented in the flow direction, so even with slight shearing It exhibits a behavior in which the melt viscosity suddenly decreases, or a behavior in which the melt viscosity sharply decreases due to a rise in temperature, and the melt tension during melting is extremely low. Therefore, it is extremely difficult to maintain the shape in the molten state, and furthermore, 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 film forming, There was a big problem that the utility in fields such as blow molding was poor. Therefore, a film made of a liquid crystal polyester utilizing the function of the liquid crystal polyester has not been put to practical use.

[0006] Such a liquid crystal polyester is disclosed in JP-A-52-109787 and JP-A-58-317.
Japanese Patent No. 187 discloses a laminate in which uniaxially oriented liquid crystal polyester films are laminated in a direction that cancels out the anisotropy of strength. However, the productivity is poor and there is a problem of film peeling. U.S. Pat. Nos. 4,975,312 and WO9015706 disclose a method of canceling the anisotropy of liquid crystal polyester by rotating a ring die.
JP-A-3-95930 and JP-A-63-24251 propose a special device in the T-die method.
However, each of these shows a method of relaxing anisotropy due to molecular orientation by a very special molding method,
There is a drawback that the cost is high, the thinning is limited, and the utility is poor.

[0007] Also, Japanese Patent Application Laid-Open No. Sho 62-187033,
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 proposes a multilayer (laminated) sheet and a multilayer (laminated) film of a liquid crystal polyester and a thermoplastic resin. However, peeling occurs due to the interposition of an adhesive layer between the layers, There are problems in that the inherent properties of polyester, such as gas barrier properties and heat resistance, are deteriorated and that it is difficult to produce a thin film.

On the other hand, an attempt has been made to form an inflation film in order to obtain a high-strength liquid crystal polyester film in which the anisotropy of the liquid crystal polymer is reduced. Inflation film formation is a process in which a resin melt-kneaded in an extruder is extruded into a cylindrical melt using a die having an annular slit, a certain amount of air is fed into it, and the resin is expanded to expand the film. A method of making a cylindrical film while cooling the periphery. Examples thereof include JP-A-63-173620, JP-A-3-288623, JP-A-4-4126, JP-A-4-50233 and JP-A-4-49.
No. 026 and the like describe a method for inflation film formation of a liquid crystal polyester. However, any of these methods is directed to inflation film formation using a special film formation apparatus or liquid crystal polyester having a limited structure. Or inflation film formation under extremely limited conditions, and was not a versatile film formation method.

[0009]

The present invention provides an inexpensive liquid crystal polyester resin composition having excellent tensile properties, improved anisotropy, good film forming properties and gas barrier properties, and an inexpensive liquid crystal polyester resin composition.
Another object of the present invention is to provide a film obtained by forming such a composition.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve such a problem, and have completed the present invention. That is, the present invention contains (A) a liquid crystal polyester and (B) a graft copolymer of a copolymer having an epoxy group and a thermoplastic resin, and the ratio of the component (A) to the component (B) is as follows. (A) 0.1 to 99.9% by weight, component (B) is 99.9 to 0.1% by weight, and a film formed by forming the liquid crystal polyester resin composition. Such is the case.

[0011]

Next, the present invention will be described in detail.
The liquid crystal polyester of the component (A) of the liquid crystal polyester resin composition in the present invention is a polyester called a thermotropic liquid crystal polymer.

More 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) A) a combination of an aromatic dicarboxylic acid and a nucleus-substituted aromatic diol; and (4) a product obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate. To form an anisotropic melt. In addition, in place of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, ester-forming derivatives thereof 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:

[0015]

A repeating structural unit derived from an aromatic diol:

[0017]

A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

A liquid crystal polyester which is particularly preferable from the balance of heat resistance, mechanical properties and workability is And more preferably contains at least 30 mol% of such repeating structural units. Specifically, combinations of repeating structural units are as shown in the following (I) to (VI).

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

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

[0028] (In the formula, Ar is a divalent aromatic group.)

The component (B) of the liquid crystal polyester resin composition of the present invention is a graft copolymer of a copolymer having an epoxy group and a thermoplastic resin.

The copolymer having an epoxy group in the component (B) is not particularly limited, but is preferably a copolymer obtained by copolymerizing a monomer having a glycidyl group as one of the monomers. As the monomer having a glycidyl group, unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether are preferably used.

Specific examples of the unsaturated carboxylic acid glycidyl ester include, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester and p-glycidyl ester.
Glycidyl styrene carboxylate; Specific examples of the unsaturated carboxylic acid glycidyl ether include vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether and the like.

Preferably, the copolymer having an epoxy group in component (B) contains 0.1 to 30% by weight of unsaturated glycidyl ester units and / or unsaturated glycidyl ether units. More preferably, the copolymer having an epoxy group in the component (B) contains 0.1 to 3 unsaturated glycidyl ester units and / or unsaturated glycidyl ether units.
0% by weight, 99.9 to 70% by weight of ethylene unit
It is a copolymer containing.

Such a copolymer may be obtained by copolymerizing ethylene, unsaturated carboxylic acid glycidyl ester, unsaturated carboxylic acid glycidyl ether, and another monomer copolymerizable therewith. . Examples of the monomer include isobutylene, styrene and its derivatives, and halogenated olefins such as vinyl acetate, tetrafluoroethylene and hexafluoropropylene.

Specific examples of the thermoplastic resin in component (B) include polyolefin, polystyrene, styrene-acrylonitrile copolymer, styrene-methyl (meth) acrylate copolymer, and styrene-methyl (meth). Acrylate-acrylonitrile copolymer,
Ethylene-methyl (meth) acrylate copolymer, acrylonitrile-methyl (meth) acrylate copolymer, polymethyl (meth) acrylate, polyester,
Examples thereof include polyvinyl chloride, polyphenylene ether, and cellulose acetate butyrate.

Among them, polyethylene, polypropylene, polystyrene, styrene-acrylonitrile copolymer, ethylene-methyl (meth) acrylate copolymer,
A thermoplastic resin selected from polymethyl (meth) acrylate is preferred. More preferably, the thermoplastic resin in the component (B) is polymethyl (meth) acrylate, acrylonitrile-styrene copolymer or polystyrene.

The method for producing the graft copolymer of the copolymer having the epoxy group of the component (B) and the thermoplastic resin in the present invention is not particularly limited. For example, a copolymer of ethylene and unsaturated carboxylic acid glycidyl ester is produced by a high-pressure radical polymerization method, and then the copolymer is melt-kneaded with polystyrene and / or polymethyl (meth) acrylate in the presence of a peroxide. Then, a method of graft copolymerization can be exemplified.

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 0.1 to 99.9% by weight, preferably 60.0% by weight.
-99.9% by weight, component (B) is 99.9-0.1% by weight, preferably 40.0-0.1% by weight. When the content of the component (A) is less than 0.1% by weight, the heat resistance of the composition decreases, which is not preferable. Component (A) is 99.9.
If the amount is more than 10% by weight, the effect of improving the film-forming properties of the composition may not be sufficient, and the cost is high, which is not preferable.

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. At the time of 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 if necessary, the mixing may be omitted, and each component may be separately supplied to the kneading device. Methods can also be used.

In the liquid crystal polyester resin composition used in the present invention, an inorganic filler is used if desired.
Examples of such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flake, glass fiber, carbon fiber, alumina fiber, silica alumina fiber, and aluminum borate. Examples include 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,
Various additives such as inorganic or organic colorants, rust inhibitors, cross-linking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, release improvers such as fluororesins, etc. during or after the manufacturing process It can be added in the processing step.

Usually, a liquid crystal polyester resin composition film can be obtained by melt-kneading the liquid crystal polyester resin composition obtained by the above-mentioned method with an extruder and collecting the molten resin extruded through a die. However, without going through the kneading process in advance, dry blending each component at the time of molding and kneading during the melt processing operation to form a resin composition,
Direct molded products can also be obtained. The base (die)
Usually, a T-shaped die (sometimes called a T-die) or a die having an annular slit can be used.

In the case of forming a film using a T-die, the liquid crystal polyester resin composition melt-kneaded by an extruder usually passes through a downward T-die to form a sheet-like melt, and then passes through a pressure roll in the longitudinal direction. Is taken up by the take-up device.

The setting conditions of the extruder at the time of such film formation are appropriately selected according to the composition of the composition. The setting temperature of the cylinder of the extruder is preferably in the range of 200 to 360 ° C., and 230 to 355 ° 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
1.2 mm is preferred. The thickness of the liquid crystal polyester resin composition film of the present invention can be controlled in the range of 1 to 1000 μm, but those having a thickness of 5 to 100 μm are practically preferred and are preferred. The draft ratio of the liquid crystal polyester resin composition film of the present invention is in the range of 1.1 to 40.0. Preferably, it is in the range of 1.2 to 20.0. Further, a biaxially stretched film of the resin composition extruded from a T-die can also be obtained.

The method of biaxial stretching in the production of the liquid crystal polyester resin composition film of the present invention is not particularly limited. Specifically, a melt of the composition of the present invention extruded from a T-die of an extruder is machined in the MD direction. Uniaxially stretched (longitudinal direction),
Then, successive stretching in the TD direction (lateral direction), T
Simultaneous stretching, in which the sheet extruded from the die is simultaneously stretched in the MD and TD directions, and biaxial stretching, such as sequential or simultaneous stretching of an unstretched sheet extruded from the T die with a biaxial stretching machine, a tenter or the like, are also available. No.

In any case, the film formation temperature is preferably in the temperature range of the flow start temperature of the liquid crystal polyester resin composition of the present invention minus 60 ° C. or more and the flow start benefit plus 60 ° C. or less. It is more preferable that the film is formed in a temperature range of 30 ° C. or less plus the flow start.

The slit interval of the T die is 0.2 m
m to 1.2 mm is preferred. An appropriate value is determined for the stretching ratio according to the molding method. For example, in the case of stretching with a biaxial stretching machine, if the stretching ratio is defined as (length after stretching / original length), MD stretching direction, TD The stretching ratio in each of the directions is 1.2 to 20.0, preferably 1.5 to 5.
0 is used. If the stretching ratio is less than 1.2, the stretching effect is small, and the tensile properties may be reduced.
If it is larger, the smoothness of the film may be insufficient.

In the case of inflation molding (film formation) using an annular slit die, the obtained liquid crystal polyester resin composition is supplied to a melt kneading extruder equipped with an annular slit die, and set at a cylinder set temperature of 200 to 360.
C., preferably 230 to 350.degree. C., and the molten resin is extruded upward or downward through the annular slit of the extruder. The annular slit interval 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.
６００600 mm.

The melt-extruded cylindrical molten resin film is drafted 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 form a longitudinal direction. The film can be stretched and stretched in a transverse transverse direction (TD). In the blown film of the liquid crystal polyester resin composition of the present invention, the preferable blow ratio is 1.5.
And a preferred MD stretching ratio is 1.5 to 40.
If the setting conditions during the inflation film formation are outside the above range, it is difficult to obtain a high-strength liquid crystal polyester resin composition film having a uniform thickness and no wrinkles, which is not preferable. After the circumference of the expanded film is air-cooled or water-cooled, the film is passed through a nip roll and taken out.

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

The thickness of the liquid crystal polyester resin composition film obtained according to the present invention is not particularly limited, but is preferably 1 to 500 μm, more preferably 1 to 200 μm.
It is.

[0053]

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) Liquid crystal polyester of component (A) (i) 10.8 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. 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.
The following particles were used. 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. Here, the flow temperature refers to a high flow type flow tester CFT-5 manufactured by Shimadzu Corporation.
Using a mold 00, a resin heated at a temperature rising rate of 4 ° C./min was applied under a load of 100 kgf / cm ² to an inner diameter of 1 mm.
The temperature at which the melt viscosity shows 48,000 poise when extruded from a nozzle having a length of 10 mm.

Hereinafter, the liquid crystal polyester is abbreviated as A-1. This polymer showed optical anisotropy at 340 ° C. or more under pressure. The repeating structural units of the liquid crystal polyester A-1 are as follows.

(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 a particulate repeating unit having a flow temperature of 270 ° C. Was obtained. Hereinafter, the liquid crystal polyester is abbreviated as A-2. This polymer 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.

(Iii) Unitika Ltd., which uses polyethylene terephthalate and parahydroxybenzoic acid as main raw materials,
Liquid crystal polyester, rod run LC-5000 was used. Hereinafter, the polymer may be abbreviated as A-3.

(2) Component (B) Abbreviations and contents of the graft copolymer of the copolymer having an epoxy group and the thermoplastic resin used in this example are as follows.

Abbreviation: B-1 Contents: MODIPER A4200 manufactured by NOF CORPORATION EGMA-PMMA graft copolymer MI (190 ° C., 2.16 kg load) = 0.6 g / 10 min Composition: EGMA / PMMA = 70/30 (Weight ratio)

Abbreviation: B-2 Contents: Modiper A4100 EGMA-PS graft copolymer MI (190 ° C., 2.16 kg load) = 0.7 g / 10 min, manufactured by NOF CORPORATION Composition: EGMA / PS = 70/30 (Weight ratio)

Abbreviation: B-3 Contents: Modiper A4400 EGMA-AS graft copolymer MI (190 ° C., 2.16 kg load) manufactured by NOF CORPORATION = 0.3 g / 10 min Composition: EGMA / AS = 70/30

Here, EGMA: ethylene-glycidyl methacrylate copolymer glycidyl methacrylate content 15% by weight PMMA: polymethyl (meth) acrylate PS: polystyrene AS: acrylonitrile-styrene copolymer

(3) Method of Measuring Physical Properties of Injection-Molded Product Tensile physical properties: An ASTM No. 4 tensile dumbbell was molded and subjected to AST.
Tensile strength and elongation were measured according to MD638.

Deflection temperature under load (TDUL): TDUL measurement test piece (127 mm length × 12.7 mm width × 6.4 m)
m thickness) and TDUL according to ASTM D648.
(A load of 18.6 kg) was measured.

(4) Method for measuring physical properties of film Oxygen gas permeability: JIS K7126 A method (differential pressure method)
The measurement was carried out at a temperature of 20 ° C. in accordance with The unit is cc /
m ² · 24 hr · latm.

Water vapor transmission rate: 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 · latm. The oxygen gas transmission rate and the water vapor transmission rate were determined by setting the film thickness to 2
It was determined by converting to 5 μm.

Examples 1 to 7 and Comparative Examples 1 to 6 Each component was mixed with a stabilizer in a composition shown in Table 1 with a Henschel mixer, and then mixed using a TEX-30 type twin screw extruder manufactured by Nippon Steel Corporation. Cylinder set temperature 270-355
The mixture was kneaded at 200 ° C. at a screw rotation speed of 200 rpm to obtain a pellet of the resin composition, which was subjected to injection molding and film molding. Injection molded test pieces were manufactured by Nissei Plastic Industry Co., Ltd., PS4
Using a 0E5ASE type injection molding machine, the molding temperature is 270-270.
It was produced by injection molding at 355 ° C. and a mold temperature of 80 ° C., and was subjected to measurement. The results are as shown in Table 1.

Using a 30 mmφ single screw extruder equipped with a cylindrical die, the pellets of the composition obtained in the composition shown in Table 1 were melt-kneaded at a cylinder set temperature of 270 to 350 ° C. and a rotation speed of 50 rpm. The molten resin is extruded downward from a cylindrical die having an interval of 1.5 mm and a die setting temperature of 270 to 350 ° C., and dry air is pressed into the hollow portion of the cylindrical film to expand the cylindrical film, and then cooled. , Through a nip roll, take-off speed 10 to 20 m / mi
n, and a liquid crystal polyester resin composition having a thickness of 21 to 42 μm was obtained. The stretching ratio of the liquid crystal polyester resin composition film in the take-up direction (MD direction) and the direction perpendicular to the take-up direction (TD direction) was controlled by the amount of dry air to be injected and the film take-up speed. At this time, the stretching ratio in the MD direction is 1.9 to 3.2, and the blow ratio in the TD direction is 4.3 to 5.4.
And Table 1 shows the physical property values of the obtained liquid crystal polyester resin composition film.

[0070]

[Table 1]

[0071]

The liquid crystal polyester resin composition of the present invention has excellent moldability, mechanical properties, tensile properties, heat resistance, etc., is inexpensive, has improved film formability, and has very good gas barrier properties. is there. By utilizing such characteristics, it can be widely used for molded articles, containers, tubes, sheets, fibers, coating materials, food packaging films, chemical packaging films, electronic material packaging films, and the like.

Claims (11)

[Claims] 1. A composition comprising (A) a liquid crystal polyester and (B) a graft copolymer of a copolymer having an epoxy group and a thermoplastic resin, wherein the ratio of the component (A) to the component (B) is A) is 0.1 to 99.9% by weight, and component (B) is 9
9.9 to 0.1% by weight of a liquid crystal polyester resin composition. 2. The copolymer having an epoxy group in the component (B) contains an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit in an amount of from 0.1 to 0.1.
2. The liquid crystal polyester resin composition according to claim 1, which contains 30% by weight. 3. The copolymer having an epoxy group in the component (B) contains an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit in an amount of 0.1 to 0.1.
The liquid crystal polyester resin composition according to claim 1, which is a copolymer containing 30% by weight and 99.9 to 70% by weight of an ethylene unit. 4. The thermoplastic resin of the component (B) is selected from the group consisting of polyethylene, polypropylene, polystyrene and styrene.
Acrylonitrile copolymer, ethylene-methyl (meth)
The acrylate copolymer is selected from polymethyl (meth) acrylate.
3. The liquid crystal polyester resin composition according to any one of 3. 5. The liquid crystal polyester resin according to claim 1, wherein the thermoplastic resin in the component (B) is polymethyl (meth) acrylate, acrylonitrile-styrene copolymer or polystyrene. Composition. 6. The ratio of component (A) to component (B) is such that component (A) is 60.0 to 99.9% by weight and component (B) is 4%.
2. The composition according to claim 1, wherein the content is 0.0 to 0.1% by weight.
6. The liquid crystal polyester resin composition according to any one of items 1 to 5. 7. The liquid crystal polyester resin composition according to claim 1, wherein the liquid crystal polyester of the component (A) contains at least 30 mol% of the following repeating structural units. 8. The method according to claim 1, wherein (A) the liquid crystal polyester is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. The liquid crystal polyester resin composition according to the above. 9. The liquid crystal polyester resin composition according to claim 1, wherein (A) the liquid crystal polyester is obtained by reacting a combination of different kinds of aromatic hydroxycarboxylic acids. Stuff. 10. A melt extruded from a T-die.
10. A film obtained by subjecting the liquid crystal polyester resin composition according to 9 to uniaxial stretching or biaxial stretching. 11. A film obtained by inflation molding the liquid crystal polyester resin composition according to claim 1.