JP3339296B2 - Liquid crystal polyester resin composition film and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-strength liquid crystal polyester resin composition film having excellent tensile strength and gas barrier properties, and a method for producing the same.

[0002]

2. Description of the Related Art 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 due to rigid molecules, and 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 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.

With respect to such a liquid crystal polyester, Japanese Patent Application Laid-Open No. 52-109578 and Japanese Patent Application Laid-Open No. 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, WO9
JP-A No. 015706 discloses a method of canceling the anisotropy of liquid crystal polyester by rotating a ring die. Japanese Patent Application Laid-Open Nos. Sho 62-25513 and Sho 63-9593
No. 0 and JP-A-63-24251 propose a special device in the T-die method. However, these methods all show a method of relaxing the anisotropy due to molecular orientation by a very special molding method, and have disadvantages that the cost is high, the thinning is limited, and the practicability is poor.

[0006] Also, Japanese Patent Application Laid-Open No. 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, inflation film formation has been attempted in order to obtain a liquid crystal polyester film in which the anisotropy of the liquid crystal polymer is relaxed and which has a high strength. 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.

As an example, see, for example, Japanese Patent Application Laid-Open No. 63-173.
620, JP-A-3-288623, JP-A-4-4126, JP-A-4-50233 and JP-A-4-49026 disclose a method for inflation film-forming a liquid crystal polyester. However, all of them are inflation film formation using a special film formation apparatus, are intended for liquid crystal polyester with a limited structure, or are used for inflation film formation under extremely limited conditions. It was not a versatile film forming method.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal polyester resin composition film having high strength, low anisotropy, excellent gas barrier properties, and being inexpensive and easy to form a film. It is to provide a method.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve such a problem and arrived at the present invention. That is, the present invention relates to a resin containing (A) a liquid crystal polyester and (B) a thermoplastic resin, wherein the liquid crystal polyester is a continuous phase and the thermoplastic resin is a dispersed phase, and the resin heated at a heating rate of 4 ° C./min. At a flow start temperature defined as a temperature (unit: ° C.) at which the melt viscosity shows 48,000 poise when 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 , a shear rate of 100
a melt viscosity measured at least one of the shear rate sec ^-1 or of 1,000 sec ^-1 (viscosity 1), at 20 ° C. higher temperature than the flowable starting temperature, melt viscosity measured at the same shear rate as measured at flow temperature The value of the ratio (viscosity 2 / viscosity 1) to (viscosity 2) is 0.1 to 0.7,
A liquid crystal polyester resin composition obtained by inflation molding a liquid crystal polyester resin composition having a flow start temperature (FT1) and a liquid crystal polyester (A) flow start temperature (FT2) satisfying the following formula (1): the film,
And a liquid crystal polyester resin composition film obtained by laminating inflation molding of the liquid crystal polyester resin composition and (C) a thermoplastic resin excluding the liquid crystal polyester and the liquid crystal polyester resin composition, and a blow ratio of 1. The present invention relates to the above-mentioned method for producing a liquid crystal polyester resin composition film, which is subjected to inflation molding at 5 to 15 and MD stretching ratio of 1.5 to 40. FT1> FT2-10 (1) Next, the present invention will be described in detail.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid crystal polyester of the component (A) of the liquid crystal polyester resin composition of the present invention is a polyester called a thermotropic liquid crystal polymer. In particular,

(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 dicarboxylic acid. And a combination of a nucleus-substituted aromatic diol and
(4) Those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate

[0013] An anisotropic melt is formed at a temperature of 400 ° C or less. 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:

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[0015]

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A repeating structural unit derived from an aromatic diol:

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[0017]

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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.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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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]

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

The component (B) of the liquid crystal polyester resin composition used in the present invention is a thermoplastic resin. In the liquid crystal polyester resin composition, the liquid crystal polyester forms a continuous phase and the thermoplastic resin forms a dispersed phase. The liquid crystal polyester resin composition used in the present invention, in the temperature (flow temperature), which begins to form an anisotropic molten phase, was measured at least one of the shear rate of shear rate 100 sec ^-1, or of 1,000 sec ^-1 The value of the ratio (viscosity 2 / viscosity 1) of the melt viscosity (viscosity 1) to the melt viscosity (viscosity 2) measured at a temperature 20 ° C. higher than the flow start temperature at the same shear rate as the measurement at the flow start temperature is 0. .1 to
0.7, the flow start temperature (FT1) and the component (A)
Is a liquid crystal polyester resin composition having a flow start temperature (FT2) of the liquid crystal polyester satisfying the following formula (1). FT1> FT2-10 (1) The type of the thermoplastic resin as the component (B) is not particularly limited as long as the thermoplastic resin can satisfy such requirements.

Specific examples of such a thermoplastic resin include a thermoplastic resin having an epoxy group.
As a functional group having an epoxy group, a glycidyl group can be preferably exemplified.

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 specific examples of the thermoplastic resin (B) having an epoxy group include (a) 50 to 99.9% by weight, preferably 60 to 98% by weight of ethylene units, and (b) an unsaturated carboxylic acid. Glycidyl ester unit and / or unsaturated glycidyl ether unit is 0.1 to
Epoxy group-containing ethylene copolymers comprising 30% by weight, preferably 1 to 30% by weight, and (c) 0 to 50% by weight, preferably 1 to 40% by weight of an ethylenically unsaturated ester compound unit.

When the constituents (a), (b) and (c) of the epoxy group-containing ethylene copolymer are within the above ranges, the resulting liquid crystal polyester resin composition has excellent heat resistance and moldability. And preferred.

Compounds providing an unsaturated carboxylic acid glycidyl ester unit and an unsaturated glycidyl ether unit are represented by the following general formulas 19 and 20, respectively.

[0035]

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

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

Embedded image It is. )

Specifically, the unsaturated carboxylic acid glycidyl ester includes, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester,
Glycidyl p-styrenecarboxylate and the like can be mentioned. As unsaturated glycidyl ethers,
Examples thereof include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl 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 monomers, other monomers copolymerizable therewith. Examples of the monomer include isobutylene, styrene and derivatives thereof, and halogenated olefins such as tetrafluoroethylene and hexafluoropropylene.

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

The melt index (hereinafter sometimes referred to as MFR; JIS K6760, 190 ° C., 2.16 kg load) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 min. Preferably it is 2 to 50 g / 10 minutes. The melt index may be out of this range, but if the melt index exceeds 100 g / 10 minutes, it is not preferable in view of the mechanical properties of the composition, and if the melt index is less than 0.5 g / 10 minutes, the component (A) Is inferior in compatibility with the liquid crystal polyester.

The epoxy group-containing ethylene copolymer having a flexural rigidity of preferably 10 to 1300 kg / cm ² , more preferably 20 to 1100 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 ethylene copolymer containing an epoxy group 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 of the present invention is such that component (A) is 5%.
The content is preferably 6 to 99% by weight, more preferably 65 to 9% by weight.
The content is 8% by weight, particularly preferably 70 to 98% by weight, and the component (B) is preferably 44 to 1% by weight, more preferably 35 to 2% by weight, particularly preferably 30 to 2% by weight. If the content of the component (A) is less than 56% by weight, the heat resistance, gas barrier properties and tensile strength of the film obtained from the composition may be 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 Combinations consisting only of these are preferably used.

In the liquid crystal polyester resin composition used in the present invention, the liquid crystal polyester is a continuous phase and the thermoplastic resin is a dispersed phase. If the thermoplastic resin is in a continuous phase, the gas barrier properties are undesirably reduced. The liquid crystal polyester resin composition used in the present invention has a shear rate of 1 at a temperature at which an anisotropic molten phase starts to be formed (flow starting temperature).
The melt viscosity (viscosity 1) measured at a shear rate of at least one of 00 sec ^-1 or 1000 sec ^-1 and the melt viscosity (viscosity measured at a temperature 20 ° C. higher than the flow start temperature at the same shear rate as the measurement at the flow start temperature) A liquid crystal polyester resin composition having a ratio (viscosity 2 / viscosity 1) with respect to 2) of 0.1 to 0.7.

Preferably, a liquid crystal polyester resin composition having a ratio value of 0.1 to 0.5 is used. If the value of the ratio is less than 0.1, film formation processing is difficult,
In some cases, the effect of improving the anisotropy of the tensile strength of the obtained film is not sufficient. On the other hand, when it exceeds 0.7, the film forming process may be difficult, which is not preferable. Flow start temperature is 4 ℃
/ Kg of resin heated at a temperature rise rate of / kg
It is defined as the temperature at which the melt viscosity shows 48,000 poise when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under cm ² .

The flow onset temperature (FT1) of the liquid crystal polyester resin composition used in the present invention is determined by subtracting the flow onset temperature (FT2) of the liquid crystal polyester of component (A) of the composition.
Higher than 10 ° C. More preferably, FT1 is higher than FT2. When FT1 is higher than FT2-10 ° C, the mechanical properties of the liquid crystal polyester resin composition are excellent, which is 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, there is a method in which each component is mixed in a solution state and the solvent is evaporated or precipitated in the solvent. From an industrial point of view, a method of kneading each component 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. In addition, each component can be mixed and melt-kneaded at the time of inflation molding without a kneading process in advance, and a film can be directly obtained.

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

In the liquid crystal polyester resin composition used in the present invention, an 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.

From the liquid crystal polyester resin composition obtained by the above method, a film can be obtained by an inflation molding (film formation) method. That is, the liquid crystal polyester resin composition is supplied to a melt kneading extruder equipped with a die having an annular slit, and is set at a cylinder set temperature of 200 to 360.
C., preferably 230 to 350.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 be in the longitudinal direction. The film is expanded and stretched in the transverse direction (TD) at right angles.

In the inflation film formation of the liquid crystal polyester resin composition of the present invention, a preferable blow ratio is 1.5 to 15, and more preferably, a blow ratio is 2.5 to 15. The preferred MD stretching ratio is 1.
It is 5-40, More preferably, it is 2.5-30. Here, the MD stretching ratio is obtained by (area of annular slit) / (cross-sectional area of film), and the stretching ratio of TD is as follows:
That is, the blow ratio is determined from (diameter of cylindrical film) / (diameter of die). 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.

The circumference of the expanded film is air-cooled,
Alternatively, after cooling with water, it is passed through a nip roll and taken out.

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

The thickness of the 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.

In the present invention, an inflation film obtained by laminating a liquid crystal polyester resin composition film and (C) a thermoplastic resin film excluding the liquid crystal polyester and the liquid crystal polyester resin composition can also be obtained. The thermoplastic resin here is not particularly limited as long as it is other than liquid crystal polyester or liquid crystal polyester resin composition, but it is not limited to polyethylene, polypropylene, polyolefin such as ethylene-α-olefin copolymer, polystyrene, polycarbonate, polyethylene terephthalate. And polyesters such as polybutylene terephthalate, polyacetal, polyamide, polyphenylene ether, polyether sulfone, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, and fluororesin. Among them, polyethylene, polypropylene, ethylene-α-olefin copolymer and polyethylene terephthalate are more preferred. As the thermoplastic resin, one type or a mixture of two or more types can be formed into a film. The thermoplastic resin in the present invention includes a thermoplastic resin modified by introducing a functional group into a molecular chain.

The method for producing the laminated blown film is not particularly limited, but a method in which the molten resins of the respective constituent components are overlapped inside the die and then extruded from the die, and each molten resin is extruded from the die and then laminated. A method of combining them, or a method of laminating each molten resin in front of the die and then extruding the resin from the die can be used, and a production method can be selected according to the purpose.

The reason why the liquid crystal polyester resin composition film of the present invention exhibits excellent gas barrier properties, tensile strength, relaxation of tensile strength anisotropy, etc. is not necessarily clear, but the liquid crystal polyester and the epoxy group-containing ethylene copolymer have the same properties. It is considered that a chemical reaction occurs between the liquid crystal polyester and the union and the compatibility between the liquid crystal polyester and the epoxy group-containing ethylene copolymer is improved.

[0062]

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 for Measuring Physical Properties Regarding the obtained liquid crystal polyester resin composition film,
Physical properties were measured in the following manner.

Flow starting temperature: High-grade floater manufactured by Shimadzu Corporation
It was measured with a Star CFT-500. That is, 4 ° C /
The resin heated at a heating rate of 1 minute is loaded with a load of 100 kgf /
cm ^TwoA nozzle with an inner diameter of 1 mm and a length of 10 mm
When extruded, melt viscosity shows 48000 poise
The temperature was measured.

Melt viscosity: Melt viscosity was measured by Capillograph 1B manufactured by Toyo Seiki Co., Ltd.
The measurement was performed at 00 / sec and 1000 / sec.

MD stretching ratio: determined by (area of annular slit) / (cross-sectional area of film). TD stretching ratio (blow ratio): determined from (diameter of cylindrical film) / (diameter of die).

Tensile properties: The tensile properties in the MD and TD directions were measured using a No. 2 type test piece according to ASTM D882. The test speed was 20 mm / min.

Oxygen gas permeability: JIS K7126
According to the method A (differential pressure method), the measurement was performed at a temperature of 20 ° C. using oxygen gas. The unit is cc / m ² · 24 hr · 1 atm. -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 · 1 atm. The oxygen gas transmission rate and the water vapor transmission rate were determined by setting the film thickness of the composition to 2.
It was determined by converting to 5 μm.

Observation of morphology: A cross section of a dumbbell test piece obtained by injection molding was polished, etched with chloroform, and observed by SEM. Observation results were classified as follows. A: The thermoplastic resin forms a clear dispersed phase in the liquid crystal polyester. B: The thermoplastic resin is continuous and does not form a clear dispersed phase.

(2) Liquid crystal polyester (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 4,4 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.
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 start temperature of 320 ° C. and comprising the following repeating structural units. 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.

[0071]

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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 a particulate recurring unit having a flow start temperature of 263 ° 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.

[0073]

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(3) Thermoplastic resin (B) Abbreviation, epoxy resin composition (weight ratio), melt flow index (MFR), flexural rigidity of epoxy group-containing ethylene copolymer obtained by high pressure radical polymerization It is as follows. Here, the MFR is 1 based on JIS K6760.
Value at 90 ° C. and 2.16 kg load (unit: g / 10
min), the flexural rigidity refers to a value based on ASTM D747.

B-1 (abbreviation): manufactured by Sumitomo Chemical Co., Ltd.
Bond First 7B E / GMA / VA = 83/12/5 (weight ratio), MFR
= 7, flexural rigidity = 400 kg / cm ² .

B-2 (abbreviation): manufactured by Sumitomo Chemical Co., Ltd.
Bond First 2CE / GMA = 94/6 (weight ratio), MFR = 3, flexural rigidity = 1000 kg / cm ² .

B-3 (abbreviation): manufactured by Sumitomo Chemical Co., Ltd.
Bond First 7M E / GMA / MA = 64/6/30 (weight ratio), MF
R = 9, flexural rigidity = 40 kg / cm ² .

B-4 (abbreviation): manufactured by Sumitomo Chemical Co., Ltd.
Bond First 7L E / GMA / MA = 64/3/30 (weight ratio), MF
R = 9, flexural rigidity = 60 kg / cm ² . (here,
E indicates ethylene, VA indicates vinyl acetate, and MA indicates methyl acrylate. )

Examples 1 and 2 and Comparative Examples 1 and 2 The components shown in Table 1 were mixed with a Henschel mixer, and the cylinder temperature was set at 335 ° C. using a TEX-30 twin screw extruder manufactured by Nippon Steel Corporation. To obtain a composition. The melt viscosity of the composition was as shown in Table 1. Using a PS40E5ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd., a dumbbell piece was molded at a cylinder set temperature of 350 ° C. and a mold temperature of 80 ° C., and subjected to morphology observation. The morphology observation results of Examples 1 and 2 and Comparative Example 2 were all A. Using a 30 mmφ single screw extruder equipped with a cylindrical die, the pellets of this composition were melt-kneaded at a cylinder set temperature of 347 ° C. and a rotation speed of 40 rpm,
A molten resin is extruded upward from a cylindrical die having a diameter of 100 mm, a lip interval of 1.5 mm, and a die setting temperature of 351 ° C., and dry air is pressed into a hollow portion of the cylindrical film to expand the cylindrical film, and then cooled. Thereafter, the resultant was passed through a nip roll and taken out to obtain a liquid crystal polyester resin composition film. 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 take-up speed, the stretching ratio in the MD direction, T
The blow ratio and film thickness in the D direction are as shown in Table 2. Table 3 shows the physical property values of the obtained liquid crystal polyester resin composition film.

Examples 3, 4 and Comparative Example 3 The components shown in Table 1 were mixed with a Henschel mixer, and a cylinder set temperature of 298 ° C. was set using a TEX-30 twin screw extruder manufactured by Nippon Steel Corporation. 90 rpm
To obtain a composition. The melt viscosity of the composition was as shown in Table 1. This composition was subjected to injection molding in the same manner as in Example 1 except that the cylinder set temperature was set to 300 ° C., and was subjected to morphology observation. The morphology observation results of Examples 3 and 4 were both A.
Using a 30 mmφ single screw extruder equipped with a cylindrical die, the pellets of this composition are melt-kneaded at a cylinder setting temperature of 303 ° C. and a rotation speed of 40 rpm, and a cylinder having a diameter of 100 mm, a lip interval of 1.5 mm and a die setting temperature of 303 ° C. The molten resin was extruded upward from the die, and the tubular film was expanded by injecting dry air into the hollow portion of the tubular film, and then cooled, and then passed through a nip roll to obtain a liquid crystal polyester resin composition film. 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, take-up speed, MD
The stretching ratio in the direction, the blow ratio in the TD direction, and the film thickness are as shown in Table 2. Table 3 shows the physical property values of the obtained liquid crystal polyester resin composition film.

Example 5 Each component having the composition shown in Table 1 was mixed with a Henschel mixer and melt-kneaded in the same manner as in Example 3 to obtain pellets of a liquid crystal polyester resin composition. The melt viscosity of the composition was as shown in Table 1. The composition was subjected to injection molding in the same manner as in Example 3. The morphological observation result was A. Using a cylindrical die for two layers with a diameter of 50 mmφ,
Cylinder set temperature 298 ° C, screw rotation speed 90r
The above liquid crystal polyester resin composition melt was extruded into an inner layer die by a 45 mmφ single screw extruder under the condition of pm, while the cylinder setting was 265 ° C., screw rotation speed was 60 rpm, 45 mmφ, L / D = 28 single screw extrusion. From Sumitomo Chemical Co., Ltd. polyethylene, Sumikasen F2
00 (MFR = 2, flexural rigidity = 2400 kg / c
m ² ) was extruded into an outer layer die, and two layers were merged in the die. Then, the die set temperature was 298 ° C., and the slit interval was 1.
It is extruded upward from a cylindrical die of 0 mm, dry air is pressed into the hollow portion of the cylindrical film to expand the cylindrical film, and then cooled, and then taken through a nip roll at a take-up speed of 15 m / min. A laminated film was obtained. At that time, the stretching ratio in the MD direction was 6.3, the blow ratio in the TD direction was 12.3, and the adhesiveness of the two layers was good. In the obtained two-layer laminated film, the inner layer has a thickness of 14 μm.
And the outer layer was composed of a polyethylene film having a thickness of 9 μm.
Table 4 shows the physical property values of the laminated film.

Comparative Example 4 Extrusion from a cylindrical die was attempted in the same manner as in Example 5 except that the liquid crystal polyester A-2 was used instead of the liquid crystal polyester resin composition in Example 5, but the liquid crystal polyester in the inner layer was tried. The film forming property on the side was poor, and a laminated film was not obtained.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

Industrial Applicability The liquid crystal polyester resin composition film of the present invention has high strength, low anisotropy, excellent gas barrier properties, and is inexpensive and easy to form a film. Film, cosmetic packaging film,
It can be widely used for electronic material packaging films.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI B29K 67:00 B29L 7:00 B29L 7:00 JP-A-43779 (JP, A) JP-A-5-239364 (JP, A) JP-A-6-306261 (JP, A) JP-A-7-216198 (JP, A) Table 8-509923 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 5/18 C08L 67/00-67/08 CA (STN) REGISTRY (STN)

Claims (19)

(57) [Claims] 1. A composition comprising (A) a liquid crystalline polyester and (B) a thermoplastic resin, wherein the proportions are (A) 65 to 98 % by weight, (B) 35 to 2 % by weight, and (A) is a continuous phase. And (B) is a dispersed phase, and the resin heated at a temperature rising rate of 4 ° C./min is applied with a load of 100 kgf / cm ² and an inner diameter of 1 mm.
The melt viscosity is 4 when extruded from a 10 mm long nozzle.
Temperature showing a 8000 poise (unit: ° C.) at flow temperature which is defined as a melt viscosity measured at least one of the shear rate of shear rate 100 sec ^-1 or of 1,000 sec ^-1 (viscosity 1), from the flowable starting temperature At a temperature 20 ° C. higher, the ratio (viscosity 2 / viscosity 1) to the melt viscosity (viscosity 2) measured at the same shear rate as the measurement at the flow start temperature is 0.1 to 0.7, A liquid crystal polyester resin composition in which the start temperature (FT1) and the flow start temperature (FT2) of the liquid crystal polyester (A) satisfy the following formula (1) . FT1> FT2-10 (1) 2. The method according to claim 1 , which is for inflation molding.
Liquid crystal polyester resin composition described above. Wherein the thermoplastic resin (B) is according to claim 1 or 2 Symbol characterized in that it is a thermoplastic resin having an epoxy group
The resin composition described above . 4. The thermoplastic resin (B) contains 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units . 3. The resin composition according to item 1 . 5. 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. The resin composition according to any one of claims 1 to 4, wherein the resin composition is an epoxy group-containing ethylene copolymer containing 30% by weight and (c) an ethylenically unsaturated ester compound unit of 0 to 50% by weight. 6. An epoxy group-containing ethylene copolymer having a melt index [JIS K6760, 190.degree.
The resin composition of claim 5, wherein the 16kg load] is in the range of 0.5 to 100 g / 10min. 7. The epoxy group-containing ethylene copolymer, bending the resin composition according to claim 5, wherein the modulus of rigidity is characterized in the range of 10~1300kg / cm ^2. 8. The resin according to claim 1, wherein the liquid crystal polyester (A) contains at least 30 mol% of the following repeating structural units.
Composition . Embedded image 9. A liquid crystal polyester (A) is according to any one of claims 1-7, characterized in that is obtained by reacting an aromatic dicarboxylic acid, aromatic diol and aromatic hydroxycarboxylic acid Resin composition . 10. A liquid crystal polyester (A) is serial to claims 1-7 or, wherein is obtained by reacting a combination of different aromatic hydroxycarboxylic acids
The resin composition described above . 11. A liquid crystal polyester (A) is, according to claim 1, characterized in that is made of the following repeating units
The resin composition according to any one of claims 1 to 7, Embedded image 12. A liquid crystal polyester (A) is, according to claim 1, characterized in that is made of the following repeating units
The resin composition according to any one of claims 1 to 7, Embedded image 13. A liquid crystal polyester (A) is, according to claim 1, characterized in that is made of the following repeating units
The resin composition according to any one of claims 1 to 7, Embedded image 14. A liquid crystal polyester (A) is, according to claim 1, characterized in that is made of the following repeating units
The resin composition according to any one of claims 1 to 7, Embedded image 15. The resin set according to claim 1.
It is characterized by being obtained by inflation molding of a product
Liquid crystal polyester resin composition film. Features and 16. Tree fat composition according to any one of claims 1 to 14, that the thermoplastic resin, obtained by molding laminated inflation except (C) liquid crystalline polyester and liquid crystalline polyester resin composition Liquid crystal polyester resin composition film. 17. A thermoplastic resin (C) excluding a liquid crystal polyester and a liquid crystal polyester resin composition, wherein the thermoplastic resin (C) is polyolefin, polystyrene, polycarbonate, polyester,
Claims characterized by containing at least one selected from polyacetal, polyamide, polyphenylene ether, polyether sulfone, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, and fluororesin. Item 1
7. The liquid crystal polyester resin composition film according to item 6 . 18. The liquid crystal polyester resin composition film according to claim 15 , wherein the film is blown at a blow ratio of 1.5 to 15 and an MD draw ratio of 1.5 to 40. . 19. Blow ratio 1.5 to 15, manufacture of the liquid crystal polyester resin composition film according to any one of claims 15 to 17 MD stretching ratio is equal to or to inflation molding at 1.5 to 40 Method.