JP3391647B2 - Liquid crystal polyester resin composition, injection molded article and film comprising 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 liquid crystal polyester resin composition which can be used for molded articles by injection molding, extrusion molding and the like, and a gas barrier film formed by film-forming the composition.

[0002]

2. Description of the Related Art Liquid crystal polyesters, unlike crystalline polyesters such as polyethylene terephthalate and polybutylene terephthalate, do not cause entanglement even in a molten state because they have rigid molecules, form a polydomain having a liquid crystal state, and have low shear. It exhibits a behavior in which molecular chains are significantly oriented in the flow direction, and is generally called a melt-type liquid crystal (thermotropic liquid crystal) polymer. Due to this peculiar behavior, the melt fluidity is extremely excellent, a thin-walled molded product of about 0.2 to 0.5 mm can be easily obtained, and the molded product has high strength and high rigidity. Have However, there is a drawback that the anisotropy is extremely large. Moreover, its vibration damping performance and impact resistance were not sufficient, and its molding processing temperature was high, so its applications were limited. Another problem is that liquid crystal polyesters are generally expensive.

A liquid crystal polyester resin composition which retains excellent heat resistance and mechanical properties of liquid crystal polyester, is improved in moldability, impact resistance, and anisotropy of a molded article and is inexpensive is strongly demanded from the market. Was there. JP-A-56-11535
No. 7 discloses a resin composition containing a melt-processable polymer and an anisotropic melt-forming polymer, wherein the anisotropic melt-forming polymer is added to the melt-processable polymer. It is described that the processability of the melt-processable polymer can be improved thereby. For example, polyphenylene ether /
An example in which a liquid crystal polyester is added to a polystyrene mixture is mentioned. JP-A-2-97555 discloses a resin composition in which various polyarylene oxides are mixed with liquid crystal polyester for the purpose of improving solder heat resistance. However, in general, a composition obtained by blending a liquid crystal polyester having a high molding temperature with an amorphous polymer having a lower molding temperature such as polyphenylene ether has a high melting temperature even if the melt processability of the composition is improved. There is a problem that the appearance of the molded product is deteriorated due to thermal decomposition of the compounded resin during the molding process. There is also a problem that the heat resistance, mechanical properties, impact resistance, etc. of the composition are insufficient.

Further, compositions such as liquid crystal polyester and aromatic polycarbonate are disclosed in JP-A-57-40551 and JP-A-2-102257, but they have sufficient heat resistance and mechanical properties. It wasn't. Further, JP-A-58-201850, JP-A-1-121357, and JP-A-1-193351.
JP, EP67272 / A2, JP 7-30
Japanese Patent No. 4936 discloses a composition obtained by blending a liquid crystalline polymer with a copolymer of α-olefins and, for example, glycidyl methacrylate. However, it does not have mechanical properties such as impact resistance and tensile strength. In terms of aspect, further improvement was desired. U.S. Pat. No. 5,216,073 describes a molded article using an epoxidized rubber and a liquid crystal polymer, and relates to a thermosetting polymer for crosslinking an epoxidized rubber forming a continuous phase.

On the other hand, from the viewpoint of a film raw material, a liquid crystal polyester is a polyester characterized in that molecules are oriented in a molten state by strong intermolecular interaction. Due to the strong intermolecular interaction and molecular orientation, , High strength, high elastic modulus, well known for liquid crystal polyester,
In addition to performance such as high heat resistance, industrialization as a film material having functions such as gas barrier properties has been expected. However, unlike aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyesters do not entangle even in the melted state because the molecules are rigid, 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, and a behavior in which the melt viscosity sharply decreases due to a temperature rise and the melt tension during melting is extremely low. Therefore, it is very difficult to maintain the shape in the molten state, and further, since the molecules are oriented, it is difficult to balance the performance in the vertical and horizontal directions, and in an extreme case, the film is torn in the molecular orientation direction. There was a big problem that it was not practical in fields such as blow molding. Therefore, a film made of liquid crystal polyester, which makes the best use of the function of liquid crystal polyester, has not been put to practical use sufficiently.

Regarding such a liquid crystal polyester, JP-A-52-1095787 and JP-A-58-317 are known.
Japanese Patent No. 187 discloses a laminated body 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. In U.S. Pat. No. 4,975,312 and WO 9015706, a method of canceling the anisotropy of a liquid crystal polyester by rotating a ring die is disclosed, and in JP-A-62-25513 and 63-95930. Japanese Patent Laid-Open No. 63-24251 discloses a special device for the T-die method. However, all of them show a method of relaxing the anisotropy due to molecular orientation by a very special molding method, and there are drawbacks that the cost is high, there is a limit to thinning, and the practicality is poor.

[0007] Further, JP-A-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 proposes a multilayer (laminate) sheet and a multilayer (laminate) film of a liquid crystal polyester and a thermoplastic resin. The liquid crystal polyester has a large orientation and an adhesive layer is interposed between the layers. By doing so, there is a problem that peeling occurs, deterioration of performance such as gas barrier property and heat resistance originally possessed by liquid crystal polyester, and production of a thin film is difficult.

On the other hand, inflation film formation has been attempted in order to obtain a high-strength liquid crystal polyester film in which the anisotropy of the liquid crystal polymer is relaxed. 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, and a fixed amount of air is introduced into the film to expand the film. A method of making a tubular film while cooling the circumference. As an example thereof, Japanese Patent Laid-Open No. 173620/1988,
JP-A-3-288623, JP-A-4-4126, JP-A-4-502233 or JP-A-4-4
Although a method for inflation film formation of liquid crystal polyester is described in Japanese Patent No. 9026 and the like, both are intended for inflation film formation using a special film formation apparatus or liquid crystal polyester having a limited structure. However, the film formation is inflation film formation under extremely limited conditions, and is not a versatile film formation method. Moreover, the obtained film has problems such as poor stretchability and flexibility, insufficient gas barrier properties, easy occurrence of pinholes, low surface tension and poor printability.

Therefore, the present applicant previously proposed an inexpensive liquid crystal polyester resin composition having good film-forming property and gas barrier property (Japanese Patent Application Laid-Open No. 7-304936), but further improvement in terms of stretchability. Was wanted.

[0010]

Under these circumstances, the problem to be solved by the present invention is to maintain the excellent heat resistance and mechanical properties of liquid crystal polyester, to provide excellent moldability and impact resistance, and to achieve anisotropy. Of a film that can be obtained as a molded product with improved properties and has excellent film-forming properties, gas barrier properties, stretchability, bending resistance, pinhole resistance, molding processability, and high surface tension. An object of the present invention is to provide an inexpensive liquid crystal polyester resin composition obtained, and a null injection molded article and film from the composition.

[0011]

Means for Solving the Problems The present inventors have conducted extensive studies to solve such problems, and found that a composition comprising liquid crystal polyester and a specific rubber solves the above problems, and the present invention Has been completed. That is, the present invention is
A liquid crystal polyester resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a rubber having a functional group reactive with the liquid crystal polyester as a dispersed phase, and (A) a liquid crystal polyester 56.0 to 99.9. %, And (B) a liquid crystal polyester resin composition containing 44.0 to 0.1% by weight of a rubber having a functional group reactive with the liquid crystal polyester, (A) a liquid crystal polyester 56.0 to 9
The present invention relates to a liquid crystal polyester resin composition obtained by melt-kneading 9.9% by weight and (B) 44.0 to 0.1% by weight of a rubber having a functional group reactive with a liquid crystal polyester. Furthermore, the present invention relates to injection-molded articles and films made of these liquid crystal polyester resin compositions.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in detail.
The liquid crystal polyester as the component (A) of the liquid crystal polyester resin composition in 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,
(4) A product obtained by reacting a polyester such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid,

And the like. An anisotropic melt is formed at a temperature of 400 ° C. or lower. Incidentally, instead 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 the following, but are not limited thereto.

Repeating structural unit derived from aromatic dicarboxylic acid:

[0016]

Repeating structural units derived from aromatic diols:

[0018]

Repeating structural unit derived from aromatic hydroxycarboxylic acid:

From the viewpoint of the balance of heat resistance, mechanical properties and processability, a particularly preferred liquid crystal polyester is The repeating structural unit is more preferably contained, and more preferably at least 30 mol% of the repeating structural unit is contained. Specifically, the combinations of repeating structural units are those of the following (I) to (VI).

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

Regarding the method for producing the liquid crystal polyesters (I) to (VI), for example, Japanese Patent Publication No. 47-47870, Japanese Patent Publication No. 63-3888, Japanese Patent Publication No. 63-3891, and Japanese Patent Publication No. 56-18016. , Tokuhei 2-515
No. 23 publication 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 liquid crystal polyester resin composition of the present invention, in the field where high heat resistance is required, the liquid crystal polyester of component (A) contains 30 to 80 mol% of the following repeating units (a ') and repeating units ( 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.

[0029] (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 rubber having a functional group reactive with the liquid crystal polyester.

The term "rubber" as used herein corresponds to a polymer substance having rubber elasticity at room temperature according to a new edition dictionary of polymer (edited by The Polymer Society of Japan, published in 1988, Asakura Shoten),
Specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (random copolymer, block copolymer (including SEBS rubber or SBS rubber, etc.), graft copolymer, etc. are all included) or The hydrogenated product, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber,
Isobutylene-isoprene copolymer, acrylic ester-ethylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene-propylene-styrene copolymer rubber, styrene-isoprene copolymer Rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluororubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-non-conjugated diene copolymer rubber, thiol rubber, polysulfide Examples thereof include rubber, polyurethane rubber, polyether rubber (eg polypropylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer and the like. Among them, acrylic ester-ethylene copolymer is preferably used, and (meth) acrylic ester-ethylene copolymer rubber is more preferable.

These rubber-like substances are produced by any production method (eg emulsion polymerization method, solution polymerization method, etc.) and any catalyst (eg peroxide, trialkylaluminum, lithium halide, nickel catalyst etc.). It may be one.

The rubber (B) of the present invention is a rubber having a functional group reactive with the liquid crystal polyester in the above rubber. The functional group having reactivity with the liquid crystal polyester is not particularly limited as long as it has reactivity with the liquid crystal polyester, and examples thereof include an epoxy group, an oxazolyl group and an amino group, and an epoxy group is preferable. The epoxy group may be present as part of other functional groups, examples of which include a glycidyl group.

In the rubber (B) of the present invention, a method for introducing a functional group reactive with a liquid crystal polyester into the rubber is not particularly limited, and a known method can be used. For example, it is possible to introduce the monomer having the functional group by copolymerization in the step of synthesizing the rubber, or to graft-copolymerize the monomer having the functional group on the rubber.

As the monomer having a glycidyl group,
Unsaturated carboxylic acid glycidyl ester and unsaturated glycidyl ether are preferably used.

The rubber (B) having a functional group reactive with the liquid crystal polyester of the present invention is preferably a copolymer containing an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit,
Specific examples thereof include (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber.

As a preferred specific example of the rubber (B), (meth) acrylic acid ester-ethylene-
(Unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) The (meth) acrylic acid ester, which is a main constituent of the copolymer rubber, is an ester obtained from acrylic acid or methacrylic acid and alcohol. As the alcohol, an alcohol having 1 to 8 carbon atoms is preferable. Specific examples of the (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, and n.
-Butyl acrylate, n-butyl methacrylate, t
Examples thereof include ert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.
As the (meth) acrylic acid ester, one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

The compound giving the unsaturated carboxylic acid glycidyl ester unit has the general formula (R is a hydrocarbon group having 2 to 13 carbon atoms and having an ethylenically unsaturated bond.), And a compound giving an unsaturated glycidyl ether unit has a general formula: (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or Is. ).

Specifically, as the unsaturated carboxylic acid glycidyl ester, for example, glycidyl acrylate,
Examples thereof include glycidyl methacrylate, itaconic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester, and p-styrenecarboxylic acid glycidyl ester. Examples of unsaturated glycidyl ethers include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, and styrene-p-glycidyl ether.

The above (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and /
Alternatively, the unsaturated glycidyl ether) copolymer rubber can be produced by a conventional method, for example, bulk polymerization using a free radical initiator, emulsion polymerization, solution polymerization, or the like. A typical polymerization method is Japanese Patent Publication No. 46-450.
No. 85, JP-A No. 61-127709, etc., pressure 500 kg / cm ² or more, temperature 40 to 30 in the presence of a polymerization initiator that generates free radicals.
It can be produced under the condition of 0 ° C.

The above-mentioned (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and //
Alternatively, the constituent component of the unsaturated glycidyl ether) copolymer rubber has a (meth) acrylic acid ester unit of preferably more than 40% by weight, less than 97% by weight, more preferably 45 to 70% by weight, and preferably an ethylene unit. 3% by weight
Or more and less than 50% by weight, more preferably 10 to 49% by weight, and the unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether unit is preferably 0.1.
-30 wt%, more preferably 0.5-20 wt%.

40% by weight of (meth) acrylic acid ester
When it is below, the rubber elasticity is lowered, the effect of improving the impact resistance of the composition becomes small, and when the content of (meth) acrylic acid ester is 97% by weight or more, the brittle point of the copolymer rubber is It is not preferred because the composition may become high and the mechanical properties of the composition at low temperature may deteriorate. Further, when the unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether is less than 0.1% by weight, the impact resistance of the liquid crystal polyester resin composition decreases, and when it exceeds 30% by weight, the rigidity of the composition is increased. May decrease, which is not preferable.

The above-mentioned (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and //
Or unsaturated glycidyl ether) copolymer rubber, in addition to the above-mentioned (meth) acrylic acid ester, ethylene and unsaturated carboxylic acid glycidyl ester, unsaturated glycidyl ether, other monomers copolymerizable with these It may be contained. Examples of the monomer include isobutylene, styrene and its derivatives, vinyl acetate,
Mention may be made of halogenated olefins such as tetrafluoroethylene and hexafluoropropylene.

The rubber (B) of the present invention can be used as a vulcanized rubber after being vulcanized if necessary. The above-mentioned (meth) acrylic acid ester-ethylene-unsaturated carboxylic acid glycidyl ester and / or unsaturated carboxylic acid glycidyl ether copolymer rubber is vulcanized by using a polyfunctional organic acid, a polyfunctional amine compound, an imidazole compound, or the like. However, it is not limited thereto.

The rubber (B) of the present invention has a Mooney viscosity of 3
To 70 are preferred, those from 3 to 30 are more preferred, and those from 4 to 25 are even more preferred. The Mooney viscosity here means a value measured using a 100 ° C. large rotor according to JIS K6300. The rubber (B) of the present invention preferably has a crystal heat of fusion of less than 3 J / g because it has better stretchability.

The liquid crystal polyester resin composition of the present invention is
It is a resin composition in which the liquid crystal polyester of component (A) is a continuous phase and the rubber of component (B) is a dispersed phase.

In a preferred embodiment of the liquid crystal polyester resin composition of the present invention, the liquid crystal polyester of component (A) is
6.0 to 99.9% by weight, preferably 65.0 to 99.
9% by weight, more preferably 70 to 98% by weight, rubber of component (B) is 44.0 to 0.1% by weight, preferably 35.0 to 0.1% by weight, more preferably 30 to 2% by weight. % Liquid crystal polyester resin composition. When the amount of the component (A) is less than 56.0% by weight, the heat resistance of the composition is lowered, which is not preferable. On the other hand, if the content of the component (A) exceeds 99.9% by weight, the effect of improving the film-forming property of the composition may not be sufficient, and the cost becomes expensive, which is not preferable.

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, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferable. For melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable. In melt-kneading, the cylinder temperature of the kneading device is preferably in the range of 200 to 360 ° C, more preferably 230 to 350 ° C.

Upon kneading, the respective components may be mixed in advance by a device such as a tumbler or a Henschel mixer. If necessary, the mixing may be omitted and the respective amounts 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 optionally used.
Such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flakes, glass fibers, carbon fibers, alumina fibers, silica-alumina fibers, aluminum borate. Examples thereof include 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, if necessary.
Various additives such as inorganic or organic colorants, rust preventives, cross-linking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, release improvers such as fluororesins, etc. may be added during or after the manufacturing process. It can be added in the processing step.

The kneaded resin composition is molded by various molding methods such as injection molding, extrusion molding and the like, but it is melt-processed by dry blending at the time of injection molding or extrusion molding without undergoing the kneading process in advance. It is also possible to directly knead into the resin composition of the present invention to obtain a molded product.

A well-known method can be applied as an injection molding method of the above resin composition, and an injection molded article excellent in impact resistance and tensile properties can be obtained. The setting conditions of the injection molding machine during such molding are appropriately selected according to the composition of the composition, but the molding temperature of the injection molding machine is preferably in the range of 200 to 360 ° C, more preferably in the range of 230 to 350 ° C. .
If it is out of this range, thermal decomposition of the composition may occur or molding may be difficult, which is not preferable.

The film forming method of the above resin composition is usually
The liquid crystal polyester resin composition obtained by the above method is melt-kneaded with an extruder, and by taking out the molten resin extruded through a die (die), a liquid crystal polyester resin composition film can be obtained. It is also possible to directly obtain a molded product by dry blending the components during molding without any process and kneading them during the melt processing operation to obtain a resin composition. The die is usually a T-shaped die (hereinafter, T
A die may be used) or a die having an annular slit can be used.

In the case of film forming using a T-die, the liquid crystal polyester resin composition melt-kneaded by an extruder is usually passed through a downward T-die to form a sheet-like melt, and then is passed through a pressure bonding roll in the longitudinal direction. It is taken up by a 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, but the set temperature of the cylinder of the extruder is preferably in the range of 200 to 360 ° C, and 230 to 350 ° C. Ranges are more preferred. If it is out of this range, thermal decomposition of the composition may occur or film formation may become difficult, which is not preferable.

The slit gap of the T die is 0.2 to 1.2 m
m 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 of 5 to 100 μm are practically used in many cases and are preferable. The draft ratio of the liquid crystal polyester resin composition film of the present invention is preferably in the range of 1.1 to 40.0.

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, but specifically, a melt of the composition of the present invention extruded from a T die of an extruder is MD-direction (longitudinal direction). ), And then in the TD direction (transverse direction), sequential drawing, simultaneous drawing in which the sheet extruded from the T die is simultaneously drawn in the MD and TD directions, and biaxial drawing in the unstretched sheet extruded from the T die. A biaxial stretching method such as sequential or simultaneous stretching with a machine, a tenter, or the like can also be used.

In any method, the film forming temperature is preferably within the temperature range of the flow initiation temperature of the liquid crystal polyester resin composition of the present invention minus 60 ° C. or more and the flow initiation temperature plus 60 ° C. or less. It is further preferable that the film formation is performed within a temperature range of the starting temperature plus 30 ° C. or less.

An appropriate value for the draw ratio is determined depending on the molding method. For example, when the draw ratio is defined by (length after drawing / original length) in the case of drawing with a biaxial drawing machine, MD
The stretching ratio in each of the stretching direction and the TD direction is 1.
2 to 20.0, preferably 1.5 to 5.0 is used. If the draw ratio is less than 1.2, the tensile properties may deteriorate, and if it is more than 20.0, 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 fed to a melt-kneading extruder equipped with an annular slit die, and usually a cylinder set temperature of 200 to 36
Melt kneading is performed at 0 ° C., preferably 230 to 350 ° C., and the molten resin is extruded upward or downward from the tubular film 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.
~ 600 mm.

The melt-extruded tubular molten resin film is drafted in the longitudinal direction (MD), and air or an inert gas such as nitrogen gas is blown from the inside of the tubular film to form a right angle with the longitudinal direction. The film can be expanded and stretched in various transverse directions (TD). In the inflation film formation of the liquid crystal polyester resin composition of the present invention, a preferable blow ratio is 1.5 to 1.
0, the preferred MD stretch ratio is 1.5-40. If the set conditions during inflation film formation are out of 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 expanded film is air-cooled or water-cooled around its circumference and then passed through a nip roll to be taken up.

The film thickness of the film obtained by inflation film formation is not particularly limited, but is preferably 1 to 50.
It is 0 μm, more preferably 1 to 200 μm.

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

The liquid crystal polyester resin composition film is
If necessary, surface treatment can be applied. Examples of such surface treatment methods include corona discharge treatment, plasma treatment, flame treatment, sputtering treatment, solvent treatment and the like.

In the present invention, a laminated film of the above-mentioned liquid crystal polyester resin composition film and another film, for example, a liquid crystal polyester and a thermoplastic resin film excluding the liquid crystal polyester resin composition can be obtained. Examples of the thermoplastic resin here include polyethylene, polypropylene, polyolefin such as ethylene-α-olefin copolymer, polystyrene, polycarbonate, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyacetal,
Polyamide, polyphenylene ether, polyether sulfone, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, fluororesin and the like are preferably used. Among these, polyethylene, polypropylene, ethylene-α-
Olefin copolymer and polyethylene terephthalate are more preferable. As the thermoplastic resin, one kind or two or more kinds can be mixed to form a film. As the thermoplastic resin, a thermoplastic resin modified by introducing a functional group into the molecular chain can also be used.

[0067]

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. (1) Component (A) liquid crystal polyester

(I) p-acetoxybenzoic acid 10.8k
g (60 mol), terephthalic acid 2.49 kg (15 mol), isophthalic acid 0.83 kg (5 mol) and 4,
5.45 kg of 4'-diacetoxydiphenyl (20.2
(Mol) was charged into a polymerization tank having a comb-type stirring blade, and the temperature was raised with stirring under a nitrogen gas atmosphere to perform polymerization at 330 ° C. for 1 hour. Polymerization was performed under strong stirring while removing acetic acid by-produced during this period. After that, the system is gradually cooled down to 200 ° C.
The polymer obtained in 1. was taken out of the system. The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This 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. Here, the flow temperature means that the resin heated by a Shimadzu high-performance flow tester CFT-500 type at a temperature rising rate of 4 ° C./min under a load of 100 kgf / cm ² has an inner diameter. The temperature at which the melt viscosity is 48,000 poise when extruded from a nozzle having a length of 1 mm and a length of 10 mm.

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

(Ii) p-hydroxybenzoic acid 16.6k
g (12.1 mol), 6-hydroxy-2-naphthoic acid 8.4 kg (4.5 mol) and acetic anhydride 18.6 kg
(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 at 320 ° C.
320 ° C. under reduced pressure of 2.0 torr
It was polymerized for 1 hour. During this period, acetic acid produced as a by-product was continuously distilled out of the system. Then, 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 under a nitrogen gas atmosphere at 240 ° C. for 5 hours to obtain the following repeating units in the form of particles having a flow temperature of 270 ° C. A wholly aromatic polyester was obtained. Hereinafter, the liquid crystal polyester is abbreviated as A-2. This polymer 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.

(Iii) Polyethylene terephthalate and parahydroxybenzoic acid as the main raw materials manufactured by Unitika Ltd.,
A liquid crystal polyester, Rod Run LC-5000 was used. Hereinafter, the polymer may be abbreviated as A-3.

(2) Rubber having reactivity with the liquid crystal polyester as the component (B)

Here, the Mooney viscosity is JIS K630.
It is a value measured according to 0 using a large rotor at 100 ° C.

(I) Methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38. According to the method described in Example 5 of JP-A-61-127709.
A rubber having a Mooney viscosity of 15 and a weight ratio of 7 / 2.3 was obtained. Hereinafter, the rubber may be abbreviated as B-1.

(Ii) According to the method described in Example 5 of JP-A-61-127709, methyl acrylate / ethylene / glycidyl methacrylate = 56.0 / 40.
A rubber having a Mooney viscosity of 12 (7 / 3.3 (weight ratio)) was obtained. Hereinafter, the rubber may be abbreviated as B-2.

(Iii) According to the method described in Example 5 of JP-A-61-127709, methyl acrylate / ethylene / glycidyl methacrylate = 52.5 / 45.
A rubber having a Mooney viscosity of 20 and a weight ratio of 0 / 2.5 was obtained. Hereinafter, the rubber may be abbreviated as B-3.

(3) Method of measuring physical properties of injection molded article Tensile physical properties: ASTM No. 4 tensile dumbbell was molded and AST
Tensile strength and elongation were measured according to MD638.

Izod impact strength: test piece (3.2 mm
The thickness was measured according to JIS K7110 with a notch, at room temperature and -30 ° C.

Hardness: Rockwell hardness (R) was measured according to ASTM D785.

(4) Method for measuring physical properties of film Oxygen gas permeability: JIS K7126 A method (differential pressure method)
The temperature was measured at 20 ° C. according to the above. The unit is cc /
It is m ² · 24 hr · latm.

Water vapor permeability: Measured in accordance with JIS Z0208 (cup method) under the conditions of a temperature of 40 ° C. and a relative humidity of 90%. The unit is g / m ² · 24 hr · latm. It should be noted that the oxygen gas permeability and the water vapor permeability are determined by the film thickness being 2
It was calculated in terms of 5 μm.

Tensile physical properties: According to JIS Z1727
Using a No. 2 type test piece, the tensile physical properties of MD and TD were measured.

Bending test: Samples were cut out in the MD and TD directions of the film, and MIT bending tester Folding Endurance tester M manufactured by Toyo Seiki Co., Ltd.
Using IT-D type, load 1kgf, bending surface curvature radius 1mm, bending speed 1 based on JIS-p-8115
75 times / min. The bending test was performed to determine the number of times of bending until the film broke.

Bending fatigue pinhole test: Toyo Seiki Co., Ltd.
After using Gelvo Flow Tester 5000ES manufactured by the company, after setting the film, the film was bent 1000 times at a bending speed of 40 rpm, the film was placed on a blank paper, and the ink was applied on the film. The bending fatigue pinhole property was evaluated by the standard. ◯: Ink is not soaked on the white paper below the film. X: Stain of ink is recognized on the white paper under the film.

Surface tension: Based on JIS K6768
The surface tension was determined by a wetting test method in which a wetting reagent manufactured by Wako Pure Chemical Industries, Ltd. was applied onto the film. The measurement was carried out on an untreated film and a corona discharge treatment machine manufactured by Kasuga Electric Co., Ltd., which was subjected to surface treatment at an output of 1.1 kW, and immediately after the treatment and 4 weeks after the treatment.

(5) Manufacture of resin composition After mixing each component in the composition shown in Table 1 with a stabilizer using a Henschel mixer, a cylinder set temperature of 280 was set using a TEX-30 twin-screw extruder manufactured by Nippon Steel Co., Ltd. ℃ ~ 350
° C (350 for Examples 1-3 and Comparative Examples 1-4)
C, 310 for Examples 4-5 and Comparative Examples 5-6.
C., 280 ° C. for Example 6 and Comparative Example 7), and kneading at a screw rotation speed of 200 rpm to obtain pellets of the resin composition, which were subjected to injection molding and film molding.

(6) Injection Molding Examples 1 to 6 and Comparative Examples 1 to 7 Injection molding test pieces were PS40E manufactured by Nissei Plastic Industry Co., Ltd.
Using a 5ASE type injection molding machine, a molding temperature of 280 ° C to 3
50 ° C. (3 for Examples 1-3 and Comparative Examples 1-4)
50 ° C., 3 for Examples 4-5 and Comparative Examples 5-6
10 ° C., 280 for Example 6 and Comparative Example 7
C.) and a mold temperature of 80.degree. The results are shown in Table 1.

(7) Film Molding Examples 1 and 2 and Comparative Examples 1 to 3 The composition pellets obtained by kneading were fed to a 20 mmφ uniaxial extruder (manufactured by Tanabe Plastics Machinery Co., Ltd.) as a sample to set the cylinder temperature and An unstretched film was prepared by extruding from a T-die having a width of 100 mm and a slit interval of 0.3 mm to 0.8 mm at a set temperature of the T-die of 350 ° C. and taking it out with a cast roll. The film was stretched at a stretching temperature of 330 with a biaxial stretching tester (manufactured by Toyo Seiki).
C., the stretching ratio (MD.times.TD) is 2.7.times.2.7, and the film is simultaneously biaxially stretched.
A 29 μm film was obtained and the physical properties were measured. The evaluation results are shown in Tables 1 and 2.

Examples 3 to 6 and Comparative Examples 4 to 7 Pellets of the compositions obtained by the compositions in Table 1 were used in a cylinder set temperature of 295 to 352 ° C. using a 45 mmφ single screw extruder equipped with a cylindrical die. 352 ° C. for Example 3 and Comparative Example 4, 310 ° C. for Examples 4-5 and Comparative Examples 5-6, 290 for Examples 6 and Comparative Example 7.
℃), melt kneading at a rotation speed of 80 rpm, diameter 100 m
m, lip interval 1.5 mm, die set temperature 295-35
Melt upwards from a 2 ° C. (352 ° C. for Example 3 and Comparative Example 4, 310 ° C. for Examples 4-5 and Comparative Examples 5-6, 290 ° C. for Example 6 and Comparative Example 7) cylindrical die. The resin is extruded, dry air is pressed into the hollow portion of the tubular film to expand the tubular film, and then the tubular film is cooled and passed through a nip roll to take up at a take-up speed of 15 to
The film was pulled at 20 m / min to obtain a liquid crystal polyester resin composition film having a thickness of 18 to 37 μm. The drawing direction (MD direction) of the liquid crystal polyester resin composition film and the draw ratio in the direction perpendicular to the drawing direction (TD direction) were controlled by the amount of dry air to be pressed in and the film drawing speed. At this time, M
The draw ratio in the D direction was 2.5 to 4.0, and the blow ratio in the TD direction was 4.1 to 5.9. The physical properties of the obtained liquid crystal polyester resin composition film are shown in Tables 1 and 2.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

The liquid crystal polyester resin composition of the present invention has heat resistance, moldability, mechanical properties, especially impact resistance,
It has excellent tensile properties and improves the anisotropy of molded products.
Moreover, it is inexpensive and the film forming processability is improved, and the film obtained from the composition has very good gas barrier properties, stretchability, flex resistance, and pinhole resistance, and a large surface tension.
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.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 67/00 C08L 67/04

Claims (25)

(57) [Claims] 1. A liquid crystal polyester (A) as a continuous phase,
(B) (meth) acrylic acid ester-ethylene- (satiated
Japanese carboxylic acid glycidyl ester and / or unsaturated
A liquid crystal polyester resin composition comprising a glycidyl ether) copolymer rubber as a dispersed phase. 2. A liquid crystal polyester 56.0 to 99.
9% by weight, and (B) (meth) acrylic acid ester-
Ethylene- (unsaturated carboxylic acid glycidyl ester and
And / or unsaturated glycidyl ether) copolymer rubber 4
A liquid crystal polyester resin composition containing 4.0 to 0.1% by weight. 3. The rubber (B) comprises, as constituent components, (meth) acrylic acid ester units of more than 40% by weight and less than 97% by weight, ethylene units of 3% by weight to less than 50% by weight, unsaturated carboxylic acid glycidyl ester. The liquid crystal polyester resin composition according to any one of claims 1 and 2 , wherein the unit and / or the unsaturated glycidyl ether unit is a copolymer composed of 0.1 to 30% by weight. 4. The (meth) acrylic acid ester is methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-
The liquid crystal polyester resin composition according to any one of claims 1 to 3 , which comprises at least one selected from ethylhexyl acrylate and 2-ethylhexyl methacrylate. 5. A liquid crystal polyester (A) as a continuous phase,
(B) A rubber having a functional group reactive with a liquid crystal polyester, the Mooney viscosity of the rubber being in a range of 3 to 70.
A liquid crystal polyester resin composition, characterized in that the surrounding rubber is used as a dispersed phase. The Mooney viscosity here is JI
According to the S K6300 using the Rajiro over data at 100 ℃
The value measured by 6. A liquid crystal polyester (A) 56.0 to 99.
9% by weight, and (B) a rubber having a functional group reactive with a liquid crystal polyester, the Mooney viscosity of the rubber being
44.0 to 0.1% by weight of rubber having a degree of 3 to 70
A liquid crystal polyester resin composition comprising: The Mooney viscosity here is in accordance with JIS K6300.
The value measured with a large rotor at 100 ° C
U The Mooney viscosity of 7. Rubber (B) is a liquid crystal polyester resin composition according to any one of claims 1 to 4, characterized in that in the range of 3 to 70. The Mooney viscosity referred to here is a value measured using a large rotor at 100 ° C. according to JIS K6300. 8. A liquid crystal polyester (A) as a continuous phase,
(B) A rubber having a functional group reactive with a liquid crystal polyester , wherein the heat of fusion of crystals of the rubber is 3 J / g.
A liquid crystal polyester resin composition, characterized in that a rubber which is less than the above is used as a dispersed phase. 9. (A) Liquid crystal polyester 56.0 to 99.
9% by weight, and (B) a rubber having a functional group reactive with a liquid crystal polyester, the melting of crystals of the rubber.
A liquid crystal polyester resin composition comprising 44.0 to 0.1% by weight of rubber having a heat quantity of less than 3 J / g . 10. The heat of fusion of the rubber (B) crystals is 3 J /
It is less than g, The liquid crystal polyester resin composition in any one of Claims 1-7 characterized by the above-mentioned. 11. The liquid crystal polyester resin composition according to any one of claims 1 to 10 , wherein the liquid crystal polyester (A) contains at least 30 mol% of the following repeating structural units. 12. A liquid crystalline polyester (A) is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid.
The liquid crystal polyester resin composition according to claim 1 . 13. The liquid crystal polyester resin composition according to claim 1 , wherein the liquid crystal polyester (A) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids. object. 14. A liquid crystal polyester (A) comprising the following repeating unit :
10. The liquid crystal polyester resin composition according to any one of 10 to 10 . 15. A liquid crystal polyester (A) is, according to claim 1, characterized in that is made of the following repeating units
10. The liquid crystal polyester resin composition according to any one of 10 to 10 . 16. A liquid crystal polyester (A) as a continuous phase,
(B) having a functional group reactive with the liquid crystal polyester
Liquid crystal polyester which is made of rubber as a dispersed phase
And a liquid crystal polyester (A) comprising the following repeating unit:
Liquid crystal polyester resin composition . 17. A liquid crystalline polyester (A) 56.0-9
9.9% by weight, and (B) reactive with liquid crystal polyester
44.0 to 0.1% by weight of a rubber having a functional group having
Liquid crystal polyester resin composition characterized by containing
A is, liquid crystal polyester (A), characterized in that it is made of repeating units of the following Poriesu
Tell resin composition . 18. The functional groups reactive with liquid crystal polyester in the rubber (B) is an epoxy group, claims, characterized in that an oxazolyl group or an amino group 5-10
And the liquid crystal polyester resin composition according to any one of claims 15 to 17 . 19. The rubber (B) comprises a copolymer rubber containing unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units, and claims 5 to 10 and 15 to 15. 18. The liquid crystal polyester resin composition according to any one of 17 . 20. The liquid crystal polyester (A) is composed of the following repeating units :
The liquid crystal polyester resin composition according to any one of 5 to 17 . 21. A liquid crystal polyester (A) is, according to claim 1, characterized in that is made of the following repeating units
The liquid crystal polyester resin composition according to any one of 5 to 17 . 22. (A) Liquid crystal polyester 56.0-9
9.9% by weight, and (B) reactive with liquid crystal polyester
44.0 to 0.1% by weight of a rubber having a functional group having
An injection-molded article comprising a liquid crystal polyester resin composition containing . 23. An injection-molded article comprising the liquid crystal polyester resin composition according to any one of claims 1 to 21. 24. (A) Liquid crystal polyester 56.0-9
9.9% by weight, and (B) reactive with liquid crystal polyester
44.0 to 0.1% by weight of a rubber having a functional group having
A film comprising the liquid crystal polyester resin composition containing . 25. A film comprising the liquid crystal polyester resin composition according to any one of claims 1 to 21 .