JPH08325446A - Liquid-crystal resin composition toughened with glass bead - Google Patents

Abstract

PURPOSE: To improve flowability during molding, dimensional accuracy, mechanical anisotropy, and surface appearance by mixing a liquid-crystal polyester resin and/or a liquid-crystal polyamide resin with specific glass beads. CONSTITUTION: A least either of a liquid-crystal polyester resin which is a polyester forming an anisotropic molten phase and a liquid-crystal polyesteramide resin which is a polyesteramide forming an anisotropic molten phase is melt-kneaded in an amount of 100 pts.wt. together with 5-200 pts.wt. glass beads which have an average central particle diameter of 10-50μm and 80wt.% or more of, which each has a central particle diameter of 100μm or smaller, optionally further with a filler such as glass fibers, carbon fibers, or mica, an antioxidant, a thermal stabilizer, etc. At least 90wt.% of the glass beads preferably satisfy the relationship [wherein (d) is the average central particle diameter of the beads and D is the central particle diameter of a bead, provided that (d-20)=1 when (d-20)<=1]. In the glass beads, the content of beads each having a central particle diameter of 1μm or smaller is preferably below 5wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystalline resin which is excellent in moldability, dimensional accuracy and mechanical properties, particularly good in fluidity and extremely improved in anisotropy and which can give a molded product having an excellent surface appearance. It relates to a composition.

[0002]

2. Description of the Related Art In recent years, demands for higher performance of plastics have been increasing, and many polymers having various new properties have been developed and put on the market. Among them, optics characterized by parallel arrangement of molecular chains Attention has been paid to the fact that anisotropic liquid crystal polymers have excellent fluidity and mechanical properties.

As a polymer for forming these anisotropic molten phases, for example, a liquid crystal polymer obtained by copolymerizing polyethylene terephthalate with p-hydroxybenzoic acid (Japanese Patent Laid-Open No. 49-49).
-72393), p-hydroxybenzoic acid and 6-
A liquid crystal polymer obtained by copolymerizing hydroxy-2-naphthoic acid (JP-A-54-77691), a liquid crystal polymer obtained by copolymerizing p-hydroxybenzoic acid with 4,4'-dihydroxybiphenyl, terephthalic acid and isophthalic acid (special Liquid crystalline polyester resins such as JP-A-57-24407), liquid crystal polymers formed from 6-hydroxy-2-naphthoic acid, P-aminophenol and terephthalic acid (JP-A-57-172921), P -Hydroxybenzoic acid, 4,4'-dihydroxybiphenol, a liquid crystal polymer formed from terephthalic acid, P-aminobenzoic acid and polyethylene terephthalate (JP-A-64-3
3123) and liquid crystal polyester amide resins are known.

It is also known to incorporate an inorganic filler such as glass fiber for the purpose of improving heat resistance, mechanical strength and dimensional accuracy of the liquid crystal polymer. Further, it is known that glass beads, which is one of the inorganic fillers, is blended with a liquid crystal polymer for the same purpose (JP-A-63-63).
16275).

[0005]

However, what has been known as a liquid crystal polymer containing an inorganic filler such as glass fiber has improved the heat resistance, mechanical strength and anisotropy of the liquid crystal polymer to some extent. However, the fluidity and dimensional accuracy during molding, and the appearance of the molded product were not always sufficient. Further, since the glass beads have various particle diameters, there is a problem that even if they are added, the particle diameters are not uniform, or if the particle diameter is inappropriate, the effect is not sufficiently exhibited. An object of the present invention is to solve the above problems and obtain a glass bead reinforced liquid crystalline resin composition having excellent fluidity and dimensional accuracy during molding, mechanical anisotropy and surface appearance.

[0006]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, in the present invention, 100 parts by weight of a liquid crystalline polyester resin and / or a liquid crystalline polyesteramide resin (A) forming an anisotropic molten phase and an average central particle diameter of 10 to 50 are used.
A composition comprising 5 to 200 parts by weight of glass beads (B) having a diameter of μm, wherein the ratio of the glass beads having a median particle diameter of 100 μm or less in the composition is 80% by weight or more of the glass beads. The glass bead reinforced liquid crystalline resin composition, further 90% by weight or more of the glass beads in the composition satisfy the following formula (1), and the ratio of the glass beads having a central particle diameter of 1 μm or less is 5 of the glass beads. The glass bead reinforced liquid crystalline resin composition, characterized in that it is less than wt%, (d-20) μm ≦ D ≦ (d + 20) μm (1) (where d in the formula is the average central particle of glass beads) Diameter, D
Indicates the median particle diameter of the glass beads, and when (d-20) ≦ 1, (d-20) = 1. ) A molded article obtained by molding the above glass bead reinforced liquid crystalline resin composition and a connector comprising the above glass bead reinforced liquid crystalline resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline polyester resin as used in the present invention is a polyester which forms an anisotropic melt phase, and includes, for example, aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenediene units. A polyester that forms an anisotropic molten phase composed of structural units selected from oxy units and the like, and a liquid crystalline polyesteramide resin is a polyesteramide that forms an anisotropic molten phase. A polyesteramide comprising a structural unit selected from a carbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit and the like.

In the present invention, the following structural units (I) and (I
Liquid crystalline polyester resin consisting of (I) and (IV), (I) and (II
I), a liquid crystalline polyester resin consisting of (IV) and (I)
One or more kinds of liquid crystalline polyester resins selected from the liquid crystalline polyester resins composed of the structural units of (II), (III) and (IV) can be preferably used. More preferably, a liquid crystalline polyester resin comprising the following structural units (I), (II) and (IV) and / or (I), (II), (III) and (IV)
Is a liquid crystalline polyester resin.

[0009]

[Chemical 4] (However, R ₁ in the formula is

Embedded image R ₁ represents one or more groups selected from

[Chemical 6] Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)]
And the structural units (IV) are substantially equimolar. ) The structural unit (I) is a structural unit of polyester produced from p-hydroxybenzoic acid, and the structural unit (II) is 4,
4'-dihydroxybiphenyl, 3,3 ', 5,5'-
Tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,
A structural unit produced from an aromatic dihydroxy compound selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, a structural unit (III) is a structural unit produced from ethylene glycol, Structural unit (IV) is terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2 ' -Bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and a structural unit formed from an aromatic dicarboxylic acid selected from diphenyl ether dicarboxylic acid. Of these, in the case of a copolymer composed of the structural units (I), (II), (III) and (IV), R1 is

[Chemical 7] Occupies 70 mol% or more of the structural unit (II), and R
2 is

Embedded image Particularly preferably those having 70 mol% or more of the structural unit (IV).

Further, in the case of a copolymer comprising the above structural units (I), (III) and (IV), R 2 is

[Chemical 9] Are particularly preferred.

In the case of a copolymer comprising the above structural units (I), (II) and (IV), R1 is

[Chemical 10] And / or

[Chemical 11] R2 is

[Chemical 12] And / or

[Chemical 13] Are particularly preferred.

The copolymerization amount of the above structural units (I) to (IV) is arbitrary. However, from the viewpoint of fluidity, the following copolymerization amount is preferable.

That is, the above structural units (I), (III) and (I
In the case of a copolymer comprising V), the structural unit (I) is preferably 30 to 95 mol% of [(I) + (III)],
˜95 mol% is more preferred. Further, the structural unit (IV) is substantially equimolar to the structural unit (III).

In the case of a copolymer comprising the above structural units (I), (II), (III) and (IV), the above structural units [(I) + (II)]
Is preferably 60 to 95 mol% of [(I) + (II) + (III)], and more preferably 80 to 92 mol%. Also, the structural unit
(III) is preferably 40 to 5 mol% of [(I) + (II) + (III)], and more preferably 20 to 8 mol%. The molar ratio of structural unit (I) / (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7 from the viewpoint of the balance between heat resistance and fluidity. Also, the structural unit (I
V) is substantially equimolar to the structural unit [(II) + (III)].

In the case of a copolymer comprising the above structural units (I), (II) and (IV), the structural unit (I) is 40 to 90 of [(I) + (II)] from the viewpoint of fluidity. It is preferably mol%, particularly preferably 60 to 88 mol%, and the structural unit (IV) is substantially equimolar to the structural unit (II).

When the above-mentioned liquid crystalline polyester which can be preferably used in the present invention is polycondensed, the above structural unit (I) is used.
To an aromatic dicarboxylic acid such as 3,3′-diphenyldicarboxylic acid or 2,2′-diphenyldicarboxylic acid, or an aliphatic compound such as adipic acid, azelaic acid, sebacic acid or dodecanedioic acid Alicyclic dicarboxylic acids such as dicarboxylic acid and hexahydroterephthalic acid, chlorohydroquinone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 3,
Aromatic diol such as 4'-dihydroxybiphenyl,
1,4-butanediol, 1,6-hexanediol,
Aliphatic and alicyclic diols such as neopentyl glycol, 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and m-hydroxybenzoic acid,
Aromatic hydroxycarboxylic acids such as 2,6-hydroxynaphthoic acid can be further copolymerized in a small proportion within a range that does not impair the object of the present invention.

Preferred liquid crystalline polyesteramides are p in the above liquid crystalline polyester.
-Aminophenol, p-aminobenzoic acid and the like are copolymerized.

There is no particular limitation on the reaction-mechanical production method of the liquid crystalline polyester and the liquid crystalline polyesteramide in the present invention, and it can be produced according to the known polycondensation method of the liquid crystalline polyester and the liquid crystalline polyesteramide.

For example, in the production of the above-mentioned liquid crystalline polyester which is preferably used, (1) and (2) when the structural unit (III) is not contained, and (3) when the structural unit (III) is contained. Are preferred.

(1) p-acetoxybenzoic acid, 4,4 '
A method for producing a diacylated aromatic dihydroxy compound such as diacetoxybiphenyl or diacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction.

(2) p-hydroxybenzoic acid, 4,4 '
A method in which an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone or an aromatic dicarboxylic acid such as terephthalic acid is reacted with acetic anhydride to acylate a phenolic hydroxyl group, and then a deacetic acid polycondensation reaction is used for production.

(3) In the presence of (1) or (2) in the presence of a polyester polymer such as polyethylene terephthalate, an oligomer or a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate. A method of manufacturing by a method.

Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, or magnesium metal. .

The melt viscosity of the liquid crystalline polyester and the liquid crystalline polyesteramide in the present invention is 1 to 2,000.
0 Pa · s is preferable, and 2 to 1,000 Pa · s is particularly preferable.

The melt viscosity is the melting point (Tm) +10.
It is a value measured by a Koka type flow tester under conditions of a shear rate of 1,000 (1 / sec) under conditions of ° C.

Here, the melting point (Tm) is the endothermic peak temperature (T) observed when the polymerization-completed polymer is measured from room temperature to 20 ° C./min in the differential calorimetric measurement.
After the observation of m1), the temperature was maintained at Tm1 + 20 ° C for 5 minutes, then once cooled to room temperature under the temperature lowering condition of 20 ° C / min, and then measured again under the temperature rising condition of 20 ° C / min. Refers to the endothermic peak temperature (Tm2).

The glass beads in the glass bead reinforced liquid crystalline resin composition of the present invention have an average central particle diameter of 10 to 50 μm, preferably 12 to 35 μm, more preferably 15 to 20 μm. In addition, the central particle size in the composition is 100 μm
The ratio of the following glass beads is 80% by weight or more of the glass beads, and when the ratio of the glass beads having a central particle diameter of 100 μm or more exceeds 20% by weight of the glass beads, the moldability is lowered and the surface appearance is also reduced. It is not preferable because it worsens.
If the average median particle size exceeds 50 μm, the moldability is deteriorated and the surface appearance of the molded product is impaired, which is not preferable.
On the other hand, when the average central particle size is smaller than 10 μm, anisotropy becomes large, which is not preferable. Further, it is more preferable that 90% by weight or more of the glass beads satisfy the following formula (1) from the viewpoint of suppressing dimensional variation among molded products. The ratio of glass beads having a median particle diameter of 1 μm or less in the composition is less than 5% by weight of the glass beads,
Less than wt% is preferred.

(D-20) μm ≦ D ≦ (d + 20) μm (1) (where d is the average central particle diameter of the glass beads, D
Indicates the median particle diameter of the glass beads, and when (d-20) ≦ 1, (d-20) = 1. The term "center particle size of the glass beads" as used in the present invention means the maximum diameter passing through the center of the glass beads.

The glass beads (B) in the glass bead reinforced liquid crystalline resin composition of the present invention are obtained by subjecting commercially available glass beads to sieving with a sieve having an opening of 10 to 50 μm and classifying the target central particle diameter. Glass beads having can be obtained.

The filling amount is a liquid crystalline polyester resin and /
Or 5 to 200 parts by weight, preferably 10 to 140 parts by weight based on 100 parts by weight of the liquid crystalline polyesteramide resin (A).
Parts by weight. When the filling amount exceeds 200 parts by weight, the fluidity at the time of molding is lowered, which is not preferable.

The distribution of the median particle diameter of glass beads and the measurement of the average median particle diameter shall be carried out by the following method. After about 5 g of the pellet of the composition was ashed in a crucible, 100 mg was collected from the remaining glass beads, and 100 cc
Disperse in soapy water. Then, 1-2 drops of the dispersion liquid is placed on a glass slide using a dropper, observed under a microscope, photographed, and the median particle diameter of the glass beads photographed is measured. The measurement was performed 500 to 1000 pieces, and a weight distribution chart was prepared at a median particle diameter of 1 μm to determine an average median particle diameter. At this time, the broken glass beads are not measured.

The effect of the present invention is that the average median particle size of the glass beads is in the range of 10 to 50 μm and the median particle size is 1.
It is expressed when the ratio of the glass beads of 00 μm or less satisfies 80% by weight or more of the glass beads, more preferably 90% by weight or more of the glass beads in the composition satisfy the following formula (1), and It is exhibited when the condition that the ratio of glass beads having a particle diameter of 1 μm or less is less than 5% by weight of the glass beads is simultaneously satisfied. As a result, it is possible to obtain a glass bead reinforced liquid crystalline resin composition which is excellent in moldability, mechanical properties and surface appearance, particularly excellent in fluidity and anisotropy, and which can give a molded article with low warpage.

(D-20) μm ≦ D ≦ (d + 20) μm (1) (where d is the average central particle size of the glass beads, D
Indicates the median particle diameter of the glass beads, and when (d-20) ≦ 1, (d-20) = 1. The glass beads (B) used in the present invention are preferably coated with an epoxy polymer, a urethane polymer or an acrylic polymer or treated with a sizing agent, and an epoxy polymer is particularly preferable. Further, silane-based, titanate-based coupling agent, preferably treated with other surface treatment agent, epoxy silane,
Aminosilane coupling agents are particularly preferred.

The glass bead reinforced liquid crystalline resin composition of the present invention may further contain a filler other than glass beads.

As the filler which can be used in the present invention, glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, aluminum borate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber. , Boron whisker fiber, mica, talc, silica, calcium carbonate, glass flakes, glass microballoons, clay, wollastenite, titanium oxide,
Examples thereof include fibrous, powdery, granular or plate-like inorganic fillers such as graphite.

Furthermore, in the composition of the present invention, antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, phosphites and substitution products thereof, etc.) are used to the extent that the object of the present invention is not impaired. , UV absorbers (eg resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc.), dyes (eg nigrosine) Etc.) and pigments (eg cadmium sulfide, phthalocyanine, carbon black, etc.), colorants, plasticizers, antistatic agents, flame retardants and other usual additives and other thermoplastics Can be granted.

The glass bead reinforced liquid crystalline resin composition of the present invention is preferably produced by melt kneading, and a known method can be used for melt kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, and the like, the composition can be obtained by melt-kneading at a temperature of 250 to 370 ° C.

The glass bead reinforced liquid crystalline resin composition of the present invention thus obtained has excellent melt fluidity, moldability and optical anisotropy, and is excellent in heat resistance, chemical resistance and resistance by a usual molding method. It can be processed into three-dimensional molded products, sheets, container pipes, etc. that have hydrolyzability and mechanical properties. For example, various gears, various cases, sensors,
LED lamp, connector, socket, resistor, relay case switch coil bobbin, condenser, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, Magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD
Chassis, HDD parts, motor brush holder,
Electrical and electronic parts such as parabolic antennas and computer related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio / laser disks / compact disks , Lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc.
Office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, and other bearings,
Mechanical parts such as motor parts, lighters and typewriters, optical devices such as microscopes, binoculars, cameras and watches, precision mechanical parts; alternator terminals, alternator connectors, IC regulators, light deer potentiometers Various valves such as base, exhaust gas valve, fuel related / exhaust system / intake system various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor , Oil temperature sensor, brake pad wear sensor,
Throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, air conditioner thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, Duss Tributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch substrates, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamps Reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter , Motor vehicles, such as the ignition device case
It is useful for vehicle-related parts and other various applications.

[0039]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Reference Example 1 p-Hydroxybenzoic acid 994 parts by weight, 4,4'-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112
Parts by weight, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride are charged into a reaction vessel equipped with a stirring blade and a distilling tube to carry out polycondensation to complete polycondensation. (A-1) was obtained. The melting point (Tm) of this polymer was 314 ° C., the melt viscosity at 324 ° C. and the shear rate of 1000 (1 / sec) was 400 poise.

Reference Example 2 994 parts by weight of p-hydroxybenzoic acid, 222 parts by weight of 4,4'-dihydroxybiphenyl, 147 parts by weight of 2,6-diacetoxynaphthalene, 1078 parts by weight of acetic anhydride and 299 parts by weight of terephthalic acid were stirred. It was charged in a reaction vessel equipped with blades and an outflow pipe, polycondensation was performed, and the polycondensation was completed to obtain a polymer (A-2). The melting point (Tm) of this polymer is 336 ° C., 346 ° C., and the shear rate is 1000 (1 /
The melt viscosity in seconds) was 520 poise.

Reference Example 3 According to JP-A-49-72393, 1296 parts by weight of p-hydroxybenzoic acid and an intrinsic viscosity of about 0. 6dl /
346 parts by weight of polyethylene terephthalate (g) was charged into a reaction vessel equipped with a stirring blade and an outflow tube to carry out polycondensation,
Polymerization was completed to obtain a polymer (A-3). The melting point (Tm) of this polymer was 283 ° C., the melt viscosity at a shear rate of 1000 (1 / sec) was 293 ° C., and it was 1200 poise.

Reference Example 4 According to JP-A-54-77691, 921 parts by weight of p-hydroxybenzoic acid and 435 parts by weight of 6-acetoxy-naphthoic acid were charged in a reaction vessel equipped with a stirring blade and an outflow tube, and polycondensed. To complete the polycondensation and polymer (A-4)
I got The melting point (Tm) of this polymer is 283 ° C.,
The melt viscosity at 293 ° C. and the shear rate of 1000 (1 / second) was 2000 poise.

Examples 1 to 8 and Comparative Examples 1 to 6 Using a 35 mmφ twin-screw extruder having a raw material supply port and an intermediate addition port, the liquid crystalline polyester (A
-1 to 4) are supplied to a raw material supply port of a 35 mmφ twin-screw extruder, and then an average central particle size is 18 μm from an intermediate addition port.
(Examples 1 to 6), 45 μm (Example 7), 13 μm
(Example 8), 85 μm (Comparative Example 1), 8 μm (Comparative Example 2), 58 μm (Comparative Example 3) glass beads or inorganic fillers were supplied in the proportions shown in Table 1, melt-kneaded, and resin. It was a pellet of the composition. For the composition to which the glass beads were added, the pellets were ashed in a crucible, and the median particle diameter of the remaining glass beads, the average median particle diameter, and the distribution of the median particle diameter were determined by the method described above. Further, the range of the following formula (1) was determined, and the weight% of glass beads that satisfied the formula (1) was determined from the distribution chart.

(D−20) μm ≦ D ≦ (d + 20) μm (1) (where d is the average central particle diameter of the glass beads, D
Indicates the median particle diameter of the glass beads, and when (d-20) ≦ 1, (d-20) = 1. ) These pellets were subjected to Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of melting point + 10 ° C and a mold temperature of 90 ° C.
A 70 × 70 × 2 mm square plate was formed.

From a 70 × 70 × 2 mm square plate, the resin was cut into ½ ″ widths in the flow direction (MD) and the right angle direction (TD), and the flexural modulus was measured according to the ASTM D790 standard to determine MD / TD. The flexural modulus ratio was calculated as the mechanical anisotropy.

Using the above molding machine, 40 1/4 "Izod impact test pieces were molded under the conditions of a cylinder temperature of melting point + 10 ° C and a mold temperature of 90 ° C. Ten of them were randomly picked and The thickness was measured and the difference between the maximum value and the minimum value of the variation was obtained.

For the evaluation of fluidity, the above-mentioned molding machine is used, the cylinder temperature is melting point + 10 ° C., and the mold temperature is 90.
The flow length of a test piece having a thickness of 0.5 mm and a width of 12.7 mm was determined under the conditions of ° C, an injection speed of 99% and an injection pressure of 500 kgf / cm ² .

As an evaluation of warpage, the above pellets were
A 20E2ASE injection molding machine was used, and the cylinder temperature was set to a melting point + 10 ° C and the mold temperature was set to 130 ° C.
A release small box having a size of 5 × 35 × 25 mm and a thickness of 2 mm was formed, and the warp of the central portion on the side opposite to the pin gate was observed. FIG. 1 is a perspective view of the release small box 2, and the release small box 2 is injection molded with the pin gate 1 as a gate. The warp was judged as ⊚: warp amount less than 0.3 mm, x: 0.30 mm or more.

The appearance of the molded product was visually inspected, and it was judged that ∘: smooth and glossy, ∘: smooth, ×: rough, and traces of flow can be seen. Table 1 shows the results.

[0051]

[Table 1]

[0052]

The glass bead reinforced liquid crystalline resin composition of the present invention has excellent mechanical properties and moldability, particularly good fluidity, extremely improved anisotropy, low warpage and low shrinkage. Because of its good surface appearance, it is suitable for various applications such as electrical / electronic related equipment, precision machinery related equipment, office equipment and automobiles.

[Brief description of drawings]

FIG. 1 is a perspective view of a release small box formed in an example for warpage evaluation.

[Explanation of symbols]

 1 Pin gate 2 Warp evaluation point

Claims (6)

[Claims] 1. 100 parts by weight of a liquid crystalline polyester resin and / or a liquid crystalline polyesteramide resin (A) forming an anisotropic molten phase and glass beads (B) 5-2.
00 parts by weight, the average median particle size of the glass beads in the composition is 10 to 50 μm, and the ratio of the glass beads having a median particle size of 100 μm or less is 80% by weight or more of the glass beads. A glass bead reinforced liquid crystalline resin composition characterized by being present. 2. 90% by weight of glass beads in the composition
The glass bead reinforced liquid crystalline resin composition according to claim 1, wherein the above satisfy the following formula (1), and the ratio of the glass beads having a central particle diameter of 1 μm or less is less than 5% by weight of the glass beads. (D-20) μm ≦ D ≦ (d + 20) μm (1) (where d is the average central particle diameter of the glass beads, D
Indicates the median particle diameter of the glass beads, and when (d-20) ≦ 1, (d-20) = 1. ) 3. A liquid crystalline polyester resin (A) comprising a liquid crystalline polyester resin comprising the following structural units (I), (II) and (IV), and (I), (II), (III) and (IV) The glass bead reinforced liquid crystalline resin composition according to claim 1, which is at least one selected from liquid crystalline polyester resins and liquid crystalline polyester resins consisting of (I), (III) and (IV). Embedded image (However, R1 in the formula is R1 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)]
And the structural units (IV) are substantially equimolar. ) 4. A liquid crystal polyester resin (A) comprising a structural unit (I), (II) or (IV) and a liquid crystal comprising (I), (II), (III) or (IV). The glass bead reinforced liquid crystalline resin composition according to claim 2, which is one or more kinds selected from the organic polyester resins. 5. A molded product obtained by molding the glass bead reinforced liquid crystalline resin composition according to claim 1. 6. A connector comprising the glass bead reinforced liquid crystalline resin composition according to claim 1.