JP3362489B2 - Liquid crystalline resin composition and molded article - 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 crystalline resin composition and a molded product which are excellent in heat resistance, mechanical properties and moldability, are stable thermally and chemically, do not generate decomposition gas, and are colored black. It is a thing.

[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 Anisotropic liquid crystalline polymers are attracting attention because they have excellent fluidity, heat resistance, and mechanical properties.

Polymers that form an anisotropic molten phase include
For example, a liquid crystalline polymer obtained by copolymerizing polyethylene terephthalate with p-hydroxybenzoic acid (Japanese Patent Laid-Open No. 49-723).
93), a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (JP-A-54-77691), and p-hydroxybenzoic acid containing 4,4′- Liquid crystalline polymer obtained by copolymerizing dihydroxybiphenyl with terephthalic acid and isophthalic acid
7-24407), 6-hydroxy-2-naphthoic acid, a liquid crystalline polymer formed from p-aminophenol and terephthalic acid (JP-A-57-172921),
A liquid crystalline polymer formed from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (JP-A-64-33123) is disclosed.

These liquid crystalline polymers have a drawback that they have large mechanical anisotropy and dimensional anisotropy, but for example, a method of adding glass fiber to the liquid crystalline polymer (rubber digest, Vol. 27, No. 8, 7-14). Page (1975)), a method of blending a liquid crystalline polymer with a plate-like powder typified by mica, talc and graphite (JP-A-63-146959).
The mechanical strength, heat resistance, moldability and dimensional stability are further improved by alleviating the anisotropy, and it is used as engineering plastic for various parts such as automobiles, electric / electronics, precision machines, office machines, etc. It is used for a wide range of purposes.

Particularly, a molded article made of a liquid crystalline resin is often used in a high temperature atmosphere because of its excellent heat resistance, and at this time, it is colored black for the purpose of preventing discoloration.

As a method of coloring a liquid crystalline resin black, a method of adding carbon black is generally used like other resins, but the liquid crystalline resin is difficult to be colored because of its characteristics such as easy orientation. It is necessary to add a large amount of carbon black as compared with the resin, and the mechanical properties are lowered because the molding is performed at a high temperature, and in particular, the weld strength is lowered and decomposition gas is likely to be generated. Problems such as deterioration in solder resistance and unusability for functional applications have come to be pointed out. This problem is particularly noticeable when using a liquid crystalline polymer containing ethylenedioxy units.

[0007]

Therefore, the present invention solves the above-mentioned problems and eliminates the generation of decomposition gas, heat resistance,
An object of the invention is to obtain a liquid crystalline resin composition and a molded product which are excellent in mechanical properties and moldability and which are colored in black.

[0008]

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, the pH is 5 to 8 with respect to 100 parts by weight of one or more liquid crystalline resins selected from (A) the liquid crystalline polyester and the liquid crystalline polyesteramide which form the anisotropic molten phase. Carbon black 0.01 ~
A liquid crystalline resin composition containing 10 parts by weight, the liquid crystalline resin having the following (I), (II) and (IV), or (I), (II), (III) and (IV) : also,
The above liquid crystalline resin composition which is a liquid crystalline polyester comprising the structural units (I), (III) and (IV),

[Chemical 5] (However, R ₁ is

[Chemical 6] R ₁ represents one or more groups selected from

[Chemical 7] Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural units (II) and (III)
And the structural unit (IV) are substantially equimolar. ) A filler 300 is added to 100 parts by weight of the liquid crystalline resin.
The above-mentioned liquid crystalline resin composition containing 100 parts by weight or less of the above liquid crystalline resin composition, and the above liquid crystalline resin composition and an organic compound obtained by further adding 05 to 60 parts by weight of an organic bromide to 100 parts by weight of the above liquid crystalline resin. The above liquid crystalline resin composition, wherein the bromide is polybrominated styrene having a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ and having, as a main constituent, one or more of the following structural units produced from brominated styrene monomer: And a molded article.

[0010]

[Chemical 8] The liquid crystalline polyester and the liquid crystalline polyesteramide that form the anisotropic molten phase in the liquid crystalline resin (A) used in the present invention are an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, and ethylenedioxy. A liquid crystalline polyester forming an anisotropic molten phase consisting of structural units selected from the units, and also selected from the structural units and aromatic iminocarbonyl units, aromatic diimino units, aromatic iminooxy units, etc. It is a liquid crystalline polyesteramide that forms an anisotropic molten phase composed of structural units.

As an example of the liquid crystalline polyester which forms an anisotropic melt phase, a liquid which forms an anisotropic melt phase preferably composed of the structural units (I), (II) and (IV) described above is preferably used.
Forming a crystalline polyester or an anisotropic melt phase composed of structural units of (I), (II), (III) and (IV)
Examples thereof include liquid crystalline polyester , and liquid crystalline polyester that forms an anisotropic molten phase composed of structural units (I), (III) and (IV).

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, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2
-Bis (4-hydroxyphenyl) propane and 4,
A structural unit produced from an aromatic dihydroxy compound selected from 4'-dihydroxydiphenyl ether, a structural unit (III) is a structural unit produced from ethylene glycol, a 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 4,
Each of the structural units formed from an aromatic dicarboxylic acid selected from 4'diphenyl ether dicarboxylic acid is shown.

As examples of the liquid crystalline polyesteramide, 6-hydroxy-2-naphthoic acid, a liquid crystalline polyesteramide produced from p-aminophenol and terephthalic acid, p-hydroxybenzoic acid, 4,4'-dihydroxy. Liquid crystalline polyesteramide produced from biphenyl, terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (Japanese Patent Laid-Open No. 64-33123).
And so on.

The liquid crystalline polyester which can be preferably used in the present invention is one of the above structural units (I), (II) and (IV) .
Or a copolymer of (I), (II), (III) and (IV), wherein the structural units (I), (II), (III) and (IV) The amount of copolymerization is arbitrary. However, from the viewpoint of fluidity, the following copolymerization amount is preferable.

That is, when the structural unit (III) is contained, the total of the structural units (I) and (II) is the structural units (I) and (I) in view of heat resistance, flame retardancy and mechanical properties.
60-95 mol% is preferable with respect to the total of I) and (III) , and 75-93 mol% is more preferable. The structural unit (III) is the sum of structural units (I), (II) and (III).
40 to 5 mol% is preferable, and 25 to 7 mol% is more preferable. The molar ratio [(I) / (II)] of the structural unit (I) to (II) is preferably 75/25 to 95/5 from the viewpoint of the balance between heat resistance and fluidity, It is more preferably 78/22 to 93/7. Further, the structural unit (IV) is substantially equimolar to the total of the structural units (II) and (III) .

On the other hand, when the structural unit (III) is not contained, the structural unit (I) is the structural unit (I) in view of fluidity.
It is preferably 40 to 90 mol%, particularly preferably 60 to 88 mol%, with respect to the total of (II) and the structural unit (IV) is substantially equimolar to the structural unit (II). is there.

In the polycondensation of the above liquid crystalline polyester which can be preferably used in the present invention, in addition to the components constituting the above structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid, 2,2 '-Diphenyldicarboxylic acid and other aromatic dicarboxylic acids, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, hexahydroterephthalic acid and other alicyclic dicarboxylic acids, chlorohydroquinone, methylhydroquinone, 4 , 4'-dihydroxydiphenyl sulfone, 4,
4'-dihydroxydiphenyl sulfide, 4,4'-
Aromatic diols such as dihydroxybenzophenone, 1,
Aliphatic such as 4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
Alicyclic diol and m-hydroxybenzoic acid, 2,6
-Aromatic hydroxycarboxylic acids such as hydroxynaphthoic acid, p-aminophenol, p-aminobenzoic acid and the like can be further copolymerized in a small proportion within a range not impairing the object of the present invention.

The method for producing the (A) liquid crystalline resin in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystal polyester preferably used above, (1) and (2) when the structural unit (III) is not contained, and (3) when the structural unit (III) is contained. A preferable method is a method.

(1) p-acetoxybenzoic acid and 4,
A method for producing a diacylated aromatic dihydroxy compound such as 4′-diacetoxybiphenyl or 4,4′-diacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction. (2) p-Hydroxybenzoic acid, aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, A method for producing by deacetic acid polycondensation reaction. (3) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β of aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate
-A method for producing by the method (1) or (2) in the presence of hydroxyethyl) ester.

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 metal magnesium. .

Some of the liquid crystalline resins (A) in the present invention are capable of measuring the logarithmic viscosity in pentafluorophenol. In that case, the concentration is 6 at a concentration of 0.1 g / dl.
The value measured at 0 ° C. is preferably 0.5 dl / g or more, particularly 1.0 to 3.0 dl when the above structural unit (III) is contained.
/ G is preferable, and when the structural unit (III) is not contained, 2.0 to 10.0 dl / g is preferable.

The melt viscosity of the liquid crystalline resin (A) in the present invention is preferably 10 to 20,000 poise, more preferably 20 to 10,000 poise.

The above melt viscosity is the melting point (Tm) +1.
It is a value measured by a Koka flow tester under conditions of 0 ° C. and a shear rate of 1,000 (1 / sec).

Here, the melting point (Tm) is Tm1 after the endothermic peak temperature Tm1 observed when the polymer is measured by a differential calorimetry at a temperature rising condition from room temperature to 20 ° C./min.
After the temperature was raised to + 20 ° C. and kept at the same temperature for 5 minutes, the temperature was once cooled to room temperature under the temperature lowering condition of 20 ° C./min.
The endothermic peak temperature observed when measured again under the temperature rising condition of 20 ° C./min.

Examples of the carbon black used in the present invention include channel black type, harness black type and lamp black type, and among these, particularly lamp black type can be preferably used.

The PH of carbon black is in the range of 5 to 8, preferably 6 to 8, and more preferably 6.5 to 7.8. When the PH is less than 5 , mechanical properties represented by impact resistance and Weld strength is greatly reduced, which is not preferable. On the other hand, if the pH exceeds 8 , not only the impact resistance and weld strength will be deteriorated, but also the retention stability during molding will be poor and the physical properties will be degraded and decomposed gas will be generated, resulting in a poor appearance of the molded product, which is not desirable. . In particular, when a liquid crystalline polymer having an ethylenedioxy unit is used, these physical properties are greatly deteriorated.

The above-mentioned PH is a value obtained by preparing an aqueous suspension in which 1 g of carbon black is dispersed in 20 ml of distilled water and measuring the pH of the suspension.

As the filler which can be used in the present invention, glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber, boron whisker fiber, Asbestos fiber, mica, talc, silica, calcium carbonate, glass beads, glass flakes,
Glass micro-balloon, clay, molybdenum disulfide,
Wollastonite, titanium oxide, calcium polyphosphate,
Examples thereof include fibrous, powdery, granular or plate-like fillers such as graphite. Among the above fillers, glass fiber is preferably used.

The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, chopped strands of long fiber type or short fiber type, milled fiber and the like can be selected and used.

The addition amount of the above-mentioned filler is 100
It is not more than 400 parts by weight, preferably 50 parts by weight.
To 250 parts by weight, more preferably 70 to 200 parts by weight. The surface of the above-mentioned filler used in the present invention may be treated with a known coupling agent (eg, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent. .

The glass fibers may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like.

The organic bromine compound used in the present invention includes a known organic bromine compound usually used as a flame retardant, and a bromine content of 20% by weight or more is particularly preferable. Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetra Bromophthalimide), low molecular weight organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A as a raw material or a copolymer thereof with bisphenol A), a brominated epoxy compound (for example, For the reaction of diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin and the reaction of brominated phenols with epichlorohydrin Those obtained I epoxy compound), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A,
Halogenated polymers and oligomers such as condensates of cyanuric chloride and brominated phenol, brominated polystyrene, cross-linked brominated polystyrene, cross-linked brominated poly α-methylstyrene, and mixtures thereof, among which ethylene bis ( Tetrabromophthalimide), brominated epoxy oligomer or polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred,
Brominated polystyrene is most preferably used.

The above-mentioned preferable organic bromide will be described in more detail. As the brominated epoxy polymer, those represented by the following general formula (i) are preferable.

[0035]

[Chemical 9]

The degree of polymerization n in the above general formula (i) is preferably 15 or more, more preferably 50 to 80.

As the brominated polystyrene used in the present invention, brominated polystyrene and crosslinked brominated polystyrene produced by brominating polystyrene obtained by radical polymerization or anionic polymerization, or brominated styrene monomer by radical polymerization or anion Examples thereof include polybrominated styrene having a brominated styrene unit represented by the formula (ii) and / or (iii) produced by polymerization, preferably radical polymerization. )and/
Alternatively, polybrominated styrene having a structural unit represented by the formula (iii) as a main constituent and a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ is preferable.

[0038]

[Chemical 10]

The term "brominated styrene monomer" as used herein is preferably a styrene monomer having two to three bromine atoms introduced into the aromatic ring by a substitution reaction per one styrene monomer, such as dibrominated styrene and / or tribrominated. In addition to styrene, monobrominated styrene and the like may be contained.

The polybrominated styrene preferably contains dibrominated styrene and / or tribrominated styrene units in an amount of 60% by weight or more, more preferably 70% by weight or more. 40% by weight of monobrominated styrene in addition to dibrominated styrene and / or tribrominated styrene
The following may be polybrominated styrene, preferably 30% by weight or less copolymerized. The weight average molecular weight of this polybrominated styrene is more preferably 1 × 10 ⁴ to 15 × 10 ⁴ . The weight average molecular weight is a value measured using a gel permeation chromatograph and is a relative value based on polystyrene molecular weight.

The crosslinked brominated polystyrene is preferably polystyrene obtained by brominated porous polystyrene crosslinked with divinylbenzene.

As the brominated polycarbonate, those represented by the following general formula (iv) are preferable.

[0043]

[Chemical 11] (R1 and R2 each represent a substituted or unsubstituted aryl group, and a pt-butylphenyl group is most preferable.)

The degree of polymerization n in the general formula (iv) is 4
The above is preferable, 8 or more, especially 8 to 2
5 can be used more preferably.

The amount of the organic bromide compounded is 0.5 to 60 parts by weight, especially 1 to 100 parts by weight of the liquid crystalline resin.
30 parts by weight is preferred.

In the liquid crystalline resin composition of the present invention, the organic bromide is preferably dispersed in the composition with an average diameter of 25 μm or less, more preferably 2.0 μm or less.

The liquid crystalline resin composition of the present invention contains an antioxidant and a heat stabilizer (eg hindered phenol, hydroquinone, phosphites and their substitution products), an ultraviolet absorber (eg resorcinol, salicylate, benzo). Triazole, benzophenone, etc.),
Coloring agents including lubricants and mold release agents (such as montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide and polyethylene wax), dyes (such as nigrosine) and pigments (such as cadmium sulfide and phthalocyanine), Common additives such as plasticizers, flame retardant aids, antistatic agents, and other thermoplastic resins (such as fluororesins) can be added to impart predetermined characteristics.

The method for producing the liquid crystalline resin composition and the molded product of the present invention is not particularly limited, but it is preferably produced by melt kneading, and a known method can be used for melt kneading. For example, a Banbury mixer,
Using a rubber roll machine, a kneader, a single-screw or twin-screw extruder, etc., melt kneading at a temperature of 200 to 400 ° C. to obtain a composition, and the thus obtained liquid crystalline resin composition of the present invention is injection molded, extrusion molded, Examples include a method of forming a molded product by a usual molding method such as blow molding.

Further, a method in which a master pellet in which the carbon black used in the present invention is blended at a high concentration is prepared and this is mixed with a non-colored pellet at the time of molding and then molded is also preferably used. The composition and molded product thus obtained can be processed into a three-dimensional molded product having excellent heat resistance, moldability, mechanical properties and surface appearance, a sheet, a container pipe, etc., for example, various gears, Various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switch coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators,
Various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, Electric / electronic parts typified by 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 Home, office electric product parts, office computer related parts, telephone related parts, facsimile related parts Copier related parts such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Cleaning jigs, various bearings such as oilless bearings, stern bearings, submersible bearings, mechanical parts such as motor parts, lighters and typewriters, and optical devices such as microscopes, binoculars, cameras and watches. , Precision machinery related parts; alternator terminal, alternator connector, IC regulator,
Potentiometer base for light deer, various valves such as 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 warm air flow control valve, radiator holder brush holder. , Water pump impeller, Turbine vane, Wiper motor related parts, Dust tributor, Starter system H, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, fuse connector, horn terminal, electrical component insulating plate, step motor rotor, lamp socket, lamp reflector, lamp housing ,
It is useful for automobile / vehicle related parts such as brake piston, solenoid bobbin, engine oil filter, ignition device case, and other various applications.

[0050]

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. The melting point (Tm) of this resin obtained in (A) is 314 ° C., 324 ° C., and the shear rate is 100.
The melt viscosity at 0 / 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 a distillation tube, polycondensation was performed, and the polycondensation was completed to obtain a resin (B). The melting point (Tm) of this resin is 336 ° C.
And the melt viscosity at 346 ° C. and a shear rate of 1000 / sec was 520 poise.

Reference Example 3 According to the production method described in JP-A-49-72393, 1296 parts by weight of p-acetoxybenzoic acid and polyethylene terephthalate 34 having an intrinsic viscosity of about 0.6 dl / g.
Charge 6 parts by weight into a reaction vessel equipped with a stirring blade and a distillation tube,
A resin (C) was obtained by polycondensation, and the melting point (T
m) was 283 ° C, and the melt viscosity at a shear rate of 1000 / sec at 293 ° C was 1,200 poise.

Reference Example 4 According to the production method described in JP-A-54-77691, 921 parts by weight of p-acetoxybenzoic acid and 435 parts by weight of 6-acetoxynaphthoic acid were added to a reaction vessel equipped with a stirring blade and a distillation tube. Was charged and polycondensed to obtain a resin (D). The melting point (Tm) of this resin is 283 ° C. and is 293
The melt viscosity was 2,000 poises at a shear rate of 1000 / sec.

Reference Example 5 Table 1 shows the structure of the organic bromide used in the present invention.

[0056]

[Table 1]

Example 1, Comparative Examples 1 to 7 The liquid crystalline resins obtained in Reference Examples 1 to 4 were dry blended with the carbon blacks shown in Table 2 in the proportions shown in Table 2,
Cylinder temperature was set to the melting point of each liquid crystalline resin 30
The mixture was melt-kneaded into pellets using a mmφ twin-screw extruder.

The pellets were subjected to a Sumitomo Nestal Promat 40/25 injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.), and gates were provided at both ends under the conditions of a cylinder temperature of melting point + 10 ° C and a mold temperature of 90 ° C. A bending test piece having a thickness of 1 mm and having a weld line formed in the center of the test piece was formed, and the weld strength was measured. The results are shown in Table 2.

[0059]

[Table 2]

Examples 2 to 9 and Comparative Examples 8 to 17 The liquid crystalline resins obtained in Reference Examples 1 to 4 were filled with the fillers shown in Table 3,
After carbon black and other additives were dry blended in the proportions shown in Table 3, they were melt-kneaded into pellets using a 30 mmφ twin-screw extruder whose cylinder temperature was set to the melting point of each liquid crystalline resin.

The pellets were subjected to a Sumitomo Nestal Promat 40/25 injection molding machine (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 for 2 1/2. "(Width) x 1/2" x (length) x 1
4 "(thickness) impact test piece and gates at both ends
A bending test piece having a thickness of 1 mm that forms a weld line at the center of the test piece was molded, and the impact strength and the weld strength were measured. In addition, this pellet was manufactured by Toshiba IS55EPN injection molding machine (Toshiba Machine Plastic Engineering Co., Ltd.).
Manufactured), the cylinder temperature is melting point + 15 ° C., the mold temperature is 90 ° C., the ASTM No. 1 dumbbell test piece is molded under two conditions in which the molding residence time is changed to 4 minutes and 20 minutes, and the tensile strength is measured, Tensile strength when the molding retention time was 20 minutes / tensile strength when the molding retention time was 4 minutes × 100 was determined as the tensile strength retention rate.

Under the condition of 90 ° C., the molding residence time was changed to A
STM No. 1 dumbbell test pieces were molded and the tensile strength was measured. The blackness and appearance of these molded products were visually observed. The results are shown in Table 3.

[0063]

[Table 3]

[0064] except that blended in proportions shown in Table 4 with respect to further 100 parts by weight of liquid resin to organic bromide shown in Table 1 in Example 1 0-1 5 Example 2 In the same manner as in Example 4 A pellet of the composition was produced. These pellets were subjected to Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), 0.5 mm (thickness) x under the conditions of a cylinder temperature of melting point + 10 ° C and a mold temperature of 90 ° C. A combustion test piece of 12.7 mm × 127 mm was molded, and a vertical combustion test was carried out in accordance with UL94 standard using the combustion test piece, and the flame retardancy was evaluated in the same manner as in Example 2 .

The results are shown in Table 4.

[0066]

[Table 4]

[0067]

The liquid crystalline resin composition and the molded product of the present invention are colored black and have excellent heat resistance and mechanical properties. Therefore, electrical / electronic-related equipment, precision machinery-related equipment, office equipment, automobiles / vehicles. It is suitable for various other applications such as related parts.

Continuation of the front page (56) References JP 62-131067 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 67/00 C08L 77/12

Claims (6)

(57) [Claims] 1. The amount of PH is 100 parts by weight of one or more liquid crystalline resins selected from (A) a liquid crystalline polyester and a liquid crystalline polyesteramide that form an anisotropic molten phase.
A liquid crystalline resin composition containing 0.01 to 10 parts by weight of carbon black of 5 to 8 . 2. A liquid crystalline polyester comprising (A) a liquid crystalline resin comprising the following structural units (I), (II) and (IV), or (I), (II), (III) and (IV) The structure of
Liquid crystalline polyester consisting of position, or, (I), (II
The liquid crystalline resin composition according to claim 1, which is a liquid crystalline polyester comprising the structural units I) and (IV). [Chemical 1] (However, R1 in the formula is R2 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 units (II) and (II
The total of I) and the structural unit (IV) are substantially equimolar. ) 3. A liquid crystal resin of 100 parts by weight,
The liquid crystalline resin composition according to claim 1, further comprising 400 parts by weight or less of a filler. 4. (A) 100 parts by weight of the liquid crystalline resin,
The liquid crystalline resin composition according to claim 1, further comprising 0.5 to 60 parts by weight of an organic bromide. 5. The organic bromide is a polybrominated styrene having a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ and having at least one of the following structural units produced from a brominated styrene monomer as a main constituent. Item 4. The liquid crystalline resin composition according to item 4. [Chemical 4] 6. The (A) PH is added to 100 parts by weight of one or more liquid crystalline resins selected from a liquid crystalline polyester and a liquid crystalline polyesteramide that form an anisotropic molten phase.
A liquid crystalline resin molded product containing 0.01 to 10 parts by weight of 5 to 8 carbon black.