JP3182756B2 - Method for producing thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a thermoplastic resin composition capable of providing a molded article having excellent surface properties and mechanical properties.

[Conventional technology]

In recent years, the demand for higher performance of plastics has been increasing, and many polymers having various new properties have been developed and marketed. Among them, optically anisotropic liquid crystals characterized by parallel arrangement of molecular chains Attention has been paid to polymers having excellent fluidity and mechanical properties. However, this liquid crystal polymer has a problem that the anisotropy is large. It is also known to add a filler such as talc or glass fiber in order to improve the anisotropy of the liquid crystal polymer. It is also known that a liquid crystal polymer is blended with a thermoplastic polymer to improve fluidity and mechanical properties (JP-A-56-115357).

[Problems to be solved by the invention]

However, even if these fillers are added to the liquid crystal polymer, the degree of anisotropy is not always at a satisfactory level. In order to further reduce the degree of this anisotropy, a study has been made and it has been found that a thermoplastic polymer may be added simultaneously with the filler. However, when these two polymers and the filler were mixed simultaneously as in Example 4 of JP-A-56-115357, it was found that when the amount of the liquid crystal polymer was large, the mechanical properties were greatly reduced.

Accordingly, an object of the present invention is to produce a thermoplastic resin composition having excellent mechanical properties and low anisotropy.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention relates to a liquid crystal polymer (A) having a structural unit selected from the following structural units (I), (II) and (III): Polymer (B) 50
In the production of a thermoplastic resin composition in which the filler (C) is contained in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the resin composition of 1 to 1% by weight, the thermoplastic polymer (B) and the filler (C) are used. A) Bambury mixer, rubber roll machine,
The present invention relates to a method for producing a thermoplastic resin composition, which comprises melt-kneading using a kneader, a single-screw or twin-screw extruder, and then melt-mixing the liquid crystal polymer (A).

(In the formula, X represents a divalent aromatic residue, Y represents a divalent aromatic or aliphatic or relaxed residue, and R represents O or NH.

The structural units (II) and (III) are substantially equimolar.

Further, as a further preferred means, the present invention is characterized in that the liquid crystal polymer (A) is a liquid crystal polyester having the following structural units (I ') to (IV') and a heat deformation temperature of 150 to 280 ° C. The method for producing a thermoplastic resin composition, and wherein the thermoplastic polymer (B) is at least one selected from polyamide, polycarbonate, polyarylene oxide, polyalkylene terephthalate, polyarylene sulfide, and polyetheretherketone. The present invention relates to a method for producing the above thermoplastic resin composition.

And the carbonyl groups of the structural unit (IV ′) are in a para or meta position with each other, and 50 mol% or more of the carbonyl groups are in the para position.

The sum of the structural units (II ') and (III') and (IV ') are substantially equimolar. Preferable examples of the aromatic hydroxycarboxylic acid constituting the structural unit (I) include p-hydroxybenzoic acid and m
-Hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 6-
And hydroxy-2-naphthoic acid.

Preferred examples of the dihydroxy compound or 4-amino-1-hydroxy compound constituting the structural unit (II) include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. -Dihydroxynaphthalene, hydroquinone,
Examples include methylhydroquinone, chlorohydroquinone, phenylhydroquinone, ethylene glycol, 1,4-butanediol, and p-aminophenol.

Preferred examples of the dicarboxylic acid constituting the structural unit (III) include terephthalic acid, isophthalic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, and 1,2-bis (2-chlorophenoxy) ) Ethane-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like.

The structural units (II) and (III) are substantially equimolar.

On the other hand, in the preferred liquid crystal polymer (A) of the present invention, the structural unit (I ′) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II ′) is formed from 4,4′-dihydroxybiphenyl. The structural unit (III ′) is a structural unit formed from one or more dihydroxy compounds selected from hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, and ethylene glycol. (IV ') represents a structural unit formed from terephthalic acid and / or isophthalic acid.

The preferred liquid crystal polymer (A) of the present invention is a liquid crystal polyester comprising the above structural units (I '), (II'), (III ') and (IV').

The copolymerization amount of the structural units (I '), (II'), (III ') and (IV') is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity. That is, the structural units (I ′) are represented by (I ′), (II ′) and (II)
It is preferably from 40 to 90 mol%, particularly preferably from 60 to 75 mol%, based on the total of I '). The molar ratio of the structural unit (II ') / (III') is preferably from 9/1 to 1/9, and in the structural unit (III '), -X- is -C.
In the case of H ₂ CH ₂ —, the structural unit (III ′) is (I ′),
23 to 5 mol% based on the sum of (II ') and (III')
It is particularly preferred -X- is -CH ₂ CH ₂ in - otherwise particularly preferably 7.5 / 2.5 to 4/6.

The sum of structural units (II ') and (III') and (I
V ') is substantially equimolar.

Thermotropic liquid crystal polymer (A) in the present invention
Has a heat deformation temperature of preferably 150 to 280 ° C., and 19
0-270 ° C is particularly preferred.

When the heat distortion temperature is less than 150 ° C, the effect of improving heat resistance is insufficient. appear.

Here, the heat distortion temperature is a value obtained by measuring a 1/8 ″ thick test piece at a stress of 18.6 kg / cm ² based on ASTM D648.

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

For example, in the above structural units (III '), -X- is -CH ₂ CH
₂ - Otherwise (1) ~ (4), - 2 X- is -CH CH ₂ -
In the case of (1), the production method (5) is preferably mentioned.

(1) It is produced from a diacylated aromatic dihydroxy compound such as p-acetoxybenzoic acid, 4,4'-diacetoxybiphenyl, paraacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction. Method.

(2) After reacting acetic anhydride with an aromatic dihydroxy compound such as p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, or hydroquinone, or an aromatic dicarboxylic acid such as terephthalic acid to acylate a phenolic hydroxyl group, A method of producing by a deacetic acid polycondensation reaction

(3) phenyl ester of p-hydroxybenzoic acid,
A method of producing from an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone and a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid by a phenol removal polycondensation reaction.

(4) An aromatic dicarboxylic acid such as p-hydroxybenzoic acid and terephthalic acid is reacted with a desired amount of diphenyl carbonate to form a diphenyl ester, and then an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl and hydroquinone is added. In addition, a method of producing by a dephenol polycondensation reaction.

(5) In the presence of polyethylene terephthalate (1)
Or a method of manufacturing by the method of (2).

Typical catalysts used for the polycondensation reaction include stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, magnesium, and metal compounds such as sodium acetate, and are particularly effective for dephenol polycondensation. is there.

Some liquid crystal polymers (A) of the present invention can measure intrinsic viscosity in pentafluorophenol,
In this case, a value measured at 60 ° C. at a concentration of 0.1 g / dl is preferably 0.5 or more, particularly preferably 1.0 to 15.0.

Further, the melt viscosity of the liquid crystal polymer of the present invention is preferably from 10 to 20,000 poise, and more preferably from 20 to 10,000 poise.

The melt viscosity is a value measured by a Koka type flow tester under the condition of (liquid crystal onset temperature + 40 ° C.) and a shear rate of 1,000 (1 / second).

In the polycondensation of the preferred liquid crystal polymer of the present invention, the above (I '), (II'), (III ') and (IV')
Other than the components constituting 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 1,2
-Bis (phenoxy) ethane-4,4'-dicarboxylic acid,
Aromatic dicarboxylic acids such as 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, resorcinol, chlorohydroquinone, methylhydroquinone, 2,7 -Aromatic dihydroxy compounds such as dihydroxynaphthalene, bisphenol A and bisphenol S; aromatic oxycarboxylic acids such as m-oxybenzoic acid and 2,6-oxynaphthoic acid; and p-aminophenol and p-aminobenzoic acid. Copolymerization can be further performed in a small proportion that does not impair the object of the invention.

In the resin composition of the present invention, selected from polyamide, polyoxymethylene, polycarbonate, polyarylene oxide, polyalkylene terephthalate, polyarylene sulfide, polysulfone, polyethersulfone, amorphous polyarylate, polyetheretherketone, and the like. One or more thermoplastic polymers (B) are essential components.

Preferred specific examples of the thermoplastic polymer (B) include the following.

Examples of the polyamide include nylon 6, nylon 46, nylon 66, nylon 610, nylon 11, nylon 12, and the like, and copolymers thereof. Polyoxymethylene includes polyoxymethylene homopolymers and copolymers in which the main chain is largely composed of oxymethylene chains. Polycarbonates are based on hydrocarbon derivatives containing bis (4-hydroxyphenyl), bis (3,5-dialkyl-4-hydroxyphenyl) or bis (3,5-dihalo-4-hydroxyphenyl) substitution Polycarbonates are preferred, and polycarbonates based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) are particularly preferred.

Examples of polyarylene oxide include poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-
And dimethylphenol / 2,3,6-triethylphenol copolymer.

Styrene-based resins such as polystyrene and high-impact polystyrene can be added to polyarylene oxide.

Examples of the polyalkylene terephthalate include polyethylene terephthalate and polybutylene terephthalate.

Examples of polyarylene sulfide include polyparaphenylene sulfide.

Structural formula as polysulfone And the like.

Structural formula as polyether sulfone And the like.

The amorphous polyarylate has the structural formula And the like.

As polyetheretherketone, the structural formula, And the like.

Of these, polyamide, polycarbonate, polyarylene oxide, polyalkylene terephthalate, polyarylene sulfide, and polyetheretherketone are preferred.

The filler (C) in the present invention is not particularly limited, and a known filler can be used. For example, glass fiber,
Carbon fiber, calcium silicate (warastenite), calcium phosphate, calcium sulfate, calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, aluminum oxide, magnesium oxide, zinc oxide, silicon oxide, iron oxide, zirconium oxide, antimony trioxide, Molybdenum dioxide, molybdenum disulfide, mica, sericite, talc, carion, clay, feldspar, vermiculite, silica, glass powder, carbon black, graphite, resin powder, ebonite powder and the like can be preferably used.

The surface of the filler (C) is a coupling agent,
For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
Methyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, hydroxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, silane coupling agent such as vinylacetoxysilane,
Isopropyl tris isostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tris Coupling treatment with a titanate coupling agent such as decylbenzenesulfonyl titanate or isopropyl tri (dioctyl phosphate) titanate, or an aluminum coupling agent such as acetoalkoxyaluminum diisopropylate or a zircoaluminate coupling agent It is preferable to use it because the heat resistance and mechanical properties of the liquid crystal polymer resin composition are improved.

Preferred specific examples of the glass fiber used in the present invention include a chopped strand having a diameter of 5 to 15 μm and a roving type glass fiber for a general reinforcing resin.

1 to 6 m from the viewpoint of handling properties and imparting surface gloss of molded products
An m-length chopped strand is particularly preferably used.

The glass fiber which has been subjected to a normal coupling agent treatment such as a silane-based or titanium-based glass is preferably used, and may be treated with a usual sizing agent such as an epoxy resin or vinyl acetate.

The compounding amount of the liquid crystal polymer (A) in the present invention is 50 to 99% by weight, preferably 55 to 95% by weight, and the compounding amount of the thermoplastic polymer (B) is 50 to 1% by weight, preferably 45 to 5% by weight. %. If the amount of (A) is less than 50% by weight, the effects of the present invention are small and the mechanical properties are low, which is not preferable. Also
If it is more than 99% by weight, the effect of the present invention is not obtained. Filler (C)
Is from 1 to 200 parts by weight, preferably from 5 to 150 parts by weight, based on 100 parts by weight of the resin composition.

In the production of this thermoplastic resin composition, it is essential to melt-mix the thermoplastic resin (B) and the filler before melt-mixing the thermoplastic polymer (B) and the liquid crystalline polymer (A). Polymer (B) and liquid crystalline polymer (A)
If the filler and the filler are melt-kneaded at the same time, the liquid crystal polyester may coat the filler surface or break the coupling agent of the filler, or the mechanical properties will not improve or decrease even if the filler is added. Sometimes. On the other hand, if the filler is melt-mixed in advance with the thermoplastic polymer, the filler is covered with the thermoplastic polymer, so even if the liquid crystal polymer (A) is melt-kneaded, the filler (C) is coupled. It can be seen that the mechanical properties are greatly improved without destroying the agent. Even if the liquid crystal polymer (A) is separately melt-kneaded with the filler (C) in advance, the reinforcing effect of the thermoplastic polymer (B) and the filler (C) makes it difficult to melt and knead these at the same time. Has good surface gloss and heat resistance.

The composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof) and an ultraviolet absorber (to the extent that the object of the present invention is not impaired). For example, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (such as montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide, and polyethylene wax), dyes (for example, nitrosine) and pigments (for example, nitrosine). For example, a colorant containing cadmium sulfide, phthalocyanine, carbon black, etc.), a usual additive such as a flame retardant, a plasticizer, an antistatic agent, a reinforcing agent, or another thermoplastic resin is added to impart a predetermined property. be able to.

A known method can be used for melt-kneading the thermoplastic resin composition of the present invention. For example, the composition can be melt-kneaded at a temperature of 200 to 400 ° C. using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, and the like to obtain a composition.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Reference Example 1 466 parts by weight of p-hydroxybenzoic acid, 84 parts by weight of 4,4'-dihydroxybiphenyl, 480 parts by weight of acetic anhydride, 75 parts by weight of terephthalic acid and 130 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g The reaction vessel was equipped with a stirring blade and a distillation tube, and subjected to deacetic acid polycondensation under the following conditions.

First, after reacting at 250 to 300 ° C for 2.5 hours under a nitrogen gas atmosphere, the pressure was reduced to 0.2 mmHg at 300 ° C, and the reaction was further completed for 3.25 hours to complete the polycondensation. A resin (a) having the following theoretical structural formula was obtained.

Further, the polyester was placed on a sample stage of a polarizing microscope and heated to check the optical anisotropy. As a result, the liquid crystal onset temperature was 264 ° C., indicating good optical anisotropy. The logarithmic viscosity of the polyester (measured in pentafluorophenol at 60 ° C. at a concentration of 0.1 g / dl) was 1.25.

Reference Example 2 519 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4,4'-diacetoxybiphenyl, 85 parts by weight of t-butyl hydroquinone diacetate, hydroquinone diacetate 1
9.4 parts by weight and 186 parts by weight of terephthalic acid were charged into a reaction vessel equipped with a stirring blade and a distillation
After reacting at ~ 340 ° C for 3.0 hours, the temperature is raised to 350 ° C and then 1.5mmHg
The system was further decompressed and further heated for 1.0 hour to carry out a polycondensation reaction to obtain a resin (b) having the following theoretical structural formula.

The polyester was placed on a sample stage of a polarizing microscope, and the temperature was raised to confirm the optical anisotropy. As a result, the liquid crystal onset temperature was 307 ° C., indicating good optical anisotropy. The logarithmic viscosity of the polyester (measured under the same conditions as in Reference Example 1) was 4.3.

Reference Example 3 541 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4,4'-diacetoxybiphenyl, 62 parts by weight of hydroquinone diacetate, 124 parts by weight of terephthalic acid, and 42 parts by weight of isophthalic acid were stirred with a stirring blade and a distillation tube. After the reaction was carried out at 250 to 360 ° C. for 3 hours under a nitrogen gas atmosphere, the pressure was reduced to 1 mmHg, and the mixture was further heated for 1 hour to complete the polycondensation. c) was obtained.

Example 1 A dry blend of 45 parts by weight (B) of polyethylene terephthalate having a logarithmic viscosity of 0.65 (manufactured by Toray Industries, Ltd.) and 55 parts by weight of glass fiber (C) (3 mm length, 10 μm chopped strand) was used, and then a 40 mm unit set at 280 ° C. The mixture was melt-mixed with a screw extruder to obtain reinforced polyethylene terephthalate containing 55% of glass fiber.

100 parts by weight of this glass fiber reinforced polyethylene terephthalate [(B) + (C)] and 100 parts by weight of the liquid crystal polymer (a) [(A)] of Reference Example 1 ((A) / (B) = 69/31,
(C) / [(A) + (B)] = 38/100), and then Sumitomo Nestal injection molding machine Promat 40/25.
(Sumitomo Heavy Industries, Ltd.), cylinder temperature 29
1/8 "thick x 1/2" wide 5 "long test piece, 1/8" thick ASTM NO1 dumbbell and 70 at 0 ° C, mold temperature 120 ° C
A square plate of × 70 × 2 mm thickness was formed. Flexural strength is 1/8 "thickness x 1
Using a test piece of 2 "width x 5" length, the measurement was performed using a Tensilon UTM-200 manufactured by Toyo Baldwin Co., Ltd. under the conditions of a strain rate of 1 mm / min and a distance between spans of 50 mm. And ASTM D638
The tensile strength of ASTM No. 1 dumbbell was measured in accordance with the above.

The square plate was cut out to a width of 14 mm in the flow direction and the right angle direction, using a Toyo Baldwin Tensilon UTM-200, measuring the flexural modulus under the conditions of a strain rate of 1 mm / min and a span distance of 40 mm to evaluate the anisotropy. I went. The resulting bending strength is 2150
kg / cm ^2, the tensile strength was found to be 1770kg / cm ^2. And the bending elastic modulus in the direction perpendicular to the flow direction of the square plate was measured to be 13.8 × 10 ⁴ kg / cm ² and 7.3 × 10 ⁴ kg / cm ² , respectively, and the ratio was 1.9, which is relatively small. I can tell you. Also,
The surface gloss of the molded product was also good.

Comparative Example 1 69 parts by weight of the liquid crystal polymer (a) [(A)] of Reference Example 1 and a logarithmic viscosity of 0.65 (0.5 g / dl in orthochlorophenol at 25 ° C.)
31 parts by weight of polyethylene terephthalate (B) and 38 parts by weight of glass fiber (C) (3 mm length, 10 μm chopped strand) (A) / (B) = 69/31, (C) /
(A) + (B) = 290 ° C after dry blending of 38/100
Melt-mixed with a 40 mmφ single screw extruder, and the resulting chips are Sumitomo Nestal injection molding machine Promat 40/25
(Sumitomo Heavy Industries, Ltd.) cylinder temperature 290
1/8 "thick x 1/2" wide x 5 "long test piece, 1/8" thick ASTM No.1 dumbbell and 70 ° C, mold temperature 120 ° C
A square plate of × 70 × 2 mm thickness was formed. Flexural strength is 1/8 "thickness x 1
The measurement was performed using a test piece 2 "wide x 5" long with a Tensilon UTM-200 manufactured by Toyo Baldwin Co., Ltd. under the conditions of a strain rate of 1 mm / min and a distance between spas of 50 mm. Then, the tensile strength of ASTM No. 1 dumbbell was measured according to ASTM D638.

The square plate was cut out to a width of 14 mm in the flow direction and the right angle direction, using a Toyo Baldwin Tensilon UTM-200, measuring the flexural modulus under the conditions of a strain rate of 1 mm / min and a span distance of 40 mm to evaluate the anisotropy. I went.

As a result, the bending strength is 1,640 kg / cm ² and the tensile strength is 1,230 kg
/ cm ^2, which is lower than Example 1 of the present invention. When the flexural modulus in the flow direction and the direction perpendicular to the rectangular plate was measured, they were 13.4. × 10 ⁴ kg / cm ² and 3.8 × 10 ⁴ , respectively.
kg / cm ² , and the ratio was 3.5, indicating that the anisotropy was larger than in the examples of the present invention.

Further, when the surface gloss of the molded article was observed, it was rough and defective.

Examples 2 to 9 Liquid crystal polymers (a) to (c) of Reference Examples 1 to 3 [(A)]
Then, the thermoplastic polymer and glass fiber (3 mm length, 10 μm chopped strand) (C) previously reinforced with glass fiber (C ′) shown in Table 1 were dry-blended at the ratio shown in Table 1 and then 290 to 360. The chips obtained by melting and mixing with a 40 mmφ single screw extruder set to ° C. were subjected to Sumitomo Nestal injection molding machine Promat 40/25, and the cylinder temperature was 290 to 360.
A test piece similar to that of Example 1 was molded at a temperature of 80 ° C. and a mold temperature of 80 to 160 ° C.

Table 1 shows the results of measuring the bending strength and the tensile strength of the obtained test piece under the same conditions as in Example 1. Table 1 also shows the results of observation of the surface gloss of the molded product.

Comparative Examples 2 to 9 Liquid Crystal Polymers of Reference Examples 1 to 3 (a) to (c) [(A)]
And the thermoplastic resin (B) and glass fiber (C) (3 mm long, 10 μm chopped strand) shown in Table 1
After dry blending at the ratios shown in the table, the chips obtained by melt mixing with a 40 mmφ single screw extruder set at 290 to 360 ° C. were subjected to a Sumitomo Promat injection molding machine, and a cylinder temperature of 290 to 3
A test piece similar to that of Comparative Example 1 was molded at a temperature of 60 ° C. and a mold temperature of 80 to 160 ° C.

The bending strength and tensile strength of the obtained test piece were measured under the same conditions as in Comparative Example 1, and the results are shown in Table 1. Table 1 also shows the results of observation of the surface gloss of the molded product. From Table 1, it can be seen that the strength is lower than that of Examples 2 to 7 of the present invention and the surface gloss of the molded product is also poor.

Example 10 72.5 parts by weight of the liquid crystal polyester (a) of Reference Example 1 and 27.5 parts by weight of glass fiber (3 mm long, 10 μm chopped strand) were dry-blended and then melt-mixed with a 40 mmφ single screw extruder set at 300 ° C. A reinforced liquid crystal polymer (a ') was obtained.

Next, 72.5 parts by weight of polyethylene terephthalate (product of Toray) with logarithmic viscosity of 0.65 and 27.5 parts by weight of glass fiber (3 m
m length, 10 μm chopped strand) was dry-blended and then melt-mixed with a 40 mmφ single screw extruder set at 290 ° C. to obtain glass fiber reinforced polyethylene terephthalate (b).

After dry blending 69 parts by weight of this glass fiber reinforced liquid crystal polymer (a ') and 31 parts by weight of glass fiber reinforced polyethylene terephthalate (b), the mixture is supplied to a Sumitomo Nestal injection molding machine Promat 40/25, and the cylinder temperature is 290 ° C. temperature
Under the conditions of 120 ° C., the same test pieces and square plates as in Example 1 were formed.

The bending strength and the tensile strength of the obtained test piece were measured under the same conditions as in Example 1. As a result, the bending strength was 1,930 kg /.
cm ² , and the tensile strength was 1,580 kg / cm ² .

The flexural modulus in the direction perpendicular to the flow direction of the square plate is 13.4 × 10 ⁴ k
g / cm ² , 6.5 × 10 ⁴ kg / cm ² and the ratio was 2.1. The surface gloss of the molded product was also good.

It can be seen that the mechanical properties are excellent and the surface gloss is also excellent as compared with Comparative Example 1.

〔The invention's effect〕

In the present invention, a thermoplastic resin having excellent mechanical properties and surface gloss can be obtained by adding a thermoplastic resin reinforced in advance to a specific liquid crystal polyester having a limited structural formula.

Claims (3)

(57) [Claims] (1) The following structural units (I), (II) and (II)
50 to 99% by weight of a liquid crystal polymer (A) selected from a liquid crystal polyester and a liquid crystal polyesteramide having a structural unit selected from I) and 50 to 1% of a thermoplastic polymer (B)
In the production of a thermoplastic resin composition in which the filler (C) is contained in an amount of 1 to 200 parts by weight based on 100 parts by weight of the resin composition consisting of 100% by weight, the thermoplastic polymer (B) and the filler (C) are used. A method for producing a thermoplastic resin composition, which comprises melt-kneading in advance using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, and then melt-mixing the liquid crystal polymer (A). (X in the formula represents a divalent aromatic residue, Y and Z each represent a divalent aromatic, aliphatic, or alicyclic residue, and R represents O or NH. In addition, the above structural unit ( (II) and (III) are substantially equimolar.) 2. The liquid crystal polymer (A) has the following structural unit (I ')
The method for producing a thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a liquid crystal polyester having a heat deformation temperature of 150 to 280 ° C. (However, X in the formula is And the carbonyl groups of the structural unit (IV ′) are in a para or meta position with respect to each other, and 50 mol% or more of the carbonyl groups are in the para position. The sum of the structural units (II ') and (III') and (IV ') are substantially equimolar. ) 3. The method according to claim 1, wherein the thermoplastic polymer (B) is at least one selected from the group consisting of polyamide, polycarbonate, polyarylene oxide, polyalkylene terephthalate, polyarylene sulfide, and polyetheretherketone. ) Or the method for producing the thermoplastic resin composition according to (2).