JPH073137A - Liquid crystal polyester resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition excellent in moldability, heat resistance, mechanical properties, appearance and gloss. CONSTITUTION:The composition comprises a modified polyphenylene ether (A) corresponding to a polyphenylene ether comprising repeating units of the formula (wherein R1 and R2 are each independently hydrogen or a 1-20C hydrocarbon group), has a number-average degree of polymerization X of 20-1200 and further contains 0.02/X to 1/X repeating units of the formula in which the methyl groups at the positions 2 and/or 6 of the phenylene group are aminomethyl groups, a liquid crystal polyester (B) and a glass fiber (C) having a number-average fiber diameter of 5-25mum, a number-average fiber length of 30-1000mum and a number-average fiber length to number-average fiber diameter ratio of 2-150 and containing nonsurface-treated glass fibers. Component A is used in an amount of 1-65wt.% based on the total weight of components A and B, component B is used in an amount of 99-35wt.% based on the total weight of components A and B, and component C is used in an amount of 1-200 pts.wt. per 100 pts.wt. total weight of components A and B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystal polyester resin composition which can be used for molded articles by injection molding or extrusion molding.

[0002]

2. Description of the Related Art Unlike crystalline polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyesters do not cause entanglement even in a molten state because they have rigid molecules and form a polydomain having a crystalline state, which results in low shear. It exhibits a behavior in which molecular chains are significantly oriented in the flow direction, and is generally called a melt-type liquid crystal (thermotropic liquid crystal) polymer. Due to this peculiar behavior, the melt fluidity is extremely excellent, and a thin-walled molded product of about 0.2 to 0.5 mm can be easily obtained, and this molded product has the advantage of exhibiting high strength and high rigidity. However, there is a problem that the anisotropy is extremely large and therefore the weld strength is low. Further, depending on the application, higher heat resistance, higher strength and higher rigidity are required.

Another problem is that liquid crystal polyesters are generally expensive. Maintains the excellent heat resistance and mechanical properties of liquid crystal polyester, and improves the anisotropy of molded products.
Further, an inexpensive liquid crystal polyester resin composition has been strongly demanded from the market. As an attempt to improve the moldability and strength of the liquid crystal polyester by blending the liquid crystal polyester with an amorphous polymer, Japanese Patent Laid-Open No.
There is a description in JP-A-115357 in which a polymer such as polyphenylene ether is blended with a liquid crystal polyester to improve the melt processability of the liquid crystal polyester. In addition, JP-A-2-
In Japanese Patent No. 97555, there is a description in which various polyarylene oxides are mixed with liquid crystal polyester for the purpose of improving solder heat resistance.

[0004]

However, a composition obtained by blending a liquid crystal polyester having a high molding temperature with an amorphous polymer such as polyphenylene ether having a lower molding temperature generally has a melt processability of the composition. However, there is a problem that the appearance of the molded product is deteriorated due to the thermal decomposition of the compounded resin during the molding process. Further, there is a problem that the mechanical properties and heat resistance of the composition are insufficient.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies to solve these problems. That is, the present invention provides (A) the following repeating structural unit (1) (Wherein R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms),
Polyphenylene ether having a number average degree of polymerization X of 20 to 1200, and a modified polyphenylene having a repeating structural unit in which the methyl group at the 2-position and / or the 6-position of the phenylene group is an aminomethyl group. Consisting of ether, (B) liquid crystal polyester and (C) glass fiber, having a number average fiber diameter of 5 to 25 μm, a number average fiber length of 30 to 1000 μm, and a number average fiber length / number average fiber diameter of 2 to 150, The surface-untreated glass fiber is blended, and the component (A) is 1 to 65% by weight and the component (B) is 99 to 3 with respect to the total amount of the component (A) and the component (B).
The present invention relates to a liquid crystal polyester resin composition containing 5% by weight and 1 to 200 parts by weight of the component (C) per 100 parts by weight of the total amount of the components (A) and (B).

The component (A) of the liquid crystal polyester resin composition of the present invention comprises the repeating structural unit (1), and in the polyphenylene ether having a number average degree of polymerization X of 20 to 1200, the repeating structural unit (1). Of the repeating structural unit in which the methyl group at the 2-position and / or the 6-position of the phenylene group is an aminomethyl group (—CH ₂ NH ₂ ).
A modified polyphenylene ether having 2 / X to 1 / X, preferably 0.05 / X to 1 / X.

The structural unit having an aminomethyl group is 0.0
When it is less than 2 / X, the heat resistance and mechanical properties are not sufficiently improved when used as a component of the resin composition, which is not preferable. Structural unit having aminomethyl group is 0.02
/ X or more, when used as a component of the resin composition,
It is preferable because it is highly reactive with the liquid crystal polyester and the heat resistance and mechanical properties of the resin composition are improved.

The structural unit having the aminomethyl group may be a terminal structural unit of the polyphenylene ether, or may be in the middle of the main chain instead of at the terminal. Particularly, when the structural unit having the aminomethyl group is a terminal structural unit of polyphenylene ether, the secondary amine, which is the source of the aminomethyl group during the polymerization of polyphenylene ether, is often present at the end of the polyphenylene ether. It is preferable because it can be easily bound.

As the modified polyphenylene ether of the component (A), those having a number average degree of polymerization of 20 to 1200, more preferably 30 to 1000 are used. If the number average degree of polymerization is less than 20, the glass transition point is low and the heat resistance (mainly the deflection temperature under load) is lowered, and if it exceeds 1200, the melt viscosity is high and the workability is deteriorated, which is not preferable.

Next, a method for producing the modified polyphenylene ether of the component (A) will be described. The modified polyphenylene ether of the component (A) can be produced by the following general formula (2).

[0011]

[Chemical 2] (In the formula, R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.) A nucleus-substituted phenol represented by the formula is polymerized using an oxidation coupling catalyst. In the method of formula (3)

[Chemical 3] (In the formula, Q ₁ and Q ₂ are each independently selected from hydrogen, an alkyl group having 1 to 24 carbon atoms and an aralkyl group having 7 to 24 carbon atoms, provided that both Q ₁ and Q ₂ are hydrogen. And an amine represented by Q ₁ and Q _{2 each} being an alkylene group which is linked to form a ring).
A method for producing a modified polyphenylene ether, which comprises polymerizing the polyphenylene ether in an amount of 01 to 0.2 mol and melt-kneading the obtained polyphenylene ether, is preferable.

More specifically, in the method of polymerizing the nuclear-substituted phenols represented by the general formula (2) using an oxidative coupling catalyst, the polymerization is carried out in the presence of the amines represented by the general formula (3). To do. The amines are 0.001 to 1 mol with respect to 1 mol of the nuclear-substituted phenols used.
0.2 mol, preferably 0.005-0.05 mol is present. If the amount used is less than 0.001 mol with respect to 1 mol of the nuclear-substituted phenols, polyphenylene ether of excellent quality cannot be obtained, and if it is more than 0.2 mol, a polyphenylene ether having a practical molecular weight is used. Is not preferable because it cannot be obtained. In this way, a polyphenylene ether having the amines in its side chain can be obtained. The nuclear-substituted phenols represented by the general formula (2) can be used alone or in combination of two or more.

Preferred nuclear-substituted phenols are 2,
6-dimethylphenol, 2,3,6-trimethylphenol and the like can be mentioned. Particularly, 2,6-dimethylphenol is preferable.

Next, as the amines represented by the general formula (3), specifically, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-hexylamine, n-
1 such as octylamine, 2-ethylhexylamine, cyclohexylamine, laurylamine, benzylamine
And secondary amines such as diethylamine, di-n-propylamine, di-n-butylamine, di-iso-butylamine, di-n-octylamine, piperidine and 2-pipecoline. The general formula (3)
Is also equivalent to the amine represented by the general formula (3), and examples of such polyamine include ethylenediamine, piperazine, and 1,3-dipiperidylpropane. Etc.

Specifically, a catalyst system in which an amine represented by the general formula (3) is combined with a known copper compound, manganese compound or cobalt compound and a ligand selected from bases is used. preferable. For example, JP-A-53-
As described in JP-A-79999, a method of oxidatively coupling a phenolic monomer and oxygen in the presence of a catalyst composed of a manganese salt, a basic reaction medium and a secondary amine, or JP-A-63-54424. As described in
A method of oxidatively polymerizing a nuclear-substituted phenol with an oxygen-containing gas in an organic solvent in the presence of a catalyst, wherein the catalyst comprises a manganese compound containing one or more divalent manganese salts, a Group IA metal of the periodic table. Examples include a method using a catalyst system containing at least one basic compound selected from hydroxides, alkoxides or phenoxides, hydroxides of Group IIA metals, oxides, alkanolamines, and amines.

Thus, the methyl group at the 2-position and / or the 6-position of the phenylene group of the repeating structural unit represented by the general formula (1) has the following general formula (4).

[Chemical 4] (Wherein Q ₁ and Q ₂ are each independently selected from hydrogen, an alkyl group having 1 to 24 carbon atoms and an aralkyl group having 7 to 24 carbon atoms. Provided that both Q ₁ and Q ₂ are hydrogen. It is also possible to obtain a polyphenylene ether having a structural unit which is a group represented by the formula ( _{1), which} is not included, and in which Q ₁ and Q ₂ are alkylene groups and which are linked by forming a ring.

The structural unit to which the secondary or tertiary amine is bonded may be a terminal structural unit of polyphenylene ether, or may be an intermediate unit of the main chain instead of the terminal. In particular, it is preferable that the structural unit is a terminal structural unit of polyphenylene ether because it is easy to obtain.

Next, the methyl group at the 2-position and / or the 6-position of the phenylene group thus obtained is secondary or tertiary.
The modified polyphenylene ether of the component (A) of the liquid crystal polyester resin composition of the present invention can be obtained by melt-kneading the polyphenylene ether to which a primary amine is bound.

The melt kneading is carried out at a resin temperature of 200 to 300.
C., preferably 230 to 280.degree. C. If the resin temperature is lower than 200 ° C., the moldability of the raw material polyphenylene ether is poor, and if the resin temperature exceeds 300 ° C., the polyphenylene ether is decomposed, which is not preferable. For melt kneading, it is preferable to use a generally used kneading device such as a single-screw or twin-screw extruder and various kneaders.

It is also possible to blend a radical initiator at the time of melt-kneading and melt-knead. Further, the polyphenylene ether may be blended with a radical initiator in advance and melt-kneaded. Radical initiators preferably used include cumene hydroperoxide and t
-Butyl hydroperoxide, dimethyl-2,5-
Bis (hydroperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-
Butyl peroxide, 2,6-di-t-butyl-4 methylphenol and the like can be mentioned.

The fact that the component (A) constituting the resin composition obtained by the above method is a modified polyphenylene ether containing a primary amine means that a modified polyphenylene ether or polyphenylene ether is used from the composition with a solvent. It can also be confirmed by extracting, reprecipitating, and quantifying the amine species in the extracted component by a potentiometric titration method or the like.

If desired, the modified polyphenylene ether of component (A) in the thermoplastic resin composition of the present invention may be blended with unmodified polyphenylene ether, styrene-grafted polyphenylene ether, polystyrene or the like.

Component (A) of the thermoplastic resin composition of the present invention
Of the modified polyphenylene ether and its raw material polyphenylene ether η _{SP /} c (0.5 g / dl
Value measured at 25 ° C. for the chloroform solution of
The range of 0.30 to 0.65 dl / g is preferable. η _SP /
When c is less than 0.30 dl / g, the heat resistance of the composition remarkably decreases, and when η _SP / c exceeds 0.65 dl / g, the moldability of the composition deteriorates, which is not preferable.

The liquid crystal polyester as the component (B) of the liquid crystal polyester resin composition of the present invention is a polyester called a thermotropic liquid crystal polymer. Specifically, (1) a combination of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid (2) a combination of different aromatic hydroxycarboxylic acids (3) an aromatic dicarboxylic acid (4) Polyester such as polyethylene terephthalate reacted with an aromatic hydroxycarboxylic acid, and the like, which forms an anisotropic melt at a temperature of 400 ° C. or lower. It is a thing. Incidentally, instead of these aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids, ester-forming derivatives thereof may be used. Examples of the repeating structural unit of the liquid crystal polyester include the following, but are not limited thereto. Repeating structural unit derived from aromatic dicarboxylic acid:

[0025]

[Chemical 5]

[0026]

[Chemical 6] Repeating structural units derived from aromatic diols:

[0027]

[Chemical 7]

[0028]

[Chemical 8] Repeating structural unit derived from aromatic hydroxycarboxylic acid:

[0029]

[Chemical 9] From the balance of heat resistance, mechanical properties, and processability, as a preferred liquid crystal polyester

[0030]

[Chemical 10] That includes a repeating structural unit. As a particularly preferred liquid crystal polyester, a combination of repeating structural units is represented by the following (I), (II), (III),
Examples include (IV) and (V).

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

The liquid crystal polyesters (I), (II),
Regarding (III) and (IV), for example, JP-B-47-47870, JP-B-63-3888, JP-B-63-3891 and JP-B-56-18, respectively.
No. 016, etc.

The glass fiber as the component (C) of the liquid crystal polyester resin composition of the present invention has a number average fiber diameter of 5 to 25, preferably 5 to 20 μm and a number average fiber length of 30 to 100.
0, preferably 30 to 300 μm is used. If the number average fiber diameter or the number average fiber length is out of this range, the reinforcing effect of the glass fiber becomes small, and sufficient rigidity, heat resistance, workability, etc. cannot be obtained, which is not preferable.

Further, a glass fiber having a number average of the morphological ratio (hereinafter sometimes referred to as an aspect ratio) represented by the ratio of the fiber length and the fiber diameter of the glass fiber is 2 to 150, preferably 3 to 20. To use. If the number average aspect ratio is out of this range, the appearance of the molded article of the composition is poor and the molding processability is unfavorable.

The glass fiber of the component (C) in the present invention has no surface treatment. Although the reason why the surface-untreated glass fiber brings about excellent physical properties is not clear, the surface-untreated glass fiber is mainly dispersed in the liquid crystal polyester of the component (B), and therefore has an effect of enhancing the reinforcing effect of the resin composition. It is thought that there is.

In the present invention, the intended liquid crystal polyester resin composition can be obtained by setting the composition ratio of the component (A), the component (B) and the component (C) within a specific range. . The ratio of the component (A) to the component (B) in the present invention is preferably 1 to 65% by weight for the component (A) and 99 to 35% by weight for the component (B). More preferably, the component (A) is 5 to 60% by weight, and the component (B) is 95 to
It is 40% by weight. When the content of the component (A) is less than 1% by weight, the improvement of the anisotropy of the composition is insufficient and the advantage is small in terms of cost.

In the present invention, the component (C) is 1 to 200 parts by weight, preferably 2 to 100 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). When the amount of the component (C) is less than 1 part by weight, the effect of improving the mechanical strength, heat resistance and the like of the liquid crystal polyester resin composition of the present invention is small, and the cost is small. On the other hand, if the amount of the component (C) exceeds 200 parts by weight, the molding processability of the composition will be deteriorated and the appearance of the injection-molded product will be poor, which is not preferable.

In the liquid crystal polyester resin composition of the present invention, it is more preferable that the component (A) is a dispersed phase and the component (B) is a continuous phase. In this case, the composition is excellent in chemical resistance, heat resistance, mechanical properties and the like, which is preferable.

The reason why the liquid crystal polyester resin composition of the present invention exhibits excellent physical properties is not always clear, but the effect of the amino group contained in the modified polyphenylene ether exerting a chemical action on the liquid crystal polyester and the effect of the glass fiber This is probably due to the high reinforcing effect.

In the liquid crystal polyester resin composition of the present invention, an inorganic filler is optionally used. Such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, carbon black, carbon fiber,
Alumina fibers, aluminum borate whiskers, potassium titanate fibers and the like are exemplified.

In the liquid crystal polyester resin composition of the present invention,
If necessary, further antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, inorganic or organic colorants, rust inhibitors, cross-linking agents, foaming agents, fluorescent agents, surface smoothing agents. Various additives such as a surface gloss improver and a release improver such as a fluororesin can be added during the manufacturing process or in the subsequent process.

As the method for producing the liquid crystal polyester resin composition in the present invention, for example, a method of kneading each component in a molten resin component, a method of dissolving the resin component in a solvent and mixing each component in a solution, And the like, or a method of precipitating the resin composition by pouring into a solvent in which the resin component is not dissolved. Among these, the method of kneading each component in a molten state of the resin component is preferable from the industrial viewpoint. For melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.

At the time of kneading, it is preferable that the respective components are preliminarily uniformly mixed by a device such as a tumbler or a Henschel mixer, but if necessary, the mixing is omitted, and a method of separately supplying a fixed amount to the kneading device is also used. be able to. The kneaded resin composition is molded by various molding methods such as injection molding, extrusion molding, etc., but does not undergo a kneading process in advance, and is dry-blended during injection molding or extrusion molding and kneaded during the melt processing operation. Then, the resin composition of the present invention can be used to directly obtain a molded product.

In the present invention, the component (A), the component (B) and the component (C) may be kneaded together, or the components (A) and (C) may be previously kneaded and then the component (B). May be kneaded. In addition, other kneading orders are possible. Alternatively, the component (A), the component (B) and the like may be charged from the first feed port of the kneader and the component (C) and the like may be charged from the second feed port and kneaded to obtain the resin composition of the present invention. it can.

[0049]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited to these.

The methods for measuring physical properties are described below. Physical properties were measured by kneading the composition at a cylinder temperature of 325 ° C. using a PCM-30 type twin-screw extruder manufactured by Ikegai Tekko Co., Ltd., and then using a PS40E5ASE type injection molding machine manufactured by Nissei Plastic Co.
The molding was carried out at a molding temperature of 335 ° C. and a mold temperature of 120 ° C. for injection molding.

Reduced viscosity of polyphenylene ether (η _SP
/ C): A value measured at 25 ° C. for a chloroform solution of 0.5 g / dl solution.

Tensile strength, deflection temperature under load (TDUL):
ASTM No. 4 tensile dumbbell, TDUL test piece (1
27 mm length x 12.7 mm width x 6.4 mm thickness), respectively, ASTM D638, ASTM D648
The tensile strength and TDUL (load 18.6 kg) were measured according to the above.

Mold shrinkage ratio: flow direction of injection molded product (M
D) and the dimension in the direction perpendicular to the flow (TD) were measured and determined as a ratio to the original size of the mold. Further, the anisotropy ratio of the molding shrinkage is the ratio of the shrinkage in the TD direction and the shrinkage in the MD direction (TD
/ MD).

Flexural modulus: Measured according to ASTM D790 on a test piece (6.4 mm thick). Izod impact strength: A test piece (6.4 mm thick) was measured according to JIS K7110 without notching.

Weld portion strength, non-weld portion strength: Test pieces shown in FIG. 1 were molded from the composition of the present invention. This test piece had a thickness of 3 mm, an outer dimension of 64 mm and an inner dimension of 38 mm. From this, the shaded part (64 x 13 mm) including the weld line shown in Fig. 1 was cut out, and the distance between spans was 40 m.
The bending strength was measured at m and a bending speed of 2 mm / min. Also,
Non-weld part (64 x 13 mm) from the same shape test piece
Was cut out and the bending strength was measured in the same manner.

Appearance of injection-molded product: The following criteria were used for evaluation. ◯: Appearance is beautiful and no change in color tone is observed. X: A change in color tone is recognized on the surface of the molded product.

Number average molecular weight: determined by a gel permeation chromatography method (hereinafter sometimes referred to as GPC method) according to a conventional method.

Determination of amine in raw material polyphenylene ether and modified polyphenylene ether: Nitrogen content in total amine: About 1 g of sample was weighed and dissolved in 50 cc of chloroform, and 5 cc of acetic acid was added,
Potentiometric titration was performed using a potentiometer AT-310 (glass-calomel electrode, titrant 0.1 mol perchloric acid, (acetic acid solution)) manufactured by Kyoto Electronics Co., Ltd., and nitrogen in all amines was calculated according to the following formula. The content was determined. N _T = 0.0014 × A × C ₁ × 100 / S N _T : Nitrogen content (%) of all amines A: Titration amount (cc) S: Sample amount (g) C ₁ : Concentration of perchloric acid solution ( Mol / liter)

Nitrogen content in tertiary amine: Approximately 1 g of sample was weighed and dissolved in 50 cc of chloroform to obtain 5 parts of acetic anhydride.
After adding cc and leaving it to stand, after adding 5 cc of acetic acid, potentiometric titration was carried out in the same manner as in the titration of nitrogen content in all amines, and the nitrogen content in the tertiary amine was determined according to the following formula. N ₃ = 0.0014 × B × C ₂ × 100 / S N ₃ : Nitrogen content in tertiary amine (%) B: Titration amount (cc) S: Sample amount (g) C ₂ : Perchloric acid solution Concentration (mol / liter)

Nitrogen content in secondary amine: Approximately 1 g of sample
Weigh it, dissolve in 50 cc of chloroform, salicyl
Add 0.5 cc of aldehyde, leave it for a while, and then add the titration reagent.
As a 2-propanol solution of 0.1 mol / liter hydrochloric acid
Potentiometric titration as in the case of total amine titration except
Then, according to the following formula, first, (secondary amine +
Nitrogen content N of tertiary amine) ₂，₃(%) Was calculated.

N ₂ , ₃ = 0.014 × C × D × 100 / S C: Concentration of titrated hydrochloric acid (mol / liter) D: Titration amount (cc) S: Sample amount (g) Next, according to the following equation: Nitrogen content N of secondary amine in the sample
₂ (%) was calculated. N ₂ = N ₂ , _3- N ₃

Nitrogen content in primary amine: The nitrogen content N ₁ (%) of the primary amine in the sample was determined according to the following formula. N ₁ = N _T −N ₂ −N ₃

Reference Example 1 (Polyphenylene ether and modified polyphenylene ether) 3420 g of xylene was added to a jacketed autoclave having a capacity of 10 liters equipped with a stirrer, a thermometer, a condenser, and an air introduction tube reaching the bottom of the autoclave.
Methanol 1366 g, 2,6-dimethylphenol 1
222 g (10.02 mol) and sodium hydroxide 2
After charging 4 g to make a uniform solution, 33.8 g of diethanolamine and 27.7 g of di-n-butylamine were added to the solution.
(0.233 mol, 0.0233 mol based on 1 mol of 2,6-dimethylphenol) and 0.99 g of manganese chloride tetrahydrate were added to a solution of 100 g of methanol.

Then, while vigorously stirring the contents, air was blown into the contents at a flow rate of 5 l / min. The reaction temperature and pressure were maintained at 35 ° C. and 9 kg / cm ² , respectively. After 7 hours from the start of blowing air, the air supply was stopped and the reaction mixture was thrown into a mixture of 66 g of acetic acid and 4,900 g of methanol. The obtained slurry was filtered under reduced pressure to isolate wet polyphenylene ether. The isolated polyphenylene ether was washed with 7,200 g of methanol and then dried under reduced pressure at 150 ° C. overnight to obtain 1160 g of dried polyphenylene ether. The number average molecular weight of this polyphenylene ether is 6
And the number average degree of polymerization was 50. Hereinafter, the polyphenylene ether may be abbreviated as R-1. Table 1 shows the nitrogen contents of various amines of R-1. From this, it can be seen that 0.0047 (0.47%) of the number of methyl groups at the 2- and 6-positions of polyphenylene ether has one hydrogen thereof replaced with a dibutylamino group.

100 parts by weight of polyphenylene ether R-1, radical initiator Sampelox T0 (trade name, manufactured by Sanken Kako Co., Ltd.) 0.2 parts by weight, antioxidant Irganox 1330 (trade name) 0.3 Parts by weight, 2,6-di-t
-Butyl-4 methylphenol 0.2 Polymerization part was mixed with a Henschel mixer, and then twin-screw extruder PC manufactured by Ikegai Tekko KK
Kneading was performed using M-30 at a cylinder temperature of 273 ° C. and a screw rotation speed of 80 rpm. The obtained pellet was dissolved in chloroform, reprecipitated in methanol and dried. The modified polyphenylene ether had a number average molecular weight of 6,800 and a number average degree of polymerization of 56.7. Hereinafter, this modified polyphenylene ether may be abbreviated as A-1. Table 1 shows the nitrogen contents of various amines of A-1.
It can be seen that compared with the raw material polyphenylene ether, a modified polyphenylene ether in which the tertiary amine was significantly reduced and the primary amine was significantly increased was obtained.

[0066]

[Table 1] Quantitative results of nitrogen in polyphenylene ether and modified polyphenylene ether

From the above, about 70% of the dibutylamino groups bonded to methyl groups are amino groups (primary amines).
You can see that it has changed to.

Reference Example 2 [Liquid Crystal Polyester of Component (B)] p-acetoxybenzoic acid 10.8 kg (60 mol), terephthalic acid 2.49 kg (15 mol), isophthalic acid 0.83 kg (5 mol) and 4, 5.45 kg (20.2 mol) of 4'-diacetoxydiphenyl was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was raised with stirring under a nitrogen gas atmosphere to carry out polymerization at 330 ° C for 1 hour. Polymerization was performed under strong stirring while removing acetic acid by-produced during this period. Then, the system was gradually cooled, and the reaction mixture was taken out of the system at 200 ° C. The reaction mixture was crushed with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles having a size of 2.5 mm or less.
This is further 2 in a rotary kiln under nitrogen gas atmosphere.
By treating at 80 ° C. for 3 hours, the flow temperature becomes 32.
A wholly aromatic polyester having the following repeating structural units in the form of particles at 4 ° C. was obtained. Hereinafter, the liquid crystal polyester is referred to as B-
Abbreviated as 1. This polymer exhibited optical anisotropy at 340 ° C. or higher under pressure. The repeating structural unit of liquid crystal polyester B-1 is as follows.

[0069]

[Chemical 16]

Reference Example 3 [Glass Fiber of Component (C)] The glass fiber used as the component (C) is described below together with the fiber diameter and the fiber length. C-1 (abbreviation): Central Glass Co., Ltd., trade name EF
H75-01, number average fiber diameter 13 μm, number average fiber length 5
0 μm, number average aspect ratio 3.8, no surface treatment. C-2 (abbreviation): Central Glass Co., Ltd., trade name EC
S03T461, number average fiber length 3 mm, sizing treatment.

Examples 1 and 2 and Comparative Examples 1 to 4 Each component having the composition shown in Table 2 was blended and kneaded with a stabilizer, and various physical properties were measured. The obtained results are shown in Table 2. It can be seen that the liquid crystal polyester resin composition of the present invention is excellent in heat resistance, mechanical properties, various physical properties such as weld strength, melt processability, good appearance of molded articles, and is an inexpensive resin composition.

[0072]

[Table 2]

[0073]

The liquid crystal polyester resin composition of the present invention is a resin composition excellent in molding processability, heat resistance, mechanical properties, appearance and luster, and taking advantage of such characteristics, injection molding and extrusion molding. Molded products, sheets, tubes,
It is preferably used for films, fibers, laminates, coating materials and the like.

[Brief description of drawings]

FIG. 1 is a plan view of a test piece for measuring weld strength.

[Explanation of symbols]

 1. Weld line 2. Cutout part including weld line (hatched part) 3. Gate

Claims (1)

[Claims] (A) The following repeating structural unit (1): (Wherein R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms),
Polyphenylene ether having a number average degree of polymerization X of 20 to 1200, and a modified polyphenylene having a repeating structural unit in which the methyl group at the 2-position and / or the 6-position of the phenylene group is an aminomethyl group. Consisting of ether, (B) liquid crystal polyester and (C) glass fiber, having a number average fiber diameter of 5 to 25 μm, a number average fiber length of 30 to 1000 μm, and a number average fiber length / number average fiber diameter of 2 to 150, The surface-untreated glass fiber is blended, and the component (A) is 1 to 65% by weight and the component (B) is 99 to 3 with respect to the total amount of the component (A) and the component (B).
A liquid crystal polyester resin composition containing 5% by weight and 1 to 200 parts by weight of the component (C) per 100 parts by weight of the total amount of the components (A) and (B).