JPH08325441A - Liquid-crystal polyester resin mixture and method for molding the same - Google Patents

Abstract

PURPOSE: To obtain a liquid-crystal polyester resin mixture which itself is stably plasticated during molding, can be stably molded, and gives a molded object excellent in mechanical properties and thermal stability. CONSTITUTION: This resin mixture is obtained by incorporating 0.001-5 pts.wt. phosphorus compound into 100 pts.wt. liquid-crystal polyester resin composition consisting mainly of 100 pts.wt. liquid-crystal polyester and 0-150 pts.wt. filler, at a temp. below a fluidization temp. of the composition. The fluidization temp. is the temp. at which the resin heated at a rate of 4 deg.C/min comes to have a melt viscosity of 48,000P when extruded under a load of 100kgf/cm<2> from a nozzle having an inner diameter of 1mm and a length of 10mm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal polyester which is capable of stable plasticization of a liquid crystal polyester during molding and can be stably molded, and which provides a molded product excellent in mechanical properties and thermal stability. The present invention relates to a resin mixture and a method for molding a liquid crystal polyester using the liquid crystal polyester resin mixture.

[0002]

2. Description of the Related Art Since liquid crystal polyesters are rigid, molecules do not become entangled even in a molten state to form a polydomain having a liquid crystal state, and a molecular chain exhibits a behavior of remarkably aligning in a flow direction at a low shear rate. It is called liquid crystal type (thermotropic liquid crystal) polymer. Liquid crystal polyester has extremely excellent melt fluidity due to this peculiar behavior, and has a heat distortion resistance of 300 ° C or more depending on the structure, and is a molded product for applications such as electronic parts, OA, AV parts, and heat-resistant tableware. Is used for.

As a molding method for obtaining these molded bodies,
It is common to use an extruder using a screw such as injection molding or extrusion molding. At this time, the liquid crystal polyester often had a problem of instability in its plasticizing process. That is, the plasticization time is not constant and becomes unstable, and in the injection molding, there are cases where the plasticization does not end within the cooling time, molding cannot be performed in a constant cycle, and productivity decreases and at the same time The quality could be adversely affected.

The reason why the plasticizing time of the liquid crystal polyester becomes unstable is not clear, but one of the causes is that the melt viscosity of the liquid crystal polyester itself has a large dependence on the shear rate and the temperature. It can be mentioned that only the surface is selectively plasticized and the fusion tends to occur.

As means for suppressing such a phenomenon, Japanese Patent Laid-Open No. 125259/1993 discloses the use of a composition prepared by mixing a higher fatty acid metal salt and a higher fatty acid with a thermotropic liquid crystal polymer. ing.
Further, JP-A-5-125258 discloses that stable plasticization can be achieved by using a particle mixture of thermotropic liquid crystal polymer particles and a higher fatty acid metal salt.

However, in any case, since a higher fatty acid or a metal salt thereof which decomposes at a high temperature is used together with a liquid crystal polymer having high heat resistance, when a molded product of the liquid crystal polymer is obtained, a gas in a molding machine is used. Since it is difficult to carry out stable molding work due to the large number of occurrences, and there is concern that the thermal stability of the obtained molded product may decrease, it is not always sufficient for the purpose of higher practicality. is not.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and the resin mixture itself is stably plasticized during molding so that stable molding can be performed, and the mechanical properties and It is an object of the present invention to provide a liquid crystal polyester resin mixture which gives a molded article having excellent thermal stability, and a method for molding a liquid crystal polyester using the liquid crystal polyester resin mixture.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a liquid crystal polyester or a liquid crystal polyester resin composition containing a liquid crystal polyester and a filler as main components is added to a phosphorus compound. Alternatively, by mixing a specific amount of a mixture of a phosphorus compound and a higher fatty acid or a higher fatty acid metal salt, a liquid crystal polyester resin mixture that achieves the above object is obtained, and by using the mixture, the liquid crystal polyester is stably plasticized during molding. The present invention has been found to be realized, and the present invention has been achieved.

That is, the present invention is the invention described below. (1) 100 parts by weight of liquid crystal polyester and filler 0 to 15
Liquid crystal polyester resin composition 1 whose main component is 0 part by weight
A liquid crystal polyester resin mixture, wherein 0.001 to 5 parts by weight of a phosphorus compound is mixed with 00 parts by weight at a flow temperature of the liquid crystal polyester resin composition defined below. Flowing temperature: Resin heated at a heating rate of 4 ° C./min under a load of 100 kgf / cm ² ,
When extruding from a nozzle with an inner diameter of 1 mm and a length of 10 mm,
This is the temperature at which the melt viscosity shows 48,000 poise. (2) The components of the liquid crystal polyester resin mixture are
In addition to those described in (1), it contains 0.001 to 5 parts by weight of higher fatty acid, and the total amount of phosphorus compound and higher fatty acid is 0.00.
A liquid crystal polyester resin mixture, characterized in that it is 2 to 5 parts by weight. (3) The components of the liquid crystal polyester resin mixture are
(2) In addition to those described above, it contains 0.001 to 5 parts by weight of at least one compound selected from oxides, peroxides, double oxides and carbonates of metals belonging to the 1A or 2A group. , Phosphorus compounds, higher fatty acids and 1A or 2
Liquid crystal polyester resin, wherein the total amount of at least one compound selected from oxides, peroxides, complex oxides and carbonates of metals belonging to Group A is 0.003 to 5 parts by weight. blend. (4) The components of the liquid crystal polyester resin mixture are
(1) In addition to those described above, higher fatty acid metal salt 0.001
The liquid crystal polyester resin mixture is characterized in that the total amount of the phosphorus compound and the higher fatty acid metal salt is 0.002 to 5 parts by weight. (5) The liquid crystal polyester resin mixture according to (1), (2), (3) or (4), wherein the liquid crystal polyester contains at least 30 mol% of the repeating structural unit represented by the following formula (A ₁ ). .

[0010]

Embedded image (6) A method for molding a liquid crystal polyester, which comprises using the liquid crystal polyester resin mixture according to (1), (2), (3), (4) or (5).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystal polyester used in the present invention is a polyester called a thermotropic liquid crystal polymer, which is composed of (1) a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. , (2) different aromatic hydroxycarboxylic acids, (3) combinations of aromatic dicarboxylic acids and aromatic diols, (4) polyesters such as polyethylene terephthalate reacted with aromatic hydroxycarboxylic acids And the like, 400 ℃
It forms an anisotropic melt at the following temperatures. 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 hydroxycarboxylic acid:

[0013]

Embedded image Repeating structural unit derived from aromatic dicarboxylic acid:

[0014]

[Chemical 4] Repeating structural unit derived from aromatic diol:

[0015]

Embedded image

[0016]

[Chemical 6]

A particularly preferred liquid crystal polyester in view of the balance among heat resistance, mechanical properties and processability is _one containing at least 30 mol% of the repeating structural unit represented by the formula A ₁ .

Specifically, the following combinations of repeating structural units are preferred (a) to (f). (A): (A ₁ ), (B ₁ ) or (B ₁ ) and (B ₂ )
A mixture of (C ₁ ). (B): (A ₁ ) and (A ₂ ). (C) in those combinations of the structural units of :( a), obtained by replacing a part of A ₁ in A _2. (D): A combination of the structural units shown in (a) in which a part of B ₁ is replaced with B ₃ . (E): A combination of the structural units shown in (a) in which a part of C ₁ is replaced with C ₃ . (F): A combination of the structural units of (b) with the structural units of B ₁ and C ₁ added. The liquid crystal polyesters (a) and (b) having the basic structure are, for example, Japanese Patent Publication No. 47-47870.
Japanese Patent Publication No. 63-3888.

In the present invention, a filler is added to the liquid crystal polyester as needed. When adding filler,
Filler 150 per 100 parts by weight of liquid crystal polyester
Below 100 parts by weight, preferably 20 to 100 parts by weight of the filler is added to 100 parts by weight of the liquid crystal polyester. When the compounding ratio of the filler is more than 150 parts by weight, the melt viscosity of the composition becomes high, the granulation property and the moldability are deteriorated, and even if the phosphorus compound is added to the liquid crystal polyester resin composition in a solid state. However, the effect of stabilizing the plasticization during molding is reduced. The liquid crystal polyester resin composition used in the present invention is. It is generally in the form of particles such as pellets or chips. A preferred shape of the liquid crystal polyester resin composition is a cylinder or a sphere having an average particle diameter of 1 mm or more and 10 mm or less. If the average particle size is smaller than 1 mm, gas is likely to be entrained when the resin is plasticized by the screw during molding, and the surface condition of the obtained product is deteriorated, which is not preferable. Further, if the average particle diameter is larger than 10 mm, it becomes difficult to plasticize during the molding process and the rotating torque of the screw is improved, which is not preferable.
Means for obtaining particles or chips of the liquid crystal polyester resin composition is not particularly limited, but liquid crystal polyester and fillers, if necessary release modifiers, heat stabilizers, colorants and the like in a Henschel mixer, tumbler, etc. After mixing using, melt kneading is performed using an extruder, the molten resin extruded from the die hole is cut into particles with a rotary blade, or the resin strand extruded from the die hole is cooled and solidified. A method of later cutting into particles with a rotary blade is common. It is also possible to directly connect an extruder downstream of the polymerized liquid crystal polyester reactor to obtain liquid crystal polyester particles or chips.

The filler used in the present invention is a fibrous or needle-shaped reinforcing material such as glass fiber, silica-alumina fiber, wollastonite, carbon fiber, potassium titanate whiskers, aluminum borate whiskers and titanium oxide whiskers. Calcium carbonate, dolomite, talc,
Examples thereof include inorganic fillers such as mica, clay, and glass beads, and one or more of them can be used.

The phosphorus compound used in the present invention is not particularly limited, but a trivalent or pentavalent phosphorus compound is preferable. Examples of the trivalent phosphorus compound include distearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and tris (2,4-diphenyl). -T-butylphenyl) phosphite, 2,2-methylenebis (4,4
6-di-t-butylphenyl) octyl phosphite,
Tetrakis (2,4-ditert-butylphenol)
4,4'-biphenylene diphosphonate and the like can be mentioned. The higher fatty acid used in the present invention has 10 carbon atoms.
The above fatty acids are shown. Examples of higher fatty acids include capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, montanic acid and the like. Of these, stearic acid is particularly preferable.

The oxides and peroxides of metals belonging to Group 1A or 2A used in the present invention are represented by the general formulas M ₂ O and M ′.
O or M′O ₂ (in these formulas, M is a metal element belonging to 1A group and M ′ is a 2A group). Particularly, M is preferably selected from Na and K,
M'is preferably selected from Mg, Ca and Ba. Examples of this are calcium oxide (99.9%), magnesium oxide (heavy, special grade), barium oxide (for chemistry), barium peroxide (Wako grade 1), Kyowa available from Wako Pure Chemical Industries, Ltd. Examples include Micromag 3-30 available from Chemical Industry Co., Ltd., but are not limited thereto.

The complex oxide containing a metal belonging to the 1A or 2A group used in the present invention is represented by the general formula M ₂ O.m.
M "O ₂ · xH ₂ O, M'O · mM” O ₂ · xH ₂
O, M ₂ O ・ pM '" ₂ O ₃・ mM" O ₂ xH ₂
O or M ₂ O ・ pM'OmM ''' ₂ O ₃・ nM''
O ₂ · xH ₂ O (In these formulas, M is a metal element belonging to the 1A group, M ′ is a metal element belonging to the 2A group, M ″ is a tetravalent metal element, and M ″ ′ is a trivalent metal. Elements, p, m, and n are positive numbers of 1 or more, and x is a positive number of 0 or more). Particularly, M is preferably K, M ′ is Mg,
It is preferably selected from Ca and Ba. Examples of this include wollastonite, attapulgite,
Examples thereof include, but are not limited to, sericite, mica, potassium titanate, barium titanate, and the like.

The carbon salt containing a metal belonging to Group 1A or 2A used in the present invention is represented by the general formula M ₂ CO ₃ , M'C.
O ₃ or M ′ · M ″ (CO ₃ ) ₂ (where M is 1 A
Group M'and M '' are represented by metal elements belonging to Group 2A). In particular, M is preferably K,
M ′ and M ″ are preferably selected from Mg, Ca and Ba. Examples of this include, but are not limited to, potassium carbonate, calcium carbonate, dolomite, and the like.

The higher fatty acid metal salt used in the present invention is a metal salt of a fatty acid having 10 or more carbon atoms. Examples of higher fatty acid metal salts include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Examples thereof include metal salts such as behenic acid, lignoceric acid and montanic acid. Further, as the metal in these higher fatty acid metal salts, metals of the 1A group, 1B group, 2A group and 2B group are generally used. Preferred metals include lithium, sodium, potassium, magnesium, calcium, barium and the like. As a particularly preferred higher fatty acid metal salt,
Examples thereof include calcium stearate and barium stearate. Phosphorus compounds used in the present invention, higher fatty acids,
The higher fatty acid metal salt is preferably in powder or particle form in order to facilitate mixing with the liquid crystal polyester resin composition.

Further, phosphorus compounds, higher fatty acids, oxides, peroxides and complex oxides of metals belonging to Group 1A or 2A,
The particle size of at least one compound selected from carbonates and higher fatty acid metal salts is 10
It is preferably less than 0 μm, more preferably less than 50 μm. When the particle size is 100 μm or more, the effect of stabilizing plasticization during molding is insufficient, which is not preferable.

In the liquid crystal polyester resin mixture of the present invention, the compounding ratio of the phosphorus compound is 100.
1 part by weight or total of liquid crystal polyester and filler
It is 0.001 to 5 parts by weight with respect to 00 parts by weight, and a particularly preferable mixing ratio is 0.003 to 1 part by weight. When the compounding ratio of the phosphorus compound is more than 5 parts by weight, gas resulting from the decomposition of the phosphorus compound is generated during the molding process, the molded product tends to swell, and the gas generated from the molded product increases. Not preferable. Also, when the compounding ratio of the phosphorus compound is less than 0.001 part by weight, the effect of stabilizing the plasticization at the intended molding process is insufficient, which is not preferable.

In the liquid crystal polyester resin mixture of the present invention, the total compounding ratio of the phosphorus compound and the higher fatty acid or the phosphorus compound and the higher fatty acid metal salt is 100 parts by weight of the liquid crystal polyester, or 100 parts by weight of the liquid crystal polyester and the filler. The amount is 0.002 to 5 parts by weight, and the particularly preferred mixing ratio is 0.003 to 1 part by weight. When the total compounding ratio of the phosphorus compound and the higher fatty acid, or the total compound of the phosphorus compound and the higher fatty acid metal salt is more than 5 parts by weight, gas due to the decomposition of the phosphorus compound, the higher fatty acid and the like is generated during the molding process, It is not preferable because the molded product is likely to swell and a large amount of gas is generated from the molded product. Further, when the total compounding ratio of the phosphorus compound and the higher fatty acid, or the total compound of the phosphorus compound and the higher fatty acid metal salt is less than 0.002 part by weight, the desired plasticizing stabilization effect during molding is insufficient. Is not preferable.

In the liquid crystal polyester resin mixture of the present invention, a phosphorus compound, a higher fatty acid and 1A or 2A
The total compounding ratio of at least one compound selected from oxides, peroxides, double oxides, and carbonates of metals belonging to the group is 100 parts by weight of liquid crystal polyester, or 100 parts by weight of liquid crystal polyester and filler. To the department
The content is 0.003 to 5 parts by weight, and a particularly preferable blending ratio is 0.005 to 1 part by weight. When the total compounding ratio of at least one compound selected from phosphorus compounds, higher fatty acids, and oxides, peroxides, complex oxides, and carbonates of metals belonging to the 1A or 2A group is more than 5 parts by weight. Is not preferable because a gas caused by decomposition of a phosphorus compound, a higher fatty acid, or the like is generated during the molding process, the molded product is likely to swell, and the generated gas from the molded product is increased. Further, even when the total compounding ratio of the phosphorus compound and the higher fatty acid or the total compound of the phosphorus compound and the higher fatty acid metal salt is less than 0.003 parts by weight, the desired plasticizing stabilization effect during the molding process is insufficient. Is not preferable.

In the liquid crystal polyester resin mixture of the present invention, at least one compound selected from the group consisting of higher fatty acids, 1A or 2A group metal oxides, peroxides, double oxides and carbonates, and higher fatty acid metals. It is also possible to mix a salt, a phosphorus compound or the like having an external lubricant effect together with the fluorocarbon surfactant into the liquid crystal polyester resin composition.

With respect to the liquid crystal polyester resin composition used in the present invention or the liquid crystal polyester resin mixture of the present invention, coloring agents such as dyes and pigments; antioxidants; One or more ordinary additives such as agents, ultraviolet absorbers, antistatic agents, and surfactants can be added. Further, a small amount of thermoplastic resin, for example, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and its modified products, polysulfone, polyether sulfone, polyetherimide and the like, a small amount of thermosetting resin, For example, one kind or two or more kinds of phenol resin, epoxy resin, polyimide resin, etc. can be added.

The liquid crystal polyester resin mixture of the present invention is
Liquid crystal polyester or liquid crystal polyester resin composition containing liquid crystal polyester and filler as main components, phosphorus compound or phosphorus compound and higher fatty acid and 1A or 2A
As long as a mixture of at least one compound selected from oxides, peroxides, double oxides, and carbonates of metals belonging to the group or a higher fatty acid metal salt is mixed below the flow temperature of the liquid crystalline polyester, The compounding means is not particularly limited. For example, particles of a liquid crystal polyester resin composition and a phosphorus compound or a phosphorus compound and at least one compound selected from oxides, peroxides, complex oxides and carbonates of higher fatty acids and metals belonging to Group 1A or 2A. Alternatively, it can be obtained by mixing powder or particles of a mixture with a higher fatty acid metal salt in a solid state at room temperature or in a warm atmosphere using a Henschel mixer, a tumbler or the like.

[0033]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. The measurements and tests of various physical properties in the examples were carried out by the following methods. (1) Measuring property during injection molding: The average measuring time of 50 consecutive shots and its standard deviation were calculated. (2) Tensile physical properties: ASTM No. 4 tensile dumbbells are molded,
It was measured according to ASTM D638.

(3) Relative amount of low boiling point gas generated from molded product: JIS 1 (1/2) dumbbell (thickness 0.8 mm)
Was molded, and the obtained molded product was cut into chips having a length of 5 mm, a width of 5 mm and a thickness of 0.8 mm. 4 g of this chip is precisely weighed, washed with distilled water, put in a vacuum-dried 25 cc vial, sealed with packing made of polytetrafluoroethylene, and heated in a hot air dryer set at 120 ° C. for 20 hours. , Gas was generated from the molded product. This vial was attached to a Shimadzu Headspace Gas Chromatograph (GC-15A / HSS-3A) and kept at 120 ° C while using DB-WAX as a filler.
(Manufactured by J & WSCIENTIFIC Co., Ltd.) was injected into a 15 m long column, the column temperature was raised from 80 ° C. to 2 ° C./min simultaneously with the injection, and the total amount of gas up to a retention time of 25 minutes was detected by a detector. F as a detector
The ID type was used, and helium was used as the carrier gas.

The relative amount of this gas is indicated by the total area of various gases, and the relative amount of gas generated from the molded article was compared with this value. If you did not put the sample in the vial,
That is, the measured value in an empty bottle is 3000, and the larger this value is, the more the low boiling point gas is generated from the molded product. Also, the gas detected by the retention time of 25 minutes is
From gas chromatography / mass spectrometry, it was confirmed to be aromatic hydrocarbons, aliphatic hydrocarbons, acetic acid, phenols and the like.

Examples 1 to 4 and Comparative Examples 1 to 3 The repeating structural unit is the above-mentioned A.₁ , B₁ , B₂ , C₁ From
Becomes A₁ : B₁ : B ₂ : C₁ The molar ratio of 60:15:
5:20 and the flow temperature defined above is 323 ° C.
Liquid crystal polyester and milled glass fiber (cell
EFH75-01 manufactured by General Glass Co., Ltd. is shown in Table 1.
After mixing with a Henschel mixer with the composition, twin-screw extruder (Ikegai
Cylinder temperature using PCM-30 type manufactured by Iron Works Co., Ltd.
Granulation at 340 ° C to obtain liquid crystal polyester resin composition
Was. Each of the obtained liquid crystal polyester resin compositions was
It has a cylindrical shape with an average particle size of 2 mm and a length of 2.5 mm.
Was. The obtained liquid crystal polyester resin composition and phosphorus compound
(Distearyl pentaerythritol diphosphite
G) and) in the ratio shown in Table 1 at room temperature using a tumbler.
To obtain a liquid crystal polyester resin mixture.

These liquid crystal polyester resin mixtures were dried at the temperatures shown in Table 2 for 3 hours and then, using an injection molding machine (PS40E5ASE manufactured by Nissei Jushi Kogyo Co., Ltd.), the cylinder temperature was 350 ° C. and the mold temperature was 130 ° C. (1/2)
No. dumbbell was molded, the weighing time of 50 consecutive shots was measured, and its stability was evaluated. The tensile properties and the amount of generated gas were measured from the obtained dumbbell pieces. Similarly, the liquid crystal polyester resin composition containing no phosphorus compound (Comparative Example 1) was measured for stability in measuring time, tensile properties, and amount of generated gas. Table 2 shows the results.

The ones in which the phosphorus compound was mixed with the liquid crystal polyester resin composition (Examples 1 to 4) showed less fluctuation in the measuring time between shots, as compared with the composition containing no phosphorus compound (Comparative Example 1). It can be seen that the time itself is shortened, the resin is stably plasticized, has excellent mechanical properties, and the gas generated from the molded product is at a low level. Further, the phosphorus compound to the liquid crystal polyester resin composition,
The mixture of 0.0005 parts by weight (Comparative Example 2) had an insufficient effect of stable plasticization during molding. On the other hand, the phosphorus compound was added to the liquid crystal polyester resin composition at 1
In the case of mixing 0 parts by weight (Comparative Example 3), discoloration was observed in the molded product, and the tensile properties were significantly lowered, and the amount of gas generated from the molded product was remarkably large.

Comparative Example 4 An experiment was conducted in the same manner as in Example 1 except that the phosphorus compound was mixed with the liquid crystal polyester in advance together with the milled glass fiber and granulated with a twin-screw extruder. The results are shown in Tables 1 and 2. In the case where the phosphorus compound was previously kneaded in the liquid crystalline polyester resin in a molten state (Comparative Example 4), both the absolute value of the measuring time and the variation between shots were large and the plasticization during molding was unstable.

Examples 5 to 9 Experiments were carried out in the same manner as in Example 1 except that a mixture of a phosphorus compound and a higher fatty acid or a mixture of a phosphorus compound and a higher fatty acid metal salt was used instead of the phosphorus compound alone. Table 2 shows the results. Even when a mixture of a phosphorus compound and a higher fatty acid, or a mixture of a phosphorus compound and a higher fatty acid metal salt is mixed with a liquid crystal polyester resin composition, there is little variation between shots in the measuring time, as in the case where the phosphorus compound is mixed, It can be seen that the measuring time itself is shortened, the resin is stably plasticized, has excellent mechanical properties, and the gas generated from the molded product is at a low level.

Comparative Examples 5 and 6 Examples were carried out except that a mixture of a phosphorus compound and a higher fatty acid or a mixture of a phosphorus compound and a higher fatty acid metal salt was preliminarily mixed with liquid crystal polyester together with milled glass fiber and granulated in a twin-screw extruder. An experiment was conducted in the same manner as in Example 1. The results are shown in Tables 1 and 2. A mixture of a phosphorus compound and a higher fatty acid, or a mixture of a phosphorus compound and a higher fatty acid metal salt, which has been previously kneaded in a liquid crystal polyester resin in a molten state has a large absolute value of the measuring time and a large variation between shots. It was unstable.

Examples 10 to 13 As phosphorus compounds, various phosphorus compounds N shown in Table 2 were used instead of distearyl pentaerythritol diphosphite.
An experiment was performed in the same manner as in Example 1 except that o.2 to 5 were used. The results are shown in Tables 1 and 2. Various phosphorus compounds N
Similar to the case where the distearyl pentaerythritol diphosphite phosphorus compound is mixed, the case where o.2 to 5 is mixed with the liquid crystal polyester resin composition has a small fluctuation in the measuring time, and the measuring time itself is shortened. Has stable mechanical properties and excellent mechanical properties,
It can be seen that the gas generated from the molded product is also at a low level.

Examples 14 to 16 Examples 14 to 16 except that a phosphorus compound, a higher fatty acid, and a mixture of calcium oxide having a trade name of VESTAP (manufactured by Inoue Lime Industry Co., Ltd .: average particle size 9.6 μm) are used in place of the phosphorus compound alone. An experiment was conducted in the same manner as in 1. The results are shown in Tables 1 and 2. A liquid crystal polyester resin composition prepared by mixing a mixture of a phosphorus compound, a higher fatty acid and calcium oxide is similar to the liquid mixture of a phosphorus compound alone, and the measurement time thereof does not fluctuate between shots, and the measurement time becomes short and stable. It can be seen that it is plasticized and has excellent mechanical properties, and the gas generated from the molded product is at a low level. Furthermore, the liquid crystal polyester resin mixtures of Examples 14 to 16 were pre-dried at 150 ° C. before molding.
The effect of stabilizing the measuring time was hardly reduced even when the procedure was carried out.

Comparative Examples 7 and 8 A phosphorus compound, higher fatty acid and calcium oxide were added to the liquid crystal polyester resin composition in an amount of 0.0005 respectively.
In the case of mixing by weight (Comparative Example 7), the effect of stable plasticization during molding was insufficient. On the other hand, in the case where the phosphorus compound, the higher fatty acid and the calcium oxide were mixed with the liquid crystal polyester in an amount of 10 parts by weight each (Comparative Example 8), discoloration was observed in the molded product and the tensile physical properties were significantly reduced. The amount of gas generated from was extremely large. (Table 1, Table 2)

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

EFFECT OF THE INVENTION The liquid crystal polyester resin mixture of the present invention is a molded product in which the liquid crystal polyester is stably plasticized at the time of molding, stable molding can be performed, and mechanical properties and thermal stability are excellent. give. The liquid crystal polyester molding method using the liquid crystal polyester resin mixture is useful in molding such as injection molding and extrusion molding performed using an extruder using a screw.

Claims (6)

[Claims] 1. A liquid crystal polyester resin composition comprising 100 parts by weight of a liquid crystal polyester resin composition mainly composed of 100 parts by weight of liquid crystal polyester and 0 to 150 parts by weight of a filler and 0.001 to 5 parts by weight of a phosphorus compound. A liquid crystal polyester resin mixture, which is obtained by mixing at a flow temperature lower than that defined below. Flowing temperature: A temperature at which a melt viscosity is 48,000 poise when a resin heated at a temperature rising rate of 4 ° C./min is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kgf / cm ² . 2. The liquid crystal polyester resin mixture comprises, in addition to those of claim 1, a higher fatty acid of 0.00
A liquid crystal polyester resin mixture comprising 1 to 5 parts by weight, wherein the total amount of the phosphorus compound and the higher fatty acid is 0.002 to 5 parts by weight. 3. The liquid crystal polyester resin mixture, in addition to the constituents according to claim 2, at least selected from oxides, peroxides, complex oxides and carbonates of metals belonging to Group 1A or 2A. One or more compounds 0.001-5
The total amount of at least one compound selected from the group consisting of phosphorus compounds, higher fatty acids, and oxides, peroxides, complex oxides and carbonates of phosphorus compounds, higher fatty acids, and metals belonging to the 1A or 2A group is 0.003 to. Liquid crystal polyester resin mixture, characterized in that it is 5 parts by weight. 4. The liquid crystal polyester resin mixture comprises, in addition to those of claim 1, a higher fatty acid metal salt of 0.1.
A liquid crystal polyester resin mixture comprising 001 to 5 parts by weight, and the total amount of the phosphorus compound and the higher fatty acid metal salt is 0.002 to 5 parts by weight. 5. The liquid crystal polyester resin mixture according to claim 1, wherein the liquid crystal polyester contains at least 30 mol% of repeating structural units represented by the following formula (A ₁ ). Embedded image 6. A method for molding a liquid crystal polyester, which comprises using the liquid crystal polyester resin mixture according to claim 1, 2, 3, 4 or 5.