JP2007308619A - Liquid crystal polyester resin mixture and molded article using the same. - Google Patents

Abstract

Disclosed is a liquid crystal polyester resin mixture having an excellent stabilizing effect related to plasticization time. Furthermore, the molded object obtained by shape | molding the said liquid crystalline polyester resin mixture is provided.
[1] A liquid crystal polyester resin mixture obtained by mixing a liquid crystal polyester, a phosphorus compound having a trivalent phosphorus atom, and an amide compound represented by the following general formula (1).
[2] A liquid crystal polyester resin obtained by mixing a liquid crystal polyester resin composition containing a liquid crystal polyester and a filler with a phosphorus compound having a trivalent phosphorus atom and an amide compound represented by the following general formula (1). blend.
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.)
[3] A molded product obtained by molding the liquid crystalline polyester resin mixture of [1] or [2].
[Selection figure] None

Description

  The present invention relates to a liquid crystal polyester resin mixture and a molded article obtained by molding using the liquid crystal polyester resin mixture.

  The liquid crystal polyester is generally called a molten liquid crystal type (thermotropic liquid crystal) polymer, and has an excellent melt fluidity due to its specific behavior, and has a heat distortion resistance of 300 ° C. or higher depending on the structure. Utilizing such characteristics, it is used for molded products for applications such as electronic parts, OA, AV parts, and heat-resistant tableware.

  As a molding method for obtaining the molded body, injection molding is generally used. In injection molding, the time required for the weighing process in the injection unit (plasticization time) must be constant and stable, and the plasticization time must be within the time required for the cooling process in the mold unit (cooling time). is necessary. However, in the liquid crystal polyester, the plasticizing time is difficult to be constant, and the plasticizing may not be completed within the cooling time. For this reason, it becomes difficult to perform molding in a constant cycle, and the quality of the molded product may be adversely affected at the same time as the decrease in productivity.

The reason why the plasticization time of the liquid crystal polyester becomes unstable is not clear. However, as one of the causes, Patent Document 1 describes that the melt viscosity of the liquid crystal polyester itself is highly dependent on the shear rate and temperature, and thus the liquid crystal It has been estimated that only the polyester particle surface is selectively plasticized and is likely to be fused. As means for suppressing such a phenomenon, a mixture obtained by blending a higher fatty acid amide with the liquid crystal polyester is disclosed. By using the mixture, the plasticization time can be extremely stabilized, so that molding can be performed at a constant cycle, and molding with excellent productivity can be achieved in obtaining a molded body.
Japanese Patent Laid-Open No. 2003-12908

  However, when the mixture disclosed in Patent Document 1 is subjected to a heating treatment such as drying, the stabilization effect related to the plasticizing time may be reduced. The present invention provides a liquid crystal polyester resin mixture in which the stabilization effect relating to the plasticizing time is maintained even when such a heating treatment is performed. Furthermore, this invention provides the molded object excellent in productivity obtained by shape | molding the said liquid crystalline polyester resin mixture.

The inventors of the present invention diligently studied to solve the above-mentioned problems and have completed the present invention.
That is, the present invention provides the following [1] or [2].
[1] 100 parts by weight of a liquid crystalline polyester, 0 to 150 parts by weight of a filler, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, and an amide compound represented by the following general formula (1): Liquid crystal polyester resin mixture formed by mixing 001 to 5 parts by weight
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.)
[2] A liquid crystal polyester resin composition containing 100 parts by weight of a liquid crystal polyester and 20 to 100 parts by weight of a filler, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, and the following general formula (1) A liquid crystal polyester resin mixture obtained by mixing 0.001 to 5 parts by weight of the represented amide compound.
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.)

（式中の、芳香環は、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数６〜２０のアリール基で置換されていてもよい。）
［６］上記液晶ポリエステルにおける、上記（ロ）が、下記の（Ｂ₁）、（Ｂ₂）または（Ｂ₃）で表される繰り返し構造単位から選ばれる、上記［３］〜［５］のいずれかに記載の液晶ポリエステル樹脂混合物。

（式中の、芳香環は、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数６〜２０のアリール基で置換されていてもよい。）
［７］上記３価リン原子を有するリン化合物がリン系酸化防止剤である、上記いずれかの液晶ポリエステル樹脂混合物
８］上記アミド化合物の融点が３０℃以上である、上記いずれかの液晶ポリエステル樹脂混合物 Furthermore, the following [2] to [7] are provided as suitable constituents related to the liquid crystal polyester resin mixture of [1] or [2].
[3] The liquid crystalline polyester is
(I) a repeating structural unit derived from an aromatic hydroxycarboxylic acid,
(B) a repeating structural unit derived from an aromatic dicarboxylic acid,
(C) a repeating structural unit derived from at least one selected from the group consisting of an aromatic diol, an aromatic diamine and an aromatic amine having a hydroxyl group;
The liquid crystal polyester resin mixture of [1] or [2] [4], wherein the liquid crystal polyester has the above (a), (b) and (c) as a sum of 100 mol%. The liquid crystal polyester resin mixture of [3] above, which is a liquid crystal polyester containing 30 mol% or more of the structural unit represented by ()), the above (A) in the above liquid crystal polyester is represented by the following (A ₁ ): The liquid crystalline polyester resin mixture according to the above [3] or [4], which is a repeating structural unit and / or a repeating structural unit represented by (A ₃ )

(In the formula, the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
[6] In the above liquid crystal polyester, the above (b) is selected from the repeating structural units represented by the following (B ₁ ), (B ₂ ) or (B ₃ ): The liquid crystal polyester resin mixture according to any one of the above.

(In the formula, the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
[7] The liquid crystal polyester resin mixture 8 according to any one of the above, wherein the phosphorus compound having a trivalent phosphorus atom is a phosphorus-based antioxidant. The liquid crystal polyester resin according to any one of the above, wherein the amide compound has a melting point of 30 ° C. or higher. blend

The liquid crystal polyester resin mixture described in the above [1] and [2] may be heated and melted during mixing to form a composition, and provides the following [9] and [10].
[9] 100 parts by weight of liquid crystalline polyester, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, 0.001 to 5 parts by weight of an amide compound represented by the following general formula (1), and 0 to 150 fillers Liquid crystal polyester resin composition containing parts by weight
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.)
[10] 100 parts by weight of a liquid crystalline polyester, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, 0.001 to 5 parts by weight of an amide compound represented by the following general formula (1), and 20 to 100 fillers Liquid crystal polyester resin composition containing parts by weight
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.)

Furthermore, the present invention provides the following [11] and [12] using the liquid crystal polyester resin mixture or liquid crystal polyester resin composition described above.
[11] A molded product obtained by molding the liquid crystalline polyester resin mixture according to any one of [1] to [8] [12] The liquid crystalline polyester resin composition according to [9] or [10] is molded. Molded product

  Since the liquid crystal polyester resin mixture of the present invention stabilizes the plasticizing time during the injection molding process, it becomes possible to perform a stable molding process, and further, the resin mixture is subjected to a heat treatment by drying or the like. Even if applied, the effect of stabilizing the plasticizing time is retained, which is industrially advantageous.

<Liquid crystal polyester>
The liquid crystal polyester used in the present invention is a polyester called a thermotropic liquid crystal polymer, and forms an anisotropic melt at a temperature of 450 ° C. or lower. Among these liquid crystal polyesters, suitable examples include:
(1) A product obtained by condensing an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid (2) A part or all of the aromatic diol of the above (1) is converted into an aromatic diamine and / or Or obtained by condensation with an aromatic amine having a hydroxyl group (3) obtained by condensation of different kinds of aromatic hydroxycarboxylic acids (4) condensed with an aromatic dicarboxylic acid and an aromatic diol Obtained (5) Obtained by condensing a part or all of the aromatic diol of (4) above with an aromatic diamine and / or an aromatic amine having a hydroxyl group (6) Polyester such as polyethylene terephthalate And those obtained by reacting an aromatic hydroxycarboxylic acid.
In addition, these aromatic dicarboxylic acids, aromatic diols, aromatic amines having hydroxyl groups, and aromatic hydroxycarboxylic acids may be used instead of their ester-forming derivatives, having aromatic diamines or hydroxyl groups. Instead of aromatic amines, their amide-forming derivatives can also be used.

なお、これらの繰り返し構造単位は、その芳香環に結合している水素原子の一部または全部が、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。 Among the above examples, (1) or (2) is preferable because it is more excellent in heat resistance. That is, the liquid crystalline polyester is preferably composed of repeating structural units represented by the following (a), (b) and (c).
(I) Repeating structural unit derived from aromatic hydroxycarboxylic acid (b) Repeating structural unit derived from aromatic dicarboxylic acid (c) Selected from the group consisting of aromatic diol, aromatic diamine and aromatic amine having a hydroxyl group The repeating structural unit derived from at least one Here, although the said repeating structural unit is illustrated concretely, it is not limited to these.
Repeating structural units derived from aromatic hydroxycarboxylic acids:

In these repeating structural units, some or all of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. May be.

なお、これらの繰り返し構造単位は、その芳香環に結合している水素原子の一部または全部が、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。 Repeating structural units derived from aromatic dicarboxylic acids:

In these repeating structural units, some or all of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. May be.

なお、これらの繰り返し構造単位は、その芳香環に結合している水素原子の一部または全部が、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。 Repeating structural units derived from aromatic diols:

In these repeating structural units, some or all of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. May be.

なお、これらの繰り返し構造単位は、その芳香環に結合している水素原子の一部または全部が、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。 Repeating structural unit derived from an aromatic diamine having a hydroxyl group:

In these repeating structural units, some or all of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. May be.

なお、これらの繰り返し構造単位は、その芳香環に結合している水素原子の一部または全部が、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。 Repeating structural units derived from aromatic diamines:

In these repeating structural units, some or all of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. May be.

  As the alkyl group which may be substituted with the above structural unit, for example, an alkyl group having 1 to 10 carbon atoms is usually used, and among them, a methyl group, an ethyl group, a propyl group or a butyl group is preferable. Moreover, as an aryl group which may be substituted, for example, a phenyl group, a toluyl group, a xylyl group, a naphthyl group or a biphenyl group is usually used, and among them, a phenyl group is preferable. The halogen atom is selected from a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  The above-mentioned repeating structural unit constituting the liquid crystalline polyester is a liquid crystalline polyester containing a large number of repeating units derived from the above (ii) aromatic hydroxycarboxylic acid in terms of the balance of heat resistance, mechanical strength and processability. More specifically, when the total of the above (a), (b) and (c) (hereinafter also referred to as “structural unit total”) is 100 mol%, (a) is 30 mol. It is preferable that it is a liquid crystalline polyester containing at least%.

Furthermore, among the repeating structural units exemplified as (a) above, preferred are the repeating structural unit represented by (A ₁ ) and / or the repeating structural unit represented by (A ₃ ). The liquid crystalline polyester containing the repeating structural unit represented by (A ₁ ) is particularly preferable because of its excellent heat resistance. The liquid crystalline polyester containing the repeating structural unit represented by (A ₃ ) is obtained by hydrolysis of the resulting molded product. Since the thing excellent in durability with respect to is obtained, it is preferable.

In addition, the repeating structural unit derived from the (b) aromatic dicarboxylic acid is a repeating structural unit selected from the repeating structural units represented by the above (B ₁ ), (B ₂ ) and (B ₃ ). ,preferable. The liquid crystal polyester in which the above (b) has such a repeating structural unit can be obtained which is excellent in the dimensional stability of the resulting molded article.

A particularly preferred liquid crystal polyester is specifically exemplified by combining these viewpoints. In terms of a combination of the above repeating structural units, a liquid crystal polyester having a structural unit selected from the following combinations (a) to (f) is preferable.
(A): A combination consisting of (A ₁ ), (B ₁ ), and (C ₁ ).
(B): A combination in which part or all of (B ₁ ) in (a) is replaced with (B ₂ ) and / or (B ₃ ).
In (c) :( a) or (b), the combination was replaced with (A ₁₎ of the part or whole (A _2).
(D): A combination of (a), (b) or (c) in which a part or all of (C ₁ ) is replaced with (C ₃ ) and / or (C ₄ ).
(E): A combination in which (C ₁ ) is partially or entirely replaced with (D ₁ ) and / or (D ₂ ) in (a), (b) or (c).
(F): A combination in which (C ₁ ) is partially or wholly replaced with (E ₁ ) and / or (E ₂ ) in (a), (b) or (c).

In such a preferable combination of repeating structural units, the lower limit of (A) is preferably 30 mol% or more, more preferably 40 mol%, particularly preferably, based on the total structural units. It is 45 mol% or more. On the other hand, the upper limit of (A) is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 65 mol% or less. Thus, it is preferable that the molar fraction of (A) with respect to the total structural unit is in the above range because liquid crystallinity tends to be more easily exhibited and processability tends to be excellent.
On the other hand, the molar fraction of (b) and the molar fraction of (c) with respect to the total structural units are preferably in the range of 10 to 35 mol%. Furthermore, the lower limit of the molar fraction of (b) and the molar fraction of (c) is preferably 15 mol% or more, and particularly preferably 17.5 mol% or more. On the other hand, the upper limit is preferably 30 mol% or less, and particularly preferably 27.5 mol% or less.
Further, when the molar fraction of (b) in the liquid crystal polyester is compared with the molar fraction of (c), it is arbitrarily selected within the range of 100/85 to 85/100, expressed by (b) / (c). However, it is preferable that the molar fraction of (b) and the molar fraction of (c) are substantially equivalent ((b) / (c) is about 1).

  The production method of the liquid crystalline polyester used in the present invention is not particularly limited, but the aromatic hydroxycarboxylic acid that derives the repeating structural unit (a), the aromatic dicarboxylic acid structural unit that induces the repeating structural unit (b), Using at least one compound selected from the group consisting of aromatic diols, aromatic diamines, and aromatic amines having a hydroxyl group that induce repeating structural units (c), or ester-forming derivatives or amide-forming derivatives thereof. It can be obtained by condensation. In particular, it is preferable to use the ester-forming derivative or amide-forming derivative because polycondensation easily proceeds.

Here, an ester-forming derivative or an amide-forming derivative will be described.
Examples of the ester-forming derivative or amide-forming derivative of carboxylic acid include derivatives that promote a polyester-forming reaction or a polyamide-forming reaction, such as derivatives such as acid chlorides and acid anhydrides with improved reaction activity, transesterification reactions, or Examples thereof include esters or amide derivatives (carboxyl groups formed by reaction with alcohols, ethylene glycol, amines, etc.) capable of producing polyester or polyamide by an amide exchange reaction.

  Examples of the ester-forming derivative of a hydroxyl group include those in which a phenolic hydroxyl group forms an ester with a carboxylic acid (acylation) so as to produce a polyester by a transesterification reaction.

  Examples of the amide-forming derivative of an amino group include those in which an amide is formed (acylated) with a carboxylic acid that forms a polyamide by an amide exchange reaction.

Among the above, as ester-forming derivatives of hydroxyl groups related to aromatic hydroxycarboxylic acids, aromatic diols or aromatic amines having hydroxyl groups, derivatives obtained by acylating these hydroxyl groups, aromatic diamines or aromatic amines having hydroxyl groups. Amide-forming derivatives obtained by acylating such amino groups are preferred.
In the acylation method, it is preferable to use a fatty acid anhydride. This addition amount is preferably 1.0 to 1.2 times equivalent, more preferably 1.05 to 1.1 times equivalent to the total of hydroxyl groups and amino groups. When the amount of fatty acid anhydride added is less than 1.0 times equivalent, acylated products, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and the like tend to sublimate during polycondensation due to transesterification / amide exchange, and the reaction system tends to block. In addition, when the amount exceeds 1.2 times equivalent, the resulting liquid crystal polyester tends to be remarkably colored.

  The acylation reaction is preferably performed at 130 to 180 ° C. for 5 minutes to 10 hours, more preferably at 140 to 160 ° C. for 10 minutes to 3 hours.

  The fatty acid anhydride used in the acylation reaction is not particularly limited. For example, acetic anhydride, propionic acid anhydride, butyric acid anhydride, isobutyric acid anhydride, valeric acid anhydride, pivalic acid anhydride, 2-ethylhexane Acid anhydride, bis (monochloroacetic acid) anhydride, bis (dichloroacetic acid) anhydride, bis (trichloroacetic acid) anhydride, bis (monobromoacetic acid) anhydride, bis (dibromoacetic acid) anhydride, bis (tribromoacetic acid) anhydrous Bis (monofluoroacetic acid) anhydride, bis (difluoroacetic acid) anhydride, bis (trifluoroacetic acid) anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, bis (β-bromopropionic acid) anhydride A thing etc. are mentioned, These may mix and use 2 or more types. From the viewpoint of price and handleability, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferable, and acetic anhydride is more preferable.

  The polycondensation by transesterification / amide exchange is preferably carried out at a temperature of 130 to 400 ° C. at a rate of 0.1 to 50 ° C./min, and a rate of 0.3 to 5 ° C./min at 150 to 350 ° C. It is more preferable to carry out while raising the temperature. At this time, in order to move the equilibrium, it is preferable to distill out the by-product fatty acid and the unreacted fatty acid anhydride, for example, by evaporating.

  The polycondensation by acylation reaction or transesterification / amide exchange may be carried out in the presence of a catalyst. As the catalyst, those conventionally known as polyester polycondensation catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide. And metal salt catalysts such as N, N-dimethylaminopyridine and organic compound catalysts such as N-methylimidazole. The catalyst is usually present during the acylation reaction, and it is not always necessary to remove it after acylation. If the catalyst is not removed, the next treatment can be carried out as it is. Moreover, you may add the above catalysts when performing the next process.

Polycondensation by transesterification / amide exchange is usually carried out by melt polymerization, but melt polymerization and solid phase polymerization may be used in combination. The solid-phase polymerization can be performed by a known solid-state polymerization method after extracting the prepolymer from the melt polymerization step, solidifying and then pulverizing it into powder or flakes. Specifically, for example, a method of heat treatment in a solid state at 200 to 350 ° C. for 1 to 30 hours under an inert atmosphere such as nitrogen can be used. Solid phase polymerization may be carried out while stirring or in a state of standing without stirring. In addition, by providing an appropriate stirring mechanism, the melt polymerization tank and the solid phase polymerization tank can be made the same reaction tank. After the solid phase polymerization, the obtained liquid crystal polyester may be used after being pelletized by a known method.
Such a liquid crystal polyester can be produced using, for example, a batch apparatus, a continuous apparatus or the like.

Among the liquid crystal polyesters thus obtained, liquid crystal polyesters having a flow temperature determined by the following measuring method of 250 ° C. or higher, preferably 300 ° C. or higher are suitable. A liquid crystal polyester resin mixture using such a liquid crystal polyester is preferable because the resulting molded article has good heat resistance. The following flow temperature measurement method is an index representing the molecular weight of liquid crystal polyesters well known in the art (for example, Naoyuki Koide, “Liquid Crystal Polymer—Synthesis / Molding / Application—”, pages 95 to 105, see (See MC, published 5 June 1987). As described above, the liquid crystal polyester having such a flow temperature can be easily produced by controlling the copolymerization ratio of (A ₁ ) or (A ₃ ) in the repeating structural units constituting the liquid crystal polyester.
[Flow temperature measurement method]
When a resin heated at a heating 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 9.8 MPa (100 kgf / cm ² ), the temperature at which the melt viscosity exhibits 48000 poise is set. taking measurement.

<filler>
In the present invention, a filler may be added as necessary from the viewpoint of improving the properties such as mechanical strength of the obtained molded article. When the filler is added, the filler is added in an amount of 150 parts by weight or less with respect to 100 parts by weight of the liquid crystal polyester, and preferably 20 to 100 parts by weight of the filler is added to 100 parts by weight of the liquid crystal polyester. When the blending ratio of the filler is more than 150 parts by weight, the melt viscosity of the composition comprising the liquid crystal polyester and the filler is increased, and the granulating property and moldability are lowered, which is not preferable in practice.
The composition comprising the liquid crystal polyester resin and the filler applied to the present invention is preferably in the form of particles such as pellets, chips or particles from the viewpoint of facilitating mixing with the additives described later. A preferable shape of the composition is 1 mm or more and 10 mm or less in terms of number average particle diameter. When the average particle diameter is 1 mm or more, it is preferable that gas is not easily involved when plasticizing the resin with a screw at the time of molding, and the surface state of the obtained product is good. Further, it is preferable that the average particle diameter is 10 mm or less because plasticization during molding becomes easier and the rotational torque of the screw becomes stable.
Means for obtaining particles or chips of the composition is not particularly limited, but liquid crystal polyester and filler, if necessary, mold release improver, heat stabilizers, colorant, etc. using a Henschel mixer, tumbler, etc. After mixing, 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 and rotated. A method of cutting into particles with a blade is common. It is also possible to obtain particles or chips by directly connecting an extruder downstream of the polymerized liquid crystal polyester reactor.

  Such fillers include general inorganic fibers such as glass fiber, silica alumina fiber, carbon fiber, metal fiber, alumina fiber, boron fiber, titanate fiber, asbestos, calcium carbonate, alumina, aluminum hydroxide, kaolin, talc. , Clay, mica, glass flakes, glass beads, quartz sand, silica sand, wollastonite, dolomite, various metal powders, powder materials such as carbon black, graphite, barium sulfate, potassium titanate, calcined gypsum, silicon carbide, alumina , Powdered or plate-like inorganic compounds such as aluminum borate, potassium titanate, boron nitride and silicon nitride, whiskers, wood powder, coconut shell powder, walnut powder, pulp powder, etc. One kind or a mixture of two or more kinds can be used.

<Phosphorus compound>
The phosphorus compound used in the present invention has a trivalent phosphorus atom in the molecule. Having a trivalent phosphorus atom is a compound having a phosphine group or a phosphonic acid ester group in the molecule, and the trivalent phosphorus atom is self-oxidized to pentavalent, resulting in a peroxide decomposition effect (peroxidation). It is preferable that the compound has antioxidant properties due to elimination of radicals generated from the product.

  It is preferable to use a phosphorus-based antioxidant as the antioxidant having a trivalent phosphorus atom. Here, the “phosphorus antioxidant” is a trivalent phosphorus which is listed as an antioxidant in “Polymer Dictionary” (translated by Tatsuta Mita, Maruzen, page 413, issued on September 20, 1994). It is a phosphorus-based antioxidant having atoms.

Specific examples of these phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl) diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphine. Phyto, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5 t- butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis ( 3-methyl-6-tert-butylphenol) diphosphite, Scan (3,5-di -t- butyl-4-hydroxyphenyl) phosphite, tris (mono-di mixed nonylphenyl) phosphite,
Hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphos Phyto, phenyl (4,4'-isopropylidene diphenol) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, di (Isodecyl) phenyl phosphite, 4,4′-isopropylidenebis (2-tert-butylphenol) bis (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, bis (2,4-di-t-butyl-6-methylphenyl) Nyl) ethyl phosphite, 2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphin-6-yl} oxy] -N , N-bis [2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphin-6-yl} oxy] ethyl] ethanamine , 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -Dioxaphosphepine etc. are mentioned.

（式中、Ｒ¹、Ｒ²、及びＲ³は、それぞれ独立に、水素原子又は炭素数１〜９のアルキル基等を表す。）
で示されるスピロ型、又は、下記一般式（２ｂ）

（式中、Ｒ⁴、Ｒ⁵、及びＲ⁶は、それぞれ独立に、水素原子又は炭素数１〜９程度のアルキル基等を表す。）
で示されるケージ形のものなどが挙げられる。 As the bis (dialkylphenyl) pentaerythritol diphosphite ester, the following general formula (2a)

(Wherein R ¹ , R ² , and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms).
Spiro type represented by the following general formula (2b)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having about 1 to 9 carbon atoms).
The cage type shown by is mentioned.

  Commercially available products may be used as the phosphorus-based antioxidant, such as Irgaphos 168 (registered trademark, manufactured by Ciba Specialty Chemicals), Irgaphos 12 (registered trademark, manufactured by Ciba Specialty Chemicals), Irgaphos 38 ( Registered trademark, manufactured by Ciba Specialty Chemicals), ADK STAB 329K (registered trademark, manufactured by Asahi Denka), ADK STAB PEP36 (registered trademark, manufactured by ASAHI DENKA), ADK STAB PEP-8 (registered trademark, manufactured by ASAHI DENKA), Sandstab P- EPQ (registered trademark, manufactured by Clariant), Weston 618 (registered trademark, manufactured by GE), Weston 619G (registered trademark, manufactured by GE), Ultranox 626 (registered trademark, manufactured by GE), Sumilyzer GP (registered trademark, manufactured by Sumitomo Chemical) Etc.

  The compounding ratio of the phosphorus compound is 0.001 to 5 parts by weight, particularly preferably 0.003 to 1 part by weight, based on 100 parts by weight of the liquid crystal polyester resin composition. It is preferable to use 0.001 part by weight or more of the phosphorus compound with respect to 100 parts by weight of the liquid crystalline polyester because the effect of stabilizing the plasticization time related to injection molding is sufficient. On the other hand, when the phosphorus compound is 5 parts by weight or less, gas generation due to decomposition of the phosphorus compound is suppressed at the time of molding processing, and it is difficult for blistering and the like to occur in the molded product, and less gas is generated from the molded product. Therefore, it is preferable.

<Amide compound>
The amide compound used in the present invention is a compound represented by the above general formula (1). R is a saturated or unsaturated hydrocarbon group having 10 to 30 carbon atoms, and is decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, nonadecyl, icosyl, docosyl, One or more carbon-carbon double bonds and one or more carbon-carbon triple bonds in a saturated hydrocarbon group such as a tricosyl group, a tetracosyl group, a hexacosyl group, an octacosyl group, and a triacontyl group, and the saturated hydrocarbon group The unsaturated hydrocarbon group which has is illustrated. Specific examples of the amide compound include decanoic acid amide (C10), lauric acid amide (C12), myristic acid amide (C14), palmitic acid amide (C15), heptadecanoic acid amide (C16), stearic acid amide (C18). ), Linoleic acid amide (C18), Linolenic acid amide (C18), Oleic acid amide (C18), Elaidic acid amide (C18), Eicosanoic acid amide (C20), Behenic acid amide (C21), Erucic acid amide (C22) And lignoceric acid amide (C24), pentacosanoic acid amide (C25), and serotic acid amide (C26).
Among these examples, lauric acid amide, myristic acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, and behenic acid amide are preferable because they can be easily obtained from the market. Specifically, Nippon Seika Co., Ltd. Neutron (registered trademark), Lion Akzo Armor slip (registered trademark), Kao Co., Ltd. aliphatic amide S, etc. may be used as they are or after purification. it can. Moreover, by calculating | requiring the purity of such a commercial item with a well-known chromatography method or an acid value measuring method, the desired compounding ratio which concerns on the mixture of this invention can also be calculated and used.

  The compounding quantity of this amide compound is 0.001-5 weight part with respect to 100 weight part of liquid crystalline polyester, Preferably it is 0.005-0.5 weight part, More preferably, it is 0.01-0. 1 part by weight. If the compounding amount of the amide compound is 0.001 part by weight or more, the effect of stabilizing the plasticizing time for injection molding is sufficient, which is preferable. On the other hand, when the blending amount of the amide compound is 5 parts by weight or less, the generation of gas due to decomposition of the amide compound itself during molding processing is suppressed, and blistering or the like hardly occurs in the molded product. This is preferable because a molded article excellent in the above can be obtained.

The melting point of the amide compound is preferably 30 ° C. or higher, and particularly preferably 50 ° C. or higher. When the melting point of the amide compound is within the above range, volatilization of the amide compound is suppressed when the liquid crystal polyester resin mixture of the present invention is pre-dried before molding, and the stabilization effect during the desired molding process is obtained. Since it is obtained, it is preferable.
Specifically, among the amide compounds exemplified above, those having a melting point of 30 ° C. or more can be selected if the total carbon number is 12 or more, and those having a total carbon number of 14 or more. If it exists, the thing of melting | fusing point 50 degreeC or more can be selected.
Further, the amide compound is preferably in the form of a powder having an average particle size of 100 μm or less in order to facilitate mixing with the liquid crystal polyester resin composition and to effectively disperse during molding, and the average particle size is 50 μm or less. More preferably, it is in the form of powder.

<Resin mixture / resin composition>
A liquid crystal polyester resin mixture obtained by mixing the liquid crystal polyester described above, a phosphorus compound having a trivalent phosphorus atom, an amide compound, and a filler as necessary is particularly limited. It can be mixed using a known mixer. Examples of the mixer include a Henschel mixer and a tumbler.
Furthermore, when mixing as described above, it can be melted by heating to obtain a resin composition. The resin composition can also be pelletized by melt extrusion. In this way, a liquid crystal polyester resin composition is obtained, and it is preferable that the melting temperature at the time of melting is mixed below the flow temperature obtained by the above flow temperature measurement method of the liquid crystal polyester to be used. Since such a liquid crystal polyester resin mixture can remarkably stabilize the plasticization stabilization time and cooling time during injection molding, the productivity of the molded article by injection molding can be further improved.
The mixing order of the components for obtaining the liquid crystal polyester resin mixture of the present invention is not particularly limited, but when mixing including the filler, the liquid crystal polyester and the filler are mixed and melted in advance. A method of obtaining a liquid crystal polyester resin mixture by mixing a phosphorus compound and an amide compound after pelletization is preferred.
Furthermore, in the process of preparing the liquid crystal polyester resin mixture of the present invention, a part of the phosphorus compound having a trivalent phosphorus atom may be oxidized by oxygen from the environment to become a phosphorus compound having a pentavalent phosphorus atom. However, the liquid crystal polyester resin mixture or liquid crystal polyester resin composition of the present invention also includes such a product. As described above, the oxidation and modification of the compound having a trivalent phosphorus atom means that an environment (for example, nitrogen or the like) in which contamination of oxygen is blocked in the process of heating and melting the liquid crystal polyester resin composition of the present invention. (Inert gas atmosphere) can also be suppressed.

  In addition, the liquid crystal polyester resin mixture of the present invention is usually used as a colorant such as a dye or pigment; an antioxidant; a heat stabilizer; an ultraviolet absorber; an antistatic agent; One or more of these additives can be added. Also, a small amount of thermoplastic resin, such as polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and modified products thereof, polysulfone, polyethersulfone, polyetherimide, etc., a small amount of thermosetting resin, For example, 1 type, or 2 or more types, such as a phenol resin, an epoxy resin, and a polyimide resin, can also be added.

<Molded body>
Since the liquid crystal polyester resin mixture or liquid crystal polyester resin composition of the present invention has a stable plasticization time, when molding a molded body by an injection molding method, a certain amount of resin pellets, screw It can use suitably for the shaping | molding method using the apparatus of the structure which uses and melts and measures. In particular, in the injection molding, since the time required for the weighing process (plasticization time) in the injection unit is constant and stable, the molding condition is stabilized so that a defective state such as short shot and burr does not occur. It can be easily found.
In addition, the liquid crystalline polyester resin mixture of the present invention is a composition in which the effect of stabilizing the plasticizing time does not deteriorate even when subjected to a heating treatment such as drying, and the production management of the injection molding is facilitated. Industrially advantageous.
As described above, the liquid crystalline polyester resin mixture of the present invention is advantageous for the production of a molded article related to injection molding, but it is also possible to obtain a molded article by other molding methods such as extrusion molding.

  Molded articles using the liquid crystalline polyester resin mixture of the present invention include, for example, connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, computer-related parts, and other electrical and electronic parts; IC trays, wafer carriers Semiconductor manufacturing process related parts such as VTR, TV, iron, air conditioner, stereo, vacuum cleaner, refrigerator, rice cooker, lighting fixtures, etc .; lighting fixture parts such as lamp reflectors, lamp holders, etc .; compact disc, laser Acoustic product parts such as discs (registered trademark) and speakers; optical cable ferrules, telephone parts, facsimile parts, communication equipment parts such as modems; copiers such as separation claws and heater holders, printer-related parts; impellers, fan gears, Gear, bearing, motor parts and case Mechanical parts such as automobile parts; automotive parts such as automobile mechanism parts, engine parts, parts in the engine room, electrical parts, interior parts, cooking utensils such as microwave cooking pots, heat-resistant dishes; flooring materials, wall materials, etc. Insulation, soundproofing materials, supporting materials such as beams and pillars, building materials such as roofing materials, or civil engineering and building materials; aircraft, spacecraft, space equipment parts; radiation facility members such as nuclear reactors, offshore facility members, cleaning Suitable for use as members for jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, sanitary equipment, sports equipment, leisure equipment, etc. It is done.

  In addition, film-like and sheet-like materials processed from the resin mixture of the present invention, and materials processed from them are industrially useful materials for display device parts, films for electrical insulation, and flexible circuit boards. It is used for applications such as films, packaging films, and recording medium films. Since the resin mixture of the present invention is excellent in extrusion moldability, it is useful as a coating material for resin molded products and metal parts, and can be used for coating in various fields such as pipe coating and wire coating. Fibrous materials such as continuous fibers, short fibers, and pulp processed from the resin mixture of the present invention, and materials processed from them are industrially useful materials, such as clothing, heat-resistant heat insulating materials, FRP reinforcing materials, It can be used for applications such as rubber reinforcements, ropes, cables, and nonwoven fabrics.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.

Example 1 and Comparative Example 1
The repeating structural unit is composed of the aforementioned (A ₁ ), (B ₁ ), (B ₂ ), (C ₁ ), and the molar ratio of (A ₁ ) :( B ₁ ) :( B ₂ ) :( C ₁ ) Is 60: 18: 2: 20, and the flow temperature defined above is 100 parts by weight of liquid crystal polyester and 66.7 parts by weight of milled glass fiber (EFH75-01 manufactured by Central Glass Co., Ltd.) After mixing with a Henschel mixer, the mixture was granulated at a cylinder temperature of 360 ° C. using a twin-screw extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) to obtain pellets. The pellets were cylindrical with an average particle diameter of 2 mm and a length of 2.5 mm.
With respect to 166.7 parts by weight of the obtained pellets, a phosphorus compound and an amide compound were mixed at room temperature using a tumbler in parts by weight shown in Table 1 to obtain a liquid crystal polyester resin mixture (note that the above-mentioned These phosphorus compounds and amide compounds were both ground in a mortar and used with a mesh of 200 mesh or less).
After drying this liquid crystal polyester resin mixture at 150 ° C. for 24 hours, using an injection molding machine (PS40E5ASE manufactured by Nissei Plastic Industry Co., Ltd.), a bending test piece (thickness: 6.4 mm) at a cylinder temperature of 380 ° C. and a mold temperature of 130 ° C. X width 12.7 mm x length 127 mm), and measurement time of 50 continuous shots was measured to evaluate its stability.
The results are shown in Table 1.

In addition, the amide compound used for the liquid-crystal polyester resin mixture and the phosphorus compound which has a trivalent phosphorus atom are as follows.
Amide compound: Armoslip E (erucic acid amide) manufactured by Lion Akzo
(Melting point of erucic acid amide: 79-81 ° C.)
Phosphorus compounds: Sumitizer GP manufactured by Sumitomo Chemical Co., Ltd.

Claims (12)

100 parts by weight of liquid crystalline polyester, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, 0.001 to 5 parts by weight of an amide compound represented by the following general formula (1), and 0 to 150 fillers A liquid crystal polyester resin mixture obtained by mixing parts by weight.
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.) 100 parts by weight of liquid crystalline polyester, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, 0.001 to 5 parts by weight of an amide compound represented by the following general formula (1), and 20 to 100 fillers A liquid crystal polyester resin mixture obtained by mixing parts by weight.
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.) The liquid crystal polyester is
(I) Repeating structural unit derived from aromatic hydroxycarboxylic acid (b) Repeating structural unit derived from aromatic dicarboxylic acid (c) Selected from the group consisting of aromatic diol, aromatic diamine and aromatic amine having a hydroxyl group The liquid crystal polyester resin mixture according to claim 1, comprising a repeating structural unit derived from at least one.   The liquid crystal polyester according to claim 3, wherein the liquid crystal polyester is a liquid crystal polyester in which (a) is 30 mol% or more when the total of the above (a), (b), and (c) is 100 mol%. Resin mixture. The liquid crystal according to claim 3 or 4, wherein (i) in the liquid crystalline polyester is a repeating structural unit represented by the following (A ₁ ) and / or a repeating structural unit represented by (A ₃ ). Polyester resin mixture.

(In the formula, the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) The liquid crystal according to claim 3, wherein (b) in the liquid crystal polyester is selected from repeating structural units represented by the following (B ₁ ), (B ₂ ), or (B ₃ ). Polyester resin mixture.

(In the formula, the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)   The liquid crystal polyester resin mixture according to claim 1, wherein the phosphorus compound having a trivalent phosphorus atom is a phosphorus-based antioxidant.   The liquid crystal polyester resin mixture according to claim 1, wherein the amide compound has a melting point of 30 ° C. or higher. 100 parts by weight of liquid crystalline polyester, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, 0.001 to 5 parts by weight of an amide compound represented by the following general formula (1) and 0 to 150 parts by weight of a filler A liquid crystal polyester resin composition.
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.) 100 parts by weight of liquid crystalline polyester, 0.001 to 5 parts by weight of a phosphorus compound having a trivalent phosphorus atom, 0.001 to 5 parts by weight of an amide compound represented by the following general formula (1), and 20 to 100 parts by weight of a filler A liquid crystal polyester resin composition comprising parts.
R-CONH ₂ (1)
(In the formula, R represents a saturated hydrocarbon group having 10 to 30 carbon atoms or an unsaturated hydrocarbon group having 10 to 30 carbon atoms.)   The molded object obtained by shape | molding the liquid-crystal polyester resin mixture in any one of Claims 1-8. The molded object obtained by shape | molding the liquid-crystal polyester resin composition of Claim 9 or 10.