JP3269207B2 - Glass fiber reinforced liquid crystalline resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystalline resin composition which is excellent in heat resistance, moldability, mechanical properties and surface appearance, and in particular, can give a molded article having good fluidity and excellent surface impact strength. is there.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, the polymer is characterized by a parallel arrangement of molecular chains. Optically anisotropic liquid crystal polymers have attracted attention because of their excellent mechanical properties and moldability. As the polymer forming these anisotropic molten phases, for example, a liquid crystal polyester obtained by copolymerizing p-hydroxybenzoic acid with polyethylene terephthalate (JP-A-49 / 1979)
-72393), p-hydroxybenzoic acid and 6-
Liquid crystal polyester obtained by copolymerizing hydroxy-2-naphthoic acid (JP-A-54-77691) and liquid crystal polyester obtained by copolymerizing p-hydroxybenzoic acid with 4,4'-dihydroxybiphenyl, terephthalic acid, and isophthalic acid JP-B-57-24407), 6-hydroxy-
Liquid crystal polyesteramide formed from 2-naphthoic acid, p-aminophenol and terephthalic acid (JP-A-57-1
No. 72921), p-hydroxybenzoic acid, 44 ′
And liquid crystal polyesteramides produced from dihydroxybiphenyl, terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (JP-A-64-33123).

Further, it is disclosed in Rubber Digest, Vol. 27, No. 8, pp. 7-14, 1975 that glass fibers are compounded for the purpose of improving the heat resistance and mechanical strength of the liquid crystal polymer. JP-A-63-101448 discloses that glass fibers having a weight average fiber length of 0.15 to 0.60 mm are blended for the purpose of improving the dimensional accuracy of the liquid crystal polymer.

[0004]

However, those known as liquid crystal polymers in which these glass fibers are blended have been improved in the heat resistance, mechanical strength and anisotropy of liquid crystal polymers to some extent. In addition, the fluidity during molding and the appearance of the molded article are not always sufficient, and the impact strength is low, so that it has been difficult to obtain a liquid crystal polymer having good balance between moldability and appearance and physical properties of the molded article.

[0005] In particular, in the case of a thin-walled molded product utilizing the good fluidity characteristic of a liquid crystal polymer, not only the thin-walled moldability is insufficient, but also the surface impact strength is insufficient, and cases, housings and the like are not provided. It was found that there was also a problem that the liquid crystal polymer could not be used in the above-mentioned application.

Accordingly, the present invention solves the above-mentioned problems, and provides a glass fiber reinforced liquid crystal resin composition having excellent moldability, mechanical properties, and heat resistance, and particularly improved thin-wall moldability and surface impact strength. Make it an issue.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention relates to (A) 100 parts by weight of at least one kind of liquid crystalline resin selected from a liquid crystalline polyester resin and / or a liquid crystalline polyester amide resin forming an anisotropic molten phase, 5) 300 parts by weight of glass fiber having an average fiber diameter of 3 to 15 μm, and a weight average fiber length in the composition of 0.20 to 0.4
The proportion of glass fibers in the range of 5 mm and having a fiber length exceeding 1 mm is 0 to 6 % by weight of the glass fibers, and the proportion of glass fibers having a fiber length of 0.1 mm or less is 8 % of the glass fibers. -4 0 glass fiber-reinforced liquid crystalline resin composition, wherein the percentages by weight, the liquid crystal polyester resin (a)

Embedded image The glass fiber reinforced liquid crystalline resin composition which is a liquid crystal polyester resin having a structural unit formed from at least one aromatic diol selected from the group consisting of the following structural units (I), (II) and (III): The present invention provides a glass fiber reinforced liquid crystal resin composition which is a liquid crystal polyester resin comprising (IV) and (IV).

[0009]

Embedded image

(Where R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image And at least one group selected from X in the formula represents a hydrogen atom or a chlorine atom. )

In the present invention, it has been found that the distribution of the glass fiber length in the composition is important, and that the expression of the effects of the present invention is regulated by the distribution state of the glass fiber length in the glass fiber reinforced liquid crystalline resin composition. It is the invention.

The liquid crystalline polyester resin preferably used in the present invention is an anisotropic melt composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. A polyester forming a phase, and a liquid crystalline polyesteramide resin forms an anisotropic molten phase composed of the above structural units and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like. Is a polyesteramide.

The structural unit (I) of the liquid crystalline polyester resin in the present invention is the same as the structural unit (II) of the polyester formed from p-hydroxybenzoic acid.
Is a structural unit formed from 4,4'-dihydroxybiphenyl, and the structural unit (III) is 3,3 ', 5,5'-
Tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,
Structural units formed from 7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, ethylene glycol and the like, and the structural unit (IV) is terephthalic acid, isophthalic acid, 4'-diphenyldicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'- The structural units generated from one or more aromatic dicarboxylic acids selected from diphenyl ether dicarboxylic acids and the like are respectively shown.

The structural unit (III) is preferably a structural unit formed from ethylene glycol or 2,6-dihydroxynaphthalene, and the structural unit (IV) is preferably a structural unit formed from terephthalic acid or the like.

The liquid crystalline polyester resin used in the present invention is preferably a copolymer comprising the above structural units (I), (II), (III) and (IV).

The copolymerization amount of the above structural units (I), (II), (III) and (IV) is arbitrary . However, the following copolymerization amount is preferable from the viewpoint of fluidity and heat resistance. That is, the structural units (I) and (II) the sum of structural units
60 to the sum of positions (I), (II) and (III)
It is preferably 95 mol%, more preferably 75 to 93 mol%, and particularly preferably 80 to 92 mol%. The structural unit (III) is composed of the structural units (I), (I
It is preferably 40 to 5 mol%, more preferably 25 to 6 mol%, and more preferably 20 to 6 mol%, based on the total of I) and (III).
-8 mol% is particularly preferred. In addition, the structural unit (I)
The molar ratio [(I) / (II)] to (II) is 75/25 to
95/5 is preferred, and the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III) .

The following are specific examples of particularly preferred liquid crystalline polyester resins used in the present invention.

That is, (i) a liquid crystalline polyester resin in which the structural unit (III) is a structural unit formed from ethylene glycol and the structural unit (IV) is a structural unit formed from terephthalic acid. Such a liquid crystalline polyester resin is referred to as (A-1)),

Embedded image Above all, the sum of the structural units (I) and (II)
60 based on the sum of units (I), (II) and (III)
９５95 mol%, preferably 80-93 mol%
Is more preferable. The structural unit (III) is
It is preferably from 40 to 5 mol%, particularly preferably from 20 to 7 mol% , based on the total of the structural units (I), (II) and (III) . The molar ratio of the structural units (I) / (II) is preferably from 75/25 to 93/7, and from 85/15 to 9/9.
2/8 is more preferred. Further, the structural unit (IV) is substantially equimolar to the structural unit [(II) + (III)] .

(Ii) A liquid crystalline polyester resin (hereinafter referred to as the present invention) wherein the structural unit (III) is a structural unit formed from 2,6-dihydroxynaphthalene and the structural unit (IV) is a structural unit formed from terephthalic acid. Such a liquid crystalline polyester resin in the invention is described as (A-2)),

Embedded image Above all, the sum of the structural units (I) and (II)
80-99 in total of the structural units (I), (II) and (III)
Mol%, more preferably 88 to 98 mol%. Further, the structural unit (III) is structural units
20 to the sum of positions (I), (II) and (III)
1 mol% is preferable, and 12 to 2 mol% is particularly preferable. The molar ratio [(I) / (II)] of the structural unit (I) to (II) is preferably from 75/25 to 95/5, more preferably from 80/20 to 90/10. further,
The molar ratio of the structural unit (II) to (III) [(II) / (II
I)] is preferably 90/10 to 40/60, and 85/15
~ 45/55 is more preferred. Again, structural unit (IV) is substantially equimolar to the sum of structural units (II) and (III) .

The method for producing the liquid crystalline polyester resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method. In the case of A-1, the method of the following 1), in the case of A-2, the following
The method 2) is preferably mentioned.

1) Reaction of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl with acetic anhydride or terephthalic acid with polyethylene terephthalate polymer, oligomer or bis- (β-hydroxyethyl) terephthalate A method of producing by acetic acid polymerization.

2) A method in which p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl is reacted with acetic anhydride, 2,6-diacetoxynaphthalene and terephthalic acid, and is produced by deacetic acid polymerization in a molten state.

Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, sodium acetate and potassium acetate, antimony trioxide, and metal magnesium. .

The melting point (T) of the thus obtained liquid crystalline polyester resin (A-1) particularly preferred for use in the present invention is
m, ° C.) is calculated by the following equation (1), and the melting point (Tm,
C) preferably satisfies the following expression (2).

| Tm + 5.89x-385.5 | <10 (1) | Tm + 7.70x-374.4 | <10 (2)

Here, x in the formulas (1) and (2) represents the ratio (mol%) of the structural unit (III) to [(I) + (II) + (III)].

In the particularly preferred liquid crystal polyester resins (A-1) and (A-2) used in the present invention, the composition ratio of the structural units (I) to (IV) satisfies the above conditions, and When the melting point of the formula (2) is satisfied, the composition distribution and randomness of the polymer are in a favorable state, and the balance of fluidity, heat resistance of the molded article and mechanical properties becomes extremely excellent. Decomposition hardly occurs, which is preferable. Here, the melting point (Tm) is defined as Tm ₁ after the endothermic peak temperature Tm ₁ observed when measured by a differential scanning calorimeter under a heating condition of 20 ° C./min.
The temperature is raised to a temperature of ₁ + 20 ° C., maintained at the same temperature for 5 minutes, and then once cooled to room temperature under a temperature lowering condition of 20 ° C./min. It refers to an endothermic peak temperature observed when the measurement is performed again at a temperature rising condition of 20 ° C./min.

When the above liquid crystalline polyester resin is polycondensed, 3,3'-diphenyldicarboxylic acid, 2,2
Aromatic dicarboxylic acids such as' -diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, Aromatic diols such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4- Aliphatic and alicyclic diols such as cyclohexane dimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, p-aminophenol, p-aminobenzoic acid and aromatic imide compounds The purpose of the present invention Can be allowed to further copolymerized in minor proportions range as not rope.

As the liquid crystal polyester amide, 6
-Hydroxy-2-naphthoic acid, liquid crystal polyesteramide formed from p-aminophenol and terephthalic acid (JP-A-57-172921), p-hydrobenzoic acid, 4,4'-dihydroxybiphenol and terephthalic acid, p-aminobenzoic acid Liquid crystal polyesteramide formed from acid and poly (ethylene terephthalate)
4-33123) and the like.

The liquid crystal polyester resin and / or liquid crystal polyester amide resin (A) used in the present invention
Logarithmic viscosity is 0.1 g / dl, the value measured with pentafluorophenol at 60 ° C. is 0.8 to 10.0 d.
1 / g is preferred. If the value of the logarithmic viscosity is less than 0.8 dl / g, the mechanical properties are insufficient, and if it exceeds 10.0 dl / g, the fluidity is impaired, and in any case, it tends to be undesirable. In the case of a particularly preferred liquid crystal polyester resin (A-1), it is preferably 1.0 to 3.0 dl / g, particularly preferably 1.3 to 2.5 dl / g, and in the case of a liquid crystal polyester resin (A-2). 3.0 to 10.
0 dl / g is preferable, and 3.5 to 7.5 dl / g is particularly preferable.

The melt viscosity of the liquid crystal polyester resin and / or liquid crystal polyester amide resin (A) used in the present invention is preferably from 100 to 20,000 poise, and particularly preferably from 1 to 20,000 poise.
00 to 1,000 poise is preferred.

The melt viscosity is calculated as melting point (Tm) +10
This is a value measured by a Koka type flow tester at a temperature of ° C. and a shear rate of 1,000 s ⁻¹ .

As the glass fiber (B) used in the glass fiber reinforced liquid crystalline resin composition of the present invention, a weakly alkaline glass fiber is excellent in mechanical strength and can be preferably used in the present invention.

The glass fiber is preferably treated with a coating or sizing agent such as epoxy, urethane or acrylic, and epoxy is particularly preferable. It is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable.

The average fiber diameter of the glass fiber (B) used for producing the glass fiber reinforced liquid crystalline resin composition of the present invention is 3 to 1.
5 μm, the fiber length is preferably 20 to 10 ⁴ μm, more preferably 1000 to 4000 μm, the filling amount is 5 to 300 parts by weight, preferably 10 to 200 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester, Particularly preferably, it is 13 to 150. If the average diameter of the glass fibers is less than 3 μm, the reinforcing effect is small and the anisotropic reduction effect is small, which is not preferable. On the other hand, if it is larger than 15 μm, the moldability decreases,
It is not preferable because the surface appearance also deteriorates.

In the glass fiber reinforced liquid crystalline resin composition of the present invention, the weight average fiber length of the glass fibers in the composition is 0.1 . It is in the range of 20-0.45 mm . The weight average fiber length is 0. If it is larger than 45 mm , the fluidity during molding and the appearance of the molded product are impaired, which is not preferred.

The glass fiber in the composition has a fiber length of 1
The ratio of glass fibers exceeding 0 mm is 0 to
It is in the range of 6% by weight. And, the proportion of glass fibers having a fiber length of the glass fibers is less 0.1mm in the composition is 8-40% by weight of the glass fibers, good Mashiku 20-35 wt%
It is in the range of. If the ratio of the glass fiber having a fiber length exceeding 1 mm exceeds 6 % by weight, not only the fluidity during molding and the appearance of the molded article become poor, but also the surface impact strength is unpreferably reduced. Further, the ratio of glass fibers having a fiber length of 0.1 mm or less in the composition is 4 mm or less.
If it exceeds 0% by weight, the fluidity during molding is good, but in particular, the surface impact strength becomes insufficient and it cannot be used for molded products having wide surfaces such as cases and housings.

The method for measuring the fiber length distribution and weight average fiber length of the glass fibers is as follows: after incineration of about 5 g of the pellets of the composition in a crucible, 10% of the remaining glass fibers are removed.
Collect 0 mmg and disperse in 100 cc of soapy water. The dispersion is then placed on a glass slide with a dropper using a dropper, observed under a microscope and photographed. The fiber length of the glass fiber photographed is measured.
The measurement is performed for 500 or more fibers, and a distribution map of the fiber length is created at an interval of 0.01 mm, and the weight average fiber length is determined at the same time.

The effect of the present invention is that the weight-average fiber length of the glass fibers in the composition is in the range of 0.20 to 0.45 mm, and the ratio of the glass fibers having a fiber length exceeding 1 mm is the ratio of the glass fibers. 0-6 wt%, and a fiber length of 0.1m
m when the ratio of the glass fiber is 8 to 40 % by weight of the glass fiber is satisfied at the same time, and is excellent in mechanical properties, heat resistance and moldability, especially thin-wall moldability and surface impact strength. And an excellent glass fiber reinforced liquid crystalline resin composition can be obtained.

The glass fiber reinforced liquid crystalline resin composition of the present invention may further contain a filler other than glass fibers.

The filler which can be used in the present invention includes carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, and talc. , Silica, calcium carbonate, glass beads,
Glass flakes, glass microballoons, clay, wollastenite, titanium oxide, fibrous materials such as graphite,
A powdery, granular or plate-like inorganic filler may be used.

Further, the composition of the present invention may contain an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof) to the extent that the object of the present invention is not impaired. UV absorbers (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (eg, montanic acid and its salts, esters, half-esters, stearyl alcohol, stearamide, and polyethylene wax), dyes (eg, nigrosine) And other additives such as colorants, plasticizers, antistatic agents, flame retardants, and other thermoplastic resins, including pigments (e.g., cadmium sulfide, phthalocyanine, carbon black, etc.) and other thermoplastic resins. Can be granted.

In the method for producing the glass fiber reinforced liquid crystalline resin composition of the present invention, the glass fibers in the composition need to have a specific range of the number average fiber length and a specific range of the fiber length distribution. It is difficult to obtain the target with a simple extrusion technique.

The method for producing the glass fiber reinforced liquid crystalline resin composition of the present invention is not particularly limited, but for example, it is recommended to apply a melt kneading method by the following method.

(1) When a liquid crystal resin (A) and a glass fiber (B) are melt-kneaded to form a composition, a twin screw extruder is used to mix the liquid crystal resin (A) and the glass fiber (B). The extruder is sequentially and continuously supplied to the extruder. Specifically, another input port is provided at an arbitrary position between the material input port and the nozzle portion of the twin-screw extruder, and a glass fiber (B) is added to the semi-molten or molten liquid crystalline resin (A). Is supplied continuously.

(2) Melting point (Tm) of liquid crystalline resin (A)
The composition is melt-kneaded at a temperature of 30 ° C. or higher to a melting point (Tm) + 30 ° C. or lower to obtain a composition.

(3) At the time of extrusion, as a screw arrangement of the twin-screw extruder, a zone for melting the liquid crystalline resin and a zone for folding and kneading the glass fiber to a predetermined size and then kneading are provided to obtain a composition by melt-kneading. .

At least one of the above methods (1) and (2)
Employing one facilitates the manufacture of the composition of the present invention. Therefore, it can be said that the composition of the present invention is easily manufactured for the first time by the above-mentioned special technique.

[0049]

The present invention will be further described with reference to the following examples.

REFERENCE EXAMPLE 1 994.5 parts by weight of p-hydroxybenzoic acid (I), 125.7 parts by weight of 4,4'-dihydroxybiphenyl (II), and terephthalic acid were placed in a reaction vessel equipped with a distilling tube and a stirring blade. 11
2.1 parts by weight, 216.2 parts by weight of polyethylene terephthalate (III) having an intrinsic viscosity of about 0.6 and acetic anhydride 9
60.2 parts by weight were charged and deacetic acid polymerization was carried out under the following conditions.

After reacting at 130 to 150 ° C. for 4 hours in a nitrogen atmosphere, the temperature was raised to 250 ° C. over 2.5 hours, and the reaction was further continued at 250 ° C. for 2.5 hours. Further, after the temperature inside the system was raised to 320 ° C. over 2 hours, the pressure inside the system was reduced to 0.3 mmHg in 1.5 hours, and the reaction was continued for further 30 minutes to complete the polycondensation. As a result of the above reaction, a beige resin (A-1) was obtained.

The Tm was 314 ° C. when the melting point of this polymer was measured at a rate of temperature rise of 20 ° C./min using a DSC-7 manufactured by Perkin Elmer.

The logarithmic viscosity of this polymer is 1.82 d
l / g and a melt viscosity of 324 ° C. with a shear rate of 1000
The fluidity was extremely good at 520 poise (1 / sec).

Reference Example 2 In a reaction vessel equipped with a distilling tube and a stirrer, 994 parts by weight of p-hydroxybenzoic acid and 44'-dihydroxybiphenyl 2 were added.
23 parts by weight, 147 parts by weight of 2,6-diacetoxynaphthalene, 299 parts by weight of terephthalic acid and 107 parts of acetic anhydride
7 parts by weight were charged and deacetic acid polymerization was carried out under the following conditions.

First, 100-250 in a nitrogen gas atmosphere.
C. for 6 hours and 250-330 ° C. for 20 hours, then reduced to 0.5 mmHg for 2 hours at 330 ° C., and further reacted for 1.5 hours to complete the polycondensation. Acetic acid was distilled off to obtain a beige resin (A-2) having the following theoretical structural formula.

The Tm was 323 ° C. when the melting point of this polymer was measured at a rate of temperature rise of 20 ° C./min using a DSC-7 manufactured by Perkin Elmer.

The logarithmic viscosity of this polymer is 4.86 d.
l / g and a melt viscosity of 333 ° C. with a shear rate of 1000
The fluidity was extremely good at 460 poise (1 / sec).

Reference Example 3 1296 parts by weight of p-acetoxybenzoic acid and 414 parts by weight of 6-acetoxy-2-naphthoic acid were subjected to a deacetic acid polymerization reaction to obtain a beige resin (B) having the following theoretical structural formula.

The melting point of this polymer was measured at a heating rate of 20 ° C./min using a DSC-7 manufactured by Perkin Elmer Co., and the Tm was 317 ° C. The logarithmic viscosity of this polymer was 4.06 dl / g.

Examples 1 to 5 A 44 mmφ twin screw extruder having an intermediate addition port (Nippon Steel Corporation)
Tokorosha made TEX44) using, as the screw Arenjime cement <br/> the melting zone of the polymer between the intermediate addition port (Z-1) provided from the supply port of the polymer, fold the glass fiber immediately after the intermediate addition port At the same time, a kneading zone (Z-2 ) was provided, and a kneading zone (Z-3) was further provided between the kneading zone and the discharge port. The extrusion temperature was 305 to 330 ° C and the screw rotation speed was shown in Table 1 . under conditions, liquid crystal polyester (a-1) which from the polymer feed port was obtained in the same manner as in reference example 1, the fiber diameter of about 6μm from the intermediate addition port, glass fiber (manufactured by Nippon Electric glass Co., Ltd. glass chopped strand fiber length 3mm EC
S-03T-790DE) to 100 parts by weight of the polymer (A-1) so as to have a blending amount shown in Table 1.
The mixture was melt-kneaded and pelletized. The fiber length distribution and the weight-average fiber length of the remaining glass fibers obtained by burning off the polymer component from the obtained pellets were determined by the methods described above. The results are shown in Table 1.

Next, the obtained pellets were supplied to a Sumitomo Nestal injection molding machine Promat (manufactured by Sumitomo Heavy Industries, Ltd.), and were measured at a cylinder temperature of 324 ° C. and a mold temperature of 90 ° C. to have a thickness of 2 mm × 70 mm × 70 mm. A square plate was formed.

The dimension of the square plate in the direction perpendicular to the flow direction (TD direction) was measured, and the shrinkage ratio from the mold dimension, ie, T
The molding shrinkage in the D direction was determined and used as a measure of dimensional accuracy. The results are shown in Table 1.

Further, the rectangular plate and the high-speed surface impact tester (Shimadzu Corporation) were used to measure the surface impact strength. The results are shown in Table 1.

As an evaluation of thin-wall moldability, using the above molding machine, an injection speed of 99%, an injection pressure of 500 kgf / cm ² and a flow length of a test piece of 0.5 mm thickness × 12.7 mm width (rod) Flow length). Table 1 shows the results.

Example 6 Example 3 was repeated except that the polymer (A-2) obtained in the same manner as in Reference Example 2 was used as the liquid crystal polyester, and the extrusion temperature was 325 ° C. and the cylinder temperature of the injection molding machine was 333 ° C.
And went the same way. The results are shown in Table 1.

Example 7 The same operation as in Example 3 was carried out except that the polymer (B) obtained in the same manner as in Reference Example 3 was used as the liquid crystal polyester, and the extrusion temperature was 317 ° C. and the cylinder temperature of the injection molding machine was 327 ° C. Was. The results are shown in Table 1.

[0067] except that lost Z-2 zones for the screw arrangement of Comparative Example 1 Example 3 was performed in the same manner as the actual施例3. The results are shown in Table 1.

[0068] Except for increased Z-2 zone of the screw arrangement in two places in Comparative Example 2 Example 3 were the same as in Example 3.
The results are shown in Table 1.

[0069] except that the glass fibers with a short axis extruder of Comparative Example 3 40 mm diameter supplied simultaneously with the polymer from the polymer feed port was the same as in Example 3. The results are shown in Table 1.

[0070]

[Table 1]

[0071]

The glass fiber reinforced liquid crystalline resin composition of the present invention is a material having excellent mechanical properties, heat resistance and moldability, and particularly improved thin wall moldability and surface impact strength.

Continuation of the front page (56) References JP-A-3-220257 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00 C08L 77/12

Claims (5)

(57) [Claims] (A) at least one kind of liquid crystalline resin 100 selected from a liquid crystalline polyester resin and / or a liquid crystalline polyester amide resin which forms an anisotropic molten phase;
(B) 5 to 300 parts by weight of glass fibers having an average fiber diameter of 3 to 15 μm with respect to parts by weight, and the weight average fiber length in the composition is in the range of 0.20 to 0.45 mm . The ratio of glass fibers having a fiber length exceeding 1 mm is 0 to 6 % by weight of the glass fibers, and the fiber length is 0.1%.
mm or less of the glass fiber is 8 to 40% of the glass fiber.
% By weight of the glass fiber reinforced liquid crystalline resin composition. 2. The method according to claim 1, wherein the liquid crystal polyester resin (A) is Formed from one or more aromatic diols selected from
Characterized by a liquid crystal polyester resin having a structural unit
The glass fiber reinforced liquid crystalline resin composition according to claim 1,
object. 3. The glass fiber reinforced liquid crystalline resin composition according to claim 2, wherein the liquid crystalline polyester resin (A) is a liquid crystalline polyester resin comprising the following structural units (I), (II), (III) and (IV). . Embedded image (However, R ₁ in the formula is R ₂ represents one or more groups selected from And at least one group selected from X in the formula represents a hydrogen atom or a chlorine atom. ) 4. R ₁ and R _{2 in} the structural units (III) and (IV) of the liquid crystal polyester resin (A) are represented by the following formula: And the sum of the structural units (I) and (II) is the structural unit
60-9 relative to the sum of (I), (II) and (III)
5 mol%, structural unit (III) is structural unit (I), (II)
And the molar ratio [(I) / (II)] of the structural unit (I) to (II) is 7 to 40 to 5 mol% with respect to the total of (III) and (III).
5/25 to 95/5, and the logarithmic viscosity is 1.0 to 3.0.
The glass fiber reinforced liquid crystalline resin composition according to claim 3, wherein the composition is dl / g. 5. R ₁ and R _{2 in} the structural units (III) and (IV) of the liquid crystal polyester resin (A) are represented by the following formula: And the sum of the structural units (I) and (II) is the structural unit
80-9 based on the sum of (I), (II) and (III)
9 mol%, structural unit (III) is structural unit (I), (II)
And 20 to 1 mol% based on the total of (III) and (III), the molar ratio of the structural unit (I) to (II) [(I) / (II)] is 7
5/25 to 95/5, wherein the molar ratio of (II) / (III) is 90
/ 10 to 40/60, and the logarithmic viscosity is 3.0 to 10.
The glass fiber-reinforced liquid crystalline resin composition according to claim 3, wherein the composition is 0 dl / g.