JPH01121357A - Aromatic polyester composition - Google Patents

Abstract

PURPOSE:To obtain the title composition melt-moldable at <=400 deg.C, having excellent fluidity, heat-resistance, etc., and suitable for exterior panel of automo bile, by compounding a specific amount of an olefinic polymer to an aromatic polyester composed of a specific structural unit and capable of forming an anisotropic molten phase. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.wt. of an aromatic polyester composed of a structural unit of formula I-formula III [X is group of formula IV and/or formula V; Y is group of formula VI, etc.; Z is group of formula VII, etc.; the carbonyl groups in the dicarboxylic acid component of the formula II are meta and/or para with each other] and capable of forming an anisotropic molten phase with (B) 0.1-60pts. wt., preferably 0.5-20pts.wt. of an olefinic polymer which is a copolymer of alpha-olefins and a glycidyl ester of an alpha,beta-unsaturated acid.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention provides an aromatic polyester composition that can be melt-molded at 400°C or lower and that can provide molded products with excellent fluidity, heat resistance, and mechanical properties. It is about things.

<Conventional technology> In recent years, the demand for higher performance plastics has increased rapidly, and many polymers with various new performances have been developed and put on the market. Optically anisotropic liquid crystal polymers are attracting attention because they have excellent mechanical properties.

Examples of polymers that form an anisotropic melt phase include liquid crystal polymers obtained by copolymerizing p-hydroxybenzoic acid with polyethylene terephthalate (Japanese Patent Application Laid-Open No. 72393/1983), p-
-Liquid crystal polymer made by copolymerizing hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (Japanese Patent Application Laid-open No. 77691/1989), and p-hydroxybenzoic acid, 4.4'-dihydroxybiphenyl, terephthalic acid, and isophthalic acid. Liquid crystal polymer copolymerized with (Japanese Patent Publication No. 57-24407)
etc. are known.

In addition, a composition comprising a copolymer of an amorphous aromatic polyester, an olefin, and glycidyl methacrylate and/or glycidyl acrylate has been disclosed in Japanese Patent Application Laid-Open No. 1983-1989-1.
It is disclosed in Japanese Patent No. 25046.

<Problems to be Solved by the Invention> The liquid crystal polymer exhibits superior Izot impact strength due to its orientation during molding, compared to crystalline polymers that do not exhibit liquid crystallinity, such as polyethylene terephthalate and polybutylene terephthalate. On the other hand, surface impacts such as falling balls and falling weight impacts were found to be inferior. It is also known that molded products have large anisotropy.

In the composition containing the non-quality aromatic polyester and the olefin copolymer, the olefin copolymer has a drop of 8! The face of the r attack 'WI! 1. The strength was hardly improved, and no effect of reducing anisotropy was found.

Therefore, an object of the present invention is to improve mechanical properties, particularly surface impact resistance and anisotropy, without impairing the excellent fluidity and heat resistance of an aromatic polyester that forms an anisotropic melt phase. It is.

Means for Solving the Problems> The present inventors have made extensive studies to solve the above problems, and as a result, have arrived at the present invention.

That is, the present invention uses an olefin polymer based on 100 parts by weight of an aromatic polyester that forms an anisotropic melt phase consisting of one or more structural units selected from the following structural units <I) to (1). This is an aromatic polyester composition containing 0.1 to 60 parts by weight.

+0-X-Co+ ・・・・・・(I)+0
-Y-0□c-z-co+ ...(III) represents one or more groups selected from C11°, 2 represents one or more selected groups, and dicarboxylic acid in (II) The carbonyl groups in the components are in a meta and/or para relationship with each other. ) The aromatic polyester used in the present invention has the above structural unit (I
) to (I[), preferably structural units (I) and (■),
It consists of structural units (I) to (III).

The above structural unit (I) is p-hydroxybenzoic acid or
It shows a structural unit of polyester produced from one or more types selected from 6-hydroxy-2-naphthoic acid, preferably p-hydroxybenzoic acid.

The above structural unit (n) is 4.4-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, 4.
One or more dihydroxy compounds selected from 4-dihydroxydiphenyl ether, 2,6-dihydroxynaphthalene, 27-dihydroxynaphthalene, chlorohydroquinone, methylhydroquinone, phenylhydroquinone and ethylene glycol, preferably 4.4
-One or more dihydroxy compounds selected from dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, and ethylene glycol, particularly preferably one or more dihydroxy compounds selected from hydroquinone, t-butylhydroquinone, phenylhydroquinone, and ethylene glycol; This shows a structural unit of a polyester produced from a diol component consisting of a dihydroxy compound consisting of .4-monodihydroxybiphenyl, and terephthalic acid and/or isophthalic acid.

The above structural unit (DI) is 4.4-monodihydroxybiphenyl, hydroquinone, t-butylhydroquinone, 4
．． a diol component consisting of one or more selected from 4-1 dihydroxydiphenyl ether, 2,6-dihydroxynaphthalene, 2゜7-dihydroxynaphthalene, chlorohydroquinone, methylhydroquinone, phenylhydroquinone, and ethylene glycol, and 1,2-bis (phenoxy)ethane-4,4'-dicarboxylic acid, 1.
A polyester produced from one or more selected from 2-bis(2-chlorophenoxy)ethane-4,4-monodicarboxylic acid, 2,6-naphthalene dicarboxylic acid and 4,4゛-dicarboxydiphenyl ether dicarboxylic acid. Indicates a structural unit.

The aromatic polyester consisting of the above structural units is required to form an anisotropic melt phase, and an aromatic polyester capable of exhibiting optical anisotropy at a temperature of 350° C. or lower is preferable.

Among these, aromatic polyesters consisting of the following structural units (I)° to (II)'' can be preferably used from the viewpoint of heat resistance and fluidity of the resulting molded product.

and -CH2CH2-, and the carbonyl groups in the dicarboxylic acid component in (II)-1 (II>'' are in a meta and/or individual relationship with each other.) The above-mentioned present invention In the aromatic polyester preferably used in the above, the structural unit (r)- represents a structural unit of a polyester produced from p-human xybenzoic acid.

The structural unit (■) indicates a structural unit of a polyester produced from 4,4-monodihydroxybiphenyl and terephthalic acid and/or isophthalic acid.

Structural unit (n)" is selected from hydroquinone, t-butylhydroquinone, 4,4-mono-diphenyl ether, 2,7-dihydroxynaphthalene, 2,6-cyhydroxynaphthalene, chlorohydroquinone, methylhydroquinone, phenylhydroquinone. It shows a structural unit of a polyester produced from one or more dihydroxy compounds and terephthalic acid and/or isophthalic acid.

There is no particular restriction on the amount of copolymerization, but from the viewpoint of fluidity, the structural unit (I)- should be 40 to 90 mol% of the total, and the structural unit [(If) −+ (If)''] should be 60 to 10 mol% of the total. It is preferable that the structural unit (I) − is 60 to 75 mol% of the total, and the structural unit [(II) −+ (
If)"] is preferably 40 to 25 mol% of the total, and the molar ratio of structural units (n)-/(■)" is 1/9
~9/1, and X is -CH2CH2-
In other cases, the range of 7.5/2.5 to 4/6 is preferable from the viewpoint of fluidity.

Furthermore, the dicarboxylic acid component in the above structural unit (■)-1(n)'' is terephthalic acid and/or isophthalic acid, and the molar ratio of terephthalic acid/isophthalic acid is 1010.
~6.5/3.5 is preferred.

Furthermore, in addition to the components constituting the above (I)--(IF)'', 1,2-bis(phenoxy)ethane-4,4-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane- A copolymer of 4,4-τ dicarboxylic acid can also be preferably used.

In addition to each component of the structural unit selected from the structural units (I) to (1), 4,4-diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as 3,4°-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, 1,2-bischlorophenoxy)ethane-4,4-monodicarboxylic acid, and alicyclic acids such as hexahydroterephthalic acid. dicarboxylic acids, aromatic dihydroxy compounds such as resorcinol, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid,
p-aminophenol, p-aminoamine, 0, franic acid, β-hydroxyethoxybenzoic acid, and the like may be further copolymerized within a proportion that does not impair the object of the present invention.

The above-mentioned aromatic polyester can be produced according to a conventional polyester polycondensation method, and there are no particular limitations, but typical examples include the following (1 ) to (4), when ethylene glycol is used, method (5) can be mentioned.

(1) Acylated product of p-acetoxybenzoic acid, 4゜4-
- A method for producing by deacetic acid polycondensation reaction from an acylated aromatic hydroxy compound such as diacetoxybiphenyl and an aromatic dicarboxylic acid such as terephthalic acid.

(2) A method for producing by deacetic acid polycondensation reaction from an aromatic dihydroxy compound such as p-hydroxybenzoic acid or 4,4-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid, and acetic anhydride.

(3) A method for producing phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4-monodihydroxybiphenyl and diphenyl esters of aromatic dicarboxylic acids such as terephthalic acid by dephenol polycondensation.

(4) Aromatic dicarboxylic acids such as P-hydroxybenzoic acid and terephthalic acid are reacted with a desired amount of diphenyl dicarbonate to form diphenyl esters, and then an aromatic dihydroxy compound such as 4.4-dihydroxybiphenyl is added. A method of producing by dephenol polycondensation reaction.

(5) A method of producing by method (1) or (2) in the presence of a polyester made from ethylene glycol and an aromatic dicarboxylic acid such as terephthalic acid.

Typical catalysts used in the polycondensation reaction are metal compounds such as 1$l of acetic acid cylinder, tetrabutyl titanate, lead acetate, antimony dioxide, magnesium, sodium acetate, potassium acetate, and trisodium phosphate. Effective during polycondensation.

Further, the aromatic polyester that can be preferably used in the present invention forms an anisotropic melt phase, but at a shear rate of 1.0 at a temperature 40°C higher than the temperature at which it starts to show anisotropy (liquid crystal start temperature).
Melt viscosity measured under the condition of 00 (1/sec) is 10~
15,000 voids can be preferably used.

In addition, as the olefin polymer used in the present invention, a copolymer consisting of α-olefins and glycidyl ester of α,β-unsaturated acid, ethylene and α-olefin having 3 or more carbon atoms, or ethylene-3 carbon atoms For the copolymer consisting of the above α-olefin and non-conjugated diene,
Modified ethylene polymers obtained by grafting unsaturated carboxylic acids or derivatives thereof are preferably used.

In the above-mentioned copolymer consisting of α-olefins and glycidyl ester of α,β-unsaturated acid, α-olefins preferably have 2 to 4 carbon atoms, and specifically, ethylene, propylene, butene- 1, among others, ethylene can be preferably used. Also, α, β−
The glycidyl ester of an unsaturated acid has the formula -fi (wherein, R is a hydrogen atom or a lower alkyl group).
Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. are used, and among them, glycidyl methacrylate is preferably used. The amount of copolymerized glycidyl ester of α,β-unsaturated acid is suitably in the range of 1 to 50 mol%. Furthermore, in an amount of 40 mol% or less, unsaturated monomers that can be copolymerized with the above copolymers, such as vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acids such as methyl, ethyl, and propyl, and Methacrylic acid esters, acrylonitrile, styrene, etc. may be copolymerized.

In addition, the above-mentioned ethylene and an α-olefin having 3 or more carbon atoms or a copolymer consisting of ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated diene (hereinafter both are collectively referred to as unmodified ethylene polymers) On the other hand, 0.01 to 10
In the modified ethylene polymer obtained by grafting % by weight of unsaturated carboxylic acid or its derivative, the α-olefin having 3 or more carbon atoms includes propylene, butene-1,
Pentene-1,3-methylpentene-1, octacene-
1, among others, propylene and butene-1
is preferably used. In addition, as a non-conjugated diene, 5
-Methylidene-2~norbornene, 5-ethylidene-2
-norbornene, 5-vinyl-2-norbornene, 5-
Propenyl-2-norbornene, 5-impropenyl-
2-norbornene, 5-crotyl-2-norbornene,
Norbornene such as 5-(2-methyl-2-butenyl)-2-norbornene, 5-(2-ethyl-2-butenyl)-2-norbornene, 5-methacrylnorbornene, 5-methyl-5-vinylnorbornene Compound, dicyclopentadiene, methyltetrahydroindene, 4,7,
8.9-Tetrahydroindene, 1,5-cyclooctadiene, 1,4-hexadiene, isoprene, 6-methyl-1,5-hebutadiene, 11-ethyl-i, 1. i
-hlysocacyene, etc., and preferably 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene, etc. can be used.

The unmodified ethylene copolymerization ratio of ethylene and an α-olefin having 3 or more carbon atoms is preferably in the range of 40/60 to 99/1 (molar ratio), particularly preferably 70/30 to 9515 (molar ratio).

The copolymerization amount of α-olefin having 3 or more carbon atoms in the unmodified ethylene copolymer consisting of ethylene, α-olefin having 3 or more carbon atoms, and non-conjugated diene is 5 to 80 mol%.
is preferable, particularly preferably -20 to 60 mol%, and the amount of copolymerized non-conjugated diene is preferably 0.1 to 20 mol%, particularly preferably 065 to 10 mol%.

Specific examples of unmodified ethylene copolymers include ethylene/
Propylene copolymer, ethylene/butene-1 copolymer,
Preferred examples include ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene-2-norbornene copolymer, and among others, ethylene/propylene copolymer containing no non-conjugated diene and ethylene/butene-1 copolymer. Copolymers have good heat resistance and can be used more preferably.

The unsaturated carboxylic acid for obtaining a modified ethylene copolymer by grafting onto the unmodified ethylene copolymer is preferably acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, or itaconic acid. , citraconic acid, butenedicarboxylic acid, etc. Examples of derivatives thereof include alkyl esters, glycidyl esters, acid anhydrides, and imides. Among these, glycidyl esters, acid anhydrides, and imides are preferred.

Preferred specific examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate,
Itaconic acid glycidyl ester, citraconic acid diglycidyl ester, butene dicarboxylic acid diglycidyl ester, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic acid imide, itaconic acid imide, citraconic acid imide, and especially methacrylic acid. glycidyl,
Maleic anhydride, itaconic anhydride, and maleic acid imide can be preferably used. Two or more of these unsaturated epoxy monomers may be used in combination.

The graft reaction amount of unsaturated carboxylic acid or its derivative is O, ' from the viewpoint of improving mechanical properties, especially surface impact resistance.
01 or higher, 10 in terms of heat resistance of aromatic polyester
The range is preferably 0.05 to 5% by weight or less, particularly 0.05 to 5% by weight.
It is preferable that

Note that the graft reaction here means that an unsaturated carboxylic acid or a derivative thereof is chemically bonded to an unmodified ethylene copolymer.

The modified ethylene copolymer is produced by adding an unsaturated carboxylic acid or its derivative and an organic oxide in an amount of 0.001 to 0.1% by weight based on the unmodified ethylene copolymer to an unmodified ethylene copolymer. It can be produced by melt-kneading at ~300°C. Devices for melt mixing include screw extruder and Banbury mixer.
etc. can be used.

Specifically, organic peroxides that can be preferably used in this graft reaction include tert-butylcumyl peroxide,
Di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2°5-di(tert-
butylperoxy)hexane, 2゜5-dimethyl-2,
5-di(tert-butylperoxy)hexyne-3,
α,α-di(tert-butylperoxy)diisopropylbenzene and the like.

Note that two or more of the above olefin polymers may be used in combination with the aromatic polyester forming the anisotropic melt phase.

The blending amount of the above copolymer is preferably 0.1 to 60 parts by weight, particularly 0.5 to 20 parts by weight, per 100 parts by weight of the aromatic polyester. The effect of improving impact properties is small, and if the amount exceeds 60 parts by weight, the advantages of aromatic polyester, which forms an anisotropic melt phase, such as high elastic modulus, excellent molding fluidity, and heat resistance, will be impaired, so in either case. Undesirable.

Furthermore, in addition to the above-mentioned aromatic polyester, glass fiber, carbon fiber,
By adding additives such as asbestos reinforcing agents, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and flame retardants, as well as external thermoplastics and resins, Characteristics can be given.

The method for producing the composition of the present invention is not particularly limited, but a preferred method is to melt-knead the aromatic polyester, olefin polymer, and, if necessary, additives using an extruder.

The aromatic polyester obtained according to the present invention can be easily molded by methods such as injection molding and extrusion molding, and the obtained molded product exhibits excellent performance.

<Example> The present invention will be explained in further detail below using Examples.

Reference Example 1 608 parts by weight of p-acetoxybenzoic acid, 122 parts by weight of 4.4-diacetoxybiphenyl, 75 parts by weight of terephthalic acid and 130 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.6 were mixed with a stirring blade and distilled. The mixture was charged into a reaction vessel equipped with a tube, and acetic acid depolymerization was performed.

First, the reaction was carried out at 250 to 300°C for 2.5 hours in a nitrogen gas atmosphere, and then the pressure was reduced to 0.2 HQ at 300°C, and the reaction was further carried out for 3.25 hours to complete the polycondensation. A stoichiometric amount of acetic acid was distilled out to obtain resin A having the following theoretical structural formula.

Jl/m/n=75/10/15 In addition, this polyester was placed on the sample stage of a polarizing microscope rR mirror, and the optical anisotropy was confirmed by raising the temperature. As a result, the liquid crystal start temperature was 264 ° C. It showed good optical anisotropy.

The logarithmic viscosity of this polyester (measured at 60°C in pentafluorophenol at a concentration of <0.1% by weight) is 1.25
304'C1 The melt viscosity at a sliding speed of 1°000 (1,/sec) was 300 voids.

Reference Example 2 519 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4.4-1 diacetoxybiphenyl, 85 parts by weight of 1-butylhydroquinone diacetate, 19.4 parts by weight of hydroquinone diacetate, and 186 parts by weight of terephthalic acid. The mixture was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and reacted at 250 to 340°C for 3.0 hours in a nitrogen gas atmosphere. After raising the temperature to 350°C, 1. ') The pressure inside the system was reduced to nw+IIQ, and the system was further heated for 1.0 hour to carry out a polycondensation reaction to obtain resin B having the following theoretical structural formula.

t-Bu j /m/n10=72/17/8.5/2.5 Also,
When this resin B was placed on a sample stage of a polarizing microscope and the temperature was raised to check the optical anisotropy, it showed good optical anisotropy at 307°C or higher.

The logarithmic viscosity of this polyester (measured under the same conditions as Reference Example 1) was 4.3, at 347°C and a sliding speed of 1,000.
The melt viscosity at (1/sec) was 2,600 voids.

Reference Example 3 541 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4.4-diacetoxybiphenyl, 62 parts by weight of hydroquinone diacetate, 124 parts by weight of terephthalic acid, 42 M of isophthalic acid! A certain amount was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and heated to 250 to 360 ml under a nitrogen gas atmosphere.
After reacting at ℃ for 3 hours, the pressure was reduced to 1 maHO and further heated for 1 hour to complete the polycondensation and obtain resin C having the following theoretical structural formula.

j / m / n = 75 / 18.75 / 6.25 When this polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy, good optical anisotropy was observed at 305°C or higher. showed his sexuality.

The logarithmic viscosity of this polyester (measured under the same conditions as Reference Example 1) was 4.1 at 345°C and a sliding speed of 1,000.
The melt viscosity at (1/sec) was 6,200 voids.

Reference Example 4 (Production of modified ethylene polymer) Ethylene/butene-1 copolymer (butene-1 copolymer lid 10 mol%)
To 100 parts by weight, 4 parts by weight of glycidyl methacrylate and 30,015 parts by weight of 2,5-dimethyl-2,5-(tert-butylperoxy)hexyne were charged into a Henschel mixer through which nitrogen was passed, and the mixture was mixed for 6 minutes. Stir to create a homogeneous mixture.

This mixture was extruded using a 401nIφ extruder with a L/D of 28 and equipped with a dalmage type screw at the screw rotation speed of 80 rpm and a cylinder temperature of 200°C, resulting in modified ethylene copolymer pellets (a
) was obtained.

After pulverizing the pellets, acetone was added, and unreacted glycidyl methacrylate was extracted using a Soxhlet extractor for 20 hours. Furthermore, after drying the pellet, it was dissolved in p-xylene, and the ultraviolet absorption spectrum was measured to quantify the graft reaction base of glycidyl methacrylate. As a result, it was found that 1.1 ffif% of glycidyl methacrylate had undergone a graft reaction.

Reference Examples 5 to 7 In the same manner as in Reference Example 4, a graft reaction of glycidyl methacrylate or maleic anhydride was carried out on various unmodified ethylene copolymers shown in Table 1 to obtain modified ethylene copolymers (b to d) was obtained.

The results are shown in Table 1.

Table 1 Example 1 100 parts by weight of the resin A obtained in Reference Example 1 was triblended with 10 parts by weight of an ethylene-glycidyl methacrylate <90/10 mol) copolymer, and the mixture was subjected to single-screw extrusion at 300°C. After combining the dissolved Mti with a machine, it was pelletized. The aromatic polyester composition pellet thus obtained was molded into a nestal injection molding machine using a Promat 40 injection molding machine.
/25 (manufactured by Custom Heavy Machine Industry Co., Ltd.) to form a 2-inch thick disc and a 3Il11-thick square plate under the conditions of a cylinder temperature of 300°C and a mold temperature of 90°C.

A DuPont falling ball impact test (ball radius 6fi, load 250 g) was conducted using the obtained 2fi thick disk, and molding shrinkage was measured using a 3fi thick square plate. The results are shown in Table 2.

Examples 2 to 5 100 parts by weight of the resin A obtained in Reference Example 1 was triblended with parts by weight of modified ethylene copolymers a to dlo obtained in Reference Examples 4 to 7 as olefin polymers, and the mixture was heated at 300°C.
The mixture was melt-mixed and pelletized using a single screw extruder set at . The obtained pellet was molded under the same conditions as in Example 1, and the same falling ball impact test and molding shrinkage rate measurements were performed. The results are shown in Table 2.

Example 6.7 To 8100 ff parts of the resin obtained in Reference Example 2, 10 parts by weight of ethylene-glycidyl methacrylate (90/10 mol) copolymer or #obtained in Example 4 was added as an olefin polymer. 10 parts by weight of modified ethylene copolymer a were triblended, melt mixed in a single screw extruder set at 350°C, and then pelletized.

The obtained pellets were subjected to a Density Nestal injection molding machine, Promat 40/25 (manufactured by Ordinary Heavy Machine Industry Co., Ltd.), and the cylinder temperature was 350°C and the mold temperature was 90°C.
A disk with a thickness of mm and a square plate with a thickness of 3IWII were molded, and the same tests as in Example 1 were conducted. The results are shown in Table 2.

Example 8.9 Disks and square plates obtained in the same manner as in Examples 3 to 6 except that Resin C obtained in Reference Example 3 were used were tested in the same manner as in Example 1. The results are shown in Table 2.

Examples 10 to 12 Example 1 was obtained by blending and extruding resins D to F shown in the following theoretical structural formula and polyethylene-glycidyl methacrylate (molar ratio 90/'10) copolymer at the ratio shown in Table 2.
The molding was performed under the same conditions as above, and the falling ball impact test of the discs and square plates and the measurement of the molding shrinkage rate were performed. The results are shown in Table 2.

(Liquid crystal starting temperature 182℃, 222℃, shear rate 1゜00
0 (1/sec) melt viscosity 1.600 voids) [Resin E] (Liquid crystal start temperature 256°C 1296°C, sliding speed 1°0
00 (1/sec) melt viscosity 2.200 voids) [Resin F] (Liquid crystal starting temperature 373°C, 413°C, sliding speed 1°00
Melt viscosity at 0 (1/sec) 8,600 voids) Example 1
3 To 70 parts by weight of resin A obtained in Reference Example 1, glass fiber (
3m + length, diameter 10μ, chopped strand) 30! parts and ethylene-glycidyl methacrylate (90/1
0 molar ratio) 10 overlapping parts of the copolymer were triblended, and 3
After melt mixing in a single screw extruder set at 00°C, the mixture was pelletized. The obtained pellets were molded in the same manner as in Example 1,
A falling ball test was performed on the obtained disc. The results are shown in Table 2.

Example 14 Resin B obtained in Reference Example 2, glass fiber (3III length, diameter 10μ, chopped strands and ethylene-glycidyl methacrylate (90/10 molar ratio) copolymer are shown in Table 3.
Blend extrusion was carried out at the ratio shown in Figure 1, to produce molded products similar to those in Example 1, and a falling ball impact test was conducted. Table 3 shows the results.
Shown below.

Examples 15 to 17 Resins D to F, glass fibers (3 mm length, diameter 10 μ chopped strands), and ethylene-glycidyl methacrylate (90/10 molar ratio) copolymer were blended and extruded in the proportions shown in Table 3. , molded under the same conditions as Example 1,
A falling ball test was conducted.

The results are shown in Table 3.

The above results show that the aromatic polyester composition of the present invention has excellent falling ball impact strength and reduced anisotropy.

<Effects of the Invention> The aromatic polyester composition of the present invention has excellent fluidity, heat resistance, impact strength, and reduced anisotropy, so it can be used in various fields such as automobile exterior panels. be able to.

Claims (2)

[Claims] (1) 0.00 parts by weight of an olefin polymer per 100 parts by weight of an aromatic polyester that forms an anisotropic melt phase consisting of one or more structural units selected from the following structural units (I) to (III). An aromatic polyester composition containing 1 to 60 parts by weight. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (However, X in the formula ▲ Mathematical formula, chemical formula, There are tables, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Indicates one or more groups selected from ▼ and -CH_2CH_2-, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. Indicates one or more groups selected from ▼ and ▲ mathematical formulas, chemical formulas, tables, etc. ▼. Note that the carbonyl groups in the dicarboxylic acid component in (II) are in a meta and/or para relationship with each other. ) (2) Olefin polymers are α-olefins and α, β
- The aromatic polyester composition according to claim 1, which is a copolymer consisting of a glycidyl ester of an unsaturated acid. (3) The olefin polymer contains 0.01 to 10% by weight of ethylene and an α-olefin having 3 or more carbon atoms, or a copolymer consisting of ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated diene. The aromatic polyester composition according to claim 1, which is a modified ethylene polymer obtained by grafting a saturated carboxylic acid or a derivative thereof.