JP3313515B2 - Liquid crystalline polyester 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 composition obtained by imparting elongation, flexibility and impact resistance to a liquid crystalline polyester. More specifically, liquid crystallinity, which is an advantage of a liquid crystalline polyester capable of forming an anisotropic melt, is plasticized within a range that retains high strength, high flexural modulus and low linear expansion coefficient, and elongation, flexibility and The present invention relates to a composition of a liquid crystalline polyester and an epoxidized block copolymer and / or an epoxidized hydrogenated block copolymer for the purpose of imparting impact resistance.

[0002]

2. Description of the Related Art In recent years, research on various liquid crystal compounds has been actively conducted due to expectations for application to optical materials. Especially with regard to polymer liquid crystals, Eastman Kodak's WJJaks
on announces thermotropic liquid crystalline polyester (JP
olym.Sci.Polym.Chem.Ed., 14,2043 (1976))
Attention has been paid to liquid crystallinity and the possibility of high-strength, high-elastic polymer materials, and many studies have been made. The liquid crystalline polyester reported by WJJakson et al. Is a polyester of polyethylene terephthalate and p-hydroxybenzoic acid, which is oriented in a molten state and under shear, and can be injection-molded and extruded. The molded product was highly oriented even without stretching, and had advantages of high strength and high flexural modulus.

[0003] However, various liquid crystalline polyesters have been subsequently announced, and their practical use has been studied. However, despite the high expectations for high-strength materials and optical materials, they have still been embodied as industrial products. At present.

[0004]

As described above, one of the main reasons why the liquid crystalline polyester is difficult to be put into practical use is that:
This is because the molded article has high strength and high elasticity, but has poor flexibility, is hard and brittle, and has a disadvantage that it is easily broken by bending.

There have been attempts to improve this disadvantage by adding a plasticizer, but none of them have been found to be practically usable, such as impairing the liquid crystallinity.

It is also conceivable to copolymerize a component that imparts flexibility when polymerizing the liquid crystalline polyester. However, in general, the compatibility is deteriorated, and a uniform molded product cannot be obtained. The current situation is that it gets worse.

On the other hand, JP-A-61-73731 and JP-A-61-97326
Discloses a method for imparting flexibility by reacting a specific amount of phenylenebisoxazoline with a liquid crystalline polyester. However, in these methods, expensive and sublimable components are used, and special reaction equipment is required, such as accompanied by thickening during the reaction, the operation is complicated, leading to an increase in cost, and there is an industrial problem. .

An object of the present invention is to solve these problems and to provide flexibility easily without practically impairing the properties of the liquid crystalline polyester.

[0009]

Means for Solving the Problems The inventors of the present invention have practically maintained the liquid crystallinity, high strength, high elasticity and the like, which are the advantages of the liquid crystalline polyester obtained by copolymerizing a hydroxy aromatic carboxylic acid. As a result of sincerely examining methods for imparting elongation, flexibility and impact resistance with, and eliminating defects such as brittleness, weakness, and easy cracking of molded products, epoxidized hydrogenated block specific to liquid crystalline polyester It has been found that by adding a specific amount of the copolymer, flexibility can be imparted without impairing the advantages of the liquid crystalline polyester, and that the processability can be improved, and the present invention has been completed.

That is, the present invention relates to (a) the following general formulas (I), (II) and (III): (I) -CO-R1-O- 20 to 80 mol% (II) -CO-R2 —CO—40 to 10 mol% (III) —O—R 3 —O—40 to 10 mol% [where the molar ratio of (II) to (III) is 1;
Is a divalent aromatic derivative residue having 6 to 15 carbon atoms, and R2 is a divalent aromatic derivative residue having 6 to 15 carbon atoms, a divalent alicyclic derivative residue having 4 to 20 carbon atoms or a carbon number. R1 is a divalent aromatic derivative residue having 6 to 15 carbon atoms, a divalent alicyclic derivative residue having 4 to 20 carbon atoms or a C1 to C20 divalent aliphatic derivative residue; 70-99 parts by weight of a liquid crystalline polyester capable of forming an anisotropic melt; (b) a vinyl aromatic compound in the same molecule; The double bond of unsaturated carbon of the conjugated diene compound of the partially hydrogenated block polymer obtained by partially hydrogenating a block polymer consisting of a polymer block A and a polymer block B mainly comprising a conjugated diene compound Hydropar in an inert solvent
A liquid crystalline polyester resin composition comprising 1 to 30 parts by weight of an epoxy-modified block polymer epoxidized by reacting with an epoxidizing agent such as an oxide or a peracid . ".

Hereinafter, the present invention will be described in detail.

In the present invention, the liquid crystalline polyester used as the component (a) has a hydroxyaromatic carboxylic acid residue of 20 to 80 mol% and a dicarboxylic acid residue of 40 to 10 mol%.
And the diol residue is 40 to 10 mol%, and the ratio of the dicarboxylic acid residue to the diol residue is 1.

The residue of the hydroxyaromatic carboxylic acid in the liquid crystalline polyester as the component (a) in the present invention must be in the range of 20 to 80 mol% in order to exhibit liquid crystallinity. From the viewpoint of the balance between the liquid crystallinity and the internal plasticizing effect of the polymer chain, 35 to 50 mol% is more preferable. R ^{1 in} the general formula (I) of the hydroxyaromatic carboxylic acid residue is a divalent aromatic derivative residue having 6 to 15 carbon atoms.
-Hydroxybenzoic acid, m-hydroxybenzoic acid, 3,
5-dimethyl-4-hydroxybenzoic acid, 2-hydroxy-5-naphthalenecarboxylic acid, 2-hydroxy-6-
Examples include naphthalene carboxylic acid, 1-hydroxy-5-naphthalene carboxylic acid, p-hydroxycinnamic acid and derivatives thereof such as alkylated aromatic compounds and halides thereof.

These may be used alone or as a mixture of two or more. Of these, p
-Hydroxybenzoic acid and 2-hydroxy-6-naphthalenecarboxylic acid are preferred because they give a suitable rigid straight chain and give good liquid crystallinity.

R ² in the dicarboxylic acid residue represented by the general formula (II) is a residue of a divalent aromatic derivative having 6 to 15 carbon atoms or a residue of a divalent alicyclic derivative having 4 to 20 carbon atoms. Or a divalent aliphatic derivative residue having 1 to 20 carbon atoms. Specific examples include terephthalic acid, isophthalic acid, 2-methylterephthalic acid,
Diphenic acid, 2,6-naphthalenedicarboxylic acid, 2,5
-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, p, p'-dibenzoic acid, 4,4'-methylenedibenzoic acid, 4,4'sulfonylbenzoic acid, p-oxy (p-carboxyphenyl) benzoic acid Acid, ethylene-bis-p-benzoic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Examples thereof include dicarboxylic acids such as suberic acid, azelaic acid, sebacic acid, diglycolic acid, and dipropionic acid, and derivatives thereof such as alkylated products and halides thereof. These may be used alone or as a mixture of two or more. Of these dicarboxylic acids,
Aromatic ones are preferred because they give good liquid crystalline polyesters, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferred.

Further, when 80 mol% or more of the dicarboxylic acids are used with terephthalic acid and / or 2,6-naphthalenedicarboxylic acid and the remaining less than 20 mol% are mixed with various kinds of dicarboxylic acids, the physical properties are poor. It is preferable because it gives a liquid crystalline polyester excellent in balance and transparency.

On the other hand, R ³ in the diol residue represented by the general formula (III) is a divalent aromatic derivative residue having 6 to 15 carbon atoms,
Divalent alicyclic derivative residue having 4 to 20 carbon atoms or 1 to 20 carbon atoms
Is a divalent aliphatic derivative residue of

Specific examples include hydroquinone, resorcinol, 4,4'-diphenol, 4,4'-methylenediphenol, 4,4'-isopropylidenediphenol, 4,4'-sulfonyldiphenol, 4'-
Dihydroxy diphenyl ether, 3,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl ketone, 2,5-naphthalenediol, 2,6-
Naphthalene diol, 1,4-cyclohexanediol, 1,6-cyclohexanediol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,4-dimethyl-2-ethylenehexane-1,3 -Diol, 2,
2,4-trimethyl-1,3-pentanediol, 2,
Diols such as 2-dimethyl-1,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and alkylated and halogenated compounds thereof Derivatives. These may be used alone or as a mixture of two or more. Of these, ethylene glycol, hydroquinone, 4,4'-isopropylidene diphenol, 4,4'-diphenol, 4,4 '
-Dihydroxydiphenyl ether is the preferred diol. In particular, ethylene glycol and / or hydroquinone are used for at least 80 mol% of the diol, and the remaining 20
When less than mol% is used in combination with various diols,
It is preferable because it gives a liquid crystalline polyester having a good balance of physical properties.

The liquid crystalline polyester used in the present invention is generally required to have a polymer chain composed of a rigid linear chain having a high linearity in order to exhibit liquid crystallinity. It may contain a non-linear portion to some extent, or may be one which is reacted with a chain extender such as a bifunctional epoxy compound or phenylenebisoxazoline as long as the liquid crystallinity is not impaired.

The liquid crystalline polyester in the present invention can be produced by various methods in the same manner as ordinary polyester. For example, melt polymerization may be performed using an acetylated monomer, or a polyester obtained from a dicarboxylic acid component and a diol component and a hydroxyaromatic carboxylic acid may be heated and melted, and copolymerized by an acidolysis reaction under a stream of dry nitrogen. A method in which a polyester fragment is formed and then thickened under reduced pressure may be used. The liquid crystalline polyester used in the present invention has an intrinsic viscosity (1,1,1).
2,2, tetrachloroethane / pentafluorophenol = 50/50 (measured at 30 ° C using a weight ratio solvent) is preferably 0.3 or more. When the intrinsic viscosity is less than 0.3, the polymer does not exhibit sufficient properties such as strength and the like, becomes brittle, and does not achieve the object of the present invention.

Next, the epoxidized hydrogenated block copolymer used as the component (b) in the liquid crystalline polyester resin composition of the present invention is blended with the liquid crystalline polyester as the component (a) to obtain mainly a flexibility. And an essential component for imparting impact resistance. By blending the component (b), the liquid crystalline polyester can be plasticized within a range where the inherent advantages of the liquid crystalline polyester, such as liquid crystallinity, high strength, and high flexural modulus, are practically maintained. Flexibility, elongation, and impact resistance are imparted, brittleness and fragility, which were disadvantages in practical use, are improved, and workability can be improved.

The epoxidized hydrogenated block copolymer which can be used as one of the components (b) is a hydrogenated conjugated polymer block A mainly composed of a vinyl aromatic compound in the same molecule. It is obtained by epoxidizing a block copolymer consisting of a polymer block B mainly composed of a diene compound and includes, for example, AB, ABA, BABA, (A- B) Epoxidized vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as 4Si, (BAB) 4Si or the like.

The term "block copolymer" as used herein means a block copolymer consisting of a polymer block A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a hydrogenated conjugated diene compound. Good, the copolymerization ratio of the vinyl aromatic compound and the conjugated diene compound is 5:95 to 70:30,
Particularly preferred is a polymerization ratio of 10:90 to 60:40.

The number average molecular weight of the block copolymer used in the present invention is 5,000 to 600,000, preferably 10,000.
And the molecular weight distribution is expressed as a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1
It is 0 or less.

As the vinyl aromatic compound constituting the block polymer used in the present invention, for example, styrene,
One or more of α-methylstyrene, vinyltoluene, p-tert-butylstyrene, divinylbenzene, p-methylstyrene, 1,1-diphenylstyrene and the like can be selected, and styrene is particularly preferred.
Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, and phenyl-1,3-diene. One or two or more of butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

As a method for producing the block polymer used in the present invention, any production method having the above-mentioned structure can be adopted. For example, Japanese Patent Publication No. 40-23798
No., JP-B-43-17979, JP-B-46-32415, JP-B-56-2
According to the method described in JP-A-8925, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like, and furthermore, Japanese Patent Publication No. 42-870.
No. 4, JP-B-43-6636, or JP-A-59-1
According to the method described in JP-A-33203, the partially hydrogenated block copolymer for use in the present invention can be synthesized by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst.

The method for epoxy-modifying these block copolymers is not particularly limited in the present invention. For example, a vinyl aromatic compound-conjugated diene compound block copolymer may be prepared by hydroperoxides,
It can be obtained by reacting with an epoxidizing agent such as peracids.

As the inert solvent, for example, hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, chloroform and the like can be used.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like. The peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Of these, peracetic acid is industrially produced in large quantities, can be obtained at low cost, and has high stability.
It is a poxifying agent. Further, a catalyst can be used as needed in the epoxidation. For example, in the case of peracids, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. There is no strict regulation on the amount of epoxidizing agent, and the optimal amount in each case is
It depends on variables such as the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, and the like.

There are no strict restrictions on the epoxidation reaction conditions. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. For example, 0-
70 ° C. is preferred, and if it exceeds 70 ° C., decomposition of peracetic acid occurs.

No special manipulation of the reaction mixture is required, for example, the mixture may be stirred for 2 to 10 hours. The obtained epoxy-modified copolymer can be isolated by an appropriate method, for example, a method of precipitating with a poor solvent, a method of putting the polymer into hot water with stirring, and removing the solvent by distillation.

The degree of epoxidation of the epoxy-modified block polymer in the present invention is calculated by the following equation by titration with hydrobromic acid.

[0033] The epoxy equivalent of the epoxy-modified block polymer in the present invention is 140 to 10,000 g / mol, particularly preferably 20 to 10,000 g / mol.
It is between 0 and 6000 g / mol.

The composition of the present invention comprises, as a modifying component for imparting flexibility and impact resistance to the liquid crystalline polyester of the above component (a), the epoxidized block copolymer of the above component (b) and / or Alternatively, it is constituted by essentially using an epoxidized hydrogenated block copolymer. The mixing ratio of such a composition is such that the liquid crystalline polyester used as the component (a) is 70 to 99 parts by weight, and the epoxidized block copolymer and / or epoxidized hydrogenated block used as the component (b) is 100 parts by weight of the composition. The copolymer is 30 to 1 part by weight.
When the amount of the component (a) is less than 70 parts by weight, the resulting composition does not form an anisotropic melt and does not exhibit liquid crystallinity, and also loses the high strength and high elasticity characteristics of liquid crystalline polyester. We do not like it.

On the other hand, if the component (b) is less than 1 part by weight, a plasticizing effect is insufficient and a flexible composition cannot be obtained, and only a brittle and fragile composition can be obtained. A more preferable mixing ratio of the component (b) is 20 to 3 parts by weight, particularly preferably 10 to 5 parts by weight, per 100 parts by weight of the composition.

As a method for obtaining the composition of the present invention, the component (b) may be added to a molten liquid crystalline polyester and mixed by heating, or a solid (eg, pellet, chip, powder, etc.) The composition can be obtained by previously mixing the component (a) and the component (b) with a Henschel mixer, a blender or the like, and kneading them with a heating roll or an extruder.
In the case of melting and kneading, the melting and kneading are preferably performed at a temperature of 400 ° C. or less, particularly 300 ° C. or less, in order to avoid decomposition and gelation of the components (a) and (b).

The composition thus obtained can be easily processed into a sheet by hot pressing, and various molded articles can be obtained by extrusion molding or injection molding.

[0038]

The composition obtained by the present invention has liquid crystallinity, flexibility, elongation, bending strength, impact resistance, low-temperature properties, etc. while maintaining high strength and high elastic modulus in practical use. , And the processability is also improved, so that it can be suitably used for a wide range of industrial applications such as various molding resins, fibers, films, composite materials, adhesives, and paints.

[Examples] Next, the present invention will be further described with reference to examples. In the following description, parts and% mean parts by weight and% by weight, respectively.

Reference Example A / Synthesis of Liquid Crystalline Polyester [A-1] In a 1-liter autoclave equipped with a stirrer and a condenser, 144.0 g (0.80 mol) of 4-acetoxybenzoic acid was placed.
, 99.6 g (0.60 mol) of terephthalic acid, 187.2 g (0.60 mol) of 4,4'-diacetoxyisopropylidenediphenyl
And 0.4 g of sodium acetate, and the inside of the system was replaced with nitrogen by a vacuum operation. Then, the mixture was kept at 240 ° C. for 20 minutes with stirring, and then heated to 260 ° C. to start acetic acid distillation.

After holding at this temperature for 45 minutes, at 290 ° C. for 45 minutes,
The mixture was kept at 320 ° C. for 35 minutes to further distill acetic acid. The viscosity in the system increased with the progress of the reaction. Next, the pressure inside the system was gradually reduced and maintained at 15 mmHg for 15 minutes. Then, the temperature was raised to 350 ° C. and the pressure was reduced to 0.5 mmHg or less and maintained for 20 minutes to carry out a condensation reaction.

Then, the system was returned to normal pressure by introducing dry nitrogen, and then pressurized to about 5 kg / cm ² , and the polymer was cooled while being extruded from the lower part of the autoclave in a molten state, thereby obtaining p-hydroxybenzoic acid. (Polyester) having a molar ratio of 40.0 / 30.0 / 30.0 residues / residue of terephthalic acid / residue of 4,4′-isopropylidenediphenol. This is 0.1 g / 1 in 1,1,2,2-tetrachloroethane / pentafluorophenol = 50/50 (weight ratio).
The intrinsic viscosity measured at 30 ° C. at a concentration of 0 ml was 0.85.

The present polymer was manufactured using a polarizing microscope TH-6 manufactured by Linkam.
00 forms an optically anisotropic molten phase at about 300 ° C,
It was confirmed to exhibit liquid crystallinity.

[A-2] p-Hydroxybenzoic acid is obtained in the same manner as in [A-1] except that 4,4'-diacetoxydiphenyldiphenyl is used instead of 4,4'-diacetoxyisopropylidenediphenyl. The molar ratio of the residue of ## STR1 ## / residue of terephthalic acid / residue of 4,4'-diacetoxydiphenol was 64.0 / 18.0 / 18.0, and a liquid crystalline polyester having an intrinsic viscosity of 0.82 was obtained.

[A-3] 4,4'-diacetoxydiphenyl ether is used in place of 4,4'-diacetoxyisopropylidenediphenyl, and 6-acetoxy-
In the same manner as in [A-1], except that 2-naphthalenecarboxylic acid is used, the residue of p-hydroxybenzoic acid / 6-acetoxy-2-naphthalenecarboxylic acid / the residue of terephthalic acid / 4,4 A 4'-diacetoxydiphenyl ether residue molar ratio was 49.0 / 3.0 / 24.0 / 24.0, and a liquid crystalline polyester having an intrinsic viscosity of 0.78 was obtained.

[A-4] In a 1 liter autoclave type polymerization machine equipped with a stirrer, 215.4 g (1.12 mol) of polyethylene terephthalate having an intrinsic viscosity of 0.68 and p-hydroxybenzoic acid 25
Charge 9.4g (1.88mol), 280 ℃ in dry nitrogen stream
And the acidolysis reaction was advanced according to the method described in JP-B-56-18016. Then, the reaction system was gradually reduced in pressure, polymerized at about 0.2 mmHg for 5 hours, and then cooled while extruding the polymer in a molten state from the lower part of the autoclave under a dry nitrogen pressure of 5 kg / cm ² to obtain a liquid crystalline polyester. Was. Its intrinsic viscosity, measured in the same manner as in [A-1], was 0.70, indicating that the p-hydroxybenzoic acid residue
The molar ratio of / terephthalic acid residue / ethylene glycol residue =
45.6 / 27.2 / 27.2, indicating liquid crystallinity.

[A-5] In the same manner as [A-4], it is composed of residues of 0.95 mol of terephthalic acid, 0.05 mol of isopropylic acid, 0.09 mol of ethylene glycol and 0.10 mol of 4,4'-isopropylidenediphenol. From a copolyester having an intrinsic viscosity of 0.71 and 1.03 mol of p-acetoxybenzoic acid, a p-hydroxybenzoic acid residue / terephthalic acid residue / isophthalic acid residue / ethylene glycol residue / 4,4 ′ having an intrinsic viscosity of 0.74. -A liquid crystalline polyester having a molar ratio of isopropylidene diphenol residues = 34.0 / 31.4 / 1.6 / 29.7 / 3.3 was obtained.

[A-6] In the same manner as in [A-5], except that 1.50 mol of p-acetoxybenzoic acid and 0.15 mol of 6-acetoxy-2-naphthalenecarboxylic acid were used instead of p-acetoxybenzoic acid. Having an intrinsic viscosity of 0.85 and a molar ratio of p-hydroxybenzoic acid residue / 6-hydroxy-2-naphthalenecarboxylic acid residue / terephthalic acid residue / ethylene glycol residue / 4,4′-isopropylidene diphenol residue = 41.1 / 4.1 / 26.0 / 1. 4 / 24.7 / 2.7.

Reference Example B / Synthesis of Epoxidized Hydrogenated Block Copolymer Hydrogenated polystyrene-polybutadiene was placed in a jacketed reactor equipped with a stirrer, a reflux tube and a thermometer.
300 g of block copolymer of polystyrene [manufactured by Asahi Kasei Corporation, trade name: Tuftec H1041], 1500 g of cyclohexane
Was charged and dissolved. Subsequently, 15 g of a 30% by weight solution of peracetic acid in ethyl acetate was continuously dropped, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer having an epoxy equivalent of 5730.

<< Examples 1 to 6, Comparative Examples 1 to 6 >> Reference Example A
90 parts by weight of various liquid crystalline polyesters obtained in the above and Reference Example B
10 parts by weight of the epoxidized block copolymer obtained in
It was blended at 300 ° C. in a mmφ twin screw extruder (L / D = 28) to obtain a pelletized composition. This composition was injection molded at 300 ° C., and various physical properties were measured. Table 1 shows the results. The physical properties of each liquid crystalline polyester alone are also shown in Table 2 as a comparative example, and it can be seen that the composition obtained by the present invention has improved elongation while maintaining liquid crystallinity, and imparts flexibility.

<< Examples 7 to 10 and Comparative Examples 7 and 8 >> The liquid crystalline polyester obtained in Reference Example A-4 and the block copolymer obtained in Reference Example B were mixed in various composition ratios according to Example 1. Mix and evaluate.

As shown in Table 3, the book copolymer of Comparative Example 7 using Tuftec H1041 (referred to as block copolymer C), which was the raw material of Reference Example B, was used as the block copolymer. I understand. Further, in Comparative Example 8 outside the composition range of the present invention, it can be seen that the liquid crystallinity is lost although the flexibility is provided. Table 1 Example 1 2 3 4 5 6 Polyester number used A-1 A-2 A-3 A-4 A-5 A-6 Parts by weight 92 92 92 92 92 92 Block copolymer used B B BB BB weight part 8 8 8 8 8 8 Tensile strength (kg / cm ² ) 830 1070 900 1490 1150 1500 Elongation (%) 82 60 59 75 61 64 Flexural modulus (kg / cm ² ) 249 720 465 684 520 628 Izod impact strength 30 45 39 22 34 30 (Kg · cm / cm, with 1/8 inch notch) Liquid crystal property Yes Yes Yes Yes Yes Bending elastic modulus is × 100. Table 2 Comparative Example 1 2 3 4 5 6 Polyester used No.A-1 A-2 A-3 A-4 A-5 A-6 parts by weight 100 100 100 100 100 100 Block copolymer used − − − − − − Tensile strength (kg / cm ² ) 920 1290 1000 1780 1420 1850 elongation (%) 25 6 14 11 12 16 Flexural modulus (kg / cm ² ) 280 980 530 760 579 722 Izod impact strength 4.1 13 11 7.2 6.1 7.7 (Kgcm / cm, with 1/8 inch notch) liquid crystalline Yes Yes Yes Yes Yes Yes flexural modulus × 100 table 3 example Comparative example 7 8 9 10 7 Using Polyester No. A-4 A-4 A- 4 A-4 A-4 A-4 parts by weight 75 85 95 98 95 65 Using the block copolymer B B B B C B parts by weight 25 15 5 2 5 35 Tensile strength (kg / cm ² ) 1160 1400 1610 1650 1590 980 Elongation (%) 110 95 42 25 39 165 Flexural modulus (kg / cm ² ) 532 603 685 720 685 320 Izod impact strength 38 27 14 10 9 53 (Kgcm / cm, with 1/8 inch notch) Liquid crystal Yes Yes Yes Yes Yes Yes Flexural modulus x100 (Margin below)

Claims (1)

(57) [Claims] (1) The following general formulas (I), (II) and (III): (I) -CO-R1-O- 20 to 80 mol% (II) -CO-R2-CO-40- 10 mol% (III) -OR 3 -O- 40 to 10 mol% [where the molar ratio of (II) to (III) is 1;
Is a divalent aromatic derivative residue having 6 to 15 carbon atoms, and R2 is a divalent aromatic derivative residue having 6 to 15 carbon atoms, a divalent alicyclic derivative residue having 4 to 20 carbon atoms or a carbon number. R1 is a divalent aromatic derivative residue having 6 to 15 carbon atoms, a divalent alicyclic derivative residue having 4 to 20 carbon atoms or a C1 to C20 divalent aliphatic derivative residue; 70-99 parts by weight of a liquid crystalline polyester capable of forming an anisotropic melt; (b) a vinyl aromatic compound in the same molecule; The double bond of unsaturated carbon of the conjugated diene compound of the partially hydrogenated block polymer obtained by partially hydrogenating a block polymer consisting of a polymer block A and a polymer block B mainly comprising a conjugated diene compound Hydropar in an inert solvent
A liquid crystalline polyester resin composition comprising 1 to 30 parts by weight of an epoxy-modified block polymer epoxidized by reacting with an epoxidizing agent such as an oxide or a peracid .