JPH0543779A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition producible at a low cost and exhibiting excellent properties of a liquid crystal polyester even at a low content of liquid crystal polyester. CONSTITUTION:The objective thermoplastic resin composition is composed of (A) 20-50vol.% of a liquid crystal polyester and (B) 80-50vol.% of a polymer containing epoxy group, wherein the component A forms a continuous phase.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an inexpensive thermoplastic resin composition having excellent heat resistance and mechanical properties.

[0002]

2. Description of the Related Art In recent years, basic research and applied research on liquid crystal polymers have been actively conducted. For example, a copolymer of para-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (JP-A-54-77691), para-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and terephthalic acid, isophthalic acid Copolymer (Japanese Patent Publication Sho 5)
7-24407) and the like. These liquid crystal polyesters have excellent fluidity, heat resistance, rigidity, and dimensional accuracy, but are expensive, so that their range of use is extremely limited.

On the other hand, general-purpose thermoplastic resins are cheaper than liquid crystal polyesters, but their heat resistance and rigidity are not so high, and it is desirable to further improve them in order to develop new applications. As a method for improving this, a method of blending a reinforcing material such as calcium carbonate or glass fiber is known, but since the specific gravity of the material is increased, the advantage of the lightweight characteristic of plastic is reduced, and the appearance of the molded product is poor. It has the drawback of Further, the molding machine is heavily worn during molding, which causes many practical problems.

In order to solve these problems, attempts have been made to improve the fluidity and rigidity by blending liquid crystal polyester with various thermoplastic resins. Such an example is described in J. Kiss by Polymer Engineering and Science
Volume 27 (1987) 410 tribute. However, these blends are inherently poor in compatibility and the thermoplastic resin forms a continuous phase in a region where the proportion of the liquid crystal polyester is small, so that the excellent characteristics of the liquid crystal polyester are not sufficiently exhibited. The current situation.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a liquid crystal polyester having a small composition ratio,
An object of the present invention is to provide an inexpensive thermoplastic resin composition having excellent characteristics of liquid crystal polyester.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have developed a liquid crystal polyester-thermoplastic resin composition, which is a thermoplastic resin composition having excellent characteristics of the liquid crystal polyester in a region where the composition ratio of the liquid crystal polyester is low. As a result of earnestly studying the above, the present invention has been completed.

That is, the present invention comprises (A) liquid crystal polyester 20 to 50% by volume, and (B) epoxy group-containing polymer 8
The present invention relates to a thermoplastic resin composition comprising 0 to 50% by volume, wherein the component (A) forms a continuous phase.

In the present invention, the composition ratio of the liquid crystal polyester (A) and the epoxy group-containing polymer (B) is 2 respectively.
It is 0 to 50% by volume and 80 to 50% by volume. (A) is 2
If it is less than 0% by volume, the component (A) cannot be a continuous phase, and if it exceeds 50% by volume, a large amount of the component (A) is used, and the cost of the composition becomes high, which is not preferable.

The liquid crystal polyester (A) in the present invention has a flow temperature of 160 to 350 ° C., preferably 165 to 325 ° C., more preferably 170 to 2 ° C., determined by the following method.
70 ° C is preferable. Flow temperature: 1mm inner diameter, 10mm long nozzle,
A temperature at which a melt viscosity is 48,000 poise when a heated melt is extruded from a nozzle under a load of 100 Kg / cm ^{2 at} a temperature rising temperature of 4 ° C./min using a capillary rheometer.

The liquid crystalline polyester is preferably the following repeating structural unit (III), or (I) and (II), or (I), (II) and (III).

[0011]

[Chemical 1]

[0012]

[Chemical 2] Or

[0013]

[Chemical 3] (Where R ₁ is

[0014]

[Chemical 4]

[0015]

[Chemical 5] Represents one or more groups selected from In the formula, R ₂ is

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8] Represents one or more groups selected from In the formula, R ₃ is

[0019]

[Chemical 9] Represents one or more groups selected from

However, in all of R ₁ , R ₂ and R ₃ , some or all of the hydrogen atoms of the benzene ring or naphthalene ring of the aromatic hydrocarbon are halogen atoms, aryl groups, C ₁ -C ₁₀ alkyl groups. It may be substituted with a group or an alkoxy group. )

Specific examples of the dicarboxylic acid which gives the repeating structural unit (I) include terephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, fluoroterephthalic acid, chloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, isophthalic acid and methoxy. Isophthalic acid,
Biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, naphthalene-2,6-
Examples thereof include dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, and these may be used as a mixture of two or more kinds.

Specific examples of the dioxy compound which gives the repeating structural unit (II) include ethylene glycol,
1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, cyclohexane-1,4-diol, Cyclohexane-1,3-diol, cyclohexane-1,2-
Diol, 1,4-dioxymethyl-cyclohexane,
4,4-dihydroxybiphenyl, hydroquinone, resorcin, methylhydroquinone, t-butylhydroquinone, chlorohydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like can be mentioned. You may use it.

Further, as the oxycarboxylic acid which gives the repeating structural unit (III), parahydroxybenzoic acid, 4-hydroxy-3-chlorobenzoic acid, 4-hydroxy-3-methylbenzoic acid, metahydroxybenzoic acid,
4-hydroxy-3,5-dimethylbenzoic acid, 2-oxy-6-naphthoic acid, 1-oxy-5-naphthoic acid, 1
Examples of the polyester composed of -hydroxy-4-naphthoic acid and the repeating structural units (I) and (II) include polyethylene terephthalate and polybutylene terephthalate. These may be used as a mixture of two or more kinds.

The ratio of the repeating structural units of the liquid crystalline polyester is not particularly limited, but when it comprises repeating structural units (I), (II) and (III), it has dicarboxylic acid residue (I) and dioxy residue (II). 20 to 90 mol%, preferably 30 to 80 mol%, and 80 to 10 mol%, preferably 70 to 20 mol% of the total oxycarboxylic acid residue (III).

Further, in the above structural unit, a diamino compound,
It is also possible to copolymerize an oxyamino compound and an aminocarboxylic acid. Specific examples of these include meta or para-phenylenediamine, meta or para-aminophenol, para-aminobenzoic acid and the like.
You may use these in mixture of 2 or more types.

The polyester composed of the above structural units is required to have liquid crystallinity, and one showing optical anisotropy at a temperature of 400 ° C. or lower is preferable.

The polyester can be produced in the presence or absence of a catalyst in accordance with the conventionally known polyester polymerization method, and there is no particular limitation, but the following methods are typical examples.

(1) Acylation of an aromatic oxycarboxylic acid such as parahydroxybenzoic acid and an aromatic hydroxy compound such as 4,4'-dihydroxybiphenyl with acetic anhydride and deacetic acid from an aromatic dicarboxylic acid such as terephthalic acid. A method for producing by polycondensation reaction.

(2) Dephenol polycondensation reaction from phenyl ester of aromatic oxycarboxylic acid such as parahydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid and aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl. Manufacturing method.

(3) A method produced by the method (1) in the presence of a polyester composed of a divalent aromatic diol such as ethylene glycol and an aromatic dicarboxylic acid such as terephthalic acid.

(4) A method for producing by a deacetic acid polycondensation reaction of an acylated product of an aromatic oxycarboxylic acid such as parahydroxybenzoic acid with acetic anhydride.

The epoxy group-containing polymer (B) used in the present invention may be any known one, but is preferably a copolymer of an unsaturated epoxy compound and an olefinic unsaturated compound.

The composition ratio of the copolymer is not particularly limited,
The unsaturated epoxy compound is 0.1 to 50 parts by weight, preferably 1 to 100 parts by weight of the olefinic unsaturated compound.
Copolymers of about 30 parts by weight are desirable. Further, two or more kinds of these epoxy group-containing polymers may be mixed and used.

The unsaturated epoxy compound is a compound having an unsaturated group and an epoxy group which can be copolymerized with an olefinic unsaturated compound in the molecule. Examples thereof include unsaturated glycidyl esters and unsaturated glycidyl ethers represented by the general formulas 10 and 11 and the like.

[0035]

[Chemical 10] (R is a C2-C18 hydrocarbon group having an ethylenically unsaturated bond.)

[0036]

[Chemical 11] (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -, or

[0037]

[Chemical formula 12] Is. )

Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether. Of these, glycidyl methacrylate is particularly preferably used.

The olefinic unsaturated compound is an olefin, a vinyl ester of a saturated carboxylic acid having 2 to 6 carbon atoms, an ester of a saturated alcohol component having 1 to 8 carbon atoms and acrylic acid or methacrylic acid, and a maleic acid ester. And methacrylic acid esters and fumaric acid esters, vinyl halides, styrenes, nitriles, vinyl ethers and acrylamides.

Specifically, ethylene, propylene, butene-1, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, diethyl maleate, diethyl fumarate, vinyl chloride, vinylidene chloride, styrene,
Acrylonitrile, isobutyl vinyl ether, acrylamide and the like are exemplified. They are generally used as binary copolymers with unsaturated epoxy compounds or as terpolymers containing ethylene and unsaturated epoxy compounds.

The epoxy group-containing polymer can be prepared by various methods. Both a random copolymerization method in which an unsaturated epoxy compound is introduced into the main chain of the copolymer and a graft copolymerization method in which an unsaturated epoxy compound is introduced as a side chain of the copolymer can be used. As a manufacturing method, specifically, an unsaturated epoxy compound and ethylene are added in the presence of a radical generator at 500 to 4,000 atm, 100 to 300 atm.
A method of copolymerizing in the presence or absence of a suitable solvent or a chain transfer agent at ℃, a method of mixing an unsaturated epoxy compound and a radical generator to polypropylene, melt graft copolymerization in an extruder, or Examples thereof include a method of copolymerizing an unsaturated epoxy compound and an olefinic unsaturated compound in an inert medium such as water or an organic solvent in the presence of a radical generator.

As a method for producing the thermoplastic resin composition of the present invention, at a temperature at which both (A) the liquid crystal polyester and (B) the epoxy group-containing copolymer can be melted,
(A) Liquid crystal polyester 20 to 50% by volume and (B)
A manufacturing method in which 80 to 50% by volume of the epoxy group-containing copolymer is melt-kneaded together is included.

By the production method of the present invention, a composition is obtained in which the component (A) forms a continuous phase even in a region where the composition ratio of the liquid crystal polyester component (A) is as low as 20 to 50% by volume. Further, the melt-kneading temperature of the components (A) and (B) varies depending on the composition of the components (A) and (B),
Generally, 200 to 300 ° C is preferable. Further, the melt-kneading time of the components (A) and (B) varies depending on the composition of the components (A) and (B), but is generally preferably 1 to 60 minutes.

As a method of kneading the resin composition of the present invention in a molten state, various kneading devices such as a uniaxial or biaxial extruder, a Labo Plastomill, and a Brabender can be generally used for the melt kneading. A Labo Plastomill and a twin-screw high kneading machine are particularly preferable.

At the time of kneading, it is preferable that each of the resin components (A) and (B) be in the form of powder or pellets and be uniformly mixed in advance by an apparatus such as a tumbler or a Henschel mixer.

It is also possible to add a suitable catalyst such as triphenylphosphine or a tertiary amine for promoting the crosslinking reaction of the component (B) during melt-kneading.

In carrying out the present invention, it is possible to add an additive to the present resin composition. Specific examples of the additive include glass fiber, silica-alumina fiber, alumina fiber,
Reinforcing agents such as carbon fiber, potassium titanate fiber, highly elastic polyamide fiber, inorganic fillers such as carbon black, silica, titania, talc, calcium carbonate, magnesium sulfate, wollastonite, triphenyl phosphate, phthalate ester, etc. Examples thereof include plasticizers, lubricants, stabilizers, antimony trioxide, halides, flame retardants such as phosphates, dyes and pigments.

[0048]

Industrial Applicability According to the present invention, it is possible to provide an inexpensive thermoplastic resin composition having excellent characteristics of a liquid crystal polyester, even though the composition ratio of the liquid crystal polyester is small, and thus the industrial significance is extremely high. large.

[0049]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto.

(Measurement of Flow Temperature) Inner Diameter 1 mm, Length 10
Using a capillary rheometer with a mm nozzle,
Load the heated melt at a temperature rise rate of 4 ° C / min.
When extruded from the nozzle under m ² , the melt viscosity is 4
A temperature was measured indicating 8,000 poise. (Measurement of Viscoelastic Behavior) The viscoelastic behaviors of the compositions in Examples and Comparative Examples were measured by using RDA-II manufactured by Rheometrics Co., Ltd. in the temperature range from room temperature to 300 ° C. and the storage elastic modulus G ′ (dyn / c).
It was investigated by measuring m ² ).

(Observation with Scanning Electron Microscope and Photographing) A sample obtained by press-molding the obtained thermoplastic resin composition was mirror-polished with a microtome and etched with a 5N aqueous sodium hydroxide solution at 70 ° C. for 30 minutes (hereinafter referred to as alkali). Sometimes referred to as etching). The sample was washed with water and dried under reduced pressure at 90 ° C. for 1 hour to remove water. The obtained sample was observed with a scanning electron microscope and photographed according to a conventional method. As a result, the liquid crystal polyester portion is removed by alkali etching, and the remaining thermoplastic resin portion is observed and photographed.

Styrene-glycidyl methacrylate copolymers and liquid crystal polyesters used in Examples and Comparative Examples were obtained by the following formulations, and other ethylene, styrene and ethylene-based copolymers were commercially available as shown below. I used the one.

1. Commercially available resin-Low density polyethylene: Sumitomo Chemical Co., Ltd. registered trademark Sumikasen L708 (hereinafter sometimes referred to as LDPE) -Polystyrene: Nippon Polystyrene Industrial Co., Ltd. registered trademark Esbright 8-62 (hereinafter referred to as PS) -Ethylene-glycidyl methacrylate copolymer: Sumitomo Chemical Co., Ltd. registered trademark Bondfast BF-E
(Hereinafter, it may be referred to as E-GMA.)

2. Synthesis of Styrene-Glycidyl Methacrylate Copolymer (hereinafter sometimes referred to as St-GMA) 1200 g of water and 3.2 parts of calcium phosphate dibasic in a 2 liter separable flask having a Faudler type stirring blade.
g, 0.02 g of sodium dodecylbenzenesulfonate were added, and a mixed solution of 360 g of styrene monomer, 40 g of glycidyl methacrylate monomer and 2.0 g of benzoyl peroxide was charged in a nitrogen atmosphere. Nitrogen atmosphere, under stirring,
The temperature was gradually raised, and finally polymerization was carried out at an internal temperature of 92 ° C. for 6 hours to obtain a bead-shaped polymer. The polymer was thoroughly washed with water and vacuum dried for 24 hours. The melt flow rate (MFR) of the obtained polymer was 16.6 g / 10 minutes at 200 ° C. under a load of 5 kg.

3. Synthesis of liquid crystal polyester (hereinafter sometimes referred to as LCP) Parahydroxybenzoic acid 5 was added to a polymerization tank having anchor type stirring blades and a small clearance between the wall of the polymerization tank and the stirring blades.
96 g (4.32 mol), terephthalic acid 133 g (0.
8 mol), 4,4'-dihydroxybiphenyl 149 g
(0.8 mol), polyethylene terephthalate (PET SA-1206 manufactured by Unitika Ltd.) 246 g (corresponding to 23.7% by weight of the final polymer) and acetic anhydride 6
65 g (6.52 mol) was charged, and the mixture was heated to 150 ° C. in 1 hour while stirring under a nitrogen atmosphere, and at this temperature, 3
Reflux for hours.

Thereafter, acetic acid was distilled off while raising the temperature, and finally polymerization was carried out under high shear at 320 ° C. for 2 hours, after which the mixture was gradually cooled and vigorous stirring was continued up to 200 ° C.
The polymer was taken out of the tank.

After crushing this polymer, it was transferred to a rotary oven made of aluminum, the whole system was rotated under a nitrogen stream, and the powder was thoroughly stirred for 6 hours to obtain 230
The temperature was gradually raised to 0 ° C., the mixture was treated at 230 ° C. for 3 hours, then cooled and the powder was taken out at 100 ° C. or lower. The liquid crystal polyester (LCP) obtained had a flow temperature of 250 ° C.

Example 1 Ethylene-glycidyl methacrylate copolymer (E-GM
A) and the liquid crystal polyester (LCP) are 60% by weight (69% by volume) and 40% by weight (31% by volume), respectively.
Was added to a Labo Plastomill (20R200 type, manufactured by Toyo Seiki Co., Ltd.) in such a manner that it was preliminarily homogenized at room temperature, and kneaded at 270 ° C., 120 rpm for 15 minutes.

After coarsely crushing this, press molding (press molding machine manufactured by Shindo Metal Industry Co., Ltd.) was used, and a part of the material was used for scanning electron microscope (SEMS2300 manufactured by Hitachi, Ltd.).
Type) observation and dynamic viscoelasticity measurement (RDA-II). The samples used for scanning electron microscope observation and dynamic viscoelasticity measurement were 5 × 5 × 2 (mm) and 10 respectively.
It is cut into a size of x50x2 (mm). The results are shown in Table 1 and FIG.

Example 2 The mixing ratio of E-GMA and LCP was 70% by weight (77.
6% by volume) and 30% by weight (22.4% by volume), and charged into a Labo Plastomill at 270 ° C., 80 rpm, 15
Molding and measurement were carried out in the same manner as in Example 1 except that kneading was carried out. The results are shown in Table 1 and FIG.

Example 3 The mixing ratio of E-GMA and LCP was 50% by weight (59.
7% by volume) and 50% by weight (40.3% by volume), and charged into a Labo Plastomill at 270 ° C., 150 rpm, 1
Molding and measurement were performed in the same manner as in Example 1 except that kneading was performed for 5 minutes. The results are shown in Table 1 and FIG. Further, FIG. 6 shows the particle structure of the thermoplastic resin, which is the remaining portion after removing the liquid crystal polyester after alkali etching (a photograph replacing the drawing). From this it can be seen that the liquid crystalline polyester part forms the continuous phase and the thermoplastic resin part forms the dispersed phase.

Example 4 Styrene-glycidyl methacrylate copolymer (St-G
MA) and LCP as 60% by weight (66.6% by volume) and 40% by weight (33.4% by volume), respectively, were put into a Labo Plastomill and kneaded at 270 ° C., 150 rpm for 15 minutes. Molding and measurement were performed in the same manner as in Example 1. The results are shown in Table 1 and FIG.

Example 5 St-GMA and LCP were each 70% by weight (75.
8% by volume) and 30% by weight (24.2% by volume), and charged into a Labo Plastomill at 270 ° C., 120 rpm, 3
Molding and measurement were performed in the same manner as in Example 1 except that kneading was performed for 0 minutes. The results are shown in Table 1 and FIG.

Example 6 50 wt% of St-GMA and LCP (54.
6% by volume) and 50% by weight (45.4% by volume) were placed in a Labo Plastomill and kneaded and molded in the same manner as in Example 1 except for kneading at 270 ° C., 200 rpm for 30 minutes. The results are shown in Table 1. Further, FIG. 7 shows the particle structure of the thermoplastic resin, which is the remaining portion after removing the liquid crystal polyester after alkali etching (a photograph replacing the drawing). From this it can be seen that the liquid crystalline polyester part forms the continuous phase and the thermoplastic resin part forms the dispersed phase.

Comparative Example 1 Low density polyethylene (LDPE) and LCP were each 6
A mixture of 0% by weight (69.7% by volume) and 40% by weight (30.3% by volume), which had been blended so as to be uniform, was put into a Labo Plastomill, and heated at 270 ° C., 200 rpm, and 1
After kneading for 5 minutes, press molding was performed, and electron microscope observation and dynamic viscoelasticity measurement were performed. The results are shown in Table 1 and FIG. The sample obtained from FIG. 1 in Example 1 is LCP / L.
It can be seen that the rate of decrease in storage elastic modulus is smaller than that of the DPE blend (Comparative Example 1) even at high temperatures.

Comparative Example 2 Comparative Example 1 was repeated except that LDPE and LCP were 70% by weight (78.1% by volume) and 30% by weight (21.9% by volume), respectively. The results are shown in Table 1 and FIG. The sample obtained from FIG. 2 in Example 2 is LCP / L.
It can be seen that the rate of decrease in storage elastic modulus is smaller than that of the DPE blend (Comparative Example 2) even at high temperatures.

Comparative Example 3 Comparative Example 1 was repeated except that LDPE and LCP were 50% by weight (60.5% by volume) and 50% by weight (39.5% by volume), respectively. The results are shown in Table 1 and FIG. The sample obtained in Example 3 from FIG. 3 is LCP / L.
It can be seen that the rate of decrease in storage elastic modulus is smaller than that of the DPE blend (Comparative Example 3) even at high temperatures.

FIG. 8 shows the particle structure of the voids after removal of the liquid crystal polyester after alkali etching (photograph as a drawing). From this, it can be seen that the removed liquid crystal polyester part forms a dispersed phase and the remaining thermoplastic resin part forms a continuous phase.

Comparative Example 4 Styrene homopolymer (PS) and LCP were each added to 6 parts.
The same procedure as in Comparative Example 1 was performed except that the content was 0% by weight (66.8% by volume) and 40% by weight (33.2% by volume). The results are shown in Table 1 and FIG. It can be seen from FIG. 4 that the sample obtained in Example 4 has a smaller rate of decrease in storage elastic modulus than the LCP / PS blend (Comparative Example 4) even at high temperatures.

Comparative Example 5 The same procedure as in Comparative Example 1 was carried out except that PS and LCP were 70% by weight (75.8% by volume) and 30% by weight (24.2% by volume), respectively. The results are shown in Table 1 and FIG. The sample obtained from FIG. 5 in Example 5 is LCP / P
It can be seen that the decrease rate of the storage elastic modulus is smaller than that of the S blend (Comparative Example 5) even at high temperature. Comparative Example 6 The procedure of Comparative Example 1 was repeated, except that PS and LCP were 50% by weight (57.3% by volume) and 50% by weight (42.7% by volume), respectively. The results are shown in Table 1. Also,
FIG. 9 shows a particle structure of voids after removal of the liquid crystal polyester after alkali etching (a photograph replacing a drawing). From this, it can be seen that the removed liquid crystal polyester part forms a dispersed phase and the remaining thermoplastic resin part forms a continuous phase.

[0071]

[Table 1]

However, in Table 1, those in which the component (A) forms a continuous phase are indicated by ◯, and those which are not formed are indicated by x. Whether or not the component (A) forms a continuous phase was confirmed by a scanning electron microscope (SEM).

[Brief description of drawings]

FIG. 1 is a graph showing a storage elastic modulus (G ′) in a temperature range of room temperature to 300 ° C. 1 (LCP), 2 (Example 1), 3 (Comparative Example 1), and 4 (E-GMA) are compared.

FIG. 2 is a graph showing storage elastic modulus (G ′) in a temperature range of room temperature to 300 ° C. 1 (LCP), 5 (Example 2), 6 (Comparative Example 2), and 4 (E-GMA) are compared.

FIG. 3 is a graph showing a storage elastic modulus (G ′) in a temperature range of room temperature to 300 ° C. 1 (LCP), 7 (Example 3), 8 (Comparative Example 3), 4 (E-GMA) are compared.

FIG. 4 is a graph showing storage elastic modulus (G ′) in a temperature range of room temperature to 300 ° C. 1 (LCP), 9 (Example 4), 10 (Comparative Example 4), 11 (St-GMA) are compared.

FIG. 5 is a graph showing storage elastic modulus (G ′) in a temperature range from room temperature to 300 ° C. 1 (LCP), 12
(Example 5), 13 (Comparative Example 5), 11 (St-GM
It is a comparison of A).

6 is a photograph as a substitute for a drawing, which shows the particle structure of a thermoplastic resin after alkali-etching the sample obtained in Example 3. FIG. (Scanning electron micrograph)

FIG. 7 is a photograph as a substitute for a drawing, which shows a particle structure of a thermoplastic resin after alkaline etching of the sample obtained in Example 6. (Scanning electron micrograph)

FIG. 8 is a photograph instead of a drawing, which shows a particle structure of voids of a liquid crystalline polyester after alkali etching of the sample obtained in Comparative Example 3. (Scanning electron micrograph)

9 is a photograph as a substitute for a drawing, which shows a particle structure of liquid crystal polyester voids after alkali etching of the sample obtained in Comparative Example 6. FIG. (Scanning electron micrograph)

Claims (1)

[Claims] 1. A thermoplastic resin comprising (A) a liquid crystal polyester of 20 to 50% by volume and (B) an epoxy group-containing polymer of 80 to 50% by volume, wherein the component (A) forms a continuous phase. Composition.