JP6763691B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition containing a thermoplastic resin, a liquid crystal polymer and a compatibilizer.

In recent years, polymer blends or alloy resin compositions have been developed in order to impart various physical properties to resins, and are used in a wide range of fields by taking advantage of their respective characteristics.

For example, by blending a liquid crystal polymer with another thermoplastic resin, a resin composition having excellent properties of the liquid crystal polymer (heat resistance, weather resistance, gas barrier property, chemical resistance, dimensional accuracy, etc.) has been proposed. ing.

However, since the liquid crystal polymer is generally inferior in compatibility with the thermoplastic resin, the obtained resin composition inevitably has uneven performance, layered peeling during molding, or a decrease in strength.

Against this background, resin compositions containing a compatibilizer that stabilizes the interface between the liquid crystal polymer and the thermoplastic resin and finely disperses the resin have been developed. For example, a resin composition of a liquid crystal polymer and a polyolefin (Patent Document 1) containing a compatibilizer in which a glycidyl group is incorporated in a polyolefin chain has been proposed, but since the main chain of the compatibilizer is polyolefin, A resin having poor compatibility with polyolefin has a drawback that the compatibility effect is weakened.

Further, as a compatibilizer between a liquid crystal polymer and a thermoplastic resin, a liquid crystal block copolymer obtained by copolymerizing a liquid crystal polymer (Patent Document 2) has been proposed, but the polymer block portion depends on the type of resin to be compatible. Had to be changed, and it was not versatile.

Special Table No. 7-508050 Japanese Unexamined Patent Publication No. 10-95821

An object of the present invention is to provide a thermoplastic resin composition having improved compatibility between a thermoplastic resin and a liquid crystal polymer.

Another object of the present invention is to provide a compatibilizer capable of compromising a thermoplastic resin and a liquid crystal polymer.

As a result of diligent studies on a thermoplastic resin composition in which a thermoplastic resin and a liquid crystal polymer are blended, the present inventors have obtained a thermoplastic resin and a liquid crystal polymer by adding a specific diglycidyl ether ester compound as a compatibilizer. We have found that the compatibility of the ester is improved, and have completed the present invention.

That is, in the present invention, 0.1 to 20 parts by weight of the diglycidyl ether ester compound (C) represented by the formula (1) is used with respect to 100 parts by weight of the total amount of the thermoplastic resin (A) and the liquid crystal polymer (B). Provided is a thermoplastic resin composition containing a thermoplastic resin (A) / liquid crystal polymer (B) having a weight ratio of 1/99 to 99/1.
(In the formula, n represents an integer of 0 or 1-10)

Since the thermoplastic resin composition of the present invention contains a diglycidyl ether ester compound capable of reacting with both the thermoplastic resin and the liquid crystal polymer, the compatibility between the thermoplastic resin and the liquid crystal polymer is improved. ing.

FIG. 1 shows an electron microscope image of the surface of a crushed product of a molded product made of the thermoplastic resin composition obtained in Example 1. FIG. 2 shows an electron microscope image of the surface of a crushed product of a molded product made of the thermoplastic resin composition obtained in Example 2. FIG. 3 shows an electron microscope image of the surface of a crushed product of a molded product made of the thermoplastic resin composition obtained in Example 3. FIG. 4 shows an electron microscope image of the surface of a crushed product of a molded product made of the thermoplastic resin composition obtained in Comparative Example 1. FIG. 5 shows an electron microscope image of the surface of a crushed product of a molded product made of the thermoplastic resin composition obtained in Comparative Example 2.

The thermoplastic resin (A) used in the present invention is preferably a resin having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group. Specifically, examples of the thermoplastic resin (A) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamide, polycarbonate, polyacetal, polyurethane, polylactic acid, polyamide, polyimide, and liquid crystal polymer. These can be used alone or in combination of two or more. Polyethylene terephthalate is particularly preferable because it has an excellent compatibility effect with the liquid crystal polymer (B).

When a liquid crystal polymer is used as the thermoplastic resin (A), a liquid crystal polymer different from the liquid crystal polymer (B) is naturally used.

The liquid crystal polymer (B) used in the present invention forms an anisotropic molten phase, and is not particularly limited as long as it is called a thermotropic liquid crystal polymer by those skilled in the art.

The properties of the anisotropic molten phase can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.

The main repeating unit constituting the liquid crystal polymer (B) used in the present invention is selected from (i) aromatic oxycarbonyl repeating unit, (ii) aromatic dicarbonyl repeating unit and (iii) aromatic dioxy repeating unit. One or more species.

The liquid crystal polymer (B) composed of each of these repeating units may or may not form an anisotropic molten phase depending on the constituent components, the composition ratio in the polymer, and the sequence distribution. However, the liquid crystal polymer (B) used in the present invention is limited to one that forms an anisotropic molten phase.

As the liquid crystal polymer (B) used in the present invention, a liquid crystal polyester containing 25 mol% or more of the repeating units represented by the formula (2) in all the repeating units and having a crystal melting temperature of 285 ° C. or less is preferably used. Will be done.

The liquid crystal polymer (B) used in the present invention has a content of the repeating unit represented by the formula (2) of more preferably 30 to 55 mol%, still more preferably 35 to 45 mol%. When the repeating unit represented by the formula (2) is less than 25 mol% of all the repeating units, the crystal melting temperature of the liquid crystal polymer tends to be high, which is not preferable.

The crystal melting temperature of the liquid crystal polymer (B) used in the present invention is preferably 180 to 260 ° C, more preferably 190 to 250 ° C.

When the crystal melting temperature exceeds 285 ° C., the temperature during kneading and molding becomes high, so that the decomposition of the diglycidyl ester ether compound proceeds, and it is difficult to obtain a thermoplastic resin composition having improved compatibility. Tends to be.

In the present specification and claims, the "crystal melting temperature" refers to crystal melting when measured at a heating rate of 20 ° C./min by a differential scanning calorimetry (hereinafter abbreviated as DSC). It is obtained from the temperature peak temperature. More specifically, after observing the heat absorption peak temperature (Tm1) observed when the liquid crystal polymer resin sample is measured at a temperature rising condition of 20 ° C./min from room temperature, the temperature is 20 to 50 ° C. higher than Tm1. After holding for 10 minutes and then cooling the sample to room temperature under the temperature lowering condition of 20 ° C./min, the heat absorption peak when measured again under the temperature rising condition of 20 ° C./min was observed, and the temperature indicating the peak top was observed. The crystal melting temperature of the liquid crystal polymer resin. As the measuring device, for example, Exstar6000 manufactured by Seiko Instruments Co., Ltd. can be used.

Examples of the monomer giving the repeating unit represented by the formula (2) include 6-hydroxy-2-naphthoic acid and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.

Specific examples of the monomer giving the aromatic oxycarbonyl repeating unit other than the monomer giving the repeating unit represented by the formula (2) include, for example, 4-hydroxybenzoic acid and metahydroxybenzoic acid. , Orthohydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxy Examples thereof include phenyl-3-benzoic acid, alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives such as acylated products, ester derivatives and acid halides thereof. Among these, 4-hydroxybenzoic acid is preferable because the characteristics of the obtained liquid crystal polymer and the crystal melting temperature can be easily adjusted.

(Ii) Specific examples of the monomer giving an aromatic dicarbonyl repeating unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Acids, aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives such as their ester derivatives and acid halides. Can be mentioned. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint that the mechanical properties, heat resistance, crystal melting temperature, and moldability of the obtained liquid crystal polymer can be easily adjusted to appropriate levels.

(Iii) Specific examples of the monomer giving an aromatic dioxy repeating unit include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 1,4-. Aromatic diols such as dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, alkyl, alkoxy or halogens thereof. Substituters and ester-forming derivatives such as their acylates can be mentioned. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoints of reactivity at the time of polymerization and characteristics of the obtained liquid crystal polymer.

The liquid crystal polymer (B) used in the present invention preferably has a melt viscosity of 1 to 1000 Pa · s as measured by a capillary rheometer, and more preferably 5 to 300 Pa · s.

As the liquid crystal polymer (B) used in the present invention, a liquid crystal polyester composed of repeating units represented by the formulas (2) to (5) is particularly preferably used.
[In the formula, Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s are composition ratios (mol%) in the liquid crystal polymer (B) of each repeating unit. ), Which satisfies the following equation:
0.4 ≤ p / q ≤ 2.0
2 ≦ r ≦ 15, and 2 ≦ s ≦ 15].

In the present specification and claims, "liquid crystal polyester composed of repeating units represented by formulas (2) to (5)" means that liquid crystal polyester is a constituent component thereof and formulas (2) to (5). It means that other repeating units may be contained in addition to the repeating unit represented by.

In one preferred embodiment of the present invention, the composition ratio of the repeating units represented by the above formulas (2) to (5) is p + q + r + s = 100 mol%.

Further, in the present specification and claims, the "divalent aromatic group" means an aromatic group having two substituents capable of forming an ester bond.

The above-mentioned suitable liquid crystal polyester has a repeating unit represented by the formulas (2) and (3), and the molar ratio (p / q) of both is 0.4 to 2.0, preferably 0.6 to 1. It is contained so as to be 8, particularly preferably 0.8 to 1.6.

In one embodiment, the liquid crystal polymer (B) preferably used in the present invention is preferably a liquid crystal polyester containing 35 to 48 mol% of the repeating units represented by the formulas (2) and (3), respectively, from 38 to 38. Those containing 43 mol% are particularly preferable.

The liquid crystal polyester (B) preferably used in the present invention obtains a liquid crystal polyester having a crystal melting temperature of 285 ° C. or lower by containing the repeating units represented by the formulas (2) and (3) in the above-mentioned ratios. be able to.

The liquid crystal polyester preferably used in the present invention contains the repeating units represented by the formulas (4) and (5) in an amount of preferably 2 to 15 mol%, more preferably 5 to 13 mol%, respectively. Yes, the content of the repeating unit represented by the formulas (4) and (5) is preferably equimolar.

The monomer giving the repeating unit represented by the formula (2) is as described above.

Examples of the monomer giving the repeating unit represented by the formula (3) include 4-hydroxybenzoic acid and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.

Examples of the monomer that gives the repeating unit represented by the formula (4) include hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'. Aromatic diols such as −dihydroxybiphenyl ether, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, alkyl, alkoxy or halogen substituents thereof, and acylated products thereof. Examples include ester-forming derivatives.

Examples of the monomer giving the repeating unit represented by the formula (5) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4, Examples thereof include aromatic dicarboxylic acids such as 4'-dicarboxybiphenyl and bis (4-carboxyphenyl) ether, alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives such as ester derivatives and acid halides thereof. ..

In one preferred embodiment, the repeating unit represented by the formula (4) and the formula (5) is Ar ₁ in the formula (4).
And / or
And Ar ₂
And / or
Is what it is.

The liquid crystal polymer (B) used in the present invention is the present invention in addition to the main monomer in the liquid crystal polymer (B) of the present invention which gives a repeating unit represented by the above general formulas (2) to (5). The main monomer is an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic dicarboxylic acid, or an aromatic hydroxydicarboxylic acid, an aromatic hydroxyamine, an aromatic diamine, or an aroma, as long as the purpose of the above is not impaired. A group aminocarboxylic acid, an aromatic mercaptocarboxylic acid, an aromatic dithiol, an aromatic mercaptophenol and the like may be copolymerized as other monomer components. The ratio of these other monomer components is preferably 10 mol% or less with respect to the total of the monomer components giving the repeating units represented by the general formulas (2) to (5).

The method for producing the liquid crystal polymer (B) used as the resin component in the resin composition of the present invention is not particularly limited, and a known polycondensation method for polyester for forming an ester bond with the monomer component, for example, melting. An acidlysis method, a slurry polymerization method, or the like can be used.

The molten acidlysis method is a method suitable for producing the liquid crystal polymer (B) used in the present invention. In this method, a monomer is first heated to form a melt of a reactant, and the reaction is carried out. The molten polymer is obtained by continuing. A vacuum may be applied to facilitate the removal of volatiles (eg, acetic acid, water, etc.) by-produced in the final stage of condensation.

The slurry polymerization method is a method of reacting in the presence of a heat exchange fluid, and the solid product is obtained in a state of being suspended in a heat exchange medium.

In both the melt acidlysis method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystal polymer (B) is a modified form in which a hydroxyl group is acylated at room temperature, that is, a lower acylated product. It can also be used for the reaction. The lower acyl group preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. Particularly preferably, a method of using the acetylated product of the monomer component in the reaction can be mentioned.

As the lower acylated product of the monomer, a product that is separately acylated and synthesized in advance may be used, or an acylating agent such as acetic anhydride is added to the monomer during the production of the liquid crystal polymer (B) to generate the monomer in the reaction system. You can also do it.

In either case of the molten acidlysis method or the slurry polymerization method, a catalyst may be used at the time of reaction, if necessary.

Specific examples of the catalyst include organic tin compounds such as dialkyltin oxide (eg dibutyltin oxide) and diaryltin oxide; organic titanium compounds such as titanium dioxide, antimony trioxide, alkoxytitanium silicate, and titanium alkoxide; alkalis and alkalis of carboxylic acids. Earth metal salts (eg potassium acetate); gaseous acid catalysts such as Lewis acid (eg BF ₃ ), hydrogen halide (eg HCl) and the like.

The ratio of the catalyst used is usually 10 to 1000 ppm, preferably 20 to 200 ppm, based on the monomer.

The liquid crystal polymer (B) obtained by such a polycondensation reaction is extracted from the polymerization reaction tank in a molten state and then processed into pellets, flakes, or powders.

In the thermoplastic resin composition of the present invention, the weight ratio of the thermoplastic resin (A) / liquid crystal polymer (B) is 1/99 to 99/1, and the thermoplastic resin (from the viewpoint of easily exhibiting the compatibility effect). When A) is dispersed in the liquid crystal polymer (B), it is preferably 2/98 to 30/70, and when the liquid crystal polymer (B) is dispersed in the thermoplastic resin (A), it is 70/30 to 98. It is preferably / 2.

The diglycidyl ether ester compound (C) represented by the formula (1) used in the present invention is usually produced as a mixture of a compound having n = 0 and a compound having n = 1 to 10, and a small amount of phase is used. From the viewpoint of exhibiting a solubilizing effect, it is preferable to contain 80% or more of the compound having n = 0, and more preferably 90% or more.
(In the formula, n represents an integer of 0 or 1-10)

By using the diglycidyl ether ester compound (C) represented by the formula (1) in the composition containing the thermoplastic resin and the liquid crystal polymer, the compatibility between the thermoplastic resin and the liquid crystal polymer can be improved. Therefore, the diglycidyl ether ester compound (C) represented by the formula (1) and the compatibilizer containing the diglycidyl ether ester compound (C) are suitable as compatibilizers for compatibilizing the thermoplastic resin (A) and the liquid crystal polymer (B). Can be used.

The method for obtaining the diglycidyl ether ester compound (C) used in the present invention is not particularly limited, but is obtained by reacting hydroxynaphthoic acid with epihalohydrin in the presence of a quaternary ammonium salt and / or a basic compound. Is better to use. Further, it may be further purified by recrystallization or the like. Alternatively, a commercially available preparation containing a compound represented by the formula (1) may be used.

The thermoplastic resin composition of the present invention contains a diglycidyl ether ester compound (C) represented by the formula (1) as a compatibilizer, and the total amount of the thermoplastic resin (A) and the liquid crystal polymer (B) is 100% by weight. It contains 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. When the content of the diglycidyl ether ester compound (C) represented by the formula (1) is less than 0.1 parts by weight, the compatibility effect between the liquid crystal polymer and the thermoplastic resin cannot be obtained and exceeds 20 parts by weight. , The reaction between the diglycidyl ether ester compound (C) proceeds, and a phenomenon such as gelation occurs.

The thermoplastic resin composition of the present invention is prepared by compounding a thermoplastic resin (A), a liquid crystal polymer (B) and a glycidyl ether ester compound (C) represented by the formula (1) by a twin-screw extruder or the like. Obtainable. Preferably, in the thermoplastic resin composition of the present invention, pellets of the thermoplastic resin (A), the liquid crystal polymer (B) and the glycidyl ether ester compound (C) represented by the formula (1) are dry-mixed and mixed. The resulting dry mixture is then charged into a twin-screw extruder and compounded at a temperature of 220-350 ° C.

The thermoplastic resin composition of the present invention is processed into films, sheets, bottles, other packaging materials and the like by known molding methods such as injection molding, blow molding, uniaxial stretching and inflation. In particular, it is processed into a desired molded product by blow molding suitable for molding hollow products such as PET bottles. Specific blow molding methods include direct blow molding, injection blow molding, free blow molding and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

In the examples, the following abbreviations represent the following compounds.
PET: Polyethylene terephthalate LCP: Liquid crystal polymer BON6: 6-hydroxy-2-naphthoic acid POB: 4-Hydroxybenzoic acid
HQ: Hydroquinone TPA: Terephthalic acid

[Synthesis example]
(Synthesis of compatibilizer 1)
95.0 g of 6-hydroxy-2-naphthoic acid and 467 g of epichlorohydrin were added to 1 L of 4-port corben, and the temperature was raised to 80 ° C. under a nitrogen stream. Then, a 50% aqueous solution of tetramethylammonium chloride was added dropwise at 80 ° C. over 2 hours, and the mixture was stirred at the same temperature for 1 hour. Further, 87.1 g of a 48% aqueous sodium hydroxide solution was added dropwise at 80 ° C. over 3 hours, and the mixture was stirred at the same temperature for 30 minutes, and then epichlorohydrin was removed by distillation under reduced pressure. After adding 560 g of toluene to the residue and stirring for 10 minutes, the precipitate was filtered. The filtrate was washed with 250 g of water, 19 g of a 48% NaOH aqueous solution was added, and the mixture was refluxed for 1 hour. Further, it was washed with 250 g of water, then with 250 g of a 5% phosphorus aqueous solution, and again with 250 g of water. Toluene was removed by distillation under reduced pressure to obtain 105 g of a compatibilizer. The epoxy equivalent of the resulting compatibilizer was 168.

(Synthesis of LCP)
BON6, POB, HQ and TPA were charged in a 2 L reaction vessel equipped with a stirrer with a torque meter and a distilling tube so as to have a total amount of 5 mol in the composition ratio shown below, and then 0.05 g of potassium acetate (total). 67 mol ppm with respect to the monomer) and 1.025 times mol of acetic anhydride with respect to the amount of hydroxyl groups (mol) of all the monomers were charged, and deacetic acid polymerization was carried out under the following conditions.

The polymerization was carried out in a nitrogen gas atmosphere from room temperature to 150 ° C. in 1 hour and maintained at the same temperature for 30 minutes. Next, the temperature was rapidly raised to 210 ° C. while distilling off acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, after raising the temperature to 335 ° C. over 3 hours, the pressure was reduced to 20 mmHg over 30 minutes, the polymerization reaction was terminated when a predetermined torque was exhibited, the contents of the reaction vessel were taken out, and pulverized. Pellet LCP of LCP resin was obtained. The amount of distillate acetic acid at the time of polymerization was almost the same as the theoretical value. The crystal melting temperature measured by DSC of the obtained LCP was 221 ° C.

POB: 276.23 g (40 mol parts)
BON6: 376.34 g (40 mol parts)
HQ: 55.05 g (10 mol parts)
TPA: 83.06 g (10 mol parts)

(Thermoplastic resin (A))
In the examples, polyethylene terephthalate (NEH-2070 manufactured by Unitika Ltd.) was used as the thermoplastic resin (A).

[Example 1]
3.00 parts by weight of the compatibilizer 1 was dry-mixed with 100 parts by weight of the total amount of the polyethylene terephthalate resin and the LCP obtained in the synthetic example (polyethylene terephthalate resin / LCP weight ratio = 95/5), and 2 Using a shaft extruder (manufactured by Ikekai Co., Ltd., PCM-30), the compound was compounded at a cylinder temperature of 280 ° C. to obtain pellets of a polyethylene terephthalate resin composition in which LCP and a compatibilizer were mixed, and the melt viscosity was determined. It was measured.

The obtained pellets were injection-molded using an injection molding machine (UH1000-110) manufactured by Nissei Resin Industry Co., Ltd. under the conditions of a molding temperature of 280 ° C. and a mold temperature of 80 ° C., and ASTM 4 having a thickness of 3.2 mm. No. dumbbell was made. Tensile strength and tensile elongation were measured using this dumbbell.

Next, the dumbbell was frozen in liquid nitrogen, crushed, and the crushed product was observed using an electron microscope HitachiS-300N manufactured by Hitachi, Ltd. at a magnification of 1000 times (Fig. 1), and the average particle size of the LCP particles in the composition Was measured. The results are shown in Table 1 together with the physical properties.

The melt viscosity, tensile strength, tensile elongation and the average particle size of the LCP particles in the composition were determined by the methods described below.

(Melting viscosity)
The melt viscosity was measured by a melt viscosity measuring device (Capillary Graph 1D manufactured by Toyo Seiki Co., Ltd.) at 280 ° C. using a 0.7 mmφ × 10 mm capillary.

(Tensile strength and tensile elongation)
The No. 4 dumbbell was measured using ASTMON 5567 (universal testing machine manufactured by Instron Japan Company Limited) according to ASTM D638.

(Average particle size of LCP particles in the composition)
Ten LCP particles observed from the microscope image were arbitrarily selected, the length of the long axis thereof was measured, and the average was calculated. The smaller the average particle size of the observed LCP particles, the better the compatibility.

[Examples 2 to 3]
A dumbbell was formed in the same manner as in Example 1 except that the amount of the compatibilizer 1 was changed as shown in Table 1, and the tensile strength, the tensile elongation and the average particle size of the LCP particles in the composition were measured. The results are shown in Table 1 together with the melt viscosity. Further, the microscope image of Example 2 is shown in FIG. 2, and the microscope image of Example 3 is shown in FIG.

[Comparative Example 1]
A dumbbell was formed in the same manner as in Example 1 except that no compatibilizer was added, and the tensile strength, tensile elongation and the average particle size of the LCP particles in the composition were measured. The results are shown in Table 1 together with the melt viscosity. A microscope image is shown in FIG.

[Comparative Example 2]
A dumbbell was formed in the same manner as in Example 1 except that the compatibilizer 1 was changed to Bond First 2C (manufactured by Sumitomo Chemical Co., Ltd.), and the tensile strength, tensile elongation and the average particle size of the LCP particles in the composition were measured. did. The results are shown in Table 1 together with the melt viscosity. A microscope image is shown in FIG.

[Comparative Example 3]
An attempt was made to mold a dumbbell in the same manner as in Example 1 except that the content of the compatibilizer 1 was changed to 30 parts by weight, but molding was impossible because of gelation.

As shown in Table 1, the resin compositions of Examples 1 to 3 using the compatibilizer of the present invention have a small average particle size of LCP particles in the composition, and the thermoplastic resin (A) and the liquid crystal polymer (B). It is understood that the compatibility of) is improved.
Preferred embodiments of the present invention include:
[1] The diglycidyl ether ester compound (C) represented by the formula (1) as a compatibilizer is 0.1 to 20 weight by weight based on 100 parts by weight of the total amount of the thermoplastic resin (A) and the liquid crystal polymer (B). A thermoplastic resin composition comprising a portion and having a weight ratio of the thermoplastic resin (A) / liquid crystal polymer (B) of 1/99 to 99/1.
(In the formula, n represents an integer of 0 or 1-10.)
[2] The resin composition according to [1], wherein the thermoplastic resin (A) is a resin having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group.
[3] The thermoplastic resin (A) is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamide, polycarbonate, polyacetal, polyurethane, polylactic acid, polyamide, polyimide and liquid crystal polymer. The resin composition according to [1] or [2], which is one or more kinds of resins.
[4] The resin composition according to any one of [1] to [3], wherein the thermoplastic resin (A) is polyethylene terephthalate.
[5] The liquid crystal polymer (B) is a liquid crystal polyester containing 25 mol% or more of the repeating units represented by the formula (2) in all the repeating units and having a crystal melting temperature of 285 ° C. or lower [1]. The resin composition according to.
[6] The resin composition according to any one of [1] to [5], wherein the liquid crystal polymer (B) is a liquid crystal polyester composed of repeating units represented by the formulas (2) to (5).
[In the formula, Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s are composition ratios (moles) in the liquid crystal polymer (B) of each repeating unit. %), Which satisfies the following equation:
0.4 ≤ p / q ≤ 2.0
2 ≦ r ≦ 15, and
2 ≦ s ≦ 15].
[7] The resin composition according to [6], wherein the composition ratio of the repeating unit represented by the formulas (2) to (5) satisfies the following formula:
35 ≤ p ≤ 48,
35 ≤ q ≤ 48,
2 ≦ r ≦ 15, and
2 ≦ s ≦ 15.
[8] Ar ₁ is,
And / or
And
Ar ₂ is,
And / or
The resin composition according to [6] or [7].
[9] A compatibilizer for compromising the thermoplastic resin (A) and the liquid crystal polymer (B), which comprises a diglycidyl ether ester compound represented by the formula (1).
(In the formula, n represents an integer of 0 or 1-10.)

Claims (9)

The total amount of the thermoplastic resin (A) and the liquid crystal polymer (B) is 100 parts by weight, and 0.1 to 20 parts by weight of the diglycidyl ether ester compound (C) represented by the formula (1) is contained as a compatibilizer. A thermoplastic resin composition in which the crystal melting temperature of the liquid crystal polymer (B) is 180 to 250 ° C., and the weight ratio of the thermoplastic resin (A) / liquid crystal polymer (B) is 1/99 to 99/1.
(In the formula, n represents an integer of 0 or 1-10.) The resin composition according to claim 1, wherein the thermoplastic resin (A) is a resin having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group. One type of thermoplastic resin (A) selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamide, polycarbonate, polyacetal, polyurethane, polylactic acid, polyamide, polyimide and liquid crystal polymer. The resin composition according to claim 1 or 2, which is the above resin. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (A) is polyethylene terephthalate. Liquid crystal polymer (B) is in the repeating units all repeating units 25 mol% or more including the liquid crystal polyester of formula (2), the resin composition of claim 1.
The resin composition according to any one of claims 1 to 5, wherein the liquid crystal polymer (B) is a liquid crystal polyester composed of repeating units represented by the formulas (2) to (5).
[In the formula, Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s are composition ratios (moles) in the liquid crystal polymer (B) of each repeating unit. %) And satisfies the following equation:
0.4 ≤ p / q ≤ 2.0
2 ≦ r ≦ 15, and 2 ≦ s ≦ 15]. The resin composition according to claim 6, wherein the composition ratio of the repeating unit represented by the formulas (2) to (5) satisfies the following formula.
35 ≤ p ≤ 48,
35 ≤ q ≤ 48,
2 ≦ r ≦ 15 and 2 ≦ s ≦ 15. Ar ₁
And / or
And Ar ₂
And / or
The resin composition according to claim 6 or 7. A compatibilizer for compromising the thermoplastic resin (A) and the liquid crystal polymer (B), the crystal melting temperature of the liquid crystal polymer (B) is 180 to 250 ° C., and diglycidyl represented by the formula (1). A compatibilizer containing an ether ester compound.
(In the formula, n represents an integer of 0 or 1-10.)