WO2003066734A1

WO2003066734A1 - Polyester resin composition and process for producing the same

Info

Publication number: WO2003066734A1
Application number: PCT/JP2003/001379
Authority: WO
Inventors: Takeshi Yatsuka; Hirotoshi Kizumoto; Katsumasa Yamamoto; Katsuya Shimeno
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2002-02-08
Filing date: 2003-02-10
Publication date: 2003-08-14
Also published as: AU2003207208A1

Abstract

A process for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a lamellar composite hydroxide, characterized in that the lamellar composite hydroxide swollen with a glycol is incorporated at any stage in the course of polycondensation for polyester resin production and the polycondensation is then completed; and a polyester resin composition produced by the process.

Description

Specification

Polyester resin composition and method for producing the same

Technical field

The present invention relates to a polyester resin composition having improved mechanical strength, hardness, rigidity, gas barrier properties, and the like, and a method for producing the same. In particular, the present invention relates to a polyester resin composition which is a composite of a polyester resin and layered inorganic particles and has excellent performance, and a method for producing the same.

Background art

Polyester resins such as polyethylene terephthalate and polybutylene terephthalate have excellent mechanical strength, heat resistance, and sanitation, and are widely used in the fields of fibers, films, potts, molding materials, etc. . Various functions are provided by blending these polyester resins with an inorganic reinforcing material and various additives. For example, weather resistance, flame retardancy, antistatic properties, coloring properties, sliding properties, surface properties, antibacterial properties, crystallinity, transparency, impact resistance, blocking resistance, conductivity, gas barrier properties, etc. For the purpose of improvement, various additives have been added to the inorganic reinforcing material.

In recent years, nylon clay (montmorillonite, etc.) hybrids using a monomer compound in an inorganic layered compound have been actively studied, and have been put into practical use as a nanocomposite for automobile parts and the like. With this nanocomposite, even if the filler (inorganic reinforcing material, etc.) is only a few percent filling, effects such as high elastic modulus, improved heat resistance, and improved gas barrier properties are obtained. As the filler used in the nanocomposite, clay minerals such as smectites such as montmorillonite and savonite, and power olins such as force olinate, and silicate compounds are used. As one of the particles of such an inorganic layered compound, a layered double hydroxide represented by hydrotalcite is known. Compounds of layered double hydroxides (such as hydrated talcites) are substances having a layered structure with anions between the layers, and are used as heat stabilizers, etc., when they are mixed with polyvinyl chloride in the form of fine particles. ing. It is also used as an agricultural film when added to an olefin film to have a heat storage effect, and is also used as an antacid for pharmaceuticals because it dissolves in acid and has a pH control function. WO 01/43253 discloses the use of hydrotalcites as a polyester polymerization catalyst. In addition, Japanese Patent Publications Nos. 2002-500253 and 2002-500254 disclose nanocomposite materials in which at least 20% of anions are compatible and / or reactive with a polymer matrix. It has been disclosed that a polyester resin is mixed with a hydrotalcite to suppress hydrolysis resistance at high temperatures.

Although a composite composition of layered inorganic particles and polyester resin including hydrotalcite has been studied, it has not been possible to disperse layered inorganic particles at a nanometer size in polyester resin such as polyethylene terephthalate. Those having satisfactory properties have not been obtained. For this reason, nanocomposites of layered inorganic particles and polyester resin have not been put to practical use.

Disclosure of the invention

An object of the present invention is to provide a composition comprising a polyester resin and layered inorganic particles, in which the layered inorganic particles are extremely finely dispersed in the polyester resin, and the mechanical strength, hardness, rigidity, gas barrier properties, and the like have been improved. The purpose is to provide a polyester resin composition.

The present inventors have made intensive studies on the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides the following method for producing a polyester resin composition and a polyester resin composition produced by the method.

(1) In a method for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a layered double hydroxide, the layered double hydroxide is added until the polycondensation of the polyester resin is completed. A method for producing a polyester resin composition, comprising: completing the polycondensation after blending at an optional stage of the above.

(2) The layered double hydroxide is a hydrotalcite (1) A method for producing the polyester resin composition as described above.

(3) A method for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a layered double hydroxide, comprising the steps of: after polycondensation in the polymerization process is blended at any stage until completion, process for producing a polyester resin composition characterized in that allowed to complete the polycondensation of the polyester resin ₍

(4) (3) The method for producing a polyester resin composition according to (3), wherein the layered double hydroxide is a talcite at a mouth.

(5) (1) to (4) A polyester resin composition produced by any of the methods described above.

Hereinafter, the present invention will be described in detail.

The layered double hydroxide used in the present invention has a general formula [MS +

+ x (OH) ₂ ] A layered inorganic compound represented by [A " _{-x / n} · z H ₂ 〇], in which divalent metal (M ²⁺ ) is replaced by trivalent metal (M ³⁺ ) As a result, the layer is positively charged, forming a structure in which anions (A ¹¹ —) exist between the layers.Divalent metals include magnesium, nickel, and zinc, and trivalent metals include aluminum, iron, and the like. Chromium (n is an integer of 1 to 3, X is a value of 0.15 to 0.5, z is a value of 5 or less) In addition to divalent and trivalent metals, monovalent metals such as lithium It may contain a tetravalent metal such as titanium.

The method for producing the layered double hydroxide used in the present invention is not particularly limited. For example, the method described in S. Miya, Clays Clay Miner., Vol. 28, page 50 (issued in 1980) is simple and preferred.

As the layered double hydroxide, a layer fired at a temperature of 300 to 800 ° C. may be used.

The layered double hydroxide used in the present invention is particularly preferably a hydrotalcite. The polyester resin composition of the present invention can be obtained by blending the layered double hydroxide swollen with ethylene glycol at an arbitrary stage until the polycondensation is completed in the polyester polymerization step, and then completing the polycondensation. . In order to sufficiently disperse and delaminate the layered double hydroxide, it is desirable to add the layered double hydroxide before or during the esterification reaction or transesterification reaction.

When the layered double hydroxide is added at any stage in the polymerization step of the polyester until the polycondensation is completed, it is important that the layered double hydroxide be swelled with glycol to widen the layer interval. Necessary to achieve the purpose. Swelling of the layered double hydroxide with glycol is performed by heating in glycol. The heating temperature is preferably from 50 to 20 Ot: or less, more preferably from 100 to 180 and below.

The step of swelling the layered double hydroxide with glycol can be performed in a polyester polymerization step, or may be performed in advance in a step different from the polymerization step. When the layered double hydroxide is swelled in glycol, a dibasic acid which is a component of the polyester raw material may be present. By using the layered double hydroxide swollen with glycol, the layered double hydroxide can be efficiently dispersed in the polyester resin, and the separation of the layer of the layered double hydroxide can be promoted. . As a result, the layered double hydroxide can be dispersed in the polyester resin in a nanometer size, so that molecular reinforcement can be achieved, and properties such as mechanical strength, hardness, rigidity, and gas barrier properties can be improved. .

As the glycol used for swelling the layered double hydroxide with glycol, ethylene glycol, diethylene glycol and triethylene glycol are preferred. Particularly, ethylene glycol is preferred. These glycols are considered to be replaced by water existing between the layers of the hydrotalcite by heating.

The layered double hydroxide used in the present invention preferably has a surface area of 5 to 200 m ² / g. When the surface area is less than 5 m ² Zg, the layered double hydroxide cannot be dispersed efficiently, and the transparency of the obtained polyester resin composition may be reduced. If it exceeds 20 O ms / g, the melt viscosity during polymerization sharply increases. As a result, the resin having the desired molecular weight may not be obtained.

In the present invention, the layered double hydroxide is blended in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyester resin. If it exceeds 10 parts by weight, the melt viscosity becomes too high, making it difficult to increase the molecular weight of the polyester resin, and the resulting polyester composition may be very brittle. When the amount is less than 0.1 part by weight, the effect of adding the layered double hydroxide is reduced.

As the dibasic acid component of the polyester resin used in the present invention, terephthalic acid, isophthalic acid, orthophthalic acid> naphthalenedicarboxylic acid, aromatic dibasic acids such as diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, succinic acid, Examples thereof include aliphatic dibasic acids such as adipic acid, azelaic acid, sebacic acid, dimer acid, and cyclohexanedicarboxylic acid.

The glycol components of the polyester resin used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol. , 1,6-hexanediol, diethylene glycol, triethylene glycol, 3_methyl-1,5, -pentynediol, neopentylglycol, 2-ethyl-2-butyl-1,3-propanediol, diethyleneglycol, 1 , 4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, or polyether glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Can be .

Further, a lactone component such as ε-force prolactone and δ-valerolactone and an oxycarboxylic acid component such as ρ-hydroxyethoxybenzoic acid can be used as raw materials for the polyester resin used in the present invention. In addition, a trifunctional or higher functional component such as trimethylolpropane, pentaerythritol, and trimellitic anhydride may be used in combination.

Improvement of dispersibility and delamination property of layered double hydroxide in polyester resin For this purpose, it is preferable to introduce a polar group such as a sulfonic acid metal base into the polyester resin. For example, as a raw material for introducing a metal sulfonic acid salt into a polyester resin, there are 5-sodium sulfoisophthalic acid, 5-calidosulfonic acid, sodium sulfoterephthalic acid, 2-sodium sulfo-1,4-butane Examples include diols, dicarboxylic acids such as 2,5-dimethyl-3-sodium sulfo_2,5-hexanediol, and glycols. Particularly preferred are 5-sodium sulfoisophthalic acid and 5-force lithium sulfoisophthalic acid. The amount of the metal sulfonate group introduced into the polyester resin is preferably from 0.5 mol% to 20 mol% of the total dicarboxylic acid component. If it is less than 0.5 mol%, the effect of improving the dispersibility and delamination property of the layered double hydroxide is not remarkably obtained, and if it is more than 20 mol%, the thermal stability of the polyester resin tends to deteriorate, so that it is preferable. Absent.

The polyester resin composition of the present invention can be produced by a usual polyester polymerization method. In other words, after a dibasic acid is subjected to an esterification reaction with glycol under the condition of excess glycol, melt weight is subjected to deglycolization and polycondensation under high temperature and high vacuum in the presence of a metal catalyst such as antimony, titanium, and germanium. Either a synthetic method or a method in which a methyl ester compound of a dibasic acid and an glycol are subjected to an ester exchange reaction and then similarly polycondensed can be used. Further, there is a method in which the polyester resin obtained by these methods is subjected to solid phase polymerization at a temperature not higher than the melting point of the resin to increase the molecular weight.

For example, when using a hydrated talcite as a layered double hydroxide, the polycondensation is completed after blending the hydrated talcite at an arbitrary stage until the polycondensation is completed. In order to sufficiently disperse the hydrotalcite in the polyester resin and to peel off the layer, it is preferable to introduce the talcite at the mouth before the esterification reaction or transesterification reaction.

It is even more desirable that the hydrotalcite be dispersed in glycol beforehand. Ethylene glycol and diethylene glycol are preferred as the glycol used for dispersion. Ethylene glycol, diethylene glyco It is considered that the polyester is replaced with water existing between the layers of the hydrotalcite during heating during polyester polymerization.

By dispersing the hydrotalcite efficiently in the polyester resin and promoting delamination, it can be dispersed in nanometer size.

In order to efficiently disperse the talcite at the mouth in the polyester resin and promote delamination, it is desirable to use a dibasic acid which has been previously intercalated between the layers of the hydrite site. There are two methods for obtaining hydrotalcites obtained by dibasic acid oxidation: (1) using dibasic acid as a source of anion when synthesizing the hydrotalcite, (2) previously obtained hydrotalcites. (3) A method of exchanging water with a dibasic acid anion; (3) A hydrotalcite of the original structure obtained by adding water to a talcite having a porosity that excludes interlayer anions by firing in the range of 300 to 800. For example, there is a method using a dibasic acid as a source of anion when converting the acid to an acid.

Known substances can be added to the polyester resin composition of the present invention in order to impart desired properties according to the purpose. For example, inorganic reinforcing materials, fiber reinforcing materials, heat stabilizers, antioxidants, antistatic agents, weathering agents, mold release agents, lubricants, coloring agents such as dyes and pigments, etc. can be added. .

Further, it may be blended or alloyed with another resin in order to impart desired properties according to the purpose.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples.

The measurement method and evaluation method used in the description of the examples are shown below.

(Reduced viscosity)

The reduced viscosity was measured at 30 at a composition concentration of 0.4 g Zd1 using phenol tetrachloride (6/4 weight ratio) as a solvent.

(Glass transition temperature; Tg)

The sample was measured by DSC under the following conditions, and the glass transition temperature Tg was measured according to JISK 71. Determined in accordance with 21.

Seiko Instruments Inc. DSC6200 Pan Aluminum Pan (Non-hermetic type)

5 mg

Heating start temperature: -100

Heating rate: 20 ° C / niin.

Atmosphere gas

(Distance between layers of layered double hydroxide)

The interlayer distance was measured by a powder X-ray diffraction method using an X-ray diffractometer, Rigaku Corporation, Geigerflex RAD-II.

(Composition of polyester resin)

The composition of the polyester was measured by ¹ H-NMR under the following conditions.

Nuclear Magnetic Resonance Apparatus (AVANCE 500 manufactured by BRUKER) Solvent: Deuterated chromatoform trifluoroacetic acid = 9/1 volume ratio Resonance frequency 500MHz

Number of accumulation: 5 1 2 times

Measurement temperature: room temperature

(50% tensile modulus)

The tensile modulus at 50% elongation was measured under the following conditions.

Equipment name: UYM—I—250—0 manufactured by Toyo Paul Douwin

Measurement temperature and humidity: 20%, 50% RH

Tensile speed: 20 Omm / min

Sample shape: 15 mm x 3 Omm strip (thickness: 25 ^ m)

(Storage modulus)

The dynamic storage modulus at 1 Ot: was measured under the following conditions.

Apparatus name: DVA-200 manufactured by IT Measurement Control Company

Temperature rise start temperature: One in 100

Heating rate: 20 / min Atmosphere gas: Nitrogen

Measurement frequency: 110 Hz

Measurement method: Tensile deformation

(Solution stability)

The polyester resin composition obtained to examine the degree of dispersion of the layered double hydroxide was dissolved in methyl ethyl ketone / toluene (1/1 weight ratio) at a solid content of 10%, and the solution was stable after storage at room temperature for 1 week. By observing the properties, those with no sedimentation of the layered double hydroxide were evaluated as 〇, those with slight sedimentation △, and those with significant sedimentation as X.

(Water vapor barrier property)

Place 30 cc of water in a 100 cc cylindrical glass bottle with an inner diameter of 2 cm, seal the bottle inlet with the film of Example and Comparative Example (25 m thick), and at 20 and 50% RH atmosphere. After standing in the water for 24 hours, the weight loss of water was measured. For Examples 1A to 6A, Comparative Examples 1A and 3A to 5A, the reduction in water in the film containing no layered double hydroxide of Comparative Example 2A was set to Standard 1, and the ratio was shown. . For Examples 1B to 3B and Comparative Examples 2B to 5B, the reduction amount of water in the film containing no layered double hydroxide of Comparative Example 1B was set to Standard 1, and the ratio was shown. The smaller the value, the better the water vapor barrier property.

(Oxygen barrier property)

With respect to the oxygen permeation amount of the 25 / m film, the ratio of the oxygen permeation amount of a polyester resin having the same composition not containing the layered double hydroxide was calculated and evaluated. The smaller the number, the higher the barrier property. The oxygen permeation amount was measured according to JIS K7126.

Measurement temperature and humidity: 20 and 50 RH

(Example 1A)

In a reaction vessel equipped with a thermometer, a stirrer and a distilling condenser, 163 parts by weight of isophthalic acid, 5.9 parts by weight of dimethyl 5-sodium sulfoisophthalate, 3-methyl-1,5-pentanediol and Mg ₆ A 1 ₂ (OH) ₁₆ C0 ₃ Solution 2 55 parts by weight of a dispersed high Dorotarusai preparative represented by H ₂ 0 in 1 0 0: 2 weight ratio was charged with tetrabutyl titanate 0.06 8 by weight parts as a reaction catalyst, to 2 2 0 ° C The temperature rose. After the distillation of water by the esterification reaction was completed, the esterification reaction was terminated while the temperature was raised to 240. Thereafter, the pressure in the system was gradually reduced, and finally reached 0.1 mmHg. The temperature at that time was kept at 260. Thus, a polyester resin composition containing 2% by weight of the talcite at the mouth was obtained.

The composition of the polyester was analyzed by ¹ H-NMR. The obtained composition was dissolved in phenol / tetrachloroethane (6Z4 weight ratio), and the reduced viscosity was measured. Also, the obtained composition is dissolved in methyl ethyl ketone / toluene (= 1 Z 1 weight ratio), coated and dried on a biaxially oriented polypropylene film, peeled off from the propylene film, and coated with the resin composition itself. A membrane was obtained. The strength and elongation of the coating film, the storage modulus in the glass state, and the water vapor barrier property were measured. Table 1 shows the evaluation results.

(Examples 2A and 3A)

In the same manner as in Example 1A, except that the concentration of the 3-methyl-1,5-pentyldiol Z hydrotalcite dispersion was changed to obtain polyester compositions having different hydrotalcite contents. Evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.

(Example 4A)

As in Example 1A, but without the use of 5.9 parts by weight of dimethyl 5-sodium sulfoisophthalate, the dispersion of isophthalic acid and 3-methyl-1,5-pentanediol / "hydrotalcite A polyester resin composition was obtained from the product, which was evaluated in the same manner as in Example 1 A. The evaluation results are shown in Table 1.

(Examples 5A and 6A)

In Example 5A, as in Example 1A, except that the talcite used in Example 1A dispersed in ethylene glycol at 6.3% by weight was 40 parts by weight, and 3-methyl-1,5 was used. — 16.5 parts by weight of pen diol and isophthalate The reaction was carried out with 1666 parts by weight of luic acid.

In Example 6A, as in Example 1A, except that the talcite used in Example 1A was dispersed at 4% by weight in diethylene glycol, 62 parts by weight, 3-methyl-1,5-pentene were used. 16.5 parts by weight of evening diol and 1666 parts by weight of isofluoric acid were reacted.

Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results.

(Comparative Example 1A, 2A)

A polyester resin having the same composition as in Examples 1A and 4A was obtained without using a hydrotalcite. Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results.

(Comparative Example 3A)

Comparative Example 1 Hydrotalcite was mixed with the polyester resin solution of 1A (solvent: methyl ethyl ketone toluene: 1 Z 1 weight ratio) at a solids weight ratio of 100: 2, and glass beads were added. The mixture was shaken and dispersed in a paint shaker for 6 hours. From this dispersion, a dried coating film was obtained in the same manner as in Example 1A. Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results.

(Comparative Example 4A, 5A)

As in Example 1A, except that the concentration of the 3-methyl-1,5-pentanediol Z hydrotalcite dispersion was changed to obtain polyester compositions having different hydrotalcite contents. In Comparative Examples 4A and 5A, the content of the hide mouth talcite is out of the range of the present invention. Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results. In Comparative Example 5A, the obtained coating film was very brittle, and the 50% tensile modulus and the water vapor barrier property could not be measured. Table 1 Properties of polyester resin composition

IPA: isophthalic acid MPD: 3-methyl-1,5-pentanol DSN: 5-sodium sulfoisophthalic acid EG: ethylene glycol

DEG: Diethylene glycol

(Examples 7A, 8A, 9A)

1 9 A hydrotalcite (Mg ₄ Al ₂ (OH) ₁₂ (TA), which was prepared from terephthalic acid anion synthesized by the method described in Inorganic Chemistry, vol. 27, 462, p. · 4Η ₂ 0), (the T Alpha was dispersed) 1 0 parts by weight represents terephthalic acid ion to 90 by weight of ethylene glycol. In a reaction vessel equipped with a thermometer, a stirrer, and a distilling cooling tube used in Example 1A, 166 parts by weight of terephthalic acid and 18.9 parts by weight of ethylene glycol in which the above-mentioned hydrosite was dispersed (18.9 parts by weight) 1.9 parts by weight of hydrotalcite, 17 parts by weight of ethylene glycol) and 107 parts by weight of ethylene glycol were charged, and the esterification reaction was carried out under pressure. During that time, the temperature reached 230. 0.07 parts by weight of tetrabutyl titanate was charged as a polycondensation reaction catalyst, and then the pressure inside the system was gradually reduced to finally reach 0.1 mm Hg. The temperature at that time was maintained at 27 Ot :. Thus, a high-viscosity polyethylene terephthalate (also referred to as PET) composition containing 1% by weight of hydrotalcite was obtained.

The obtained composition was dissolved in phenolnotetrachloroethane, and the reduced viscosity was measured. In addition, the oxygen barrier properties of the film obtained by the hot pressing method (a method in which the resin is melted by heating to above the melting point and softening point of the resin, stretched by applying pressure, and then rapidly cooled by water cooling) are measured in accordance with JISK 7126. It was measured. Table 2 shows the oxygen barrier properties of the films obtained by the same method using PET containing no talcite.

In Example 8A, the hydrotalcite used in Example 7 was dispersed in 1,3-propanediol to obtain polytrimethylene terephthalate (PTT) in which the hydrotalcite was dispersed by the same polymerization method.

In Example 9A, polytetramethylene terephthalate (PBT) in which hydrotalcite was dispersed was obtained in the same manner as in Example 8.

Table 2 shows the respective reduced viscosities and oxygen barrier properties. Table 2 Properties of polyester resin composition

E G: Ethylene glycol

T P A: Terephthalic acid

1,3-PG: 1,3-propanediol

1, 4-BD: 1, 4-butanediol

As is clear from Tables 1 and 2, Examples 1A to 9A, in which the hydrated talcite was added during the polyester polycondensation, were Comparative Examples 1A and 2A without the hydrotalcite and polycondensation. The strength, elastic modulus, and gas barrier properties are significantly higher than those of Comparative Example 3A, which is simply blended after completion, and Comparative Examples 4A, 5A, which have a hydrotalcite content outside the scope of the claims. It can be seen that it has improved.

(Example 1B)

Hydrotalcite as layered double hydroxide in a glass reactor equipped with a stirrer (Hydrotal talcite manufactured by Toda Kogyo Co., Ltd., average particle size 0.15 / zm, Mg / Al molar ratio 2.7, B (ET surface area 18 m ² / g) 20 parts by weight and 80 parts by weight of ethylene glycol were added, and the content was heated at 130 for 10 minutes. The ethylene glycol solution containing hydrotalcite turned into a paste with high viscosity. According to the measurement by X-ray diffraction, the interlayer distance of the talcite at the mouth was widened from 7.5 A to 8.4 A by heating in ethylene glycol.

In a reaction vessel equipped with a thermometer, a stirrer, and a distilling condenser, 194 parts by weight of dimethyl isophthalate and 236 parts by weight of 3-methyl-1,5-pentanediol And 24.8 parts by weight of the above hydrotalcite ethylene glycol solution (28 parts by weight) and 0.068 parts by weight of tetrabutyl titanate as a reaction catalyst were charged, and the mixture was heated to 18 (TC. While continuing the distillation, the transesterification reaction was completed while the temperature was raised to 23 O. Thereafter, the pressure in the system was gradually reduced to finally reach 0.3 mmHg, and the temperature at that time was maintained at 260. In this way, a polyester resin composition containing 2% by weight of a talcite at a mouth was obtained.

The composition of the polyester was analyzed by ¹ H-NMR. The obtained composition was dissolved in phenol tetrachloroethane (64 weight ratio), and the reduced viscosity was measured. Also, the obtained composition was dissolved in methyl ethyl ketone toluene (= 11 weight ratio), applied and dried on a biaxially oriented polypropylene film, peeled off from the propylene film, and the resin composition itself was coated. Obtained. The reduced viscosity, glass transition temperature, 50% tensile modulus, storage modulus, solution stability, and water vapor barrier properties of the coating film were evaluated. Table 3 shows the results.

(Example 2B)

As in Example 1B, except that the hydrotalcite / ethylene glycol (2Z8) solution used in Example 1B 6.2 parts by weight and the ethylene glycol 15 parts by weight, the hydrotalcite 0.5 parts by weight % Of a polyester resin composition. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the results. (Example 3B)

A reaction vessel equipped with a thermometer, a stirrer, and a distilling cooling tube was charged with 19.8 parts by weight of the hydrotalcite used in Example 1B and 40 parts by weight of ethylene glycol, and stirred at 150 for 10 minutes. Further, 194 parts by weight of dimethyl isophthalate, 236 parts by weight of 3-methyl-1,5-pentanediol, and 0.08 parts by weight of tetrabutyl titanate as a reaction catalyst were charged, and the transesterification reaction was carried out in the same manner as in Example 1. A polycondensation reaction was carried out to obtain a polyester composition containing 8% by weight of hydrotalcite. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the results. (Comparative Example 1B)

A polyester resin having the same composition as in Example 1B was obtained without using a hydrotalcite. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the evaluation results.

(Comparative Example 2B)

Comparative Example 1 Hydrotalcite was mixed with the polyester resin solution of B (solvent: methyl ethyl ketone toluene = 11 weight ratio) at a weight ratio of solids of 100: 2, and glass beads were added. Shake and disperse for 6 hours with a paint shear. From this dispersion, a dried coating film was obtained in the same manner as in Example 1B. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the evaluation results.

(Comparative Examples 3B, 4B)

In the same manner as in Example IB, except that the concentration of the hydrated talcite-to-ethylene glycol dispersion was changed to obtain a polyester composition having a different hydrotalcite content. In Comparative Examples 3B and 4B, the content of the talcite at the mouth was out of the scope of the present invention. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the evaluation results. In Comparative Example 4B, the obtained coating film was very brittle, and the 50% tensile modulus and the water vapor barrier property could not be measured.

(Comparative Example 5B)

In a reaction vessel equipped with a thermometer, a stirrer, and a cooling pipe for distillation, 19.8 parts by weight of a talcite having a mouth opening used in Example 1B and 40 parts by weight of 3-methyl-1,5-pentendiol were used. Then, the mixture was stirred at 150 ° C. for 10 minutes. Further, 194 parts by weight of dimethyl isophthalate, 236 parts by weight of 3-methyl-1,5-pentanediol, and 0.068 parts by weight of tetrabutyl ticnate as a reaction catalyst were prepared. A transesterification reaction and a polycondensation reaction were carried out in the same manner as described above to obtain a polyester resin composition containing 2% by weight of hydrotalcite.

Evaluation was performed in the same manner as in Example 1B. Table 3 shows the results. Table 3 Properties of polyester resin composition

IPA: Isophthalic acid

MPD: 3-Methyl-1,5-pentanediol EG: Ethylene glycol

(Examples 4B, 5B, 6B)

2 parts by weight of the layered double hydroxide described in Table 4, 124 parts by weight of ethylene glycol, 166 parts by weight of terephthalic acid, and 0.068 parts by weight of tetrabutyl titanate as a reaction catalyst were subjected to temperature. The mixture was charged into a reaction vessel equipped with a total, a stirrer, and a cooling pipe for distillation, and an esterification reaction was carried out under pressure. In the meantime, the temperature rose to 230. From around the time the temperature exceeded 200, the melt became transparent. Thereafter, the pressure in the system was gradually reduced, and finally reached 0.5 mmHg. The temperature at that time was kept at 270. Thus, a high-viscosity polyethylene terephthalate (PET) composition containing 1% by weight of the layered double hydroxide was obtained.

The obtained composition was dissolved in phenol / tetrachloroethane, and the reduced viscosity was measured. In addition, the polyester resin composition is heated and melted at 280 by a heat press method, and is then thinned by applying pressure between fluorine-based resin films having a thickness of 0.2 mm. A method for obtaining a film-like resin composition having a thickness of about 25 m) was measured for oxygen barrier properties. Table 4 shows the oxygen barrier effect of the layered double hydroxide as a reduction ratio of the amount of oxygen permeated by the layered double hydroxide.

(Comparative Examples 6B, 7B, 8B)

2 parts by weight of the layered double hydroxide described in Table 4, 254 parts by weight of bis (/ 3-hydroxyethyl) terephthalate, 0.068 parts by weight of tetrabutyl titanate as a reaction catalyst, a thermometer, The reactor was charged into a reaction vessel equipped with a stirrer and a distilling cooling tube, and the temperature in the system was raised to 230. Thereafter, the pressure in the system was gradually reduced, and finally reached 0.5 mmHg. The temperature at that time was kept at 270. Thus, a high-viscosity polyethylene terephthalate (PET) composition containing 1% of layered double hydroxide was obtained. However, the layered double hydroxide was poorly dispersed and formed a mass that could be observed with the naked eye. Evaluation was performed in the same manner as in Example 4B. Table 4 shows the results. The same layered double hydroxide was used for Example 5B and Comparative Example 6B, Example 6B and Comparative Example 7B, and Example 7B and Comparative Example 8B. Table 4 Properties of polyester resin composition

EG: ethylene glycol

TPA: Terephthalic acid

BHET: bis (/ 8-hydroxyethyl) チル phthalate

As is clear from Tables 3 and 4, Examples 1B to 6B in which the layered double hydroxide was added at the time of the polycondensation of the polyester were completed in Comparative Example 1B containing no layered double hydroxide and the polycondensation was completed. Comparative Examples 2B, 3B, 4B, and Comparative Examples 5B, 6B, and 7B in which ethylene glycol is not used. It can be seen that the appearance, strength, elastic modulus, and gas barrier properties are dramatically improved as compared with 8B and 8B.

Industrial applicability

By the method for producing a composition of the present invention in which the polyester resin and the layered double hydroxide are combined, the layered double hydroxide is extremely finely dispersed in the polyester resin, and the mechanical strength, hardness, rigidity, gas barrier property, and the like are improved. Since an improved polyester resin composition can be obtained, the polyester resin composition of the present invention can be used as an engineering plastic as various molded articles such as electric and electronic parts by utilizing its properties. It is also applicable to films, paints, and fibers, and is particularly useful as a raw material for paints and films because the layered double hydroxide is extremely finely dispersed in the polyester resin.

Claims

The scope of the claims

1. A method for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a layered double hydroxide, wherein the layered double hydroxide is reacted until the polycondensation of the polyester resin is completed. A method for producing a polyester resin composition, comprising completing polycondensation after blending at an optional stage.

2. The method for producing a polyester resin composition according to claim 1, wherein the layered double hydroxide is hydrotalcite.

3. A method for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a layered double hydroxide, wherein the layered double hydroxide swollen by glycol is polymerized into a polyester resin. after the polycondensation has blended at any stage until completion in step, the manufacturing method _t polyester resin composition characterized in that allowed to complete the polycondensation of the polyester resin

4. The method for producing a polyester resin composition according to claim 3, wherein the layered double hydroxide is hydrotalcite.

5. A polyester resin composition produced by the method according to any one of claims 1 to 4.