JP2015166439A - Polyester resin composition, and blow-molded article obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition from which a blow-molded article, that is excellent in thermal stability, color tones, transparency and impact resistance, can be molded with high productivity without causing a drawdown or crystallization problem when blow-molded.SOLUTION: The polyester resin composition contains: a polyester resin, which comprises mainly ethylene terephthalate units and contains 0.5-8 mol% of isophthalic acid as an auxiliary component and 0.5-6 mol% of an ethylene oxide adduct of bisphenol A, as a main component; and 0.05-1.0 mass% of a hindered phenol-based antioxidant. The polyester resin composition has 0.8-1.5 intrinsic viscosity (IV), 1.9-2.5 of a ratio of the weight-average molecular weight to the number-average molecular weight, and 20 equivalent/ton of a carboxyl end group concentration.

Description

  The present invention relates to a polyester resin composition containing a specific compound in a polyester resin, and relates to a polyester resin composition capable of obtaining a blow molded product excellent in color tone, transparency and impact resistance with high productivity. It is.

  Polyethylene terephthalate (PET) is excellent in mechanical properties, chemical stability, transparency and the like, is inexpensive, and is widely used as various sheets, films, containers and the like. The growth in the use of hollow containers (bottles) for fruit juice drinks, liquid seasonings, edible oils, liquors, wines, etc. is remarkable. Moreover, since there is little concern about residual monomers and harmful additives in hollow molded articles made of vinyl chloride resin, and hygiene and safety are high, replacement from conventional bottles made of vinyl chloride resin and the like is also progressing.

  In general, when plastic bottles are manufactured, melt-plasticized resin is used as die orifices in terms of ease of molding, high productivity, and relatively low equipment costs such as molding machines and molds. A so-called direct blow molding method is employed in which a cylindrical parison is formed through extrusion, and air is blown into the mold by sandwiching the parison between the molds. In the case of this direct blow molding, it is necessary to avoid that the parison extruded in the molten state is drawn down during the blow molding in order to perform the molding smoothly. Is done. Accordingly, vinyl chloride resins, polyolefin resins, and the like are widely used in direct blow molding as resins having a high melt viscosity.

  In direct blow molded products, replacement of vinyl chloride resin with polyester resin has been studied, but polyester resins generally do not have a high melt viscosity suitable for direct blow molding. For this reason, there is a problem that the extruded parison draws down during blow molding, and blow molding cannot be performed, and crystallization is likely to occur during blow, so whitening occurs even if molding is possible, and transparency is increased. There was a problem of becoming insufficient.

  In order to improve transparency, a polyester resin obtained by copolymerizing polyethylene terephthalate with other monomer components has been proposed. This can suppress crystallization, but it cannot increase the melt viscosity by itself. Therefore, a method has been proposed in which the viscosity is increased by means of crosslinking with a trifunctional or higher polyvalent carboxylic acid / polyhydric alcohol to solve the drawdown problem (see, for example, Patent Document 1). However, when the viscosity is increased by such a cross-linking means, the moldability is improved, but when the amount of polyvalent carboxylic acid or polyhydric alcohol is large, the gel is easily gelled, the heat stability is inferior, and the resulting molding is obtained. The product had a problem that it was poor in color tone, transparency and impact resistance.

Japanese Patent No. 3173755

  The present invention solves the above-mentioned problems, does not cause problems of whitening due to drawdown or crystallization during blow molding, has excellent thermal stability, and has excellent color tone, transparency, and impact resistance. An object of the present invention is to provide a polyester resin composition capable of obtaining a molded product with high productivity, and to provide a blow molded product comprising the resin composition of the present invention.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the gist of the present invention is the following (1) to (3).
(1) Mainly composed of a polyester resin mainly composed of an ethylene terephthalate unit, containing 0.5 to 8 mol% of isophthalic acid as an accessory component, and 0.5 to 6 mol% of an ethylene oxide adduct of bisphenol A A resin composition containing 0.05 to 1.0% by mass of a hindered phenol-based antioxidant, wherein the intrinsic viscosity (IV) is 0.7 to 1.5. Polyester resin composition.
(2) The ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.9 to 2.5, and the carboxyl end group concentration is 20 equivalents / t or less. Polyester resin composition for blow molding.
(3) A blow molded article comprising the polyester resin composition according to (1) or (2).

The polyester resin composition of the present invention uses a polyester having a specific composition, contains a specific compound, and has an intrinsic viscosity suitable for blow molding. A blow molded product having excellent thermal stability and excellent color tone, transparency, and even impact resistance can be obtained with high productivity without causing the problem of whitening due to crystallization.
And since the blow molded product of this invention is excellent in color tone, transparency, and impact resistance, it can be used for various uses.

Hereinafter, the present invention will be described in detail.
The polyester resin in the polyester resin composition of the present invention is mainly composed of ethylene terephthalate units, and contains both components of isophthalic acid and bisphenol A ethylene oxide adduct (hereinafter sometimes referred to as BAEO) as subcomponents. It contains.
That is, the polyester resin in the present invention may be either polyethylene terephthalate copolymerized with isophthalic acid and BAEO, or a mixture of polyethylene terephthalate copolymerized with isophthalic acid and polyethylene terephthalate copolymerized with BAEO. Good.

  By containing appropriate amounts of both isophthalic acid and BAEO components in the polyester resin, the impact resistance of the obtained direct blow-molded product can be improved.

The content of isophthalic acid is 0.5 to 8 mol%, preferably 0.8 to 6 mol%. By containing (copolymerization) isophthalic acid, the crystallization speed of the polyester resin can be adjusted to be suitable for blow molding, and whitening due to crystallization during blow molding can be prevented. As will be described later, the effect of improving the impact resistance is mainly due to the addition of BAEO, but the effect of improving the impact resistance can be made more excellent.
If the content of isophthalic acid is outside the above range, the crystallization speed cannot be adjusted, and the impact resistance improvement effect cannot be made more excellent.

  The proportion of terephthalic acid in the polyester resin is preferably 50 to 98 mol%, and the proportion of terephthalic acid is preferably 70 to 98 mol%. When the proportion of terephthalic acid is less than 50 mol%, the crystallinity of the resin composition is lowered and it tends to be amorphous. On the other hand, when the proportion of terephthalic acid exceeds 98 mol%, the amount of isophthalic acid copolymerization decreases, so the crystallization speed cannot be adjusted, and the effect of improving impact resistance is made more excellent. I can't.

  Examples of dicarboxylic acid components other than terephthalic acid and isophthalic acid include phthalic acid, 5-sodium sulfoisophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, adipic acid, sebacic acid, dimer acid, and the like, which inhibit the effects of the present invention. As long as it is within the range, two or more of these may be used in combination, and ester-forming derivatives of these acids may be used.

Moreover, the content of BAEO is 0.5 to 6 mol%, and preferably 1 to 5 mol%. By containing (copolymerizing) BAEO, the crystallization speed of the polyester resin can be adjusted to be suitable for blow molding, and whitening due to crystallization during blow molding can be prevented. And the impact resistance of the blow molded product obtained can be improved.
If the BAEO content is outside the above range, the crystallization speed cannot be adjusted, and the impact resistance of the resulting blow molded product cannot be improved.

  The proportion of ethylene glycol in the polyester resin is preferably 70 to 98 mol%, and more preferably 85 to 97 mol%. Examples of glycol components other than ethylene glycol include neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexamethylenediol, diethylene glycol, 1,4-cyclohexanedimethanol, dimer diol, and the like. Can be mentioned.

  If the proportion of ethylene glycol in the glycol component is less than 70 mol%, the crystallinity of the resin composition is lowered and it is likely to be amorphous, which is not preferable. When the proportion of ethylene glycol exceeds 98 mol%, the amount of BAEO copolymerization decreases, so that it is difficult to adjust the crystallization speed, and the impact resistance of the resulting blow molded product cannot be improved.

  The polyester resin composition of the present invention is mainly composed of the above polyester resin, and the ratio of the above polyester resin in the resin composition is preferably 90% by mass or more, It is preferably 96% by mass or more, and more preferably 99% by mass or more.

And the polyester resin composition of this invention contains 0.05-1.0 mass% of hindered phenolic antioxidants, and it is preferable to contain 0.1-0.8 mass% especially.
The hindered phenol-based antioxidant is preferably added during the polymerization reaction step of the polyester resin. By adding it during the polymerization reaction step, a part of the compound is copolymerized in the polyester resin. As a result, molecular chains are entangled in the polyester resin, and it is assumed that a state similar to cross-linking occurs, the melt viscosity of the polyester resin can be increased, and the ratio of the weight average molecular weight to the number average molecular weight (described later) ( (Weight average molecular weight / number average molecular weight) can be in a specific range.

  As the hindered phenol antioxidant, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4, 4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis { 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1′-dimethylethyl} -2,4 , 10-tetraoxaspiro [5,5] undecane, etc. are used, but tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane in terms of effect and cost Is preferred.

  In addition, by including a hindered phenolic antioxidant in the resin composition of the present invention, the thermal stability of the resin composition is improved, and the resulting molded product is excellent in color tone and transparency. Become.

  If the content of the hindered phenolic antioxidant is less than 0.05% by mass, it will not be possible to increase the melt viscosity of the resin composition because the resin composition will not be entangled as described above. , The parison drawdown during blow molding cannot be prevented. In addition, it becomes difficult to make the ratio of the weight average molecular weight and the number average molecular weight (weight average molecular weight / number average molecular weight) described later within a specific range. Furthermore, the thermal stability of the resin composition is not improved, and the resulting molded product is inferior in heat resistance, color tone and transparency.

  On the other hand, when the content exceeds 1.0% by mass, expansion of the resin composition at the exit of the extrusion die at the time of molding becomes too large, and the resulting molded product has a rough surface and a loss of gloss. Further, the melt viscosity of the resin composition becomes too high, and it is necessary to increase the molding temperature during molding, resulting in poor color tone of the molded product. Furthermore, the effect of improving the thermal stability is saturated and disadvantageous in terms of cost.

  The polyester resin composition of the present invention must have an intrinsic viscosity (IV) of 0.7 to 1.5, preferably 0.75 to 1.3, and direct blow molding. When it is used for the purpose, it is preferably 0.9 to 1.3. The intrinsic viscosity (IV) is measured at a temperature of 20 ° C. using a mixture of equal mass of phenol and ethane tetrachloride as a solvent.

  When the intrinsic viscosity is less than 0.7, since the viscosity of the resin composition is low, the drawdown of the parison becomes large at the time of blow molding, and molding becomes difficult. Also, the impact resistance is lowered. On the other hand, when the intrinsic viscosity exceeds 1.5, it is necessary to raise the molding temperature, and the color tone and transparency of the obtained molded product are deteriorated. Further, it is not preferable because expansion of the resin at the exit of the extrusion die tends to increase during blow molding.

Furthermore, the polyester resin composition of the present invention has a ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) of 1.9 to 2.5 and a carboxyl end group concentration of 20 equivalents / It is preferable to satisfy both of t or less.
When the ratio of the weight average molecular weight to the number average molecular weight is within the above range, the composition has a viscosity suitable for blow molding. However, even if the ratio of the weight average molecular weight to the number average molecular weight is within the above range before molding, if the resin is thermally decomposed by heat treatment during blow molding, drawdown occurs during molding, making molding difficult Even if a molded product is obtained, thickness unevenness occurs. Therefore, in order to prevent the thermal decomposition of the resin due to the heat treatment at the time of molding, the carboxyl end group concentration is preferably 20 equivalent / t or less.

First, in the polyester resin composition of the present invention, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is preferably 1.9 to 2.5, and more preferably 2.0 to 2. 4 is preferred.
When the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is less than 1.9, the molecular chain is entangled in the resin and the crosslink density is insufficient. It becomes difficult to make things. For this reason, the drawdown of a parison becomes large at the time of blow molding, and molding becomes difficult, and the obtained molded product tends to have thickness unevenness.

  On the other hand, when the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) exceeds 2.5, the viscosity is high, and it is necessary to increase the molding temperature. Color tone and transparency are likely to deteriorate. Further, since the thermal decomposition of the resin is promoted by increasing the molding temperature, the drawdown of the parison becomes large and molding becomes difficult, and the obtained molded product tends to have uneven thickness. Furthermore, if the mill ends are used again as a recycled material, the resin is easily decomposed during blow molding, so that stable production becomes difficult, and the resulting molded product is likely to have uneven thickness.

  Furthermore, the polyester resin composition of the present invention needs to have a carboxyl end group concentration of 20 equivalent / t or less, preferably 18 equivalent / t or less. By setting the carboxyl end group concentration of the polyester resin composition to 20 equivalent / t or less, thermal decomposition of the resin does not occur during blow molding, and stable molding becomes possible. In addition, the recyclability is excellent.

  When the carboxyl end group concentration exceeds 20 equivalents / t, even if the intrinsic viscosity of the resin and the ratio of the weight average molecular weight to the number average molecular weight are in the above ranges, the heat treatment at the time of blow molding Thermal decomposition of the resin occurs, and therefore, the drawdown of the parison increases, making it difficult to mold, and the resulting molded product tends to have uneven thickness.

  Further, since the obtained molded product has an increased carboxyl end group concentration, the end material generated during molding also has a high carboxyl end group concentration. For this reason, when the end material is subjected to blow molding again as a recycled material, thermal decomposition of the resin occurs at the time of blow molding, and stable production becomes difficult, and the resulting molded product has uneven thickness.

Next, in the polyester resin composition of the present invention, the germanium compound is preferably contained in an amount of 5 × 10 ⁻⁵ mol to 3.0 × 10 ⁻⁴ mol with respect to 1 mol of the acid component of the polyester resin. Among these, 6 × 10 ⁻⁵ mol to 2.0 × 10 ⁻⁴ mol is preferably contained.

The germanium compound is used as a polymerization catalyst when obtaining a polyester resin, and if the content of the germanium compound is less than 5 × 10 ⁻⁵ mol, a polyester resin having a target degree of polymerization cannot be obtained, or In the polymerization reaction, the polymerization time becomes longer, and as a result, the color tone of the resulting polyester resin is deteriorated. On the other hand, even if it exceeds 3.0 × 10 ⁻⁴ mol, the effect as a polymerization catalyst is saturated and disadvantageous in cost.

  Examples of the germanium compound include germanium dioxide, germanium tetrachloride, germanium tetraethoxide, and the like, and germanium dioxide is preferred from the viewpoint of polymerization catalyst activity, physical properties of the resulting polyester resin, and cost.

  Next, the manufacturing method of the polyester resin composition of this invention is demonstrated. The polyester resin composition in the present invention is preferably obtained through an esterification reaction, a melt polymerization reaction, and a solid phase polymerization reaction step. It is difficult to obtain a polyester resin composition having a target intrinsic viscosity only by the esterification reaction and the melt polymerization reaction. Even if it is obtained, the reaction time of the melt polymerization reaction becomes long, and the resulting polyester resin composition has a poor color tone.

Specifically, for example, it can be produced by the following method.
A method of blending these polyester resins after obtaining a polyester resin copolymerized with isophthalic acid and a polyester resin copolymerized with BAEO will be described.
The isophthalic acid copolymer polyester resin was charged with terephthalic acid and isophthalic acid or ester-forming derivatives thereof as acid components and ethylene glycol as a glycol component at a predetermined ratio in an esterification reactor and subjected to an esterification reaction at a predetermined temperature. Then, it transfers to a polymerization reactor, a polymerization catalyst and an additive are added, melt polymerization reaction is performed at predetermined temperature, and a prepolymer is obtained. Using the obtained prepolymer, a solid phase polymerization reaction is performed to obtain a polyester resin copolymerized with a target intrinsic viscosity isophthalic acid.

The BAEO copolymer polyester resin is prepared by charging terephthalic acid or its ester-forming derivative as an acid component and ethylene glycol and BAEO as glycol components in a predetermined ratio into an esterification reactor, and performing an esterification reaction. Transfer, a polymerization catalyst and an additive are added, and a melt polymerization reaction is performed to obtain a prepolymer. Using the obtained prepolymer, a solid-state polymerization reaction is performed to obtain a polyester resin copolymerized with BAEO having a target intrinsic viscosity.
The method of blending these two types of copolyester resins is carried out by a method of kneading in a temperature range of 250 to 300 ° C. with a single or twin screw extruder.

  As described above, the polyester resin composition of the present invention is particularly suitable for blow molding. However, even if an injection molding or stretching method is adopted, a molded product excellent in color tone and transparency (injection molding). Body, sheet, film, etc.).

  Next, the blow molded product of the present invention is composed of the polyester resin composition of the present invention. The blow molded product of the present invention can be manufactured using a general-purpose direct blow molding machine or stretch blow molding machine, and the temperature of each part of the cylinder and the nozzle of the molding machine is in the range of 230 to 280 ° C. Is preferred.

Next, the present invention will be specifically described using examples. The measurement and evaluation methods for various characteristic values in the examples are as follows.
(A) Intrinsic viscosity It was measured by the same method as described above.
(B) Copolymerization amount of copolymerization component and hindered phenol antioxidant content The obtained resin composition was mixed at a volume ratio of deuterated hexafluoroisopropanol and deuterated chloroform of 1/20. It was dissolved in a solvent, 1H-NMR was measured with a LA-400 NMR apparatus manufactured by JEOL Ltd., and the copolymerization amount and content were determined from the integrated intensity of the proton peak of each component of the obtained chart.

(C) Formability The thickness of the body part of the obtained molded product (100 samples) was measured, and the difference between the thickness of the thickest part and the thinnest part was up to 0.30 mm. The number of samples was shown. A sample having 90 or more acceptable samples was evaluated as “◯”, and a sample having less than 90 samples as “×”.
(D) Recyclability After blending 50 parts by mass of the pulverized product obtained by pulverizing the obtained molded product with a pulverizer and 50 parts by mass of the polyester resin obtained in each example, the mixture was put into a dehumidifying dryer and dried. Direct blow molding was performed in the same manner as in No. 1 to obtain a molded product. About the obtained molded product (100 samples), the moldability was evaluated in the same manner as (c).

(E) Color tone Sample pieces (20 pieces) were cut out from the obtained molded product, and the color tone of the sample pieces was measured using a color difference meter ND-Σ80 type manufactured by Nippon Denshoku Industries Co., Ltd. The color tone was determined with a Hunter Lab colorimeter, the b value was measured, and the average value of n number 20 was obtained. A b value of 2.0 or less was determined to be good color tone.
(F) Haze A sample piece (20 pieces) was cut out from the obtained molded product, and the turbidity was measured with a turbidimeter MODEL 1001DP manufactured by Nippon Denshoku Industries Co., Ltd. (air: haze 0%), n number An average value of 20 was used. The smaller this value is, the better the transparency is, and if it is 5% or less, it is judged that the transparency is excellent.
(G) Impact resistance The obtained molded product (100 samples) was filled with 500 ml of tap water, and on the P tile at room temperature from the height of 100 cm, the bottom of the molded product faced downward. The molded product was dropped one by one with face down. At this time, the impact resistance was evaluated by the number of molded products that were not broken. The number of molded products that were not cracked was determined to be 95 or more.

Example 1
[Isophthalic acid copolymer polyester resin composition]
The esterification reactor is fed with a slurry of terephthalic acid (TPA) and ethylene glycol (EG) (TPA / EG molar ratio = 1 / 1.6) and reacted under the conditions of a temperature of 250 ° C. and a pressure of 50 hPa for esterification. A reaction product (number average degree of polymerization: 5) having a reaction rate of 95% was obtained.
In another esterification reaction can, a slurry (IPA / EG molar ratio = 1 / 3.1) composed of isophthalic acid (IPA) and ethylene glycol is charged, and the esterification reaction is performed at a temperature of 200 ° C. for 3 hours. A reaction solution of ethylene glycol was obtained.
46.2 parts by mass of a reaction product of TPA and EG are charged into a polymerization reactor, followed by 6.5 parts by mass of a reaction solution of isophthalic acid and ethylene glycol, 0.008 parts by mass of germanium dioxide as a polymerization catalyst, hindered phenol 0.12 parts by mass of an antioxidant [ADEKA STAB AO-60 manufactured by ADEKA: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane) In addition, the reactor was decompressed, and after 60 minutes, a melt polymerization reaction was performed for 4 hours at a final pressure of 0.9 hPa and a temperature of 280 ° C. to obtain a prepolymer of a copolyester.
This prepolymer had an intrinsic viscosity of 0.72. This prepolymer was pre-dried at 150 ° C. for 5 hours, and then solid-phase polymerized in a nitrogen stream at 210 ° C. for 15 hours to obtain isophthalic acid copolymer polyester resin compositions having the compositions shown in Table 1 and intrinsic viscosity.

[BAE0 copolymer polyester resin composition]
The esterification reactor is fed with a slurry of terephthalic acid (TPA) and ethylene glycol (EG) (TPA / EG molar ratio = 1 / 1.6) and reacted under the conditions of a temperature of 250 ° C. and a pressure of 50 hPa for esterification. A reaction product (number average degree of polymerization: 5) having a reaction rate of 95% was obtained.
50.3 parts by mass of a reaction product of TPA and EG were charged into a polymerization reactor, followed by 3.2 parts by mass of BAEO, 0.008 parts by mass of germanium dioxide as a polymerization catalyst, a hindered phenol antioxidant (manufactured by ADEKA) “Adekastab AO-60”: 0.12 parts by mass of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) was added respectively, and the reactor was evacuated. After 60 minutes, a melt polymerization reaction was performed at a final pressure of 0.9 hPa and a temperature of 280 ° C. for 4 hours to obtain a prepolymer of a copolyester.
This prepolymer had an intrinsic viscosity of 0.72. This prepolymer was pre-dried at 150 ° C. for 5 hours, and then solid-phase polymerized in a nitrogen stream at 210 ° C. for 15 hours to obtain a BAEO copolymer polyester resin composition having the composition and intrinsic viscosity shown in Table 1.

After drying the above two types of copolymerized polyester resin compositions, they are put in an equivalent amount into a biaxial extruder (Toshiki Machine Co., Ltd .: TEM26SS) and kneaded at a temperature of 280 ° C. to obtain a polyester resin composition. It was.
And after using this polyester resin composition and drying, using a direct blow molding machine (manufactured by Tahara Co., Ltd.), molding was performed at an extrusion temperature of 260 ° C., a parison diameter of 3 cm and a length of 25 cm, and 500 cc A hollow container was obtained.

Examples 2-7, Comparative Examples 1-6
Copolymerization amount of isophthalic acid in isophthalic acid copolymerized polyester resin composition, copolymerization amount of BAEO in BAEO copolymerized polyester resin composition, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate] A polyester resin composition was obtained in the same manner as in Example 1 except that the composition was changed so that the content of methane was the value shown in Table 1.
And the direct blow molding goods were obtained like Example 1 using the obtained resin composition.

  Table 1 shows the evaluation results of the composition, intrinsic viscosity, moldability / recyclability of the polyester resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 6, and the color tone, haze, and impact resistance of the molded product. Show.

Example 8
The esterification reactor is fed with a slurry of terephthalic acid (TPA) and ethylene glycol (EG) (TPA / EG molar ratio = 1 / 1.6) and reacted under the conditions of a temperature of 250 ° C. and a pressure of 50 hPa for esterification. A reaction product (number average degree of polymerization: 5) having a reaction rate of 95% was obtained. In another esterification reaction can, a slurry (IPA / EG molar ratio = 1 / 3.1) composed of isophthalic acid (IPA) and ethylene glycol is charged, and the esterification reaction is performed at a temperature of 200 ° C. for 3 hours. A reaction solution of ethylene glycol was obtained.
47.2 parts by mass of a reaction product of TPA and EG was charged into a polymerization reactor, followed by 3.2 parts by mass of a reaction solution of isophthalic acid and ethylene glycol, 1.6 parts by mass of BAEO, and germanium dioxide 0.008 as a polymerization catalyst. 0.12 parts by mass of hindered phenol antioxidant (manufactured by ADEKA: ADK STAB AO-60) were added respectively, and the reactor was evacuated, and after 60 minutes, the final pressure was 0.9 hPa and the temperature was 280 ° C. A melt polymerization reaction was performed for a time to obtain a prepolymer of a copolyester.
This prepolymer had an intrinsic viscosity of 0.72. This prepolymer was pre-dried at 150 ° C. for 5 hours, and then solid-phase polymerized in a nitrogen stream at 210 ° C. for 15 hours to obtain IPA and BAEO copolymerized polyester resin compositions having the compositions and limiting viscosities shown in Table 2. Using the obtained polyester resin composition, a direct blow molded article was obtained in the same manner as in Example 1.

Comparative Examples 7 and 8
A copolymerized polyester resin composition was obtained in the same manner as in Example 6 except that the charged amount was changed so that the copolymerization amount of IPA and BAEO in the polyester resin composition became the values shown in Table 2.
And the direct blow molded product was obtained like Example 1 using the obtained polyester resin composition.

  Table 2 shows the composition of the polyester resin compositions obtained in Example 8 and Comparative Examples 7 and 8, the intrinsic viscosity, the evaluation of moldability / recyclability, and the evaluation results of the color tone, haze, and impact resistance of the molded product.

  As is clear from Tables 1 and 2, the polyester resin compositions obtained in Examples 1 to 8 were those having an intrinsic viscosity within the range specified by the present invention, and were excellent in thermal stability. It was possible to perform direct blow molding with good operability without causing the problem of whitening. The obtained direct blow molded article (container) had a high evaluation of moldability, was not colored, had excellent color tone, and had good transparency.

  On the other hand, since the polyester resin composition obtained in Comparative Example 1 had a low copolymerization amount of isophthalic acid, when direct blow molding was performed, the molded product crystallized and whitened, resulting in poor transparency. In Comparative Example 2, since the amount of isophthalic acid copolymerized was large, fusion occurred during solid phase polymerization, and polyester could not be obtained. For this reason, the prepolymer obtained by melt polymerization was used. As a result, the obtained polyester resin composition had a low intrinsic viscosity and was inferior in moldability. Moreover, the impact resistance was also low. Since the polyester resin composition obtained in Comparative Example 3 had a small amount of copolymerization of BAEO, the molded product crystallized and whitened when direct blow molding was performed, resulting in poor transparency. Moreover, the impact resistance was also low. In Comparative Example 4, since the copolymerization amount of BAEO was large, fusion occurred during solid phase polymerization, and polyester could not be obtained. For this reason, the prepolymer obtained by melt polymerization was used. As a result, the obtained polyester resin composition had a low intrinsic viscosity and was inferior in moldability. Moreover, the impact resistance was also low.

  Since the polyester resin composition obtained in Comparative Example 5 had a low content of hindered phenolic antioxidant, and the drawdown of the parison during molding was large, the molded product had the thickest part and the thinnest part. The difference was large and the moldability was poor. In addition, the thermal stability of the polyester was poor, the color tone was poor, and the recyclability was low. Since the polyester resin composition obtained in Comparative Example 6 had a high content of hindered phenolic antioxidants, the resin composition expanded too much at the extrusion die outlet during molding, and the resulting molded product was The surface was rough and the transparency was impaired, and the color tone was inferior.

Since the polyester resin composition obtained in Comparative Example 7 had a large amount of isophthalic acid copolymerization, fusion occurred during solid phase polymerization, and polyester could not be obtained. For this reason, the prepolymer obtained by melt polymerization was used. As a result, the obtained polyester resin composition had a low intrinsic viscosity and was inferior in moldability. Moreover, the impact resistance was also low. Since the polyester resin composition obtained in Comparative Example 8 had a small copolymerization amount of BAEO, the molded product crystallized and whitened when direct blow molding was performed, and the transparency was poor. Moreover, the impact resistance was also low.

Claims (3)

Mainly a polyester resin containing ethylene terephthalate unit as a main component, 0.5 to 8 mol% of isophthalic acid as an auxiliary component, and 0.5 to 6 mol% of ethylene oxide adduct of bisphenol A, and hindered A polyester resin composition for blow molding, which is a resin composition containing 0.05 to 1.0% by mass of a phenolic antioxidant and having an intrinsic viscosity (IV) of 0.7 to 1.5 object. The blow molding according to claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.9 to 2.5, and the carboxyl end group concentration is 20 equivalent / t or less. Polyester resin composition. A blow molded article comprising the polyester resin composition according to claim 1.