KR20130027933A - Polyester resin composition, molded article using the same and process for preparing molded article - Google Patents

Abstract

PURPOSE: Poly ester resin composition is provided to increase heat resistance; to remain the color degree and transparency as the contents of acetaldehyde is reduces; and to apply as a food or drink container as there is no deterioration in taste due to acetaldehyde. CONSTITUTION: Polyester resin composition comprises polyester resin which includes dicarboxylic acid component containing terephthalic acid, polyester resin having polycondensate of diol containing isosorbide and waxes. The manufacturing method of polyester resin mold body manufacturing method comprises a step in which polyester resin which includes dicarboxylic acid component containing terephthalic acid and polyester resin having polycondensate of diol containing isosorbide are reacted with esterification; a step that produces polyester resin by polycondensating the product from the esterific reaction; a step that obtains a polyester resin composition by adding waxes to the polyester resin; and a step that molds the polyester resin component.

Description

Polyester resin composition, molded article using the same and method for producing the molded article {Polyester resin composition, molded article using the same and process for preparing molded article}

The present invention relates to a polyester resin composition, a molded article and a method for producing the molded article using the same, and more particularly, by adding waxes to a polyester resin containing a specific diol component, which has improved heat resistance and reduced acetaldehyde content. It relates to a polyester resin composition, a molded article and a method for producing the molded article using the same.

Polyester is a polymer obtained by the polycondensation reaction of dicarboxylic acid and diol component. It has ester bond in the main chain of molecule and it is eco-friendly and does not contain harmful substances to human body. Therefore, it is conventionally used for juice, soft drink, carbonated drink. It is used in fields such as filling containers and packaging materials, molded articles, sheets, films, and the like. Typically, polyethylene terephthalate (PET) resin obtained as a polycondensation product of terephthalic acid and ethylene glycol, glycol modified polyethylene terephthalate (Glycol modified polyethylene terephthalate, PETG) copolymerized by adding CHDM (1,4-cyclohexanedimethanol) as a comonomer ) Resins and the like.

Acetaldehyde, on the other hand, is a material formed as a by-product by melt polymerization reaction of a polyester and thermal decomposition of a melting process.As a characteristic odor affects the taste of food and beverages, a polyester resin having a high acetaldehyde content There is a problem that the use of food and beverage storage is limited.

There are two ways to remove acetaldehyde, there is a method of reducing acetaldehyde by changing the conditions in the manufacturing process of the polyester resin, it is possible to remove acetaldehyde in the resin composition rather than changing the process conditions. There is a method of reducing by adding an additive or the like. The method for reducing acetaldehyde while changing the process conditions is described in Korean Patent Publication No. 2010-0078078. In addition, as a method of using an additive, a method of adding an organic additive compound to US Pat. No. 6,762,275 is disclosed.

In order to use it as a food container, it is necessary not only to have sufficient heat resistance and processability in order to make molding a polyester resin composition into a desired form, but also to remove the acetaldehyde which affects a taste and smell. By the way, when preparing a polyester resin using a conventionally known composition and method There is a disadvantage that acetaldehyde is not sufficiently removed, or affects the physical properties of the polyester resin itself, thereby deteriorating the transparency and color.

In order to solve the above problems, it is an object of the present invention to provide a polyester resin composition and molded article using the same having improved heat resistance and reduced acetaldehyde content and does not reduce the appearance characteristics.

It is also an object of the present invention to provide a method for producing a polyester resin molded article which can effectively remove acetaldehyde without lowering the physical properties of the polyester resin.

In order to achieve the above object, the present invention provides a polyester resin composition comprising a polyester resin and waxes comprising a polycondensate of a dicarboxylic acid component containing terephthalic acid and a diol component containing isosorbide. to provide.

Moreover, this invention provides the molded object manufactured using the said polyester resin composition.

In addition, the present invention comprises the step of esterifying the dicarboxylic acid component containing terephthalic acid and the diol component containing isosorbide, polycondensing the reactants of the esterification reaction to prepare a polyester resin, waxes It provides a method of producing a polyester resin molded article comprising the step of adding a polyester resin composition and molding the polyester resin composition.

Hereinafter, the polyester resin composition according to the present invention, a molded article using the same, and a method for producing the molded article will be described in more detail.

Polyester resin composition and using the same Molded body

The polyester resin composition of the present invention includes a polyester resin and waxes comprising a polycondensate of a dicarboxylic acid component containing terephthalic acid and a diol component containing isosorbide.

The dicarboxylic acid component of the present invention may be a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / or these It is used as a meaning containing an acid anhydride of, and reacts with the diol component, it is possible to form a dicarboxylic acid moiety (dicarboxylic acid moiety) such as terephthaloyl moiety (terephthaloyl moiety).

The dicarboxylic acid component may further include, in addition to terephthalic acid, an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component or a mixture thereof as other dicarboxylic acid components. In this case, the other dicarboxylic acid component means a component other than terephthalic acid among the dicarboxylic acid components.

The aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, preferably 8 to 14 carbon atoms, or a mixture thereof. Examples of the aromatic dicarboxylic acid include naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'- stilbendicarboxylic acid, 2, 5-furanedicarboxylic acid, 2,5-thiophenedicarboxylic acid, and the like, but specific examples of the aromatic dicarboxylic acid are not limited thereto.

The aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof. Examples of the aliphatic dicarboxylic acid include cyclohexanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, Linear, branched or cyclic aliphatic dicarboxylic acid components such as maleic acid, fumaric acid, adipic acid, glutaric acid, azelaic acid, and the like, but are not limited thereto.

On the other hand, according to an embodiment of the present invention, the dicarboxylic acid component is selected from the group consisting of 50 to 100 mol%, preferably 70 to 100 mol% of terephthalic acid and aromatic dicarboxylic acid and aliphatic dicarboxylic acid 0 to 50 mole%, preferably 0 to 30 mole%, of one or more dicarboxylic acids.

The diol component of the present invention includes isosorbide (1,4: 3,6-dianhydroglucitol), so that not only the mechanical properties of the polyester resin produced, but also heat resistance, chemical resistance, chemical resistance, etc. Physical properties can be improved.

According to one embodiment of the invention, the diol component is cyclohexanedimethanol such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol in addition to isosorbide It may further include. As the cyclohexane dimethanol is included, the impact strength of the polyester resin composition to be prepared may be further increased.

In addition, according to an embodiment of the present invention, the diol component may further include other diol components in addition to the isosorbide and cyclohexanedimethanol. The other diol component means a diol component except for the isosorbide and cyclohexanedimethane, and may be, for example, an aliphatic diol, an aromatic diol or a mixture thereof.

The aromatic diol may include an aromatic diol compound having 8 to 40 carbon atoms, preferably 8 to 33 carbon atoms. Examples of such aromatic diol compounds include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) Propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3) -2,2-bis (4-hydroxy Phenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Propylene- (2.4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (3.0)- Bisphenol A derivatives to which ethylene oxide and / or propylene oxide are added, such as 2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene- (6) -2,2-bis (4-hydroxyphenyl) propane (Polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) Lopane, polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane or polyoxypropylene- (n) -polyoxyethylene- (n) -2,2-bis (4-hydroxy Phenyl) propane, etc., but specific examples of the aromatic diol compound are not limited thereto, wherein n denotes the number of polyoxyethylene or polyoxypropylene units.

The aliphatic diol may include an aliphatic diol compound having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. Examples of such aliphatic diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, pentanediol, hexanediol ( 1,6-hexanediol, etc.), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Linear, branched or cyclic aliphatic diol components such as methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tetramethylcyclobutanediol, and the like, but specific examples of aliphatic diol compounds are limited thereto. It is not.

Meanwhile, according to one embodiment of the present invention, the diol component is 1 to 60 mol% of isosorbide, 1 to 80 mol% of cyclohexanedimethanol, and at least one other diol component 1 selected from the group consisting of aliphatic diols and aromatic diols. To 80 mole%. If the content of isosorbide in the diol component is less than 1 mol%, the heat resistance or chemical resistance of the polyester resin to be produced may be insufficient, if the content of the isosorbide exceeds 60 mol%, polyester resin or The appearance properties of the composition may be degraded or yellowing may occur.

According to one embodiment of the invention, the dicarboxylic acid component and the diol component may be included in a molar ratio range of about 1.1 to about 3.0.

The polyester resin composition of this invention improves heat resistance by essentially including isosorbide as a diol component. The polyester resin of the present invention has a glass transition temperature of about 85 to about 130 ° C, preferably about 90 to about 120 ° C. Therefore, compared with the conventionally known polyester resin, it has improved heat resistance properties and the workability is improved.

According to an embodiment of the present invention, the polyester resin copolymerized with the dicarboxylic acid component and the diol component has an intrinsic viscosity of about 0.3 to about 2.0 dl / g, preferably about 0.5 to about 1.0 dl has an intrinsic viscosity of / g

The polyester resin composition of this invention contains waxes. Such waxes include olefin waxes such as amide wax, montan wax, and PE wax. Preferably, the wax may be an amide wax.

The polyester resin composition of the present invention not only effectively removes acetaldehyde by including the waxes in the polyester resin, but also exhibits color, transparency, etc., when using a nylon-based resin or other additives used as an acetaldehyde remover. There is an advantage that the property degradation does not appear.

According to one embodiment of the present invention, the waxes may be included in the range of about 100 ppm to about 5,000 ppm with respect to the total weight of the polyester resin, preferably about 1,000 to about 3,000 ppm. When the waxes are included in the range of about 100 to about 5,000 ppm, the molding process can be easily performed because the appropriate friction between the resins can be maintained during molding while sufficiently exhibiting the effect of reducing the content of acetaldehyde.

The polyester resin molded object of this invention is manufactured by shape | molding using the said polyester resin composition.

At this time, the wax can lower the molding pressure by lowering the melt viscosity of the polyester resin during molding, it is possible to reduce the amount of acetaldehyde generated in the product due to the thermal decomposition rate decreases.

The waxes act as a scavenger of acetaldehyde, thereby reducing the amount of acetaldehyde generated in the polyester resin molded body. The polyester resin composition of the present invention including the wax and the molded article produced using the same contain about 20 ppm or less of acetaldehyde with respect to the total weight of the polyester resin composition.

More specifically, the polyester resin composition and molded article thereof of the present invention contain about 1 acetaldehyde relative to the total weight of the polyester resin composition. To about 20 ppm or less, preferably about 1 to about 15 ppm or less, and more preferably about 1 to about 10 ppm or less. Therefore, even when a tasteless, odorless beverage such as bottled water is stored in a molded article such as a container made of the polyester resin of the present invention, there is less odor in the product by acetaldehyde. Various food packaging applications are possible, including beverage bottles.

The polyester resin molded body of the present invention may be in the form of a food container, a food and beverage bottle, a food packaging sheet, a film, or a chip made using the polyester resin through an extrusion and injection process.

In addition, the polyester resin composition and the molded article of the present invention may have a color b value of about -1.0 or less, preferably about -1.5 or less, and a haze value indicating transparency of about 2.0 or less, preferably about 1.0 or less. Has a value. Therefore, no deterioration in physical properties in terms of appearance characteristics such as transparency and chromaticity when using the acetaldehyde removal additive used in the conventional polyester resin production can be used in various applications. In particular, according to an embodiment of the present invention, the amide wax among the waxes has a high effect of reducing the amount of acetaldehyde generated and maintaining the color and transparency.

Polyester resin Of the shaped body  Manufacturing method

In the method for producing a polyester resin molded article of the present invention, the step of esterifying a dicarboxylic acid component containing terephthalic acid and a diol component containing isosorbide, polycondensing the reactants of the esterification reaction to obtain a polyester resin Preparing, adding waxes to obtain a polyester resin composition, and molding the polyester resin composition.

In this case, the detailed description and examples of the dicarboxylic acid component and the diol component are as described in the polyester resin composition.

The dicarboxylic acid component and the diol component may be added in a range of about 1.1 to about 3.0 molar ratios, and they may be subjected to esterification at a temperature of about 200 to about 320 ° C. and a pressure of about 1.0 to about 3.0 kg / cm 2. Conduct.

Next, a polyester resin is produced by polycondensing the reactant of the esterification reaction. In this case, a polycondensation catalyst and a stabilizer may be added to the reactant. Optionally, the polycondensation catalyst and stabilizer can be added in the esterification step.

As the polycondensation catalyst, a titanium compound, a germanium compound, an antimony compound, an aluminum compound, a tin compound, or a mixture thereof may be used.

Examples of the titanium compound include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate Nitrate, triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, and the like.

The polycondensation catalyst may use about 0.1 to about 500 ppm based on the amount of metal elements relative to the weight of the final polyester resin. Since the amount of the polycondensation catalyst added affects the color of the final polyester resin composition, it may be selected differently depending on the desired color and the stabilizer and colorant to be used.

The stabilizer may typically include phosphoric acid, trimethyl phosphate, triethyl phosphate, triethyl phosphonoacetate, and the amount of the stabilizer may be 0.1 to 500 ppm relative to the weight of the final polyester resin based on the amount of phosphorus. The stabilizer can also optionally be added before the esterification reaction.

In addition, colorants may be added to enhance the color. The colorant may include a conventional colorant such as cobalt acetate or cobalt propionate, and the amount of the colorant may be about 1 to about 500 ppm based on the weight of the final polyester resin.

The polycondensation of the reactants of the esterification reaction is carried out under a temperature of about 200 to about 320 ℃ and a reduced pressure of about 400 to about 0.1 mmHg. The polycondensation step is carried out for the required time until the desired intrinsic viscosity is reached, the reaction temperature may preferably be about 260 to about 320 ℃, more preferably about 265 to about 285 ℃. In addition, the polycondensation reaction is carried out under reduced pressure of about 400 to about 0.1 mmHg to remove the glycol as a by-product.

Next, waxes are added to obtain a polyester resin composition.

The waxes include olefin waxes such as amide wax, montan wax or polyethylene wax. Preferably, the wax may be an amide wax.

According to one embodiment of the present invention, the waxes may be added after the step of polycondensing the reactants of the esterification reaction. That is, it may be added before the step of molding the polyester resin composition. When using an amide wax as said wax, it is preferable to add before the shaping | molding step of resin.

According to another embodiment of the present invention, the waxes may be added to the reactants of the esterification reaction before the polycondensation step.

According to one embodiment of the present invention, the waxes may be included in the range of about 100 to about 5,000 ppm, more preferably in the range of about 1,000 to about 3,000 ppm relative to the total weight of the polyester resin. have. When the waxes are included in the range of about 100 to about 5,000 ppm with respect to the total weight of the polyester resin, it is possible to maintain an appropriate inter- resin friction during molding while sufficiently exhibiting an effect for reducing the content of acetaldehyde. It can be performed easily.

Next, the said polyester resin composition to which the said wax was added is shape | molded, and a polyester resin molded object is manufactured.

The molding may include methods known in the art, such as thermoforming, compression molding, injection molding, extrusion molding, extrusion blow molding, foam molding, and the like.

According to an embodiment of the present invention, the forming may be performed at a temperature of about 220 to about 280 ° C. In addition, the molding step of the polyester resin composition of the present invention by including waxes may be carried out at a pressure condition lower than that usually performed, for example, under pressure conditions of about 900 to about 1,200 kgf / cm 2.

The final product may be directly obtained by injecting into a mold in the form of a product such as a food and beverage container in which the polyester resin composition of the present invention is prepared by the molding. Alternatively, a sheet or film may be formed by extrusion molding, and a container or a packaging material may be formed by secondary vacuum molding, or may be directly converted into a container by extrusion blow molding. In addition, the resin composition may be obtained in the form of chips having a constant size by using an apparatus such as a pelletizer by extrusion. The chip may be used as a master batch for melt mixing with other polyester resin compositions and processing into a desired molded body.

The polyester resin composition prepared according to the manufacturing method of the present invention and the molded article using the same may have an intrinsic viscosity of about 0.3 to about 2.0 dl / g, preferably about 0.5 to about 1.0 dl / g.

According to the method for producing the polyester resin molded article of the present invention, by adding waxes, the molding pressure in the molding step can be lowered, and the amount of acetaldehyde generated in the final polyester resin molded article is significantly reduced due to the lower thermal decomposition rate. You can.

That is, according to the present invention, a polyester resin composition having a reduced acetaldehyde content of about 1 to about 20 ppm, preferably about 1 to about 15 ppm or less, more preferably about 1 to about 10 ppm or less can be obtained. When the molded product is produced by injection molding, extrusion molding, thermoforming, etc. using a polyester resin, there is less acetaldehyde odor in the product. In addition, the polyester resin composition of the present invention has a glass transition temperature of about 85 to about 100 ° C, preferably about 90 to about 100 ° C, by including a specific diol component. Therefore, there is an advantage having improved heat resistance characteristics compared to the conventionally known polyester resin composition.

According to the polyester resin composition of the present invention, a molded article using the same, and a method of manufacturing the same, the heat resistance is improved and the color and transparency are maintained while the content of acetaldehyde is reduced. Since there is no alteration of taste, it can be applied to food and beverage bottles.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

Example

Polyester resin composition and Of the shaped body  Produce

≪ Example 1 >

2,016 parts by weight of terephthalic acid, 280 parts by weight of isosorbide, 875 parts by weight of 1,4-cyclohexanedimethanol and 400 parts by weight of ethylene glycol were charged to a 5L reactor equipped with a stirrer and an outlet condenser. At 80 atom, phosphorus stabilizer triethyl phosphate, 200 ppm germanium catalyst, and 50 ppm cobalt diacetate were added at the concentration of the atom, and the pressure was raised to 2.0 kg / cm 2 with nitrogen, followed by raising the reactor temperature to 240 to 300 ° C. Let.

At this time, the generated water is discharged out of the system to esterify the reaction, and when the generation and outflow of water are completed, the reaction product is transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser, and a vacuum system to proceed with the polycondensation reaction, and the intrinsic viscosity is 0.6 dl. When it reached / g or more, superposition | polymerization was complete | finished.

After mixing the amide wax to 500ppm to the weight of the polyester resin to the polyester resin thus prepared, using a Nissei injection machine under a barrel temperature of 250 ℃, pressure of 1,200 kgf / ㎠, mold temperature 30 ℃, injection time 10 seconds, Thermoforming was carried out under the conditions of a holding time of 15 seconds and a cooling time of 30 seconds. Physical properties of the obtained composition were measured after preparing a rectangular parallelepiped sample having a width of 3 cm, a length of 12 cm and a thickness of 0.3 cm.

<Example 2>

A sample was prepared in the same manner as in Example 1 except that the amide wax was mixed at 1,000 ppm by weight of the polyester resin.

<Example 3>

Samples were prepared in the same manner as in Example 1 except that the amide wax was mixed at 3,000 ppm relative to the weight of the polyester resin and the injection pressure was changed.

<Example 4>

Samples were prepared in the same manner as in Example 1 except that the amide wax was mixed at 5,000 ppm by weight of the polyester resin and the injection pressure was changed.

<Example 5>

Samples were prepared in the same manner as in Example 1 except that polyethylene wax was mixed at 3,000 ppm relative to the weight of the polyester resin instead of amide wax.

<Example 6>

Samples were prepared in the same manner as in Example 1 except that the montan wax was mixed at 3,000 ppm relative to the polyester resin weight instead of the amide wax and the injection pressure was changed.

&Lt; Comparative Example 1 &

Samples were prepared in the same manner as in Example 1 except that the injection pressure was changed without adding amide wax.

Comparative Example 2

Samples were prepared in the same manner as in Example 1 except that m-xyleneadipamide (MXD6, manufactured by Mitsubishi Chemical Co., Ltd.) was mixed at 3,000 ppm relative to the weight of the polyester resin and the injection pressure was changed instead of the amide wax.

&Lt; Comparative Example 3 &

The sample was prepared by mixing the amide wax to 7,000 ppm, but the molding process was impossible due to the low frictional force between resins due to the excessive injection of the wax.

&Lt; Comparative Example 4 &

In preparing polyester resin, 2,282 parts by weight of terephthalic acid, 634 parts by weight of 1,4-cyclohexanedimethanol, and 1,432 parts by weight of ethylene glycol were prepared, followed by mixing montan wax at 3,000 ppm under a pressure of 1,000 kgf / cm 2. Samples were prepared in the same manner as in Example 1.

Experimental Example

Physical properties of the samples prepared according to Examples 1 to 6 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below.

1) Acetaldehyde content: The amount of acetaldehyde generated in a sample pretreated at 150 ° C. for 45 minutes using Perkin-elmer's gas chromatography was measured.

2) Color b: Measured using the Colorgard System of Pacific Scientific.

3) Haze (%): The film sample of the copolymerized polyester resin composition was aged for 24 hours in an atmosphere of a temperature of 23 ° C. and a humidity of 65% RH, followed by a haze meter, according to Japanese Industrial Standards (JIS) K7136. Device name: NDH2000, manufacturer: Nippon Denshoku (Japan)) measured the haze (%) for three different positions of the film sample, and the average value of each measurement result was calculated as a result.

4) Heat resistance (Tg): Glass-rubber transition temperature (Tg), annealing the polyester resin for 5 minutes at 300 ℃ using DSC, cooled to room temperature, and then the temperature rise rate 10 Glass-rubber transition temperature (Tg) at 2nd scan was measured again at ℃ / min.

Additive type Additive dosage
[ppm] Injection pressure
[kgf / ㎠] Heat resistance
(Tg)
[° C] Acetaldehyde content
[ppm] color b Haze Example 1 Amide wax 500 1,200 95 19.4 -1.8 &Lt; 1.0 Example 2 Amide wax 1,000 1,200 95 13.8 -1.6 &Lt; 1.0 Example 3 Amide wax 3,000 1,000 95 7.5 -1.5 &Lt; 1.0 Example 4 Amide wax 5,000 900 95 5.6 -1.6 &Lt; 1.0 Example 5 Polyethylene wax 3,000 1,200 95 12.5 -1.2 2.0 Example 6 Montan wax 3,000 1,000 95 11.2 -1.3 1.5 Comparative Example 1 none 0 1,350 95 30.5 -1.8 &Lt; 1.0 Comparative Example 2 MXD6 3,000 1,350 95 10.2 0.0 &Lt; 1.0 Comparative Example 3 Amide wax 7,000 Not measured by overdosage. Comparative Example 4 Montan wax 3,000 1,000 80 15 -1.5 1.0

As can be seen from the results shown in Table 1 above, the polyester resin composition according to the present invention including waxes contained acetaldehyde below 20 ppm to 30.5 ppm of Comparative Example 1 without adding waxes. It can be seen that the content of acetaldehyde is significantly reduced. The higher the content of the added wax up to 5,000 ppm, the higher the effect of reducing acetaldehyde. However, when the content of the wax contained more than 7,000 ppm, the molding process was impossible because the friction between the resins was too low.

In addition, it can be seen that the polyester resin composition according to the present invention hardly exhibits a decrease in color and transparency, and thus can effectively remove acetaldehyde without affecting appearance physical properties.

Among the waxes of the same content, amide wax was found to have the greatest effect of reducing acetaldehyde.

In the case of adding MXD6, the content of acetaldehyde may be lowered to about 10 ppm, but the color b value is 0.0, indicating that the color deterioration phenomenon is not suitable for commercialization.

In addition, Comparative Example 4, which does not include isosorbide as the diol component, has a glass transition temperature of 80 ° C., whereas the polyester resin compositions of Examples 1 to 6 containing isosorbide have heat resistance at 95 ° C. It can be seen that this has been improved.

Claims (23)

Polyester resin containing the polycondensate of the dicarboxylic acid component containing terephthalic acid and the diol component containing isosorbide; And
Polyester resin composition containing a wax.
The polyester resin composition of claim 1, wherein the waxes include one or more selected from the group consisting of amide waxes, montan waxes, and olefin waxes.
The polyester resin composition of claim 1, wherein the waxes are included in a range of 100 to 5,000 ppm with respect to the total weight of the polyester resin.
The polyester resin composition of claim 3, wherein the waxes are included in a range of 1,000 to 3,000 ppm with respect to the total weight of the polyester resin.
The polyester resin composition according to claim 1, wherein the dicarboxylic acid component further comprises at least one compound selected from the group consisting of an aromatic dicarboxylic acid component and an aliphatic dicarboxylic acid component.
The method of claim 5, wherein the dicarboxylic acid component
50 to 100 mol% terephthalic acid; And
Polyester resin composition comprising 0 to 50 mol% of at least one dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acid and aliphatic dicarboxylic acid.
The method of claim 1,
The diol component is polyester resin composition, further comprising cyclohexane dimethanol.
The method of claim 7, wherein the diol component is
1 to 60 mole percent isosorbide;
1 to 80 mole% cyclohexanedimethanol; And
Polyester resin composition comprising 1 to 80 mol% of one or more other diol components selected from the group consisting of aliphatic diols and aromatic diols.
The polyester resin composition according to claim 1, comprising 1-20 ppm acetaldehyde relative to the total weight of the polyester resin composition.
The polyester resin composition according to claim 1, wherein the color b has a value of -1.0 or less and a Haze value of 2.0 or less.
The polyester resin composition according to claim 10, wherein the color b has a value of -1.5 or less and a Haze value of 1.0 or less.
The molded object manufactured using the polyester resin composition of any one of Claims 1-11.
13. The molded article according to claim 12, wherein the shaped article is in the form of a food container, a food and beverage bottle or a chip.
Esterifying a dicarboxylic acid component comprising terephthalic acid and a diol component comprising isosorbide;
Polycondensing the reactants of the esterification reaction to prepare a polyester resin;
Adding waxes to obtain a polyester resin composition; And
Method for producing a polyester resin molded body comprising the step of molding the polyester resin composition.
15. The method of claim 14, wherein the waxes include one or more selected from the group consisting of amide waxes, montan waxes, and olefin waxes.
The method for producing a polyester resin molded article according to claim 14, wherein the wax is added in a range of 100 to 5,000 ppm with respect to the total weight of the polyester resin.
The method for producing a polyester resin molded article according to claim 16, wherein the wax is added in a range of 1,000 to 3,000 ppm with respect to the total weight of the polyester resin.
15. The method of claim 14,
The dicarboxylic acid component comprises 50 to 100 mol% of terephthalic acid and 0 to 50 mol% of at least one dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acid and aliphatic dicarboxylic acid, wherein the diol component is Polyester resin comprising 1 to 60 mol% of isosorbide, 1 to 80 mol% of cyclohexanedimethanol and one or more other diol components selected from the group consisting of aliphatic diols and aromatic diols Method for producing a molded article.
The method of claim 14, wherein the adding of the waxes is performed before or after the polycondensation of the reactants of the esterification reaction.
15. The method of claim 14, wherein the step of esterifying the dicarboxylic acid component comprising terephthalic acid and the diol component comprising isosorbide is carried out at a temperature of 200 to 320 ℃ and pressure conditions of 1.0 to 3.0 kg / ㎠ Method for producing a polyester resin molded body characterized in that.
The method of claim 14, wherein the step of polycondensing the reactants of the esterification reaction is carried out at a temperature of 200 to 320 ℃ and pressure conditions of 400 to 0.1 mmHg.
15. The method of claim 14, wherein the molding of the polyester resin composition is performed at a temperature of 220 to 280 ° C and a pressure of 900 to 1,200 kgf / cm2.
15. The method of claim 14, wherein the molded body is in the form of a food container, a food and beverage bottle, or a chip.