Polyester composition and its use

Abstract

To provide a polyester composition having excellent storage properties (namely, few precipitates) and excellent heat resistance.SOLUTION: A polyester composition includes a polyester and a first component. When the polyester composition is characterized by gas chromatography (GC), the first component is flowed out with a holding time in the range of 36.38 minutes to 36.98 minutes; and the first component shown by chromatographic peaks with the holding time in a GC spectrum has an area of chromatographic peaks in the range of 1.5% to 7.0% relative to the whole area of chromatographic peaks of the polyester composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyester composition, particularly a polyester composition containing specific components in specific amounts. The polyester composition of the present invention can be used as a plasticizer for thermoplastic polymers.

Background Art

[0002] Plasticizers can be used to improve the physical properties of thermoplastic polymers, such as plasticity, flexibility, bendability, toughness, etc. Examples of thermoplastic polymers include, but are not limited to, phthalates, aliphatic esters, carboxylic acid esters, phosphates, epoxides, and polyesters.

[0003] Generally, polyesters are obtained by reacting diacids with diols. However, the polyesters obtained from these usually have precipitation problems due to the presence of by-products. Precipitation has an adverse effect on the appearance, physical properties, and mechanical properties of the products obtained from the polyester.

Summary of the Invention

Means for Solving the Problems

[0004] The present invention provides a polyester composition having good storage stability (i.e., few precipitates) and heat resistance. The polyester composition of the present invention can be used as a plasticizer for thermoplastic polymers to impart appropriate properties such as tensile strength, elongation at break, 100% tensile stress, etc. to the thermoplastic polymers.

[0005] Accordingly, an object of the present invention is to provide a polyester composition containing a polyester and a first component. Thereby, when the polyester composition is characterized by gas chromatography (GC), the first component elutes at a retention time in the range of 36.38 minutes to 36.98 minutes, and the first component indicated by the chromatography peak at the retention time in the GC spectrum has a chromatography peak area in the range of 1.5% to 7.0% with respect to the total area of the chromatography peaks of the polyester composition.

[0006] In some embodiments of the present invention, the polyester composition further contains a second component. When the polyester composition is characterized by GC, the second component elutes at a retention time in the range of 37.56 minutes to 38.29 minutes, and the second component indicated by the chromatography peak at the retention time in the GC spectrum has a chromatography peak area in the range of 3.5% to 7.5 % with respect to the total area of the chromatography peaks of the polyester composition.

[0007] In some embodiments of the present invention, when the polyester composition is characterized by gas chromatography-mass spectrometry (GC-MS), the first component elutes at a retention time in the range of 28.900 minutes to 29.000 minutes, and the fragment pattern of the first component includes one or more signals of mass / charge ratio (m / z) selected from the group consisting of 29, 41, 42, 43, 55, 56, 83, 84, 101, 111, 114, 127, 129, 141, 154, 156, 183, 201, 273, and 400.

[0008] In some embodiments of the present invention, the fragment pattern of the first component includes signals of m / z of 41, 55, 56, 83, 111, 114, 127, 129, 141, and 201.

[0009] In some embodiments of the present invention, when characterizing the polyester composition by GC-MS, the second component elutes with a retention time in the range of 29.101 minutes to 29.200 minutes, and the fragmentation pattern of the second component includes one or more signals of m / z selected from the group consisting of 29, 41, 43, 55, 56, 69, 83, 101, 111, 127, 129, 141, 147, 155, 168, 197, 215, 216, 343, and 428.

[0010] In some embodiments of the present invention, the fragmentation pattern of the second component includes signals of m / z of 41, 55, 56, 69, 83, 111, 129, 141, 155, and 215.

[0011] In some embodiments of the present invention, the first component is a compound represented by the following formula (I), and the second component is a compound represented by the following formula (II). [Chemical formula] [In the formula, R1 is the following group. [Chemical formula] R2 is the following group. [Chemical formula] * indicates the bonding position.

[0012] In some embodiments of the present invention, the polyester is a polyadipate ester.

[0013] In some embodiments of the present invention, the polyester composition has a viscosity in the range of 2000 cps to 4000 cps at 25°C.

[0014] In some embodiments of the present invention, the polyester composition has an acid value in the range of 0.1 mgKOH / g to 0.7 mgKOH / g.

[0015] In some embodiments of the present invention, the polyester composition has a hydroxyl value in the range of 5.0 mgKOH / g to 15.0 mgKOH / g.

[0016] In some embodiments of the present invention, the polyester composition further comprises a third component. When the polyester composition is characterized by GC, the third component elutes at a retention time in the range of 36.99 minutes to 37.55 minutes, and the third component indicated by the chromatographic peak at the retention time in the GC spectrum has a chromatographic peak area in the range of 8.0% to 10.0% with respect to the total area of the chromatographic peaks of the polyester composition.

[0017] In some embodiments of the present invention, the third component is a compound represented by the following formula (III).

Chemical formula

Chemical formula

Chemical formula

[0018] In some embodiments of the present invention, when the polyester composition is characterized by GC-MS, the third component elutes at a retention time in the range of 29.001 minutes to 29.100 minutes, and the fragment pattern of the third component includes one or more signals of m / z selected from the group consisting of 29, 41, 55, 56, 69, 83, 101, 111, 114, 127, 129, 141, 155, 183, 201, 215, 287, 319, and 414.

[0019] In some embodiments of the present invention, the fragment pattern of the third component includes signals of m / z of 41, 55, 56, 69, 111, 127, 129, 141, 201, and 215.

[0020] In some embodiments of the present invention, in the aforementioned GC, the polyester composition is loaded into an SGE BPI capillary column with a length of 60 m, an inner diameter of 530 μm, and a film thickness of 3 μm, and the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of nitrogen with a flow rate of 12 ml / min, 5 minutes at 50°C, a temperature increase from 50°C to 300°C at a rate of 10°C / min, a continuous stepwise temperature of 300°C for 40 minutes, an inlet temperature of 340°C, a sample injection volume of 1 μl of the polyester composition, and the use of a flame ionization detector operated at 340°C.

[0021] In some embodiments of the present invention, in the aforementioned GC-MS, the polyester composition is loaded into a ZB-1 capillary column with a length of 30 m, an inner diameter of 250 μm, and a film thickness of 0.25 μm, and the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of helium with a flow rate of 1.8 ml / min, 5 minutes at 50°C, a temperature increase from 50°C to 330°C at a rate of 10°C / min, a continuous stepwise temperature of 330°C for 27 minutes, an inlet temperature 350 °C, an electron energy of 70 eV (electron volts), an ion source temperature of 250°C, the use of a quadrupole mass filter, an interface temperature of 340°C, a mass scan range of 29.0 m / z to 900 m / z, and a solvent delay time of 1.5 minutes.

[0022] Another object of the present invention is to provide a thermoplastic polymer material containing a plasticizer and a thermoplastic polymer containing the above polyester composition.

[0023] In some embodiments of the present invention, the thermoplastic polymer is a homopolymer of vinyl chloride or a copolymer of vinyl chloride.

[0024] In order to more clearly illustrate the above objects, technical features, and advantages of the present invention, the present invention will be described in detail below with reference to several embodiments.

Brief Description of the Drawings

[0025]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0026] Some embodiments of the present invention will be described in detail below. However, the present invention may be embodied in various embodiments and should not be limited to the embodiments described herein.

[0027] Unless otherwise stated, the expressions "a", "the", etc. described in this specification and the claims should include both singular and plural forms.

[0028] Unless otherwise stated, the expressions "first", "second", etc. described in this specification and the claims have no special meaning and are merely used to distinguish the indicated elements or components. These expressions are not intended to indicate any priority.

[0029] Unless otherwise stated, the expression "viscosity" described in this specification and the claims means the viscosity measured at 25°C.

[0030] Unless otherwise stated, the expression "atmospheric pressure" described in this specification and the claims means 1 atmosphere (i.e., 760 Torr).

[0031] As used herein, when a specific component elutes within a specific retention time range, it means that the peak (peak value) of the wave of the chromatographic peak indicating the specific component falls within the specific retention time range. That is, if the peak value falls within that retention time range, the chromatographic peak can be determined as the chromatographic peak indicating the specific component.

[0032] As used herein, in the GC spectrum, the area of the chromatographic peak is determined as follows. As shown in Figure 5, the B-V-B (baseline-valley point-baseline) approach is used. The same baseline is set for all chromatographic peaks, and a line is drawn perpendicular to the baseline from the valley point of a specific chromatographic peak to determine the area of the specific chromatographic peak to be integrated. The baseline means the signal of the carrier gas detected when the test sample does not pass through the detector.

[0033] The effect of the present invention is based on a polyester composition having good storage stability (i.e., few precipitates) and heat resistance. The polyester compositions of the present invention and related applications will be described in detail below.

[0034] 1. Polyester composition The polyester composition of the present invention has specific characteristics in the GC spectrum and contains a polyester and a first component. The polyester composition of the present invention can optionally contain other components, such as a second component and / or a third component. In some embodiments of the present invention, the polyester composition also has specific characteristics in the GC-MS spectrum.

[0035] Examples of the polyester include, but are not limited to, polyadipate, polybutanedioate, polyglutarate, polypimelate, polysuberate, polysebacate, polyundecanoate, and polydecanoate. In some embodiments of the present invention, the polyester is a polyester derived from polyadipic acid, for example, adipic acid, neopentyl glycol, and propylene glycol. The molecular weight of the polyester is not particularly limited. Generally, the number average molecular weight of the polyester can be from 1200 to 4000, for example, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000, 2050, 2100, 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800, 2850, 2900, 2950, 3000, 3050, 3100, 3150, 3200, 3250, 3300, 3350, 3400, 3450, 3500, 3550, 3600, 3650, 3700, 3750, 3800, 3850, 3900 or 3950, or within the range between any two of these recited values.

[0036] 1.1. Analysis of the spectrum of the polyester composition When characterizing the polyester composition by GC, the first component elutes with a retention time in the range of 36.38 minutes to 36.98 minutes. That is, the peak (peak value) of the chromatographic wave of the first component can fall within 36.38 minutes, 36.39 minutes, 36.40 minutes, 36.41 minutes, 36.42 minutes, 36.43 minutes, 36.44 minutes, 36.45 minutes, 36.46 minutes, 36.47 minutes, 36.48 minutes, 36.49 minutes, 36.50 minutes, 36.51 minutes, 36.52 minutes, 36.53 minutes, 36.54 minutes, 36.55 minutes, 36.56 minutes, 36.57 minutes, 36.58 minutes, 36.59 minutes, 36.60 minutes, 36.61 minutes, 36.62 minutes, 36.63 minutes, 36.64 minutes, 36.65 minutes, 36.66 minutes, 36.67 minutes, 36.68 minutes, 36.69 minutes, 36.70 minutes, 36.71 minutes, 36.72 minutes, 36.73 minutes, 36.74 minutes, 36.75 minutes, 36.76 minutes, 36.77 minutes, 36.78 minutes, 36.79 minutes, 36.80 minutes, 36.81 minutes, 36.82 minutes, 36.83 minutes, 36.84 minutes, 36.85 minutes, 36.86 minutes, 36.87 minutes, 36.88 minutes, 36.89 minutes, 36.90 minutes, 36.91 minutes, 36.92 minutes, 36.93 minutes, 36.94 minutes, 36.95 minutes, 36.96 minutes, 36.97 minutes or 36.98 minutes, or within the range between any two of these described values. In addition, the first component is indicated by the chromatographic peak at the corresponding retention time of the GC spectrum. The first component has a chromatographic peak area in the range of 1.5% to 7.0% with respect to the total area of the chromatographic peaks of the polyester composition. Figure 1 is the GC spectrum of an embodiment of the polyester composition of the present invention, and more specifically, it is the GC spectrum of the polyester composition of Synthesis Example 4. Figure 2 is a partially enlarged schematic view of Figure 1 with a retention time in the range of 34.5 minutes to 40.5 minutes.

[0037] In some embodiments of the present invention, the polyester composition further comprises a second component. When the polyester composition is characterized by GC, the second component elutes with a retention time in the range of 37.56 minutes to 38.29 minutes. That is, the peak (peak value) of the chromatography wave of the second component can be 37.56 minutes, 37.57 minutes, 37.58 minutes, 37.59 minutes, 37.60 minutes, 37.61 minutes, 37.62 minutes, 37.63 minutes, 37.64 minutes, 37.65 minutes, 37.66 minutes, 37.67 minutes, 37.68 minutes, 37.69 minutes, 37.70 minutes, 37.71 minutes, 37.72 minutes, 37.73 minutes, 37.74 minutes, 37.75 minutes, 37.76 minutes, 37.77 minutes, 37.78 minutes, 37.79 minutes, 37.80 minutes, 37.81 minutes, 37.82 minutes, 37.83 minutes, 37.84 minutes, 37.85 minutes, 37.86 minutes, 37.87 minutes, 37.88 minutes, 37.89 minutes, 37.90 minutes, 37.91 minutes, 37.92 minutes, 37.93 minutes, 37.94 minutes, 37.95 minutes, 37.96 minutes, 37.97 minutes, 37.98 minutes, 37.99 minutes, 38.00 minutes, 38.01 minutes, 38.02 minutes, 38.03 minutes, 38.04 minutes, 38.05 minutes, 38.06 minutes, 38.07 minutes, 38.08 minutes, 38.09 minutes, 38.10 minutes, 38.11 minutes, 38.12 minutes, 38.13 minutes, 38.14 minutes, 38.15 minutes, 38.16 minutes, 38.17 minutes, 38.18 minutes, 38.19 minutes, 38.20 minutes, 38.21 minutes, 38.22 minutes, 38.23 minutes, 38.24 minutes, 38.25 minutes, 38.26 minutes, 38.27 minutes, 38.28 minutes or 38.29 minutes, or can fall within the range between the two values described. Additionally, the second component is indicated by the chromatography peak at the corresponding retention time of the GC spectrum. The second component has a chromatography peak area in the range of 3.5% to 7.5% with respect to the total area of the chromatography peak of the polyester composition.

[0038] The above GC analysis is carried out as follows. First, the polyester composition is loaded into an SGE BPI capillary column with a length of 60 m, an inner diameter of 530 μm, and a film thickness of 3 μm. Next, the GC analysis is performed under the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of nitrogen with a flow rate of 12 ml / min, heating from 50°C to 300°C at a rate of 10°C / min for 5 minutes at 50°C, a continuous stepwise temperature of 300°C for 40 minutes, an inlet temperature of 340°C, a sample injection volume of 1 μl of the polyester composition, and the use of a flame ionization detector operated at 340°C.

[0039] Before performing the GC analysis, it is preferable to subject the sample of the polyester composition to be analyzed to the pretreatment of the following method. First, the sample of the polyester composition is heated in an oven at 70°C for 1 hour to make the sample uniform. Next, the sample is mixed with acetone (solvent) to prepare a solution with a concentration of 5% by weight.

[0040] In some embodiments of the present invention, when characterizing the polyester composition by GC-MS, the first component elutes with a retention time in the range of 28.900 minutes to 29.000 minutes. The fragmentation pattern of the first component includes one or more signals of mass / charge ratio (m / z) selected from the group consisting of 29, 41, 42, 43, 55, 56, 83, 84, 101, 111, 114, 127, 129, 141, 154, 156, 183, 201, 273, and 400. Preferably, the fragmentation pattern of the first component includes signals of m / z of 41, 55, 56, 83, 111, 114, 127, 129, 141, and 201. The second component elutes with a retention time in the range of 29.101 minutes to 29.200 minutes. The fragmentation pattern of the second component includes one or more signals of m / z selected from the group consisting of 29, 41, 43, 55, 56, 69, 83, 101, 111, 127, 129, 141, 147, 155, 168, 197, 215, 216, 343, and 428. Preferably, the fragmentation pattern of the second component includes signals of m / z of 41, 55, 56, 69, 83, 111, 129, 141, 155, and 215. Figure 3 is the GC-MS spectrum of one embodiment of the polyester composition of the present invention, and more specifically, the GC-MS spectrum of the polyester composition of Synthesis Example 4. Figure 4 is a partially enlarged schematic view of Figure 3 in the retention time range of 26.5 minutes to 32 minutes.

[0041] The above GC-MS analysis is performed as follows. First, the polyester composition is loaded into a ZB-1 capillary column with a length of 30 m, an inner diameter of 250 μm, and a film thickness of 0.25 μm. Next, the GC analysis is carried out under the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of helium with a flow rate of 1.8 ml / min, 5 minutes at 50 °C, a temperature increase from 50 °C to 330 °C at a rate of 10 °C / min, a continuous stepwise temperature of 330 °C for 27 minutes, an inlet temperature 350 °C, an electron energy of 70 eV (electron volts), an ion source temperature of 250 °C, the use of a quadrupole mass filter, an interface temperature of 340 °C, a mass scan range of 29.0 m / z to 900 m / z, and a solvent delay time of 1.5 minutes.

[0042] Before performing GC-MS analysis, it is preferable to subject a sample of the polyester composition to be analyzed to the pretreatment of the following method. First, heat the sample of the polyester composition in an oven at 70 °C for 1 hour to make the sample uniform. Next, mix the sample with acetone (solvent) to prepare a solution with a concentration of 1% by weight.

[0043] In some embodiments of the present invention, the polyester composition further comprises a third component. When the polyester composition is characterized by GC, the third component elutes at a retention time in the range of 36.99 minutes to 37.55 minutes. That is, the peak (peak value) of the chromatographic wave of the third component is 36.99 minutes, 37.00 minutes, 37.01 minutes, 37.02 minutes, 37.03 minutes, 37.04 minutes, 37.05 minutes, 37.06 minutes, 37.07 minutes, 37.08 minutes, 37.09 minutes, 37.10 minutes, 37.11 minutes, 37.12 minutes, 37.13 minutes, 37.14 minutes, 37.15 minutes, 37.16 minutes, 37.17 minutes, 37.18 minutes, 37.19 minutes, 37.20 minutes, 37.21 minutes, 37.22 minutes, 37.23 minutes, 37.24 minutes, 37.25 minutes, 37.26 minutes, 37.27 minutes, 37.28 minutes, 37.29 minutes, 37.30 minutes, 37.31 minutes, 37.32 minutes, 37.33 minutes, 37.34 minutes, 37.35 minutes, 37.36 minutes, 37.37 minutes, 37.38 minutes, 37.39 minutes, 37.40 minutes, 37.41 minutes, 37.42 minutes, 37.43 minutes, 37.44 minutes, 37.45 minutes, 37.46 minutes, 37.47 minutes, 37.48 minutes, 37.49 minutes, 37.50 minutes, 37.51 minutes, 37.52 minutes, 37.53 minutes, 37.54 minutes or 37.55 minutes, or can fall within the range between the two values described. In addition, the third component is indicated by the chromatographic peak at the corresponding retention time of the GC spectrum, and the third component has a chromatographic peak area in the range of 8.0% to 10.0% with respect to the total area of the chromatographic peaks of the polyester composition. Further, when the polyester composition is characterized by GC-MS, the third component elutes at a retention time in the range of 29.001 minutes to 29.100 minutes. The fragmentation pattern of the third component includes one or more signals of m / z selected from the group consisting of 29, 41, 55, 56, 69, 83, 101, 111, 114, 127, 129, 141, 155, 183, 201, 215, 287, 319 and 414. The fragmentation pattern of the third component preferably includes signals of m / z of 41, 55, 56, 69, 111, 127, 129, 141, 201 and 215. The methods of GC analysis and GC-MS analysis are the same as the methods described above.

[0044] 1.1.1. First component In order to impart good storage stability and heat resistance to the polyester composition of the present invention, and to impart appropriate properties such as tensile strength, elongation at break, and 100% tensile stress to the thermoplastic polymer, the amount of the first component in the polyester composition is controlled within a specific range. Therefore, as described above, when the polyester composition of the present invention is characterized by the above-mentioned GC analysis, the first component represented by the chromatographic peak of the retention time of the GC spectrum is within the range of 1.5% to 7.0% with respect to the total area of the chromatographic peaks of the polyester composition. For example, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8% or 6.9%, or has an area percentage of the chromatographic peak within the range between the two values described. Compared with other components, the structure of the first component has insufficient heat resistance. When the amount of the first component is higher than the above-mentioned range, the thermoplastic polymer using the polyester composition may have a low residual elongation after heat aging. In addition, when the amount of the first component is lower than the above-mentioned range, the structure of the first component is soft, and the thermoplastic polymer using the polyester composition is not effectively plasticized, resulting in an excessively high 100% tensile stress.

[0045] In some embodiments of the present invention, the first component can be a compound represented by the following formula (I).

Chemical formula

[0046] In formula (I), R1 is the following group. [Chemical formula] R1 is preferably the following group. [Chemical formula] * indicates the bonding position. The compound represented by formula (I) can be obtained by reacting adipic acid with 2-methyl-1,3-propanediol, ethylene glycol or 1,3-propanediol.

[0047] 1.1.2. Second component In order to provide the polyester composition of the present invention having good storage stability and heat resistance, and to impart appropriate properties such as tensile strength, elongation at break, 100% tensile stress, etc. to the thermoplastic polymer using the polyester composition, the amount of the second component in the polyester composition is controlled within a specific range. Therefore, as described above, when the polyester composition of the present invention is characterized by the above-mentioned GC analysis, the second component represented by the chromatographic peak of the retention time of the GC spectrum with respect to the total area of the chromatographic peaks of the polyester composition has an area percentage of the chromatographic peak within the range of 3.5% to 7.5%, for example, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3% or 7.4%, or within the range between the two values described above. The structure of the second component has branches useful for improving the migration resistance of the polyester composition. When the amount of the second component is lower than the above-mentioned range, the migration resistance of the polyester composition is low. When the amount of the second component is higher than the above-mentioned range, crystal precipitation occurs and the migration resistance of the polyester composition becomes low.

[0048] In some embodiments of the present invention, the second component can be a compound represented by the following formula (II). [Chemical formula]

[0049] In formula (II), R2 is the following group. [Chemical formula] R2 is preferably the following group. [Chemical formula] * indicates the bonding position. The compound represented by formula (II) can be obtained by reacting adipic acid with neopentyl glycol or 1,4-butanediol.

[0050] 1.1.3. Third component In some embodiments of the present invention, the polyester composition of the present invention further comprises a third component. In order to provide the polyester composition of the present invention with good storage stability and heat resistance, and to impart appropriate properties such as tensile strength, elongation at break, and 100% tensile stress to the thermoplastic polymer using the polyester composition, the amount of the third component in the polyester composition is controlled within a specific range. Therefore, as described above, when the polyester composition of the present invention is characterized by the above-mentioned GC analysis, the third component represented by the chromatographic peak of the retention time of the GC spectrum accounts for 8.0% to 10.0% of the total area of the chromatographic peaks of the polyester composition, for example, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8% or 9.9%, or within the range between these two described values, in terms of the area percentage of the chromatographic peak.

[0051] In some embodiments of the present invention, the third component is a compound represented by the following formula (III). [Chemical formula]

[0052] In formula (III), R3 is the following group. [Chemical formula] R4 is the following group. [Chemical formula] * indicates the bonding position. The compound represented by formula (III) can be obtained by reacting adipic acid with neopentyl glycol and 2-methyl-1,3-propanediol.

[0053] 1.2. Preparation of the polyester composition The polyester composition of the present invention can be obtained by subjecting one or more aliphatic diacids and one or more aliphatic diols to an esterification polymerization reaction. Examples of aliphatic diacids include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecanoic acid, and decanoic acid. The above aliphatic diacids can be used alone or in combination of two or more. Examples of aliphatic diols include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2,2,4-trimethyl-1,5-propanediol. The above aliphatic diols can be used alone or in combination of two or more. In some embodiments of the present invention, the esterification polymerization reaction is carried out by reacting adipic acid with neopentyl glycol and 2-methyl-1,3-propanediol.

[0054] In addition, the esterification polymerization reaction is usually terminated by adding a mixed reaction terminator. The mixed reaction terminator includes, but is not limited to, aliphatic monocarboxylic acids and aliphatic saturated monohydric alcohols. Examples of aliphatic monocarboxylic acids include, but are not limited to, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-caproic acid, isocaproic acid, n-heptanoic acid, isoheptanoic acid, n-octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, n-decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. The above aliphatic monocarboxylic acids can be used alone or in combination of two or more. Examples of aliphatic saturated monohydric alcohols include, but are not limited to, n-pentyl alcohol, isopentyl alcohol, n-hexyl alcohol, isohexyl alcohol, n-octyl alcohol, isooctyl alcohol, 2-ethylhexanol, 2,2-dimethylpentanol, n-nonyl alcohol, isononyl alcohol, n-decyl alcohol, isodecyl alcohol, 2,2,4-trimethylpentanol, and lauryl alcohol. The above aliphatic saturated monohydric alcohols can be used alone or in combination of two or more. In some embodiments of the present invention, a mixture of lauric acid and 2-ethylhexanoic acid is used.

[0055] The polyester composition of the present invention can be prepared in the absence of a catalyst. However, a catalyst can also be used to reduce the reaction time. Examples of catalysts that can be used to prepare the polyester composition of the present invention include, but are not limited to, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, tetraisopropyl titanate, tetrabutyl titanate, tetraisooctyl titanate, and titanium.

[0056] In some embodiments of the present invention, the polyester composition of the present invention is prepared as follows. First, reactants are added to a reaction vessel, nitrogen is introduced, and an esterification reaction is carried out at 140°C to 200°C under normal pressure with stirring of the reactants to initiate a dehydration reaction. Subsequently, a catalyst is added, and an esterification reaction is carried out at 210°C to 230°C under a nitrogen atmosphere at normal pressure. Thereafter, the pressure is reduced to 460 Torr to 200 Torr, and a vacuum esterification reaction is carried out at 210°C to 240°C. When the acid value of the reaction intermediate becomes lower than 5 mgKOH / g, the esterification reaction is terminated. Next, the pressure is reduced to 0 Torr, and a vacuum polycondensation reaction is carried out at 210°C to 230°C. When the hydroxyl value of the reaction product is between 1.0 mgKOH / g and 15.0 mgKOH / g, the polycondensation reaction is terminated. Finally, the product is cooled and filtered to obtain a polyester composition.

[0057] In the polyester composition, by controlling the amount ratio of the raw materials added, the esterification temperature, the esterification time, and the polycondensation time to achieve the ideal amounts of each component, the amounts of the first component, the second component, and the third component can be adjusted.

[0058] 1.3. Characteristics of the polyester composition In some embodiments of the present invention, the polyester composition of the present invention has the following characteristics. However, the present invention is not limited to the following characteristics, and those skilled in the art can adjust the characteristics of the polyester composition as needed. The polyester composition has a viscosity at 25 °C within the range of 2000 cps to 4000 cps, for example, 2050 cps, 2100 cps, 2150 cps, 2200 cps, 2250 cps, 2300 cps, 2350 cps, 2400 cps, 2450 cps, 2500 cps, 2550 cps, 2600 cps, 2650 cps, 2700 cps, 2750 cps, 2800 cps, 2850 cps, 2900 cps, 2950 cps, 3000 cps, 3050 cps, 3100 cps, 3150 cps, 3200 cps, 3250 cps, 3300 cps, 3350 cps, 3400 cps, 3450 cps, 3500 cps, 3550 cps, 3600 cps, 3650 cps, 3700 cps, 3750 cps, 3800 cps, 3850 cps, 3900 cps or 3950 cps, or within the range between any two of these recited values. The polyester composition has an acid value within the range of 0.1 mgKOH / g to 0.7 mgKOH / g, for example, 0.15 mgKOH / g, 0.2 mgKOH / g, 0.25 mgKOH / g, 0.3 mgKOH / g, 0.35 mgKOH / g, 0.4 mgKOH / g, 0.45 mgKOH / g, 0.5 mgKOH / g, 0.55 mgKOH / g, 0.6 mgKOH / g or 0.65 mgKOH / g, or within the range between any two of these recited values. The polyester composition has a hydroxyl value within the range of 5.0 mgKOH / g to 15.0 mgKOH / g, for example, 5.5 mgKOH / g, 6.0 mgKOH / g, 6.5 mgKOH / g, 7.0 mgKOH / g, 7.5 mgKOH / g, 8.0 mgKOH / g, 8.5 mgKOH / g, 9.0 mgKOH / g, 9.5 mgKOH / g, 10.0 mgKOH / g, 10.5 mgKOH / g, 11.0 mgKOH / g, 11.5 mgKOH / g, 12.0 mgKOH / g, 12.5 mgKOH / g, 13.0 mgKOH / g, 13.5 mgKOH / g, 14.0 mgKOH / g or 14.5 mgKOH / g, or within the range between any two of these recited values.

[0059] 2. Thermoplastic polymer material The polyester composition of the present invention can be used as a plasticizer for thermoplastic polymers. Therefore, the present invention also provides a thermoplastic polymer material including a plasticizer that can include the polyester composition of the present invention and a thermoplastic polymer. Alternatively, the plasticizer can consist essentially of the polyester composition of the present invention, or the plasticizer consists of the polyester composition of the present invention. Examples of the thermoplastic polymer include, but are not limited to, homopolymers of vinyl chloride and copolymers of vinyl chloride such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-dichloroethylene copolymer, and vinyl chloride-methyl methacrylate copolymer. The thermoplastic polymer material of the present invention has good tensile strength, elongation rate, 100% tensile stress, etc., and is thus useful for the application of various processing treatments.

[0060] In the thermoplastic polymer material of the present invention, the amount of the polyester composition can be 10 to 120 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. For example, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight, 100 parts by weight, 101 parts by weight, 102 parts by weight, 103 parts by weight, 104 parts by weight, 105 parts by weight, 106 parts by weight, 107 parts by weight, 108 parts by weight, 109 parts by weight, 110 parts by weight, 111 parts by weight, 112 parts by weight, 113 parts by weight, 114 parts by weight, 115 parts by weight, 116 parts by weight, 117 parts by weight, 118 parts by weight or 119 parts by weight, or can be within the range between any two of these recited values.

[0061] The thermoplastic polymer material of the present invention can optionally contain other additives in order to optimally improve the processability of the thermoplastic polymer material during processing or to impart specific properties to the final product. Additives include, but are not limited to, stabilizers, fillers, dyes, pigments, antioxidants, flame retardants, foaming agents and antistatic agents.

[0062] In some embodiments of the present invention, the thermoplastic polymer material further comprises a stabilizer. Examples of stabilizers include, but are not limited to, epoxidized soybean oil, calcium / zinc-based stabilizers, barium / zinc-based stabilizers, and lead diamine stabilizers. In the thermoplastic polymer material of the present invention, the amount of the stabilizer can be from 0 parts by weight to 10 parts by weight, based on 100 parts by weight of the thermoplastic polymer. For example, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, or within the range between any two of these recited values.

Example

[0063] 3. Examples 3.1. Test method [GC Spectrum Analysis] A sample of the polyester composition is heated in an oven at 70 °C for 1 hour to make the sample uniform. Subsequently, the sample is mixed with acetone (solvent) to prepare a 5 wt% solution, completing the pretreatment of the sample to be tested.

[0064] The pretreated sample is loaded into an SGE BPI capillary column with a length of 60 m, an inner diameter of 530 μm, and a film thickness of 3 μm. Subsequently, the sample is analyzed using a gas chromatograph-mass spectrometer (model: QP 2020, Shimadzu Corporation). The GC analysis is performed under the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of nitrogen with a flow rate of 12 ml / min, an initial temperature of 50 °C for 5 minutes, a temperature ramp from 50 °C to 300 °C at a rate of 10 °C / min, a continuous step temperature of 300 °C for 40 minutes, an inlet temperature of 340 °C, an injection volume of 1 μl of the polyester composition sample, and the use of a flame ionization detector operating at 340 °C.

[0065] [GC-MS Analysis] A sample of the polyester composition is heated in an oven at 70 °C for 1 hour to make the sample uniform. Subsequently, the sample is mixed with acetone (solvent) to 1 prepare a solution of % by weight and complete the pretreatment of the sample to be tested.

[0066] The pretreated sample is loaded into a ZB-1 capillary column with a length of 30 m, an inner diameter of 250 μm and a film thickness of 0.25 μm. Subsequently, the sample is analyzed using a gas chromatograph mass spectrometer (model: QP 2020, Shimadzu Corporation). Using 100% dimethylpolysiloxane as the stationary phase and helium with a flow rate of 1.8 ml / min as the carrier gas, a temperature increase from 50 °C to 330 °C at a rate of 10 °C / min for 5 minutes at 50 °C and a continuous stepwise temperature at 330 °C for 27 minutes are carried out. Then, the GC-MS analysis is performed under the following conditions: inlet temperature 350℃ , electron energy 70 eV (electron volts), ion source temperature 250 °C, use of a quadrupole mass filter, interface temperature 340 °C, mass scan range of 29.0 m / z to 900 m / z, and a solvent delay time of 1.5 minutes.

[0067] [Acid value analysis] First, a KOH solution is prepared as follows. Weigh 0.7 g of KOH, dissolve it in a small amount of distilled water, and then dilute it to 1000 ml with neutral ethanol to obtain a KOH solution. Weigh 0.4 g of reagent-grade potassium hydrogen phthalate (KHP), add it to a 250 ml conical flask. Add 100 ml of distilled water to dissolve the KHP and obtain a KHP solution. Then, add 2 drops of phenolphthalein indicator to the KHP solution, and subsequently, titrate the KHP solution with the KOH solution to calculate the normality N of the KOH solution.

[0068] Next, weigh 10 g of the sample to be tested, add it to a 250 ml conical flask, and then add 100 ml of a neutral 2-propanol solution and 3 - 4 drops of phenolphthalein indicator thereto. Shake the flask and gently heat to confirm that the sample is completely dissolved. Titrate the sample with the KOH solution until the solution turns faintly pink and the pink color is maintained for 30 seconds, reaching the end point of the titration. Calculate the acid value of the sample according to the following formula (1). TIFF0007713300000016.tif2094

[0069] [Hydroxyl value analysis] First, prepare the acetylation reagent as follows. Pipette 10 ml of acetic anhydride into a 100 ml flask, add 50 ml of pyridine to the flask, and stir the resulting mixture to obtain the acetylation reagent.

[0070] Next, prepare the KOH solution according to the following method. Weigh 0.7 g of KOH, dissolve it in a small amount of distilled water, and then dilute it to 1000 ml with neutral ethanol to obtain the KOH solution. Weigh 0.4 g of potassium hydrogen phthalate (KHP) for reagent use, add it to a 250 ml conical flask. Add 100 ml of distilled water to dissolve the KHP and obtain the KHP solution. Then, add 2 drops of phenolphthalein indicator to the KHP solution and subsequently titrate the KHP solution with the KOH solution. Record the KOH titration volume (i.e., the blank titration volume) and calculate the normality N of the KOH solution.

[0071] Thereafter, weigh 10 g of the sample to be tested, add it to a stoppered conical flask, and then add 10 ml of the acetylation reagent thereto. Install an air cooler on top of the flask, shake the flask, and heat it with steam (98 ± 2 °C) 1 hourHeat it. After the reaction is completed, cool the flask to room temperature, add 25 ml of n-butanol to the flask, and shake the flask vigorously. Then, add 2 - 3 drops of phenolphthalein indicator. Titrate the sample with KOH solution until the solution turns faintly pink and the pink color is maintained for 30 seconds, reaching the end point of the titration. Record the KOH titration volume (i.e., the test titration volume), and calculate the hydroxyl value of the sample according to the following formula (2). JPEG0007713300000017.jpg19154

[0072] [Viscosity Analysis] Add the sample to be tested into a cylinder for volume measurement with a height of 180 mm and a diameter of 50 mm. Subsequently, place the cylinder for volume measurement in a constant temperature water bath at 25 ± 1 °C. Test the sample using a Brookfield Viscometer model LV with a suitable axis and rotation speed.

[0073] [Analysis of the initial tensile strength, initial elongation rate and initial 100% tensile stress] First, preheat the hot press at 170 °C for 5 minutes. Next, hot press the thermoplastic polymer material at 170 °C and a pressure of 50 kg / cm 3 for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm, and a thickness of 1 mm. Then, cool the test piece to room temperature under a pressure of 60 kg / cm 3 Subsequently, use a JIS - 6301 - 3 model die - cut mold to cut the test piece into dumbbell - shaped test pieces. Test the dumbbell - shaped test pieces using a universal testing machine (model: 3366, Instron) according to ASTM D638 to obtain the initial tensile strength, initial elongation rate, and initial 100% tensile stress.

[0074] [Volatility Analysis] First, preheat the hot press at 170 °C for 5 minutes. Next, hot press the thermoplastic polymer material at 170 °C and a pressure of 50 kg / cm 3 for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm, and a thickness of 1 mm. Then, the test piece...3 Under pressure, cool to room temperature. Measure the weight of the test piece. Subsequently, place the test piece at 136 °C for 168 hours to undergo thermal aging, and measure the weight of the test piece after thermal aging. Calculate the volatility of the test piece according to the following formula (3). TIFF0007713300000018.tif18130

[0075] [Analysis of Tensile Strength after Thermal Aging, Elongation Rate after Thermal Aging, and 100% Tensile Stress after Thermal Aging] First, preheat the hot press at 170 °C for 5 minutes. Next, hot press the thermoplastic polymer material at 170 °C and a pressure of 50 kg / cm 3 for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm, and a thickness of 1 mm. Subsequently, use a JIS-6301-3 model die-cut mold to cut the test piece into dumbbell-shaped test pieces. Place the dumbbell-shaped test pieces at 136 °C for 168 hours to undergo thermal aging. Test the thermally aged test pieces using a universal testing machine 3366 in accordance with ASTM D638 to obtain the tensile strength after thermal aging, the elongation rate after thermal aging, and the 100% tensile stress after thermal aging. The residual rate of tensile strength (hereinafter referred to as the "residual tensile rate") can be obtained by dividing the tensile strength after thermal aging by the initial tensile strength. The residual rate of elongation (hereinafter referred to as the "residual elongation rate") can be obtained by dividing the elongation rate after thermal aging by the initial elongation rate.

[0076] [Migration Resistance Test] Press the thermoplastic polymer material into test pieces with a length of 38 mm, a width of 6 mm, and a thickness of 1 mm. Place each test piece between two acrylonitrile-butadiene-styrene resin plates (model: TAIRILAC AG15E1, FORMOSA CHEMICALS & FIBRE CORPORATION) and between two high-impact polystyrene resin plates (model: TAIRIREX HP8250, FORMOSA CHEMICALS & FIBRE CORPORATION) to form a laminate. Clamp the laminate using a sandwich clamp, place a 1 kg counterweight on top of the laminate, and place the laminate in an oven at 70 °C for 72 hours. Then, observe the resin plates to confirm whether the polyester composition migrates from the test pieces made of the thermoplastic polymer material to the resin plates and whether etching occurs. Visually check the surface of the resin plates for damage. The evaluation criteria are as follows. The number "1" indicates that no traces are observed on the surface. The number "2" indicates that a pressed shadow is observed on the surface. The number "3" indicates that an obvious dent is observed on the surface. The number "4" indicates that obvious swelling and depression are observed on the surface. The number "5" indicates that significant damage and stickiness are observed on the surface. The smaller the number, the better the migration resistance.

[0077] 3.2. Preparation and characteristic analysis of the polyester composition 3.2.1. Preparation of the polyester composition [Synthesis Example 1] Add 1000 g of adipic acid, 240.53 g of neopentyl glycol, 485.63 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid to a 3 L round-bottom flask equipped with a stirrer, thermometer, distillation tube, and concentration meter. Introduce nitrogen and carry out an esterification reaction at normal pressure at 150 °C under the condition of stirring the reactants until the dehydration reaction starts. Subsequently, add 0.22 g of tetraisopropyl titanate as a catalyst and carry out an esterification reaction at normal pressure at 220 °C under a nitrogen atmosphere. Then, reduce the pressure to 460 Torr fromIt was lowered to 200 Torr and the esterification reaction was carried out under reduced pressure at 210 °C. The esterification reaction was carried out for a total of 298 minutes. The acid value indicating the end of the esterification was 4.79 mgKOH / g. Next, the pressure was lowered to 0 Torr and the polycondensation reaction was carried out under reduced pressure at 230 °C for 397 minutes. Then, the reaction product was cooled to 105 °C and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Synthesis Example 1.

[0078] [Synthesis Example 2] To a 3 L round-bottom flask equipped with a stirrer, thermometer, distillation tube and concentration meter, 1000 g of adipic acid, 320.70 g of neopentyl glycol, 416.25 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. Nitrogen was introduced and the esterification reaction was carried out at 150 °C under normal pressure under the condition of stirring the reactants, and the dehydration reaction started. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst and the esterification reaction was carried out at 220 °C under normal pressure in a nitrogen atmosphere. Then, the pressure was from lowered to 200 Torr and the esterification reaction was carried out under reduced pressure at 220 °C. The esterification reaction was carried out for a total of 318 minutes. The acid value indicating the end of the esterification was 4.69 mgKOH / g. Next, the pressure was lowered to 0 Torr and the polycondensation reaction was carried out under reduced pressure at 220 °C for 465 minutes. Then, the reaction product was cooled to 105 °C and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Synthesis Example 2.

[0079] [Synthesis Example 3] 1000 g of adipic acid, 400.88 g of neopentyl glycol, 346.88 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid were added to a 3 L round-bottom flask equipped with a stirrer, a thermometer, a distillation tube, and a concentration meter. Nitrogen was introduced, and an esterification reaction was carried out at 150 °C under normal pressure under the condition of stirring the reactants, and the dehydration reaction started. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and an esterification reaction was carried out at 220 °C under normal pressure in a nitrogen atmosphere. Then, the pressure was reduced to 460 Torr from and then to 200 Torr, and a reduced-pressure esterification reaction was carried out at 210 °C. The esterification reaction was carried out for a total of 310 minutes. The acid value indicating the end of the esterification was 4.87 mgKOH / g. Next, the pressure was reduced to 0 Torr, and a reduced-pressure polycondensation reaction was carried out at 220 °C for 450 minutes. Then, the reaction product was cooled to 105 °C, and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Synthesis Example 3.

[0080] [Synthesis Example 4] 1000 g of adipic acid, 481.05 g of neopentyl glycol, 277.50 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid were added to a 3 L round-bottom flask equipped with a stirrer, a thermometer, a distillation tube, and a concentration meter. Nitrogen was introduced, and an esterification reaction was carried out at 150 °C under normal pressure under the condition of stirring the reactants, and the dehydration reaction started. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and an esterification reaction was carried out at 230 °C under normal pressure in a nitrogen atmosphere. Then, the pressure was reduced to 460 Torr fromIt was lowered to 200 Torr, and a vacuum esterification reaction was carried out at 220 °C. The esterification reaction was carried out for a total of 271 minutes. The acid value indicating the end of esterification was 3.9 mgKOH / g. Next, the pressure was lowered to 0 Torr, and a vacuum polycondensation reaction was carried out at 210 °C for 510 minutes. Then, the reaction product was cooled to 105 °C, and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Synthesis Example 4.

[0081] [Synthesis Example 5] 1000 g of adipic acid, 481.05 g of neopentyl glycol, 277.50 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid were added to a 3 L round-bottom flask equipped with a stirrer, a thermometer, a distillation tube, and a concentration meter. Nitrogen was introduced, and an atmospheric pressure esterification reaction was carried out at 150 °C under the condition of stirring the reaction substances, and the dehydration reaction started. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and an atmospheric pressure esterification reaction was carried out at 220 °C under a nitrogen atmosphere. Then, the pressure from was lowered to 200 Torr, and a vacuum esterification reaction was carried out at 235 °C. The esterification reaction was carried out for a total of 235 minutes. The acid value indicating the end of esterification was 2.4 mgKOH / g. Next, the pressure was lowered to 0 Torr, and a vacuum polycondensation reaction was carried out at 225 °C for 413 minutes. Then, the reaction product was cooled to 105 °C, and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Synthesis Example 5.

[0082] [Comparative Synthesis Example 1] In a 3 L round-bottom flask equipped with a stirrer, thermometer, distillation tube, and concentration meter, 1000 g of adipic acid, 160.35 g of neopentyl glycol, 555.00 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid were added. Nitrogen was introduced, and an esterification reaction was carried out at 150 °C under normal pressure under the condition of stirring the reactants, and the dehydration reaction started. Subsequently, 0.21 g of tetraisopropyl titanate was added as a catalyst, and an esterification reaction was carried out at 220 °C under normal pressure in a nitrogen atmosphere. Then, the pressure was reduced to 460 Torr from 200 Torr, and a reduced-pressure esterification reaction was carried out at 230 °C. The esterification reaction was carried out for a total of 325 minutes. The acid value indicating the end of esterification was 3.21 mgKOH / g. Next, the pressure was reduced to 0 Torr, and a reduced-pressure polycondensation reaction was carried out at 210 °C for 524 minutes. Then, the reaction product was cooled to 105 °C, and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Comparative Synthesis Example 1.

[0083] [Comparative Synthesis Example 2] In a 3 L round-bottom flask equipped with a stirrer, thermometer, distillation tube, and concentration meter, 1000 g of adipic acid, 561.23 g of neopentyl glycol, 208.13 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid were added. Nitrogen was introduced, and an esterification reaction was carried out at 150 °C under normal pressure under the condition of stirring the reactants, and the dehydration reaction started. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and an esterification reaction was carried out at 220 °C under normal pressure in a nitrogen atmosphere. Then, the pressure was reduced to 460 Torr fromIt was lowered to 200 Torr, and a vacuum esterification reaction was carried out at 220 °C. The esterification reaction was carried out for a total of 310 minutes. The acid value indicating the end of esterification was 4.70 mgKOH / g. Next, the pressure was lowered to 0 Torr, and a vacuum polycondensation reaction was carried out at 220 °C for 492 minutes. Then, the reaction product was cooled to 105 °C, and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Comparative Synthesis Example 2.

[0084] [Comparative Synthesis Example 3] To a 3 L round-bottom flask equipped with a stirrer, thermometer, distillation tube, and concentration meter, 1000 g of adipic acid, 641.41 g of neopentyl glycol, 138.75 g of 2-methyl-1,3-propanediol, 155.95 g of 2-ethylhexanol, and 274.02 g of lauric acid were added. Nitrogen was introduced, and an atmospheric pressure esterification reaction was carried out at 150 °C under the condition of stirring the reactants, and the dehydration reaction started. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and an atmospheric pressure esterification reaction was carried out at 220 °C under a nitrogen atmosphere. Then, the pressure was from lowered to 200 Torr, and a vacuum esterification reaction was carried out at 225 °C. The esterification reaction was carried out for a total of 271 minutes. The acid value indicating the end of esterification was 4.98 mgKOH / g. Next, the pressure was lowered to 0 Torr, and a vacuum polycondensation reaction was carried out at 230 °C for 300 minutes. Then, the reaction product was cooled to 105 °C, and 0.05 wt% (based on the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain the polyester composition of Comparative Synthesis Example 3.

[0085] 3.2.2. Characteristic analysis of the polyester composition The properties including the GC spectrum, GC-MS spectrum, acid value, hydroxyl value, and viscosity of the polyester compositions of Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 were measured according to the above test methods. The peak areas of chromatography for the first component, second component, and third component were calculated. The results are shown in Table 1.

[0086]

Table 1

[0087] 3.3. Preparation and characteristic analysis of the thermoplastic polymer material 3.2.2. Preparation of the thermoplastic polymer material [Example 1] 100 parts by weight of polyvinyl chloride (Model: S-70, Formosa Plastics Group), 50 parts by weight of the polyester composition of Synthesis Example 1, 2 parts by weight of epoxidized soybean oil (Model: B-22, Chang Chun Petrochemical), and 2.5 parts by weight of a calcium / zinc-based stabilizer (Model: Mark 37W, Chang Chiang Chemical) were added to a Laboratory Mill (Model: MT22615, YITZUNG Precision Machinery) and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Example 1.

[0088] [Example 2] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 2, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of a calcium / zinc-based stabilizer Mark 37W were added to a Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Example 2.

[0089] [Example 3] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 3, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of a calcium / zinc-based stabilizer Mark 37W were added to a Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Example 3.

[0090] [Example 4] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 4, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of calcium / zinc-based stabilizer Mark 37W were added to Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Example 4.

[0091] [Example 5] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 5, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of calcium / zinc-based stabilizer Mark 37W were added to Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Example 5.

[0092] [Comparative Example 1] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Comparative Synthesis Example 1, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of calcium / zinc-based stabilizer Mark 37W were added to Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Comparative Example 1.

[0093] [Comparative Example 2] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Comparative Synthesis Example 2, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of calcium / zinc-based stabilizer Mark 37W were added to Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Comparative Example 2.

[0094] [Comparative Example 3] 100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Comparative Synthesis Example 3, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of calcium / zinc-based stabilizer Mark 37W were added to Laboratory Mill MT22615 and pulverized at 172 °C for 7 minutes to obtain the thermoplastic polymer material of Comparative Example 3.

[0095] 3.3.2. Characteristic analysis (I) of the thermoplastic polymer material The properties of the thermoplastic polymer materials of Examples 1 to 5 and Comparative Examples 1 to 3, including the initial tensile strength, initial elongation rate, initial 100% tensile stress, volatility rate after heat aging, residual tensile rate, residual elongation rate, and 100% tensile stress, were measured according to the above test methods. The results are shown in Table 2.

[0096] [Table 2]

[0097] As shown in Table 2, the thermoplastic polymer material using the polyester composition of the present invention as a plasticizer has good initial tensile strength, initial elongation rate, and initial 100% tensile stress, as well as good residual tensile rate, residual elongation rate, and 100% tensile stress after heat aging. On the contrary, as shown in Table 2, the thermoplastic polymer material that does not use the polyester composition of the present invention as a plasticizer does not simultaneously have good initial tensile strength, initial elongation rate, and initial 100% tensile stress, nor does it simultaneously have good residual tensile rate, residual elongation rate, and 100% tensile stress after heat aging. Specifically, as shown in Comparative Example 1, if the peak area percentage of the first component in chromatography is higher than the specified range, the thermoplastic polymer material has a reduced residual elongation rate after heat aging. As shown in Comparative Examples 2 and 3, if the peak area percentage of the first component in chromatography is lower than the specified range, the thermoplastic polymer of the thermoplastic polymer material cannot be effectively plasticized and will give a reduced initial 100% tensile stress.

[0098] 3.3.3. Characteristic analysis (II) of the thermoplastic polymer material The migration resistance of the thermoplastic polymer materials of Examples 2 to 5 and Comparative Examples 1 and 3 was measured according to the above test methods. The results are shown in Table 3.

[0099] [Table 3]

[0100] As shown in Table 3, the thermoplastic polymer material using the polyester composition of the present invention as a plasticizer has good migration resistance, that is, the polyester composition is unlikely to migrate and etch the surface of the resin plate to cause damage. On the contrary, as shown in Table 3, the thermoplastic polymer material not using the polyester composition of the present invention as a plasticizer cannot have good migration resistance. Specifically, as shown in Comparative Examples 1 and 3, if the area percentage of the peak of the chromatography of the second component in the polyester composition used as a plasticizer deviates from the specified range, the polyester composition has reduced migration resistance, and obvious depressions can be observed on the surface of the resin plate.

[0101] The above embodiments are used to explain the principle and effect of the present invention and show its inventive features, and are not used to limit the scope of the present invention. Those skilled in the art can make various changes and exchanges based on the disclosure and proposal of the described invention. Therefore, the protection scope of the present invention is defined by the appended claims.

Claims

1. A polyester composition comprising a polyester, a first component, and a second component, when the polyester composition is characterized by gas chromatography (GC), the first component elutes at a retention time in the range of 36.38 minutes to 36.98 minutes, and the first component indicated by the chromatographic peak at the retention time in the GC spectrum has a chromatographic peak area in the range of 1.5% to 7.0% with respect to the total area of the chromatographic peaks of the polyester composition, and the second component elutes at a retention time in the range of 37.56 minutes to 38.29 minutes, and the second component indicated by the chromatographic peak at the retention time in the GC spectrum has a chromatographic peak area in the range of 3.5% to 7.5% with respect to the total area of the chromatographic peaks of the polyester composition, the polyester composition has a viscosity in the range of 2900 cps to 3400 cps at 25°C, an acid value in the range of 0.1 mg KOH / g to 0.7 mg KOH / g, and a hydroxyl value in the range of 6.0 mg KOH / g to 10.8 mg KOH / g, the polyester composition is obtained by subjecting one or more aliphatic diacids and one or more aliphatic diols to an esterification polymerization reaction, the aliphatic diacid includes adipic acid, and the aliphatic diol includes 2-methyl-1,3-propanediol and at least one of neopentyl glycol and 1,4-butanediol, provided that when the aliphatic diol includes 2-methyl-1,3-propanediol and neopentyl glycol, or includes 2-methyl-1,3-propanediol, neopentyl glycol, and 1,4-butanediol, the polyester composition further includes a third component, the third component elutes at a retention time in the range of 36.99 minutes to 37.55 minutes, and the third component indicated by the chromatographic peak at the retention time in the GC spectrum has a chromatographic peak area in the range of 8.0% to 10.0% with respect to the total area of the chromatographic peaks of the polyester composition, In gas chromatography (GC), the polyester composition is loaded into a capillary column with a length of 60 m, an inner diameter of 530 μm, and a film thickness of 3 μm, and under the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of nitrogen with a flow rate of 12 ml / min, a temperature increase from 50°C to 300°C at a rate of 10°C / min for 5 minutes at 50°C, a continuous stepwise temperature at 300°C for 40 minutes, an inlet temperature of 340°C, a sample injection volume of 1 μl of the polyester composition, and the use of a flame ionization detector operated at 340°C, the polyester composition.

2. The polyester composition according to claim 1, when the polyester composition is characterized by gas chromatography - mass spectrometry (GC - MS), the first component elutes with a retention time in the range of 28.900 minutes to 29.000 minutes, and the fragment pattern of the first component contains one or more signals of mass / charge ratio (m / z) selected from the group consisting of 29, 41, 42, 43, 55, 56, 83, 84, 101, 111, 114, 127, 129, 141, 154, 156, 183, 201, 273, and 400, In GC - MS, the polyester composition is loaded into a capillary column with a length of 30 m, an inner diameter of 250 μm, and a film thickness of 0.25 μm, and under the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of helium with a flow rate of 1.8 ml / min, a temperature increase from 50°C to 330°C at a rate of 10°C / min for 5 minutes at 50°C, a continuous stepwise temperature at 330°C for 27 minutes, an inlet temperature of 350°C, an electron energy of 70 eV (electron volts), an ion source temperature of 250°C, the use of a quadrupole mass filter, an interface temperature of 340°C, a mass scan range of 29.0 m / z to 900 m / z, and a solvent delay time of 1.5 minutes, the polyester composition.

3. The polyester composition according to claim 2, wherein the fragment pattern of the first component contains signals of m / z of 41, 55, 56, 83, 111, 114, 127, 129, 141, and 201.

4. The polyester composition according to claim 1, When characterizing the polyester composition by GC-MS, the second component elutes with a retention time in the range of 29.101 minutes to 29.200 minutes, and the fragment pattern of the second component contains one or more signals of m / z selected from the group consisting of 29, 41, 43, 55, 56, 69, 83, 101, 111, 127, 129, 141, 147, 155, 168, 197, 215, 216, 343 and 428. In GC-MS, the polyester composition is loaded into a capillary column with a length of 30 m, an inner diameter of 250 μm and a film thickness of 0.25 μm, and the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of helium with a flow rate of 1.8 ml / min, heating from 50 °C to 330 °C at a rate of 10 °C / min for 5 minutes, a continuous stepwise temperature at 330 °C for 27 minutes, an inlet temperature of 350 °C, an electron energy of 70 eV (electron volts), an ion source temperature of 250 °C, the use of a quadrupole mass filter, an interface temperature of 340 °C, a mass scan range of 29.0 m / z to 900 m / z, and a solvent delay time of 1.5 minutes. The polyester composition is characterized thereby.

5. The polyester composition according to claim 4, wherein the fragment pattern of the second component contains signals of m / z of 41, 55, 56, 69, 83, 111, 129, 141, 155 and 215.

6. The polyester composition according to any one of claims 1 to 5, wherein the polyester is a polyadipate ester.

7. The polyester composition according to claim 1, When characterizing the polyester composition by GC-MS, the third component elutes with a retention time in the range of 29.001 minutes to 29.100 minutes, and the fragment pattern of the third component contains one or more signals of m / z selected from the group consisting of 29, 41, 55, 56, 69, 83, 101, 111, 114, 127, 129, 141, 155, 183, 201, 215, 287, 319 and 414. In GC-MS, the polyester composition is loaded into a capillary column with a length of 30 m, an inner diameter of 250 μm, and a film thickness of 0.25 μm, and the following conditions: a stationary phase of 100% dimethylpolysiloxane, a carrier gas of helium with a flow rate of 1.8 ml / min, a temperature rise from 50°C to 330°C at a rate of 10°C / min for 5 minutes at 50°C, a continuous stepwise temperature of 330°C for 27 minutes, an inlet temperature of 350°C, an electron energy of 70 eV (electron volts), an ion source temperature of 250°C, the use of a quadrupole mass filter, an interface temperature of 340°C, a mass scan range of 29.0 m / z to 900 m / z, and a solvent delay time of 1.5 minutes, a polyester composition.

8. The polyester composition according to claim 7, wherein the fragment pattern of the third component includes signals at m / z of 41, 55, 56, 69, 111, 127, 129, 141, 201, and 215.

9. A thermoplastic polymer material comprising a plasticizer and a thermoplastic polymer, the thermoplastic polymer comprising the polyester composition according to any one of claims 1 to 8.

10. The thermoplastic polymer material according to claim 9, wherein the thermoplastic polymer is a homopolymer of vinyl chloride or a copolymer of vinyl chloride.

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