Polyester resin, molding, preform, polyester bottle, and mechanically recycled polyester resin

Abstract

To provide a polyester resin having an excellent color tone.SOLUTION: A polyester resin contains polyester containing a diol unit and a dicarboxylic acid unit as a main component, wherein a ratio (A7.5 / Aacid) of a peak area (A7.5) at 7.43 to 7.55 ppm to a peak area (Aacid) derived from total dicarboxylic acids, which is measured using 1H-NMR, is less than 0.00060.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyester resin, a molded article made of this polyester resin, a preform, a polyester bottle, and a mechanically recycled polyester resin.

Background Art

[0002] The polyester resin is a thermoplastic resin having excellent properties such as mechanical stability, chemical stability, transparency, and heat resistance. From the viewpoint of reducing the environmental load, a method of recycling such a polyester resin by solid-phase polymerization and mechanically recycling it is known (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2000-219728

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when the mechanical recycling treatment of the polyester resin is repeatedly performed by the above technique, there is a problem that the yellowness of the polyester resin increases and the color tone deteriorates.

[0005] An object of the present invention is to provide a polyester resin having an excellent color tone.

Means for Solving the Problems

[0006] [1] According to Aspect 1 of the present invention, there is provided a polyester resin containing a polyester mainly composed of a diol unit and a dicarboxylic acid unit, wherein the peak area (A acid ) derived from all dicarboxylic acids measured using 1H-NMR, the ratio (A 7.5 ) of the peak area (A 7.5 ) at 7.43 to 7.55 ppm to A acidThere is provided a polyester resin characterized in that (

[0007] [2] According to Embodiment 2 of the present invention, the peak area (A acid ) derived from all dicarboxylic acids measured using 1H-NMR, the ratio (A 7.8 ) of the peak area (A 7.8 / A acid ) of 7.75 to 7.86 ppm is less than 0.00030. The polyester resin according to Embodiment 1 is provided.

[0008] [3] According to Embodiment 3 of the present invention, there is provided a molded article made from the polyester resin according to Embodiment 1 or 2.

[0009] [4] According to Embodiment 4 of the present invention, there is provided a preform made from the polyester resin according to Embodiment 1 or 2.

[0010] [5] According to Embodiment 5 of the present invention, there is provided a polyester bottle made from the polyester resin according to Embodiment 1 or 2.

[0011] [6] According to Embodiment 6 of the present invention, there is provided the polyester resin according to Embodiment 1 or 2, characterized in that the polyester resin is a mechanically recycled polyester resin.

Advantages of the Invention

[0012] According to the present invention, a polyester resin having an excellent color tone can be provided.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2A

Figure 2B

Figure 2C

Figure 3

Figure 4

Mode for Carrying Out the Invention

[0014] The polyester resin in the present embodiment mainly contains a polyester containing a diol unit and a dicarboxylic acid unit, and the ratio (A acid ) of the peak area (A 7.5 ) at 7.43 to 7.55 ppm to the peak area (A 7.5 / A acid ) derived from all dicarboxylic acids measured using 1H-NMR is less than 0.00060.

[0015] The polyesters contained in the polyester resin include aromatic polyesters, wholly aromatic polyesters, polycarbonates, and aliphatic polyesters. Among these, aromatic polyesters are preferred. Aromatic polyesters contain diol units and dicarboxylic acid units. Examples of diol compounds for forming diol units include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,6-hexylene glycol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, etc. Among these, ethylene glycol is preferred. Examples of dicarboxylic acid compounds for forming dicarboxylic acid units include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and furandicarboxylic acid and their derivatives. Among these, terephthalic acid is preferred. Specific examples of polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene furanoate, etc. Among these, polyethylene terephthalate, which is a copolymer of ethylene glycol and terephthalic acid, is preferred. The above-mentioned polyesters are not limited to those derived from petroleum raw materials, and may be polyesters derived from plant raw materials, or further, polyesters recycled from these polyesters derived from petroleum raw materials or plant raw materials. Also, the above-mentioned polyesters may be used alone or in combination.

[0016] The content of ethylene terephthalate units in polyethylene terephthalate is preferably 70 mol% or more, more preferably 90 mol% or more, based on all monomer units.

[0017] Polyethylene terephthalate may contain units consisting of dicarboxylic acids other than terephthalic acid copolymerizable with ethylene glycol and terephthalic acid in all monomer units. Examples of such dicarboxylic acids other than terephthalic acid include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, pimelic acid, azelaic acid, methylmalonic acid and ethylmalonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylendadicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 9,9'-bis(4-carboxyphenyl)fluorene acid, 2,5-furandicarboxylic acid and ester derivatives thereof, etc. Among them, isophthalic acid is preferable. The content of units consisting of dicarboxylic acids other than terephthalic acid is preferably 30 mol% or less, more preferably 10 mol% or less, based on all monomer units.

[0018] Polyethylene terephthalate may contain units composed of diols other than terephthalic acid copolymerizable with ethylene glycol and terephthalic acid in all monomer units. Examples of such diols other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalenedimethanol, decahydronaphthalenediethanol, norbornanedimethanol, norbornanedietanol, tricyclodecanedimethanol, tricyclodecanediethanol, tetracyclododecanedimethanol, tetracyclododecanediethanol, decalindimethanol, decalindietanol, 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiene diol, 4-cyclopentene-1,3-diol, adamantadiol, paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, trimethylolpropane, pentaerythritol, diethylene glycol, triethylene glycol, and bis-β-hydroxyethyl terephthalate (BHET), etc. Among them, diethylene glycol is preferred. The content of units composed of diols other than ethylene glycol is preferably 30 mol% or less, more preferably 10 mol% or less, based on all monomer units.

[0019] Polyethylene terephthalate may contain other components such as additives. For example, one or more of various additives such as plasticizers, light stabilizers, antioxidants, ultraviolet absorbers, flame retardants, colorants, pigments, fillers, mold release agents, antistatic agents, fragrances, foaming agents, antibacterial and antifungal agents may be blended.

[0020] Although not particularly limited, the polyester resin in the present embodiment may contain a cyclic oligomer containing a diol unit and a dicarboxylic acid unit. Such a cyclic oligomer is a by-product in the polymerization reaction of the above diol compound and dicarboxylic acid compound. The polyester resin in the present embodiment contains, as cyclic oligomers, a trimer oligomer (cyclic trimer; CT) and a pentamer oligomer (C5). For example, the trimer oligomer (CT) contained in a polyester resin containing polyethylene terephthalate as a polyester is composed of three constituent units of polyethylene terephthalate.

[0021] The content of the cyclic oligomer in the polyester resin is preferably 1% by weight or less, more preferably 0.5% by weight or less.

[0022] In the polyester resin, the ratio (A acid ) of the peak area (A 7.5 ) at 7.43 to 7.55 ppm to the peak area (A 7.5 ) of all dicarboxylic acid-derived peaks measured using 1H-NMR (A acid / A acid ) is less than 0.00060, preferably less than 0.00040. The peak derived from the dicarboxylic acid is present in the range of 7.60 to 7.75 ppm, 7.90 to 8.55 ppm, and 8.75 to 8.90 ppm, and the peak area (A acid ) of all dicarboxylic acid-derived peaks refers to the sum of the peak areas present in all these ranges. The polyester resin in the present embodiment has a suppressed yellowness and excellent color tone, and also excellent molding stability, by virtue of the ratio (A 7.5 ) of the peak area (A 7.5 ) at 7.43 to 7.55 ppm to the peak area (A acid ) of all dicarboxylic acid-derived peaks measured using 1H-NMR being within the above range.

[0023] In the polyester resin, the ratio of the peak area (A acid ) at 7.75 to 7.85 ppm to the peak area (A7.8 ) ratio (A 7.8 / A acid ) is preferably less than 0.00030, more preferably less than 0.00020. The ratio (A acid ) of the peak area (A 7.8 ) at 7.75 to 7.85 ppm to the peak area (A 7.8 / A acid ) of all dicarboxylic acids is within the above range, the polyester resin can be made excellent in color tone and molding stability.

[0024] In the polyester resin of this embodiment, the ratio (C5 / CT) of the peak area of the pentamer oligomer (C5) to the peak area of the trimer oligomer (CT) in the cyclic oligomer measured using liquid chromatography is preferably 0.068 or more and less than 0.090, more preferably 0.070 or more and less than 0.088. By setting the ratio (C5 / CT) of the peak area of the pentamer oligomer (C5) to the peak area of the trimer oligomer (CT) within the above range, the polyester resin can be made excellent in color tone and molding stability. In addition, when measuring using liquid chromatography, it is preferable to use a UV / Vis detector or a diode array detector (DAD) as the detector. The same applies when obtaining the ratio of the peak areas of the hexamer oligomer and the heptamer oligomer described later.

[0025] Although not particularly limited, the polyester resin may contain a hexamer oligomer (C6) as the cyclic oligomer. In the polyester resin, the ratio (C6 / CT) of the peak area of the hexamer oligomer (C6) to the peak area of the trimer oligomer (CT) in the cyclic oligomer measured using liquid chromatography is preferably 0.0482 or more and less than 0.0620, more preferably 0.0485 or more and less than 0.0600. By setting the ratio of the peak areas (C6 / CT) within the above range, the polyester resin can be made excellent in color tone and molding stability.

[0026] Although not particularly limited, the polyester resin may contain a heptamer oligomer (C7) as a cyclic oligomer. In the polyester resin, the ratio (C7 / CT) of the peak area of the heptamer oligomer (C7) to the peak area of the trimer oligomer (CT) in the cyclic oligomer measured using liquid chromatography is preferably 0.0225 or more and less than 0.0330, more preferably 0.0230 or more and less than 0.0320. By setting the ratio of the peak areas (C7 / CT) within the above range, the polyester resin can be made to have excellent color tone and molding stability.

[0027] In the polyester resin, the shoulder correlation parameter S derived using the differential molecular weight distribution curve obtained by GPC and represented by the following formula (1) is preferably more than 0.130 and 0.197 or less, more preferably more than 0.145 and 0.196 or less. TIFF2025084433000001.tif11134In the above formula (1), M is the molecular weight of the polyester resin, f(LogM) represents the differential molecular weight distribution curve of the polyester resin, and g(LogM) represents a linear function connected by the data of two points where LogM is 3.40 and 3.75 in f(LogM). Also, the vertical axis of the differential molecular weight distribution curve is dw / dLogM obtained by differentiating the concentration fraction w(%) with respect to LogM. By setting the shoulder correlation parameter S within the above range, the polyester resin can be made to have excellent color tone and molding stability.

[0028] In the polyester resin, the polydispersity Mw / Mn measured using GPC is preferably 2.315 or more and less than 2.500, more preferably 2.320 or more and less than 2.490. By setting the polydispersity Mw / Mn within the above range, the polyester resin can be made to have excellent color tone and molding stability.

[0029] The intrinsic viscosity (IV) of the polyester resin in this embodiment is preferably 0.60 to 1.40 dL / g, more preferably 0.70 to 1.00 dL / g.

[0030] The b color value of the polyester resin in this embodiment * is preferably 15.0 or less, more preferably 10.0 or less, in the form of pellets after solid-phase polymerization.

[0031] The cold crystallization peak top temperature Tc1 of the polyester resin in this embodiment is preferably 149 °C or higher. The upper limit of the cold crystallization peak top temperature Tc1 is not particularly limited, but is usually 170 °C or lower.

[0032] FIG. 1 is a flowchart showing an example of a method for producing a polyester resin in this embodiment. As shown in FIG. 1, the polyester resin in this embodiment can be produced by a method of performing a heat history control treatment including a first melt extrusion step, a second melt extrusion step, a crystallization step, and a solid-phase polymerization step on a polyester containing the above-described diol unit and dicarboxylic acid unit.

[0033] First, in the first melt extrusion step, pelletized polyester obtained by polymerizing the above-described diol compound and dicarboxylic acid is dried in a dehumidifying dryer set at 150 °C in advance to make the moisture content 50 ppm or less, and then melt-extruded using an extruder. The discharged molten resin is air-cooled to form pellets. The extruder is not particularly limited, and examples thereof include a single-screw extruder, a twin-screw extruder, and a multi-screw extruder. Among them, a twin-screw extruder is preferable. When using a twin-screw extruder, the extrusion temperature is preferably 0 to 60 °C higher than the melting point of the polyester, particularly 260 to 310 °C in the case of polyethylene terephthalate, and more preferably 265 to 300 °C. The screw rotation speed of the twin-screw extruder is preferably 50 to 800 rpm, more preferably 70 to 400 rpm. The discharge amount of the twin-screw extruder is preferably 5 to 30000 kg / h, more preferably 10 to 10000 kg / h.

[0034] Next, in the second melt extrusion step, melt extrusion is performed again using the pellets obtained in the first melt extrusion step, and the discharged molten resin is air-cooled to form pellets. The extruder is not particularly limited, and examples include a single-screw extruder, a twin-screw extruder, a multi-screw extruder, etc., and among them, a twin-screw extruder is preferable. Further, it is preferable that the extruder to be used is equipped with a vacuum vent facility capable of reducing the pressure to below atmospheric pressure. In the second melt extrusion step, when using a twin-screw extruder equipped with a vacuum vent facility, the melt extrusion conditions are preferably the same as those in the first melt extrusion step, except that the vacuum degree is under a pressure of 100 Torr or less.

[0035] Next, in the crystallization step, the pellets obtained in the second melt extrusion step are heated to crystallize the resin. The temperature during heating is preferably 100 to 170°C, more preferably 130 to 150°C. The heating is preferably performed under a pressure of 200 Torr or less, under a nitrogen stream, or a combination thereof. The heating time is preferably 0.5 to 6 hours, more preferably 2 to 5 hours.

[0036] Next, in the solid-phase polymerization step, the pellets subjected to the crystallization treatment are heated to perform solid-phase polymerization of the resin. The solid-phase polymerization is preferably performed under a pressure of 200 Torr or less, under a nitrogen stream, or a combination thereof. The temperature of the solid-phase polymerization is preferably 200 to 230°C, more preferably 205 to 225°C. The heating time is preferably 2 to 24 hours, more preferably 6 to 20 hours.

[0037] As described above, by performing the heat history control treatment consisting of the first melt extrusion step, the second melt extrusion step, the crystallization step, and the solid-phase polymerization step one or more times on the polyester, the polyester resin in the present embodiment can be obtained. The number of times of the heat history control treatment is preferably 1 to 3 times based on a so-called virgin polyester that has never been recycled (0 times).

[0038] Note that the method for producing the polyester resin in this embodiment is not particularly limited to the above. For example, by mechanically recycling the polyester used as a polyester bottle or the like, the thermal history can be controlled to obtain the polyester resin (mechanically recycled polyester resin) in this embodiment. As the polyester used for mechanical recycling, for example, a polyester bottle made from virgin polyester or a polyester bottle produced by performing mechanical recycling one or more times can be used.

[0039] The polyester resin in this embodiment can be suitably used for processing into molded articles such as preforms and polyester bottles. The preform can be produced by injection molding the polyester resin. Further, the polyester bottle can be produced by performing stretch blow on such a preform. The molded article produced using the polyester resin in this embodiment has an excellent color tone.

[0040] As described above, since the polyester resin in this embodiment is before being processed into a molded article, the ratios of the peak areas of the pentamer, hexamer, and heptamer oligomers (C5 / CT, C6 / CT, C7 / CT) to the peak area of the trimer oligomer (CT) measured by liquid chromatography, the ratios of the peak areas at 7.43 to 7.55 ppm and 7.75 to 7.85 ppm to the peak area derived from all dicarboxylic acids measured using 1H-NMR, the shoulder correlation parameter S, and the polydispersity Mw / Mn (hereinafter, these are collectively referred to as "thermal history parameters") cannot be judged in the state of the molded article. The molded article corresponds to the state between the first melt extrusion step and the second melt extrusion step in the flowchart shown in FIG. 1. Therefore, in order to compare the polyester resin constituting the molded article with the polyester resin in this embodiment, it is necessary to perform a second melt extrusion treatment, a crystallization treatment, and a solid-phase polymerization treatment on the molded article, evaluate the obtained pellets, and judge whether the thermal history parameters are within a specific range.

[0041] In addition, when the second melt extrusion treatment, crystallization treatment, and solid-phase polymerization treatment are performed on the molded article, it means that the heat history is additionally applied once for the heat history control treatment to the polyester resin before molding. Therefore, when the heat history parameters evaluated by performing the second melt extrusion treatment, crystallization treatment, and solid-phase polymerization treatment on a certain molded article are values near the upper limit value and the lower limit value of the specific range defined in this embodiment, in order to confirm whether the heat history parameters of the polyester resin before molding are included in the specific range, it is preferable to evaluate according to the following procedure.

[0042] First, for the molded article, record the heat history parameters of the pellets obtained by performing the second melt extrusion treatment, crystallization treatment, and solid-phase polymerization treatment as the heat history parameters with one adjustment time. Next, perform the heat history control treatment on the pellets, and record the heat history parameters of the obtained pellets as the heat history parameters with two adjustment times. Thereafter, perform the heat history control treatment a plurality of times on the pellets as necessary, and record the heat history parameters after three adjustment times. In this way, by extrapolating the correlation between the adjustment times and the heat history parameters, the heat history parameters corresponding to zero adjustment times are obtained. By evaluating the heat history parameters corresponding to zero adjustment times, it is possible to confirm whether the heat history parameters of the polyester resin before molding are included in the specific range.

Example

[0043] Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0044] <Example 1> [Production of PET resin pellets and preforms] Prepare 30 kg of pellets of isophthalic acid copolymerized polyethylene terephthalate resin (manufactured by Shin-Kosa Synthetic Fiber Co., Ltd., isophthalic acid copolymerization ratio 1.8 mol%, IV = 0.83), and perform a drying treatment using a hopper dryer under the conditions of 150 °C for 5 hours. Next, put these pellets into a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM26SS), and perform melt extrusion under the conditions of an extrusion temperature of 290 °C, a screw rotation speed of 100 rpm, and a discharge rate of 10 kg / h. The molten resin discharged in a strand form from the extruder was air-cooled while being conveyed by a belt conveyor, and made into pellets using a pelletizer (first melt extrusion treatment). Next, put these pellets into the twin-screw extruder again, and perform melt extrusion under the same conditions as above except using a vacuum vent (9 Torr), and obtain pellets in the same manner (second melt extrusion treatment).

[0045] Heat 15 kg of the obtained pellets using a stirring type vacuum dryer (manufactured by Dalton Co., Ltd., 45MV) under the conditions of 1 Torr and 150 °C for 5 hours to perform a crystallization treatment. Next, using the above stirring type vacuum dryer, heat the pellets after the crystallization treatment under the conditions of 1 Torr and 225 °C for 13 hours to perform a solid-phase polymerization treatment to obtain PET resin pellets. In the crystallization treatment and the solid-phase polymerization treatment, the rotation speed of the stirring blades of the stirring type vacuum dryer was set to 20 rpm. Also, supply a part of the obtained PET resin pellets to an injection molding machine, set the barrel temperature and the hot runner temperature to 300 °C, the mold temperature to 15 °C, and the molding cycle to 32 seconds to produce a preform for a 500 mL bottle with a weight of 25 g. For the PET resin pellets and the preform for the bottle, each evaluation was performed according to the following procedure. The results are shown in Table 2.

[0046] [Cyclic oligomer content] Weighed 0.2 g of PET resin pellets and preforms for bottles, added 1 mL of a mixed solvent of 1,1,1,3,3,3,-hexafluoro-2-propanol and chloroform (weight ratio 1 / 1) thereto, and completely dissolved them. After adding 4 mL of chloroform to the solution, 5 mL of acetonitrile was gradually added, and the mixture was left standing for 3 hours to precipitate the PET polymer. 1 mL of the supernatant of this suspension was taken out, filtered through a membrane filter with a pore size of 0.20 μm, and the filtrate was measured by high performance liquid chromatography. As the measuring device, 1200 series manufactured by Agilent Technologies was used. The measuring conditions were as follows: as the detector, Agilent Technologies 1290 Infinity Diode Array Detector (G4212A) was used, the detection wavelength was 254 nm, and the reference wavelength was 500 nm. Also, as the column, ZORBAX Eclipse Plus C18 (Rapid Resolution HD 2.1×150 mm 1.8 Micron) manufactured by Agilent Technologies was used, and the column temperature was 40 °C. The mobile phase was 0.05 wt% phosphoric acid aqueous solution as solution I and acetonitrile as solution II, and the flow rate was 0.6 mL / min, and it was flowed under the gradient conditions shown in Table 1 below. The injection volume was 2 μL. Regarding the cyclic oligomers in the pellets, the peak areas of the trimer and pentamer to heptamer (CT, C5, C6, C7) were determined respectively, and C5 / CT, C6 / CT, and C7 / CT were calculated.

[0047]

Table 1

[0048] [NMR history correlation peak] The PET resin pellets were dissolved in a mixed solvent of deuterated trifluoroacetic acid and deuterated chloroform (volume ratio 8 / 2), and a 1H-NMR spectrum was measured with an NMR apparatus (JEOL, 400SS). The peak area (A acid ) derived from all dicarboxylic acids, the area (A 7.5 ) of NMR history correlation peak 1, and the area (A 7.8) were each determined, and A 7.5 / A acid and A 7.8 / A acid were calculated. Here, the peaks derived from all dicarboxylic acids refer to the total peak area in the ranges of 7.60 to 7.75 ppm, 7.90 to 8.55 ppm, and 8.75 to 8.90 ppm, NMR history correlation peak 1 refers to the peak area in the range of 7.43 to 7.55 ppm, and NMR history correlation peak 2 refers to the peak area in the range of 7.75 to 7.85 ppm. Figure 2A is a graph showing the measurement results of the 1H-NMR spectrum in Example 1, and Figure 2B is a graph showing the measurement results of the 1H-NMR spectrum in Comparative Example 6. Also, for reference, the 1H-NMR spectrum was similarly measured for virgin isophthalic acid copolymerized polyethylene terephthalate resin without the heat history control treatment. Figure 2C is a graph showing the measurement results of the 1H-NMR spectrum in virgin isophthalic acid copolymerized polyethylene terephthalate resin.

[0049] [Polydispersity (Mw / Mn) and shoulder correlation parameter S] Using a high-speed GPC device (Tosoh, HLC-8320GPC), the differential molecular weight distribution curve was measured to obtain the polydispersity (Mw / Mn). As a sample, a solution in which PET resin pellets were dissolved in a mixed solution of 1,1,1,3,3,3-hexafluoro-2-propanol and chloroform (volume ratio 1 / 49) was used. Chloroform was used as the mobile phase, and a TSKgel SuperMultipore HZ-M column manufactured by Tosoh Corporation was used as the column. The measurement temperature was 40 °C. Standard polystyrene (Tosoh, PStQuickMP-M) was used as the molecular weight standard. Also, from the differential molecular weight distribution curve, the shoulder correlation parameter S represented by the above formula (1) was obtained. The vertical axis of the differential molecular weight distribution curve was set as dw / dLogM obtained by differentiating the concentration fraction w (%) with LogM. Figure 3(a) is a graph showing the measurement results of the differential molecular weight distribution curve in Example 1, and Figure 3(b) is an enlarged view of Figure 3(a). Also, Figure 4(a) is a graph showing the measurement results of the differential molecular weight distribution curve in Comparative Example 6, and Figure 4(b) is an enlarged view of Figure 4(a).

[0050] [b * Value The b value of PET resin pellets and preforms * was measured by an SM color computer (manufactured by Suga Test Instruments Co., Ltd.). The smaller the value, the better the color tone indicates. * The smaller the value, the better the color tone.

[0051] [Cold crystallization peak top temperature Tc1] Using 5 mg of PET resin pellets as a sample, the cold crystallization peak top temperature Tc1 was measured using a differential scanning calorimeter (PerkinElmer, Diamond DSC). The higher the cold crystallization peak top temperature, the better the molding stability of the PET resin pellets indicates. The measurement conditions were as follows. Step 1: Hold at 20°C for 5 minutes Step 2: Heat from 20°C to 290°C at a rate of 10°C / min Step 3: Hold at 290°C for 5 minutes Step 4: Cool from 290°C to 20°C at a rate of 300°C / min Step 5: Hold at 20°C for 10 minutes Step 6: Heat from 20°C to 290°C at a rate of 10°C / min Tc1 was determined from the peak top temperature (°C) of the cold crystallization peak in Step 6.

[0052] [Intrinsic viscosity recovery ΔIV] PET resin pellets were fed into a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM26SS), and melt extrusion was carried out under the conditions of an extrusion temperature of 290 °C, a screw rotation speed of 100 rpm, and a discharge rate of 10 kg / h. The molten resin discharged in a strand shape from the extruder was air-cooled while being conveyed by a belt conveyor, and then pelletized using a pelletizer. Next, these pellets were fed into the twin-screw extruder again, and melt extrusion was carried out under the same conditions as above except that a vacuum vent (9 Torr) was used, and pellet A was obtained. Pellet A was vacuum-dried at 120 °C for 2 hours, weighed 0.3 g, added to a mixed solvent of 1,1,2,2-tetrachloroethane and phenol (weight ratio 1 / 1), adjusted to a concentration of 1.00 g / dL, and stirred at 120 °C for 20 minutes to completely dissolve. The solution after dissolution was cooled to room temperature, and the relative viscosity was determined using a relative viscometer (Malvern Panalytical, Viscotec Y501C) thermostatically controlled at 30 °C, and the intrinsic viscosity A of pellet A was determined.

[0053] Next, for the above pellet A, crystallization treatment was carried out by heating at 1 Torr and 150 °C for 5 hours using a stirred vacuum dryer (manufactured by Dalton, 45MV). Then, using the above stirred vacuum dryer, the pellets after crystallization treatment were heated at 1 Torr and 225 °C for 13 hours to carry out solid-phase polymerization treatment, and pellet B was obtained. For pellet B, the relative viscosity was determined in the same procedure as for pellet A, and the intrinsic viscosity B of pellet B was determined. Using the intrinsic viscosity A and the intrinsic viscosity B, the intrinsic viscosity recovery ΔIV [dL / g] was determined based on the following formula. The larger the intrinsic viscosity recovery ΔIV, the higher the solid-phase polymerization efficiency when the molded product obtained from the PET resin pellets is recovered and recycled, indicating that the PET resin pellets are suitable for recycling. Intrinsic viscosity recovery ΔIV = Intrinsic viscosity B - Intrinsic viscosity A

[0054] Incidentally, since pellet A is obtained by performing the first melt extrusion treatment and the second melt extrusion treatment on PET resin pellets, pellet A corresponds to pellets produced by collecting a molded product (after the first melt extrusion treatment) obtained from PET resin pellets and performing extrusion molding (the second melt extrusion treatment). On the other hand, since pellet B is a pellet obtained by performing a crystallization treatment and a solid-phase polymerization treatment on pellet A, it corresponds to a pellet obtained by mechanically recycling a molded product obtained from PET resin pellets.

[0055] <Example 2> PET resin pellets of Example 1 were obtained in the same manner as in Example 1 and evaluated in the same manner, except that the first melt extrusion treatment, the second melt extrusion treatment, the crystallization treatment, and the solid-phase polymerization treatment were each additionally performed once. That is, the PET resin pellets of Example 2 are those in which the heat history control treatment was performed a total of two times on virgin pellets.

[0056] <Example 3> PET resin pellets were obtained in the same manner as in Example 1 and evaluated in the same manner, except that the total number of heat history control treatments on the pellets was three times.

[0057] <Comparative Examples 1 to 7> PET resin pellets were obtained in the same manner as in Example 1 and evaluated in the same manner, except that the total number of heat history control treatments on the pellets was set to 4 to 10 times, respectively. In Comparative Example 2 and Comparative Example 7, preforms were further manufactured using the obtained PET resin pellets, and the preforms were evaluated in the same manner as in Example 1.

[0058] <Reference Example> Pellets of an isophthalic acid copolymerized polyethylene terephthalate resin on which the heat history control treatment has not been performed at all were evaluated in the same manner as in Example 1. Also, preforms were obtained using pellets on which the heat history control treatment has not been performed, and evaluated in the same manner as in Example 1.

[0059]

Table 2

[0060] As shown in Table 2, the peak area (A) derived from all dicarboxylic acids measured using 1H-NMR acid ) for the peak area (A 7.5 ) ratio (A 7.5 / A acid The PET resin pellets of Examples 1 to 3 and the preforms molded therefrom have a b * The values ​​were small, the yellowish tinge was suppressed, and the color tone was excellent. In addition, the PET resin pellets and preforms of Examples 1 to 3 had high Tc1, and therefore had excellent molding stability. 7.5 / A acid The PET resin pellets of Comparative Examples 1 to 7, which had a value of 0.00060 or more, and the preforms molded using the pellets were inferior in color tone and molding stability.

Claims

1. A polyester resin containing, as a main component, a polyester containing diol units and dicarboxylic acid units, The ratio (A ａｃｉｄ / A ７．５ ) of the peak area (A ７．５ ) at 7.43 to 7.55 ppm to the peak area (A ａｃｉｄ ) derived from all dicarboxylic acids measured using 1H-NMR is less than 0.00060, and the polyester resin is characterized by this.

2. The ratio (A ７．８ / A ａｃｉｄ ) of the peak area (A ７．８ ) at 7.75 to 7.86 ppm to the peak area (A ａｃｉｄ ) derived from all dicarboxylic acids measured using 1H-NMR is less than 0.00030, and the polyester resin according to claim 1 is characterized by this.​​​​​​​​

3. A molded article made from the polyester resin according to Claim 1 or 2.

4. A preform made from the polyester resin according to Claim 1 or 2.

5. A polyester bottle made from the polyester resin according to Claim 1 or 2.

6. The polyester resin according to Claim 1 or 2, wherein the polyester resin is a mechanically recycled polyester resin.

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