Plasticizer composition and resin composition containing the same

Abstract

The present invention relates to a plasticizer composition, which comprises 2-ethylhexyl (2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate, and is characterized in that the content of the 2-ethylhexyl (2-hydroxyethyl) terephthalate is 20% by weight or less based on the total weight of the plasticizer composition. The plasticizer composition can improve mechanical properties, migration resistance, and heat loss properties when applied to a resin.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0024953 filed on February 25, 2022, and all the contents disclosed in the literature of the Korean Patent Application are incorporated herein by reference in their entirety.

[0002] The present invention relates to a plasticizer composition containing 2-ethylhexyl (2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate, and a resin composition containing the same.

Background Art

[0003] Generally, plasticizers are formed by the reaction of alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. Also, considering the domestic and international regulations on phthalate-based plasticizers harmful to the human body, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plasticizers has been continuously carried out.

[0004] On the other hand, regardless of the plastisol industry, calendering industry, and extrusion / injection compounding industry that manufacture finished products such as floor materials, wallpapers, soft and hard sheets, gloves, wires, hoses, and films, the need for such environmentally friendly products is increasing. In order to enhance the quality characteristics, processability, and productivity of finished products for each type, suitable plasticizers must be used considering discoloration and migration properties, mechanical physical properties, etc.

[0005] Depending on properties such as tensile strength, elongation rate, light resistance, migration property, gelling property, or absorption rate, which are characteristics required for each industry in such various usage areas, auxiliary raw materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers, and foaming agents are blended with PVC resins.

[0006] For example, when using di(2-ethylhexyl) terephthalate (DEHTP), a relatively inexpensive and widely used plasticizer composition applicable to PVC, the resulting material exhibited high hardness or sol viscosity, relatively slow absorption rates, and poor migration and stress migration properties.

[0007] As a solution, one could consider using a composition containing DEHTP, specifically the product of a transesterification reaction with butanol, as a plasticizer. However, while this improves plasticization efficiency, it results in a slight decrease in mechanical properties and a chronic problem of plasticizer leakage due to heat or physical force.

[0008] Furthermore, in recent years, ensuring environmental friendliness has become extremely important. This includes not only the environmental friendliness of the final product itself, but also ensuring environmental friendliness in the supply and demand of raw materials and in the manufacturing process. However, due to a conflict of interest with securing cost competitiveness, which is the primary challenge for industry, there is a need to develop products that are environmentally friendly in terms of raw materials, manufacturing processes, and final products, while also possessing cost competitiveness. [Overview of the Initiative] The problem the invention aims to solve

[0009] The present invention aims to provide a plasticizer composition that has performance equivalent to or better than conventional phthalate-based plasticizers, is free from reproductive and developmental toxicity, and is environmentally friendly, by applying a composition containing 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate obtained in the decomposition process of polyethylene terephthalate, to a plasticizer.

[0010] Furthermore, the present invention aims to provide a method for producing a plasticizer composition that is economical and environmentally friendly, and has excellent physical properties, by using discarded polyethylene terephthalate as a raw material. [Means for solving the problem]

[0011] To solve the above problems, the present invention provides a plasticizer composition, a method for producing the same, and a resin composition containing the plasticizer composition. (1) The present invention provides a plasticizer composition comprising 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate, wherein the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate is 20% by weight or less based on the entire plasticizer composition.

[0012] (2) The present invention provides the plasticizer composition described in (1) above, wherein the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate is 0.01 to 15% by weight.

[0013] (3) The present invention provides a plasticizer composition according to (1) or (2) above, wherein the weight ratio of 2-ethylhexyl(2-hydroxyethyl) terephthalate to di(2-ethylhexyl) terephthalate is 1:3 to 1:10000.

[0014] (4) The present invention provides a plasticizer composition according to any one of the above (1) to (3), wherein the weight ratio of 2-ethylhexyl(2-hydroxyethyl) terephthalate to di(2-ethylhexyl) terephthalate is 1:5 to 1:1000.

[0015] (5) The present invention provides a plasticizer composition according to any one of (1) to (4) above, further comprising a condensate of di(2-hydroxyethyl) terephthalate and 2-ethylhexyl(2-hydroxyethyl) terephthalate.

[0016] (6) The present invention provides a plasticizer composition according to any one of the above (1) to (5), further comprising one or more dimeric compounds represented by the following chemical formulas 1 to 3.

[0017] [ka]

[0018]

Chem.

[0019]

Chem.

[0020] (7) In the present invention, there is provided the plasticizer composition according to (6) above, wherein the total content of the dimer compound in the composition is 2.0 to 20.0% by weight.

[0021] (8) In the present invention, there is provided the plasticizer composition according to (6) or (7) above, wherein the content of the dimer compound represented by Chemical Formula 1 in the composition is 0.01 to 1% by weight.

[0022] (9) In the present invention, there is provided the plasticizer composition according to any one of (6) to (8) above, wherein the content of the dimer compound represented by Chemical Formula 3 in the composition is 0.3 to 2.5% by weight.

[0023] (10) In the present invention, there is provided the plasticizer composition according to any one of (6) to (9) above, wherein the weight ratio of the dimer compound to 2-ethylhexyl (2-hydroxyethyl) terephthalate in the composition is 1:0.001 to 5.

[0024] (11) In the present invention, there is provided the plasticizer composition according to any one of (6) to (10) above, wherein the weight ratio of the dimer compound to di(2-ethylhexyl) terephthalate in the composition is 1:2.0 to 99.0.

[0025] (12) The present invention provides a method for producing a plasticizer composition comprising the step of mixing polyethylene terephthalate and 2-ethylhexanol under a catalyst to carry out an esterification reaction, wherein the product of the esterification reaction comprises 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate.

[0026] (13) The present invention provides a method for producing the plasticizer composition described in (12), wherein the polyethylene terephthalate is mixed in an amount of 80% by weight or less relative to the total content of polyethylene terephthalate and 2-ethylhexanol.

[0027] (14) The present invention provides a method for producing the plasticizer composition described in (12) or (13), wherein the polyethylene terephthalate includes discarded and recycled polyethylene terephthalate.

[0028] (15) The present invention provides a resin composition comprising 100 parts by weight of a resin and 5 to 150 parts by weight of the plasticizer composition described in (1) above, wherein the resin is one or more selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, polylactic acid, natural rubber, and synthetic rubber. [Effects of the Invention]

[0029] The plasticizer composition according to one embodiment of the present invention is an environmentally friendly substance that is non-reproductive and developmental toxic, and when used in a resin composition, it can improve mechanical properties, migration resistance, stress migration resistance, and absorption rate compared to conventional plasticizers. Such a top-down manufacturing method is environmentally friendly and highly cost-competitive because it utilizes waste. [Modes for carrying out the invention]

[0030] The terms and words used in this specification and in the claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather in a manner consistent with the technical idea of ​​the present invention, in accordance with the principle that inventors may appropriately define the concepts of terms in order to best describe their invention.

[0031] Definition of Terms As used herein, the term “composition” includes not only reaction products and decomposition products formed from the materials of the composition, but also mixtures of materials containing the composition.

[0032] The "straight vinyl chloride polymer" used herein is a type of vinyl chloride polymer that is polymerized by suspension polymerization or bulk polymerization. This polymer is a porous particle with multiple pores, has a size of tens to hundreds of micrometers, is non-aggregating, and has excellent fluidity.

[0033] The "paste vinyl chloride polymer" used herein is a type of vinyl chloride polymer that is polymerized by methods such as fine suspension polymerization, fine seed polymerization, or emulsion polymerization. This polymer consists of fine, dense particles with no voids, ranging in size from tens to thousands of nanometers, exhibiting cohesiveness and poor fluidity.

[0034] The terms “contains,” “has,” and their derivatives are not intended to exclude the existence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any uncertainty, all compositions claimed by the use of the term “contains” may contain any additional additives, auxiliaries, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially composed of” excludes any other components, steps, or procedures from the scope of any consecutive description, except those not essential to the operation. The term “composed of” excludes any components, steps, or procedures not specifically described or enumerated.

[0035] Measurement method In this specification, the content analysis of components in the composition is performed by gas chromatography, using an Agilent gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL / min), detector: FID, injection volume: 1 uL, initial value: 70°C / 4.2 min, final value: 280°C / 7.8 min, program rate: 15°C / min).

[0036] In this specification, "tensile strength" is calculated according to the ASTM D638 method using a UTM test instrument (manufacturer: Instron, model name: 4466), by pulling the specimen at a cross head speed of 200 mm / min (1T), measuring the point at which the specimen breaks, and then calculating it using the following formula 1.

[0037] [Formula 1] Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0038] In this specification, the "elongation rate" is calculated using the following formula 2, after measuring the point at which the test specimen breaks, using the UTM described above, in accordance with the ASTM D638 method, by pulling the specimen with a cross head speed of 200 mm / min (1T).

[0039] [Formula 2] Elongation rate (%) = Length after elongation / Initial length × 100

[0040] In this specification, "migration loss" can be measured in accordance with KSM-3156. Specifically, a 1 mm thick test specimen is obtained, absorbent paper capable of absorbing organic matter that migrates and flows onto the surface is attached to both sides of the specimen, and then a plate large enough to cover the entire specimen is attached on top of that, and the measurement is 1 kgf / cm². 2 The load is applied. The test specimen is placed in a hot air circulating oven (80°C) for 72 hours, then removed and allowed to cool at room temperature for 4 hours. After removing the plates and absorbent paper attached to both sides of the test specimen, the weight of the test specimen is measured before and after being placed in the oven, and the amount of transfer loss is calculated using the following formula 3.

[0041] [Formula 3] Transfer loss (%) = {[(Initial specimen weight) - (Specimen weight after being left in the oven)] / (Initial specimen weight)} × 100

[0042] In this specification, "volatile loss" is defined as measuring the weight of a test specimen after working with it at 80°C for 72 hours.

[0043] [Formula 4] Weight loss due to heating (%) = {[(Initial weight of test specimen) - (Weight of test specimen after processing)] / (Initial weight of test specimen)} × 100

[0044] In the various measurement conditions described above, the detailed conditions such as temperature, rotation speed, and time may vary slightly depending on the circumstances. If they differ, the measurement method and conditions will be clearly indicated separately.

[0045] In this specification, "absorption rate" is evaluated by measuring the time it takes for the resin and plasticizer to be mixed together and for the mixer torque to stabilize, using a planetary mixer (Brabender, P600) under conditions of 77°C and 60 rpm.

[0046] In the various measurement conditions described above, the detailed conditions such as temperature, rotation speed, and time may vary slightly depending on the circumstances. If they differ, the measurement method and conditions will be clearly indicated separately. The present invention will be described in more detail below to aid in understanding it.

[0047] Plasticizer composition The present invention provides a plasticizer composition comprising 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate, wherein the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate is 20% by weight or less based on the entire plasticizer composition.

[0048] The plasticizer composition containing 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate is obtained from the product produced by the esterification reaction of polyethylene terephthalate (hereinafter referred to as PET) with 2-ethylhexanol.

[0049] Generally, PET and 2-ethylhexanol are reacted to obtain di(2-ethylhexyl) terephthalate, which is used as a conventional general-purpose plasticizer. However, a large amount of byproducts are generated, and in the case of bis(2-hydroxyethyl) terephthalate and 2-ethylhexyl(2-hydroxyethyl) terephthalate, which are produced during the reaction process, separation from di(2-ethylhexyl) terephthalate is not easy. Furthermore, since bis(2-hydroxyethyl) terephthalate and 2-ethylhexyl(2-hydroxyethyl) terephthalate are alcohol compounds containing a hydroxyl group in their intramolecular structure, they can cause side reactions with the target product, di(2-ethylhexyl) terephthalate, which presents another problem. Therefore, almost all manufacturers use the direct esterification reaction of terephthalic acid and 2-ethylhexanol or the transesterification reaction of dimethyl terephthalate and 2-ethylhexanol as methods for producing di(2-ethylhexyl) terephthalate, and a method using PET as a raw material has not been established.

[0050] However, the present invention focuses on the function of 2-ethylhexyl(2-hydroxyethyl) terephthalate, which has conventionally been targeted for removal as an impurity. By not removing it, but rather including it in a certain content within the plasticizer composition, it has been confirmed that a plasticizer composition with improved performance compared to conventional plasticizer products can be provided. Although 2-ethylhexyl(2-hydroxyethyl) terephthalate is not easily separated from di(2-ethylhexyl) terephthalate, it possesses the pressure transfer properties of di(2-ethylhexyl) terephthalate, that is, it has the function of solving the problem of plasticizer leakage due to heat and pressure. In particular, due to the presence of hydroxyl groups in its molecular structure, 2-ethylhexyl(2-hydroxyethyl) terephthalate can bond even more firmly with the resin it is mixed with, and can play a role in retaining di(2-ethylhexyl) terephthalate, the main component in the plasticizer composition, so that it is not discharged outside the resin.

[0051] According to one embodiment of the present invention, the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate may be 20% by weight or less based on the entire plasticizer composition. For example, the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate is 0.01% by weight or more, 0.05% by weight or more, 0.06% by weight or more, 0.08% by weight or more, 0.10% by weight or more, 0.50% by weight or more, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, 4.0% by weight or more, 4.5% by weight or more, 4.9% by weight or more, 5.0% by weight or more, 5.5% by weight or more, 6.0% by weight or more, 6.5% by weight or more, 7.0% by weight or more, 7.1% by weight or more, 7.2% by weight or more, 7.5% by weight or more, 8.0% by weight or more, 20.0% by weight or less, 19.5% by weight or less, 19.0% by weight or less, 18.0% by weight or less, 17.0% by weight or less, 16.0% by weight or less, based on the total plasticizer composition. It may also be 15.0% by weight or less, 14.9% by weight or less, 14.5% by weight or less, 13.0% by weight or less, 12.8% by weight or less, 12.5% ​​by weight or less, 12.4% by weight or less, 12.0% by weight or less, 11.7% by weight or less, 11.5% by weight or less, 11.3% by weight or less, 11.0% by weight or less, 10.5% by weight or less, 10.0% by weight or less, 9.5% by weight or less, 9.3% by weight or less, 8.0% by weight or less, 8.5% by weight or less, 8.0% by weight or less, 7.5% by weight or less, 7.2% by weight or less, 7.0% by weight or less, 6.5% by weight or less, 6.0% by weight or less, 5.5% by weight or less, 5.0% by weight or less, 4.5% by weight or less, 4.0% by weight or less, 3.5% by weight or less, 3.0% by weight or less, 2.5% by weight or less, or 2.0% by weight or less. Preferably, the terephthalate content may be 0.01 to 15% by weight based on the entire plasticizer composition. The weight ratio of 2-ethylhexyl(2-hydroxyethyl) terephthalate to di(2-ethylhexyl) terephthalate may be 1:3 to 10000, preferably 1:5 to 1:2000, or 1:5 to 1:1000.If the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate in the plasticizer composition is excessively low, the aforementioned improvement in the migration resistance of 2-ethylhexyl(2-hydroxyethyl) terephthalate will be minimal. Conversely, if the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate is excessively high, the relatively low content of di(2-ethylhexyl) terephthalate will result in poor heat loss and an excessively fast absorption rate, leading to instability in the compounding with the resin and the process conditions of the finished product. This can reduce the overall heat resistance of the resin composition or the finished product obtained from the resin composition. In particular, if 2-ethylhexyl(2-hydroxyethyl) terephthalate is included as the major component in the plasticizer composition, the relatively low molecular weight of 2-ethylhexyl(2-hydroxyethyl) terephthalate may make compounding with the resin difficult, potentially causing problems such as difficulties in the rolling process after compounding. When the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate satisfies the aforementioned preferred range, suitable heat loss and absorption rate can be achieved, thus providing a plasticizer composition that is excellent in heat resistance and can be stably incorporated into resin compositions.

[0052] On the other hand, polyethylene terephthalate contains trace amounts of isophthalate, an isomer of terephthalate, within its molecular structure, and such isophthalate structures can form di(2-ethylhexyl) isophthalate through the esterification reaction process described above. In conventional reaction processes for recovering di(2-ethylhexyl) terephthalate from PET, such di(2-ethylhexyl) isophthalate is considered an impurity, and all of it is removed from the final composition. However, in the present invention, we focused on the fact that when di(2-ethylhexyl) isophthalate is partially included in the plasticizer composition, superior physical properties can be achieved compared to when terephthalate alone is used, while maintaining a balance of physical properties. Based on this, we have derived a plasticizer composition in which di(2-ethylhexyl) isophthalate remains in the plasticizer composition without being removed.

[0053] Due to the low isophthalate content in the PET reaction material, the content of di(2-ethylhexyl) isophthalate in the plasticizer composition of the present invention obtained from PET is also at a low level, specifically, it may be 5% by weight or less, preferably 0.3 to 3% by weight, based on the entire composition. It is not easy to increase the content of di(2-ethylhexyl) isophthalate above the aforementioned range due to the structure of the PET reaction material, and when the content of di(2-ethylhexyl) isophthalate is lower than the aforementioned range, the improvement effect of di(2-ethylhexyl) isophthalate is minimal.

[0054] According to one embodiment of the present invention, the plasticizer composition of the present invention may further contain one or more dimeric compounds represented by the following chemical formulas 1 to 3.

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] In this invention, we have confirmed that by adjusting the content of a dimer compound with a (terephthalate or isophthalate)-(ethylene glycol)-(terephthalate or isophthalate) structure, which is one of the by-products, such as the aforementioned 2-ethylhexyl(2-hydroxyethyl) terephthalate, we can provide a plasticizer composition with improved performance compared to conventional plasticizer products. The isophthalate can be produced when recycled polyethylene terephthalate (PET) is used as a raw material in the manufacturing process of the plasticizer composition, and a small amount of high-purity isophthalic acid used during the production of this PET remains.

[0059] Such dimeric compounds can be produced in various forms and concentrations depending on the type of alcohol used and the reaction conditions in the depolymerization process of PET. When compounds with this structure are included in a plasticizer composition together with terephthalate-based plasticizers, they can complement the adhesion and migration properties of conventional terephthalate-based plasticizers.

[0060] For example, in the process of synthesizing the monomer di(2-ethylhexyl)terephthalate by the reaction of 2-ethylhexanol and PET, a dimer compound can be produced in which 2-ethylhexanol is bonded to each end of two terephthalic acids, and such a dimer compound can be included in the final plasticizer composition.

[0061] The aforementioned process of dimer compound formation is just one example; in addition to the formation process described above, various combinations of dimer compounds can be formed through various reactions between 2-ethylhexyl(2-hydroxyethyl) terephthalate and 2-ethylhexyl(2-hydroxyethyl) isophthalate.

[0062] Furthermore, the transesterification reaction can be intentionally controlled during the manufacturing process described above to adjust the content of di(2-ethylhexyl) terephthalate, 2-ethylhexyl(2-hydroxyethyl) and the dimer compound. On the other hand, when the reaction time is adjusted during the transesterification reaction process, a relatively large amount of by-products such as trimers and / or tetramer compounds, in addition to the dimer compound, may be produced depending on the reaction time. These by-products can be used as is in the plasticizer composition, as they do not degrade the aforementioned properties while maintaining the final workability of the entire plasticizer composition of di(2-ethylhexyl) terephthalate and 2-ethylhexyl(2-hydroxyethyl) terephthalate at a usable level.

[0063] Furthermore, the content of the dimer compound can be determined according to the amount of catalyst used in the manufacturing method, the amount of 2-ethylhexanol added, the reaction pressure and temperature, the reaction time, etc. In particular, the greater the amount of 2-ethylhexanol added, the lower the content of the condensate and dimer can be. In the plasticizer composition provided by the present invention, the total content of the dimer compound in the composition may be 2.0 to 20.0% by weight, and exemplary, the total content of the dimer compound in the composition may be 2.0% by weight or more, 3.0% by weight or more, 4.0% by weight or more, 5.0% by weight or more, 6.0% by weight or more, 7.0% by weight or more, 8.0% by weight or more, 20.0% by weight or less, 19.0% by weight or less, 18.0% by weight or less, 17.0% by weight or less, 16.0% by weight or less, 15.0% by weight or less, 14.0% by weight or less, 13.0% by weight or less, or 12.0% by weight or less. Preferably, the total content of the dimer compound in the composition may be 2.0 to 15.0% by weight. When the content of the dimer compound is controlled within the above range, it is possible to provide a plasticizer composition that has equivalent or better migration resistance and heat loss characteristics compared to conventional plasticizer products, and that is excellent in mechanical properties such as tensile strength and tensile residual ratio, as well as stress resistance characteristics.

[0064] Furthermore, the compounds represented by chemical formulas 1 to 3 may be present simultaneously in the plasticizer composition. In the plasticizer composition provided by the present invention, the content of the dimer compound represented by chemical formula 1 in the composition may be 0.01 to 1.0% by weight, the content of the dimer compound represented by chemical formula 2 may be 1.5 to 17.0% by weight, and the content of the dimer compound represented by chemical formula 3 may be 0.3 to 2.5% by weight.

[0065] Specifically, the content of the dimer compound represented by chemical formula 1 may be 0.01% by weight or more, 0.02% by weight or more, 0.03% by weight or more, 0.04% by weight or more, 0.05% by weight or more, 0.10% by weight or more, 0.20% by weight or more, 0.30% by weight or more, 0.40% by weight or more, 1.0% by weight or less, 0.90% by weight or less, 0.80% by weight or less, 0.70% by weight or less, 0.60% by weight or less, or 0.50% by weight or less.

[0066] Furthermore, the content of the dimer compound represented by chemical formula 2 may be 1.5% by weight or more, 1.7% by weight or more, 1.8% by weight or more, 2.0% by weight or more, 2.5% by weight or more, 2.7% by weight or more, 3.0% by weight or more, 3.5% by weight or more, 3.7% by weight or more, 4.0% by weight or more, 5.0% by weight or more, 17.0% by weight or less, 16.0% by weight or less, 15.0% by weight or less, 14.0% by weight or less, 13.0% by weight or less, 12.0% by weight or less, 11.0% by weight or less, 10.0% by weight or less, 9.0% by weight or less, 8.0% by weight or less, 7.0% by weight or less, or 6.0% by weight or less.

[0067] Furthermore, the content of the dimer compound represented by chemical formula 3 may be 0.3% by weight or more, 0.4% by weight or more, 0.5% by weight or more, 0.7% by weight or more, 1.0% by weight or more, 1.1% by weight or more, 1.2% by weight or more, 1.3% by weight or more, 1.5% by weight or more, 2.5% by weight or less, 2.4% by weight or less, 2.3% by weight or less, 2.1% by weight or less, 2.0% by weight or less, 1.7% by weight or less, 1.5% by weight or less, 1.3% by weight or less, 1.2% by weight or less, or 1.1% by weight or less.

[0068] When the content of each of the dimer compounds represented by the chemical formulas 1 to 3 satisfies the aforementioned range, it can have the effect of improving the workability with resins, specifically in terms of migration resistance and heat loss.

[0069] Furthermore, the weight ratio of the dimer compound to 2-ethylhexyl(2-hydroxyethyl) terephthalate in the composition may be 1:0.001 to 5.0, and exemplary ratios may be 1:0.01 or more, 0.02 or more, 0.05 or more, 0.1 or more, 0.2 or more, 0.5 or more, 0.7 or more, 1.0 or more, 1.5 or more, 5.0 or less, 4.7 or less, 4.5 or less, 4.2 or less, 4.0 or less, 3.7 or less, 3.5 or less, 3.2 or less, 3.0 or less, 2.7 or less, 2.5 or less, 2.3 or less, 2.0 or less, 1.7 or less, 1.5 or less, 1.2 or less, 1.0 or less, and 0.8 or less. Preferably, the weight ratio of the dimer compound to 2-ethylhexyl(2-hydroxyethyl) terephthalate may be 1:0.01 to 0.8. When the weight ratio of the dimer compound to 2-ethylhexyl(2-hydroxyethyl) terephthalate in the plasticizer composition satisfies the aforementioned range, the effect of improving migration resistance can be excellent, heating loss and absorption rate can be excellent, compounding with the resin and the rolling process after compounding can be carried out smoothly, and process stability can be increased.

[0070] Furthermore, the weight ratio of the dimer compound to di(2-ethylhexyl) terephthalate in the composition may be 1:2.0 to 99.0, and for example, it may be 1:2.0 or more, 2.5 or more, 2.7 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more, 6.0 or more, 7.0 or more, 9.0 or more, 10.0 or more, 12.0 or more, 15.0 or more, 20.0 or more, 25.0 or more, 27.0 or more, 30.0 or more, 35.0 or more, 99.0 or less, 95.0 or less, 92.0 or less, 90.0 or less, 85.0 or less, 80.0 or less, 75.0 or less, 70.0 or less, 65.0 or less, 60.0 or less, 55.0 or less, 50.0 or less, 45.0 or less, or 40.0 or less. Preferably, the weight ratio of the dimer compound to di(2-ethylhexyl) terephthalate in the composition may be 1:2.7 to 45. When the ratio of the dimer compound to di(2-ethylhexyl) terephthalate is within the range described above, the improvement in migration resistance achieved by including the dimer compound in the plasticizer composition can be maximized.

[0071] A hydrogenation method can be applied to the plasticizer composition of the present invention. The present invention provides a plasticizer composition comprising 2-ethylhexyl(2-hydroxyethyl)cyclohexane-1,4-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, wherein the content of 2-ethylhexyl(2-hydroxyethyl)cyclohexane-1,4-dicarboxylate is 20% by weight or less based on the entire plasticizer composition. Furthermore, the plasticizer composition may further contain hydrides of the dimer compounds represented by the chemical formulas 1 to 4.

[0072] The plasticizer composition containing the aforementioned 2-ethylhexyl(2-hydroxyethyl)cyclohexane-1,4-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate is obtained by hydrogenating the product produced by the transesterification reaction of polyethylene terephthalate (hereinafter referred to as PET) with 2-ethylhexanol, and the order of the transesterification and hydrogenation reactions may be changed. The product includes the aforementioned 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate, and may further contain the dimer compounds of chemical formulas 1 to 4.

[0073] The aforementioned plasticizer composition eliminates environmental problems and significantly improves migration and weight loss characteristics, making it possible to create products with significantly improved light resistance and heat resistance compared to conventional commercial products.

[0074] Method for producing a plasticizer composition The present invention provides a method for producing the plasticizer composition described above. Specifically, the present invention includes a method for producing a plasticizer composition comprising the step of mixing polyethylene terephthalate and 2-ethylhexanol under a catalyst to carry out an esterification reaction, wherein the product of the esterification reaction includes 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate. Furthermore, the product may further contain one or more of the dimeric compounds represented by the aforementioned chemical formulas 1 to 3.

[0075] The aforementioned PET and 2-ethylhexanol are converted into a composition containing the three components by a transesterification reaction. Specifically, PET is represented by the following chemical formula a.

[0076] [ka]

[0077] In the transesterification reaction of PET and 2-ethylhexanol, 2-ethylhexanol reacts with the ester groups present in PET, unchaining the polymerization chain of PET. The proportions of the two components can be adjusted by controlling the reaction, and it is important to adjust not only the proportions of the three components but also the proportion of the dimer compound within the aforementioned range to achieve an optimal balance.

[0078] The PET may be present in an amount of 80% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight, 40% by weight, or 35% by weight or less, relative to the total content with 2-ethylhexanol. When the PET content is within the aforementioned range, the amount of 2-ethylhexanol added is sufficient, side reactions can be minimized, and the transesterification reaction between the target PET and 2-ethylhexanol can be maximized. In particular, when the PET content is within the aforementioned range, the composition obtained through the manufacturing process satisfies the aforementioned preferred content conditions, which has the advantage of minimizing post-processing after the manufacturing process and allowing for the immediate production of a plasticizer composition with excellent physical properties.

[0079] On the other hand, the PET may contain 50% or more by weight of waste PET, preferably 60% or more by weight, and more preferably 70% or more by weight. Since the proportion of components in the final product does not change even when waste PET is used, it is possible to use the entire amount of waste PET if it is possible to control the color of the plasticizer and the impurity content. Because waste PET is utilized in this way, it is highly cost-competitive compared to di(2-ethylhexyl) terephthalate produced from terephthalic acid or dimethyl terephthalate, and it can prevent the energy consumption and environmental pollution used in the production of terephthalic acid and dimethyl terephthalate, thus making a significant contribution to environmental improvement.

[0080] In a manufacturing method according to one embodiment of the present invention, by-products generated during the reaction, such as ethylene glycol, are recovered outside the system, although a portion of it may be left in the reaction system. By keeping a portion of the ethylene glycol in the reaction system to participate in the reaction, a suitable level of 2-ethylhexyl(2-hydroxyethyl) terephthalate and the dimer compounds of chemical formulas 1 to 3 can be formed from the ethylene glycol remaining in the reaction system. Since the 2-ethylhexyl(2-hydroxyethyl) terephthalate and the dimer compounds of chemical formulas 1 to 3 contribute to improving the performance of the plasticizer composition, there is no need to consume additional energy to remove the formed 2-ethylhexyl(2-hydroxyethyl) terephthalate and the dimer compounds of chemical formulas 1 to 3, and the manufacturing process can be operated economically. In particular, since ethylene glycol is used as a reactant to form the 2-ethylhexyl(2-hydroxyethyl) terephthalate and the dimer compounds of chemical formulas 1 to 3, the content of ethylene glycol in the final composition is naturally extremely low, and the separation process can be simplified, which is an advantage.

[0081] The catalyst may be one or more selected from, for example, acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and alkylsulfuric acid; metal salts such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride, and aluminum phosphate; metal oxides such as heteropoly acids; natural / synthetic zeolites; cation and anion exchange resins; catalysts containing choline compounds such as choline hydroxide, choline bicarbonate, choline chloride, choline bitartrate, choline dihydrogen citrate, and choline sulfate; organometallic compounds such as alkyl titanates or polymers thereof, such as tetraalkyl titanate; and organometallic compounds containing zirconium or tin. Preferably, tetraalkyl titanate may be used as the catalyst.

[0082] The amount of catalyst used may vary depending on the type. For example, in the case of a homogeneous catalyst, it may be in the range of 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight relative to 100% by weight of the total reactants. In the case of a heterogeneous catalyst, it may be in the range of 5 to 200% by weight, 5 to 100% by weight, 20 to 200% by weight, or 20 to 150% by weight relative to the total amount of reactants.

[0083] According to one embodiment of the present invention, the transesterification reaction is preferably carried out at a reaction temperature of 120°C to 240°C, preferably 135°C to 230°C, more preferably 141°C to 220°C, for 10 minutes to 12 hours, preferably 30 minutes to 10 hours, and more preferably 1 to 8 hours. When the temperature and time are within the aforementioned range, the component ratio of the final plasticizer composition can be efficiently controlled. In this case, the reaction time can be calculated from the point in time when the reaction temperature is reached after the heating of the reactants.

[0084] Furthermore, the process may further include a step to remove unreacted 2-ethylhexanol and reaction by-products such as ethylene glycol after the transesterification reaction is complete. In the case of ethylene glycol, since it has high solubility in water, it can be removed after the reaction is complete through a neutralization and washing process, and after neutralization and washing, residual 2-ethylhexanol can be removed by extractive distillation. By the steps described above, a plasticizer composition that satisfies the desired components and composition ratio can be produced.

[0085] According to another embodiment of the present invention, a resin composition comprising the aforementioned plasticizer composition and resin is provided. As the resin, resins well known in the field may be used. For example, one or more mixtures selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, polylactic acid, natural rubber, synthetic rubber, and thermoplastic elastomer may be used, but are not limited thereto.

[0086] The plasticizer composition may be included in an amount of 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight, based on 100 parts by weight of the resin.

[0087] Generally, resins using plasticizer compositions can be manufactured into resin products by melt processing or plastisol processing, and the melt-processed resins and plastisol-processed resins may be produced in different ways depending on the polymerization method.

[0088] For example, when vinyl chloride polymers are used in melt processing, they are manufactured by methods such as suspension polymerization, and solid resin particles with a large average particle size are used. Such vinyl chloride polymers are called straight vinyl chloride polymers. When used in plastisol processing, they are manufactured by methods such as emulsion polymerization, and resin in a sol state is used as fine resin particles. Such vinyl chloride polymers are called paste vinyl chloride resins.

[0089] In this case, the plasticizer is preferably included in an amount of 5 to 80 parts by weight per 100 parts by weight of the polymer in the case of the straight vinyl chloride polymer, and preferably in an amount of 40 to 120 parts by weight per 100 parts by weight of the polymer in the case of the paste vinyl chloride polymer.

[0090] The resin composition may further contain a filler. The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin.

[0091] The filler may be any filler well known in the art, and is not particularly limited. For example, it may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, hard carbon, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate, and barium sulfate.

[0092] Furthermore, the resin composition may optionally contain other additives such as stabilizers. Each of these other additives may, for example, be in the amount of 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.

[0093] The stabilizer may be, for example, a calcium-zinc (Ca-Zn) stabilizer such as calcium-zinc complex stearate or a barium-zinc (Ba-Zn) stabilizer, but is not particularly limited thereto.

[0094] As described above, the resin composition can be applied to both melt processing and plastisol processing. For example, melt processing can be performed using calendering, extrusion, or injection molding, and plastisol processing can be performed using coating, etc.

[0095] Examples The present invention will be described in detail below with reference to examples. However, the examples of the present invention may be modified into various different forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to give a more complete explanation of the present invention to a person of average knowledge in the industry.

[0096] Example 1 In a reactor equipped with a stirrer, condenser, and decanter, 1.5 g of catalyst TnBT, 500 g of discarded polyethylene terephthalate, and 1220 g of 2-ethylhexanol were added, and the trans-esterification reaction was carried out under a nitrogen atmosphere at a reaction temperature of 150-230°C for 3-8 hours. After the reaction was complete, unreacted 2-ethylhexanol was removed by reducing the pressure. Then, 100 g of 3 wt% aqueous sodium hydroxide solution was added to neutralize the catalyst, and a small amount of unreacted 2-ethylhexanol was removed by distillation. Through the above process, compositions containing 12.4 wt%, 2.1 wt%, and 71 wt% of 2-hydroxyethyl(2-ethylhexyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate (DEHTP) were obtained. The remaining components of the composition, excluding the three components mentioned above, included by-products generated during the reaction process, which contained dimeric compounds in the amounts shown in Table 1 below.

[0097] Example 2 The procedure was carried out in the same manner as in Example 1, but by adjusting the amount of 2-ethylhexanol added and the reaction time, compositions containing 7.2% by weight, 2% by weight, and 78.5% by weight of 2-hydroxyethyl(2-ethylhexyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate (DEHTP) were obtained. The remaining components of the composition, excluding the three components mentioned above, consisted of by-products generated during the reaction process, and these by-products contained dimeric compounds in the amounts shown in Table 1 below.

[0098] Example 3 The procedure was carried out in the same manner as in Example 1, but by adjusting the amount of 2-ethylhexanol added and the reaction time, compositions containing 4.9% by weight, 1.75% by weight, and 90.3% by weight of 2-hydroxyethyl(2-ethylhexyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate (DEHTP) were obtained. The remaining components of the composition, excluding the three components mentioned above, consisted of by-products generated during the reaction process, and these by-products contained dimeric compounds in the amounts shown in Table 1 below.

[0099] Example 4 The procedure was carried out in the same manner as in Example 1, but by adjusting the amount of 2-ethylhexanol added and the reaction time, compositions containing 0.06% by weight, 1.9% by weight, and 95.8% by weight of 2-hydroxyethyl(2-ethylhexyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate (DEHTP) were obtained. The remaining components of the composition, excluding the three components mentioned above, consisted of by-products generated during the reaction process, and these by-products contained dimeric compounds in the amounts shown in Table 1 below.

[0100] Example 5 The procedure was carried out in the same manner as in Example 1, but by adjusting the amount of 2-ethylhexanol added and the reaction time, compositions containing 19.1% by weight, 2% by weight, and 58.9% by weight of 2-hydroxyethyl(2-ethylhexyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate (DEHTP) were obtained. The remaining components of the composition, excluding the three components mentioned above, consisted of by-products generated during the reaction process, and these by-products contained dimeric compounds in the amounts shown in Table 1 below.

[0101] Comparative Example 1 Di(2-ethylhexyl) phthalate (DEHP), manufactured by LG Chem, was used as the plasticizer composition.

[0102] Comparative Example 2 The procedure was carried out in the same manner as in Example 1, but 1400g of 2-ethylhexanol was added to remove all of the 2-hydroxyethyl(2-ethylhexyl) terephthalate from the composition, obtaining a composition containing 99.9% by weight of di(2-ethylhexyl) terephthalate (DEHTP).

[0103] Comparative Example 3 The procedure was carried out in the same manner as in Example 1, but by adjusting the amount of 2-ethylhexanol added and the reaction time, a composition was obtained that did not contain 2-hydroxyethyl(2-ethylhexyl)terephthalate, but contained 2.1% by weight of di(2-ethylhexyl)isophthalate and 96.7% by weight of di(2-ethylhexyl)terephthalate (DEHTP), respectively. The remaining components of the composition, excluding the aforementioned two components, consisted of by-products generated during the reaction process, and these by-products contained dimeric compounds in the amounts shown in Table 1 below.

[0104] Comparative Example 4 The procedure was carried out in the same manner as in Example 1, but by adjusting the amount of 2-ethylhexanol added and the reaction time, compositions containing 21.5% by weight, 1.5% by weight, and 55.2% by weight of 2-hydroxyethyl(2-ethylhexyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate (DEHTP) were obtained. The remaining components of the composition, excluding the three components mentioned above, consisted of by-products generated during the reaction process, and these by-products contained dimeric compounds in the amounts shown in Table 1 below.

[0105] [Table 1]

[0106] Experimental Example 1: Evaluation of Sheet Performance Using the plasticizers of the examples and comparative examples, test specimens were prepared in accordance with ASTM D638 under the following formulations and preparation conditions.

[0107] (1) Formulation: 100 parts by weight of straight vinyl chloride polymer (LS100), 50 parts by weight of plasticizer, and 3 parts by weight of stabilizer (BZ-153T) (2) Mixing: Mix at 98°C at 700 rpm (3) Preparation of test specimens: 1T to 3T sheets are prepared by operating a roll mill at 160°C for 4 minutes, and a press at 180°C for 2.5 minutes (low pressure) and 2 minutes (high pressure).

[0108] (4) Evaluation items 1) Tensile strength In accordance with the ASTM D638 method, a UTM (manufacturer: Instron, model name: 4466) was used to pull the 1T test specimen at a cross head speed of 200 mm / min, and the point at which the specimen broke was measured. The tensile strength was calculated as follows. Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0109] 2) Measurement of elongation rate: Following the ASTM D638 method, the UTM was used to pull the 1T specimen at a cross head speed of 200 mm / min. After measuring the point at which the specimen broke, the elongation was calculated as follows. The elongation rate (%) was calculated as: length after elongation / initial length × 100.

[0110] 3) Measurement of tensile strength and remaining elongation The tensile strength and elongation are measured by heating the test specimen at 100°C for 168 hours, and the measurement method is the same as that for measuring tensile strength and elongation.

[0111] 4) Measurement of migration loss Measurements were taken in accordance with KSM-3156. Specifically, a 1 mm thick test specimen was obtained, absorbent paper capable of absorbing organic matter that migrates and flows onto the surface was attached to both sides of the specimen, and then a plate large enough to cover the entire specimen was attached on top of that, and the temperature was measured at 1 kgf / cm². 2 A load was applied. The test specimen was placed in a hot air circulating oven (80°C) for 72 hours, then removed and allowed to cool at room temperature for 4 hours. After removing the plates and absorbent paper attached to both sides of the test specimen, the weight of the test specimen was measured before and after being placed in the oven, and the amount of transfer loss was calculated using the following formula 3. Transfer loss (%) = {(Initial weight of the specimen at room temperature - Weight of the specimen after being left in the oven) / Initial weight of the specimen at room temperature} × 100

[0112] 5) Measurement of loss on heating (volatile loss)The test specimens prepared as described above were worked at 80°C for 72 hours, and then their weight was measured. The weight loss due to heating (weight %) was calculated as follows: Initial weight of the test specimen - (Weight of the test specimen after 72 hours at 80°C) / Initial weight of the test specimen × 100.

[0113] 6) Stress test (stress tolerance) A 2mm thick test specimen was bent and left at 23°C for 168 hours. The degree of transition (exudation) was observed on days 1, 3, and 7, and the results are shown numerically. A value closer to 0 indicates superior stress resistance.

[0114] 7) Evaluation of carbonization characteristics A 0.25 mm thick test specimen was prepared to a size of 40 cm x 1 cm, and a carbonization test was performed in a Mathis Oven at 230°C and a rate of 5 mm / 10 sec. The time at which carbonization began and the specimen turned black was measured. Excellent carbonization characteristics meant that carbonization started relatively late, and poor carbonization characteristics meant that carbonization started relatively early. The degree of excellence was evaluated on a scale from 1 to 5, with 5 indicating excellent and 1 indicating poor.

[0115] 8) Measurement of absorption rate Under conditions of 73°C and 60 rpm, the processability was evaluated by measuring the time it took for the resin and plasticizer to be mixed together and for the mixer torque to stabilize using a planetary mixer (Brabender, P600).

[0116] (5) Evaluation results The evaluation results for the aforementioned items are shown in Tables 2 and 3 below.

[0117] [Table 2]

[0118] [Table 3]

[0119] Referring to Tables 2 and 3, Examples 1 to 5 showed superior results in terms of heat loss, mechanical properties, stress resistance, and carbonization characteristics compared to Comparative Example 1, which was a conventional phthalate-based plasticizer product. In other words, the plasticizer composition of the present invention, by applying both di(2-ethylhexyl) terephthalate and 2-ethylhexyl(2-hydroxyethyl) terephthalate, shows improvements in heat loss, stress resistance, and mechanical properties without a decrease in conventional properties. Generally, in the case of a composition in which two components are mixed, the effect of the mixed composition appears in a direction in which the effects of each component are diluted with each other. However, in the present invention, unlike this, the level of conventional properties is maintained, and improvements in stress resistance and mechanical properties are achieved. From this, it can be confirmed that the present invention achieves effects that cannot be predicted from the prior art.

[0120] On the other hand, Comparative Example 2 was manufactured from polyethylene terephthalate in the same manner as the examples of the present invention, but by using a larger amount of 2-ethylhexanol and undergoing further separation steps, etc., 2-ethylhexyl(2-hydroxyethyl) terephthalate was completely removed from the final composition. Although the cost of the manufacturing process was higher than that of Examples 1 to 5, the physical properties of the final plasticizer composition were at the same level as those of the plasticizer compositions of Examples 1 to 5, and in particular, the migration resistance, stress resistance, and mechanical properties were inferior to those of the examples. Furthermore, the absorption rate was also inferior to that of the examples. From this, it can be confirmed that the plasticizer composition of the present invention is cheaper to manufacture than conventional plasticizer compositions containing di(2-ethylhexyl) terephthalate recovered from polyethylene terephthalate, and also has superior functionality as a plasticizer.

[0121] On the other hand, Comparative Examples 3 and 4, while produced from polyethylene terephthalate in the same manner as the examples of the present invention, were plasticizer compositions in which the amount of 2-ethylhexanol added, reaction time, and purification process were adjusted, resulting in a content deviated from that of 2-ethylhexyl(2-hydroxyethyl) terephthalate and / or dimer compounds according to the present invention. As a result, their mechanical properties, migration loss, heat loss, and stress resistance were inferior to those of the aforementioned examples. This indicates that the plasticizer compositions of the present invention limit the content of each compound in order to maximize improvements in various physical properties such as mechanical properties, heat resistance, and migration resistance, and demonstrate superior functionality of the plasticizer itself compared to the plasticizers of Comparative Examples 3 and 4, which deviated from the content of 2-ethylhexyl(2-hydroxyethyl) terephthalate and / or dimer compounds.

Claims

1. It comprises 2-ethylhexyl (2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate, The content of the di(2-ethylhexyl) isophthalate is 0.3% by weight or more and 5.0% by weight or less based on the entire composition. A plasticizer composition in which the content of 2-ethylhexyl (2-hydroxyethyl) terephthalate is 0.01% by weight or more and 20% by weight or less based on the entire plasticizer composition.

2. The plasticizer composition according to claim 1, wherein the content of 2-ethylhexyl (2-hydroxyethyl) terephthalate is 0.01 to 15% by weight.

3. The plasticizer composition according to claim 1, wherein the weight ratio of 2-ethylhexyl (2-hydroxyethyl) terephthalate to di(2-ethylhexyl) terephthalate is 1:3 to 10000.

4. The plasticizer composition according to claim 3, wherein the weight ratio of 2-ethylhexyl (2-hydroxyethyl) terephthalate to di(2-ethylhexyl) terephthalate is 1:5 to 1000.

5. The plasticizer composition according to claim 1, further comprising one or more dimeric compounds represented by the following chemical formulas 1 to 3. 【Chemistry 1】

6. The plasticizer composition according to claim 5, wherein the total content of the dimer compound in the composition is 2.0 to 20.0% by weight.

7. The plasticizer composition according to claim 5, wherein the content of the dimer compound represented by chemical formula 1 in the composition is 0.01 to 1% by weight.

8. The plasticizer composition according to claim 5, wherein the content of the dimer compound represented by chemical formula 3 in the composition is 0.3 to 2.5% by weight.

9. The plasticizer composition according to claim 5, wherein the weight ratio of the dimer compound to 2-ethylhexyl(2-hydroxyethyl) terephthalate in the composition is 1:0.001 to 5.

10. The plasticizer composition according to claim 5, wherein the weight ratio of the dimer compound to di(2-ethylhexyl) terephthalate in the composition is 1:2.0 to 99.

0.

11. The process includes the step of mixing polyethylene terephthalate and 2-ethylhexanol under catalytic conditions to carry out an esterification reaction. The product of the esterification reaction includes 2-ethylhexyl(2-hydroxyethyl) terephthalate, di(2-ethylhexyl) isophthalate, and di(2-ethylhexyl) terephthalate. The content of the di(2-ethylhexyl) isophthalate is 0.3% by weight or more and 5.0% by weight or less based on the entire composition. A method for producing a plasticizer composition, wherein the content of 2-ethylhexyl (2-hydroxyethyl) terephthalate is 0.01% by weight or more and 20% by weight or less based on the entire plasticizer composition.

12. The method for producing the plasticizer composition according to claim 11, wherein the polyethylene terephthalate is mixed in an amount of 80% by weight or less relative to the total content of polyethylene terephthalate and 2-ethylhexanol.

13. The method for producing the plasticizer composition according to claim 11, wherein the polyethylene terephthalate includes discarded and recycled polyethylene terephthalate.

14. The material comprises 100 parts by weight of resin and 5 to 150 parts by weight of the plasticizer composition described in claim 1. The resin composition is one or more selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, polylactic acid, natural rubber, and synthetic rubber.

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