Plasticizer composition and vinyl chloride resin composition comprising the same

Abstract

The present invention relates to a plasticizer composition and a vinyl chloride resin composition comprising the same. Specifically, the present invention relates to a plasticizer composition having improved physical properties such as tensile strength, elongation, and migration resistance, and a vinyl chloride resin composition comprising the same.

Description

Technical Field

[0001] This invention relates to a plasticizer composition and a vinyl chloride resin composition comprising the plasticizer. Specifically, this invention relates to a plasticizer composition having improved physical properties, such as tensile strength, elongation, and migration resistance, and a vinyl chloride resin composition comprising the plasticizer. Cross-reference to related applications [ ]

[0002] This application claims the benefit of Korean Patent Application No. 10-2024-0191749, filed with the Korean Intellectual Property Office on December 19, 2024, the disclosure of which is incorporated herein by reference in its entirety. Prior Technology

[0003] Vinyl chloride (PVC) resin can be molded in various ways due to its rigidity and flexibility, and is suitable for a wide range of applications due to its high efficiency and excellent price competitiveness. Additives are typically used as auxiliary materials to facilitate the processing of PVC resin and improve the performance of the final product. Examples of such additives include plasticizers, stabilizers, fillers, and foaming agents, which are mixed during the resin manufacturing process to produce the final resin. Plasticizers, in particular, allow for the manufacture of various products by increasing the flexibility of the resin.

[0004] Plasticizers are classified into phthalate-based, epoxy resin-based, and polyester-based plasticizers according to their molecular structure. Among them, phthalate-based plasticizers are the most widely used and representative plasticizers due to their excellent compatibility with vinyl chloride resins and high plasticizing efficiency. Phthalate-based plasticizers are substances in which various alkyl groups are substituted into the phthalate structure. Examples of phthalate-based plasticizers include di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and dibutyl phthalate (DBP).

[0005] Despite these advantages, research shows that phthalate-based plasticizers are harmful to human health as endocrine disruptors and have been defined as hazardous substances, necessitating alternatives. Research into environmentally friendly plasticizers has begun to replace phthalate-based plasticizers. Representative examples include terephthalate-based plasticizers, epoxide-based plasticizers, vegetable oil-based plasticizers, cyclohexane-based plasticizers, and their mixtures. Among environmentally friendly plasticizers, dioctyl terephthalate (DOTP), based on terephthalic acid, is a common product. However, its harmfulness remains a concern, and in terms of quality, it cannot replace phthalate-based plasticizers.

[0006] Therefore, there is a need to develop an environmentally friendly plasticizer that is free from endocrine disruptors, is environmentally friendly, and does not degrade the physical properties of vinyl chloride resin. Summary of the Invention

[0007] [[] [Technical Issues] []] [ ]

[0008] One specific example of this disclosure provides a plasticizer composition and a vinyl chloride resin composition comprising the same.

[0009] Specifically, one particular example of this disclosure provides a plasticizer composition having excellent physical properties, such as tensile strength, elongation and migration resistance, and a vinyl chloride resin composition comprising the plasticizer.

[0010] [[] [Technical Solutions] []] [ ]

[0011] One specific example of this disclosure provides a plasticizer composition comprising: a trimellitate-based compound; a cyclohexane dicarboxylate-based compound; and a petroleum-free compound.

[0012] In addition, another specific example of this disclosure provides a vinyl chloride resin composition containing a plasticizer composition.

[0013] In addition, another specific example disclosed herein provides a vinyl chloride resin molding article comprising a vinyl chloride resin composition.

[0014] The terminology used herein is for the purpose of describing particular specific instances only and is not intended to limit the invention.

[0015] Unless the context clearly indicates otherwise, the singular form is intended to include the plural form as well.

[0016] It should be understood that the terms "comprise", "have" or "possess" as used in this specification specify the presence of the stated features, figures, steps, components or combinations thereof, but do not exclude the presence or addition of one or more other features, figures, steps, components or combinations thereof.

[0017] Since the present invention can be modified in various ways and has various forms, specific examples are shown by way of example and will be described in detail. However, it is not intended to limit the invention to the specific forms disclosed, and it should be understood that the invention includes all modifications, equivalents, and substitutions within the scope of the inventive concept and technology.

[0018] The present invention will be described in detail below.

[0019] The plasticizer composition according to the present invention comprises compounds based on trimellitate, compounds based on cyclohexane dicarboxylate, and non-petroleum-based compounds.

[0020] Compounds based on trimellitate can be represented by the following chemical formula 1. [Chemical Formula 1]

[0021] In chemical formula 1, R1 to R3 can each be independently selected from straight-chain or branched alkyl groups having 4 to 12 carbon atoms.

[0022] In chemical formula 1, R1 to R3 are each butyl, isobutyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, isononyl, 2-propylheptyl, decyl, or isodecyl.

[0023] According to one specific embodiment of the present invention, in the components of the plasticizer composition, the compound based on trimellitate can be a compound in which R1 to R3 are all 2-ethylhexyl. This compound has the following structure [Chemical Formula 1-1] and is trimellitate benzo(2-ethylhexyl) ester (TOTM). [Chemical Formula 1-1]

[0024] According to one specific embodiment of the present invention, in the components of the plasticizer composition, the mellitate-based compound may be a mellitate-based compound in which R1 to R3 are all isononyl. This compound has the following structure [Chemical Formula 1-2] and is triisononyl trimellitate (TINTM). [Chemical Formula 1-2]

[0025] According to one specific embodiment of the present invention, the compound based on hexamethyl benzoate may contain tans(2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), or a combination thereof.

[0026] Compounds based on cyclohexane dicarboxylic acid esters can be represented by the following chemical formula 2. [Chemical Formula 2]

[0027] In chemical formula 2, R4 and R5 can each be independently selected from straight-chain or branched alkyl groups having 4 to 12 carbon atoms.

[0028] Depending on the substitution position of the carboxylic acid ester group on cyclohexane, compounds represented by [Chemical Formula 2] can be represented by [Chemical Formula 2-1] to [Chemical Formula 2-3] below. [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3]

[0029] [Chemical Formula 2-1] is a compound based on cyclohexane-1,4-dicarboxylic acid ester, [Chemical Formula 2-2] is a compound based on cyclohexane-1,3-dicarboxylic acid ester, and [Chemical Formula 2-3] is a compound based on cyclohexane-1,2-dicarboxylic acid ester.

[0030] In addition, in chemical formulas 2-1 to 2-3, R6 to R11 are each independently butyl, isobutyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, isononyl, 2-propylheptyl, decyl, or isodecyl.

[0031] For example, in compounds based on cyclohexane-1,4-dicarboxylic acid esters, when R6 and R7 are the same, it can be di(butyl)cyclohexane-1,4-dicarboxylic acid ester, di(isononyl)cyclohexane-1,4-dicarboxylic acid ester, or similar; and when R6 and R7 are different, it can be butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylic acid ester, butyl(isononyl)cyclohexane-1,4-dicarboxylic acid ester, or similar.

[0032] According to one specific embodiment of the present invention, in the components of the plasticizer composition, the compound based on cyclohexane dicarboxylic acid ester may be a compound based on cyclohexane-1,4-dicarboxylic acid ester, wherein R6 and R7 are both 2-ethylhexyl. This compound has the following structure [chemical formula 2-4] and is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylic acid ester (DEHCH). [Chemical Formula 2-4]

[0033] According to one specific embodiment of the present invention, in the plasticizer composition, the compound based on cyclohexane dicarboxylate may include at least one of the following groups: di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, di(isononyl)cyclohexane-1,4-dicarboxylate, di(2-propylheptyl)cyclohexane-1,4-dicarboxylate, di(decyl)cyclohexane-1,4-dicarboxylate, and di(isodecyl)cyclohexane-1,4-dicarboxylate.

[0034] The non-petroleum-based compound that is one of the components of the plasticizer composition according to the present invention may be a compound having 14 to 22 carbon atoms and 3 to 8 chlorine atoms.

[0035] Specifically, non-petroleum-based compounds may be chlorinated bio-based oils. Chlorinated bio-based oils may include chlorinated vegetable oils, chlorinated animal oils, or chlorinated waste bio-based oils. Specifically, non-petroleum-based compounds may be chlorinated, alkyl ester-based compounds. For example, they may be compounds such as bio-based chlorinated paraffins, methyl 3-octyl ethylene oxide octanoate (CAS # 2566-91-8), or chlorinated fatty acids, animal fats, or Me esters (CAS # 68440-29-9).

[0036] Chlorinated vegetable oils may include those obtained by chlorinating vegetable oils such as soybean oil, castor oil, flaxseed oil, palm oil, pine oil, tung oil, grapeseed oil, olive oil, jojoba oil, poppy seed oil, cottonseed oil, rapeseed oil, wheat germ oil, peanut oil, walnut oil, and similar oils. Animal oils may include those obtained by chlorinating tallow, lard, lanolin, poultry oil, butter, whale oil, and similar oils. Additionally, waste bio-based oils refer to oils discarded after use in food cooking, which may be vegetable oils, animal oils, or both. For example, they may include waste cooking oils that can be recycled and chlorinated for reuse.

[0037] Chlorinated bio-based oils can be obtained by methods known in this technology that chlorinate ester-based compounds.

[0038] Currently, phthalate-based plasticizers, such as diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP), are mainly used in wire and cable compounds, thus necessitating the use of environmentally friendly plasticizers in industry. Compared to the conventionally used environmentally friendly plasticizer BIO-DEHCH, non-petroleum-based compounds exhibit excellent compatibility. Compared to phthalate-based plasticizers, which have endocrine disruptor issues, trimellitate-based compounds have a higher molecular weight, thus exhibiting relatively lower toxicity and excellent anti-volatility when used in wire and cable compounds.

[0039] Therefore, the plasticizer composition according to one specific example of this disclosure can improve physical properties, such as tensile strength, elongation and migration resistance, by including compounds based on trimellitate, non-petroleum-based compounds and compounds based on cyclohexane dicarboxylic acid esters.

[0040] In a plasticizer composition according to a specific embodiment of the present invention, the non-petroleum-based compound may be present in an amount greater than 10 parts by weight and less than 40 parts by weight, based on 100 parts by weight of the plasticizer composition. Specifically, the non-petroleum-based compound may be present in an amount greater than 10 parts by weight, 15 parts by weight or more, or 20 parts by weight or more, and less than 40 parts by weight, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less, based on 100 parts by weight of the plasticizer composition.

[0041] When excessive amounts of non-petroleum-based compounds are included, the plasticizers volatilize due to aging caused by heat generated during processing or use, resulting in poor volatility. Consequently, tensile strength retention, an important physical property of wire compounds, can increase, while elongation retention can decrease significantly. Therefore, when excessive amounts of non-petroleum-based compounds are included, physical properties may severely degrade during processing or use as wire compounds.

[0042] On the other hand, when too small a amount of non-petroleum-based compounds are included, the content of trimellitate-based compounds in the plasticizer composition increases. Because trimellitate-based compounds have high molecular weights, more energy must be used during processing, and there may be problems with reduced resistance to migration.

[0043] Furthermore, in a specific embodiment of the plasticizer composition according to the present invention, the compound based on trimellitate may be present in an amount greater than 20 parts by weight and less than 80 parts by weight, based on 100 parts by weight of the plasticizer composition. Specifically, the compound based on trimellitate may be present in an amount greater than 20 parts by weight, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, up to less than 80 parts by weight, 70 parts by weight or less, 60 parts by weight or less, or 55 parts by weight or less, based on 100 parts by weight of the plasticizer composition.

[0044] When an excessive amount of trimellitate-based compounds is included, the larger molecular weight of these compounds increases extrusion output and torque, potentially placing a heavier load on the processing machine. Therefore, there may be issues requiring increased temperatures during processing, and a possible decrease in migration resistance. On the other hand, when a small amount of trimellitate-based compounds is included, the proportion of DEHCH (a type of petroleum-based compound) with poor volatility increases. Therefore, there may be issues with degradation of physical properties due to aging caused by heat generated during processing or use of the compound.

[0045] Specifically, a plasticizer composition according to one particular example of this disclosure may be a three-component composition comprising only a compound based on trimellitate, a compound based on cyclohexane dicarboxylate, and a non-petroleum-based compound.

[0046] That is, based on 100 parts by weight of the plasticizer composition, when a non-petroleum-based compound is present in an amount of 5 to 35 parts by weight and a trimellitate-based compound is present in an amount of 5 to 70 parts by weight, the remainder may be a cyclohexane dicarboxylate-based compound.

[0047] For example, 100 parts by weight of a plasticizer composition may consist of 50 parts by weight of a trimellitate-based plasticizer, 25 parts by weight of a cyclohexane dicarboxylate-based compound, and 25 parts by weight of a non-petroleum-based compound. Alternatively, 100 parts by weight of a plasticizer composition may consist of 70 parts by weight of a trimellitate-based plasticizer, 15 parts by weight of a cyclohexane dicarboxylate-based compound, and 15 parts by weight of a non-petroleum-based compound.

[0048] According to one specific embodiment of the present invention, the plasticizer composition can be prepared by mixing and blending compounds based on trimellitate, compounds based on cyclohexane dicarboxylate, and non-petroleum-based compounds.

[0049] Furthermore, the present invention provides a vinyl chloride resin composition comprising polyvinyl chloride and a plasticizer composition. A vinyl chloride resin composition comprising a plasticizer composition according to a specific embodiment of the present invention may have improved physical properties, such as tensile strength, elongation, and migration resistance.

[0050] Throughout this disclosure, vinyl chloride resin composition refers to a (co)polymer formed by the polymerization of a monomer based solely on vinyl chloride, or by copolymerization of a monomer based on vinyl chloride and a comonomer thereof, or polyvinyl chloride. Furthermore, it can be prepared by polymerization methods such as suspension polymerization, microsuspension polymerization, emulsion polymerization, or microemulsion polymerization, using a mixture of suspending agents, buffers, and polymerization initiators.

[0051] Furthermore, in the vinyl chloride resin composition according to a specific example of the present invention, the amount of plasticizer composition present, based on 100 parts by weight of polyvinyl chloride, can be from 10 parts by weight or more to 200 parts by weight or less, preferably 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, up to 200 parts by weight or less, 180 parts by weight or less, 150 parts by weight or less, 120 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, or 60 parts by weight or less. When a relatively small amount of plasticizer composition is included, it may be difficult to achieve the desired physical properties, and when a larger amount of plasticizer composition is included, the viscosity is lower, making processing difficult, and there may be a problem of stickiness on the product surface.

[0052] In addition, vinyl chloride resin compositions may further include other additives, such as stabilizers, fillers and foaming agents.

[0053] The stabilizer is added for the purpose of preventing changes in the physical properties of the resin composition, and the stabilizer comprises at least one of the following: Ca-Zn based compounds, K-Zn based compounds, Ba-Zn based compounds, organotin based compounds, metal soap based compounds, phenol based compounds, phosphate based compounds and phosphite based compounds.

[0054] In addition, the filler is used for the purpose of improving the productivity, dry feel and the like of the resin composition, and includes at least one of the following components selected from the group consisting of: calcium carbonate, silicon dioxide, alumina kaolin and magnesium hydroxide.

[0055] In addition, foaming agents are used to reduce the weight of resin components and can be chemical or physical foaming agents. Examples of chemical foaming agents include azodimethylamine, azobisisobutyronitrile, benzenesulfonamide, p-toluenesulfonylhexacarbazide, sodium bicarbonate, ammonium bicarbonate, and the like. Examples of physical foaming agents include carbon dioxide, nitrogen, cyclohexane, toluene, 1,2-dichloroethane, acetone, methyl ethyl ketone, and the like.

[0056] In addition to the exemplary materials, other additives may be used without hindering the purpose of the invention, and such other additives may be selected in appropriate proportions according to the purpose of the vinyl chloride resin composition.

[0057] The vinyl chloride resin composition may have a degree of polymerization of 700 to 1,700, preferably 800 to 1,500. When the degree of polymerization is within the above range, the dispersibility is excellent, the compatibility with plasticizers is good, and the processability of the plastisol can be improved.

[0058] Meanwhile, the present invention can provide a vinyl chloride resin molding article comprising a vinyl chloride resin composition. Specifically, the vinyl chloride resin molding article may comprise a plasticizer composition.

[0059] Vinyl chloride resin moldings can be used for wire sheathing, flooring materials, mats, wallpaper, food packaging, medical devices and the like.

[0060] [[] [Beneficial Effects] []] [ ]

[0061] Compared with conventional environmentally friendly plasticizer compositions, the plasticizer composition disclosed herein has improved overall physical properties, such as tensile strength, elongation and migration resistance, and therefore has high utility value as an environmentally friendly plasticizer.

[0062] Furthermore, the vinyl chloride resin composition containing the plasticizer composition disclosed herein does not contain endocrine disruptors, is environmentally friendly, and has high versatility due to its improved physical properties. Simple Explanation of the Diagram

[0063] none Implementation

[0064] In the following sections, preferred specific examples are presented to facilitate understanding of the invention. However, the following embodiments are for illustrative purposes only and are not intended to limit the scope of this disclosure. [<] [Example] [>] [Example] [1]

[0065] TOTM is used as a trimellitate-based compound, DEHCH is used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 is used as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 50 parts by weight of TOTM, 25 parts by weight of DEHCH, and 25 parts by weight of CAS 68440-29-9. [Example] [2]

[0066] TINTM was used as a trimellitic acid ester-based compound, DEHCH was used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 was used as a petroleum-free compound. A plasticizer composition was prepared by mixing 50 parts by weight of TINTM, 25 parts by weight of DEHCH, and 25 parts by weight of the CAS 68440-29-9 compound. [Example] [3]

[0067] TOTM is used as a trimellitate-based compound, DEHCH is used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 is used as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 70 parts by weight of TOTM, 15 parts by weight of DEHCH, and 15 parts by weight of CAS 68440-29-9. [Example] [4]

[0068] TINTM was used as a trimellitate-based compound, DEHCH as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 70 parts by weight of TINTM, 15 parts by weight of DEHCH, and 15 parts by weight of CAS 68440-29-9. [Example] [5]

[0069] TOTM is used as a trimellitate-based compound, DEHCH is used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 is used as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 30 parts by weight of TOTM, 35 parts by weight of DEHCH, and 35 parts by weight of CAS 68440-29-9. [Example] [6]

[0070] TINTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 was used as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 30 parts by weight of TINTM, 35 parts by weight of DEHCH, and 35 parts by weight of the CAS 68440-29-9 compound. [<] [Comparative Examples] [>] [Comparative Examples] [1]

[0071] Comparative Example 1: 100 parts by weight of diisononyl phthalate (DINP) was used alone as a plasticizer composition. [Comparative Examples] [2]

[0072] 100 parts by weight of diisodecyl phthalate (DIDP) were used alone as a plasticizer composition. [Comparative Examples] [3]

[0073] 100 parts by weight of BIO-DEHCH, a compound based on cyclohexane dicarboxylic acid ester, is used alone as a plasticizer component. [Comparative Examples] [4]

[0074] 100 parts by weight of tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate (TEHCH), a compound based on cyclohexane tricarboxylic acid ester, is used alone as a plasticizer component. [Comparative Examples] [5]

[0075] TOTM is used as a trimellitate-based compound, DEHCH is used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 is used as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 80 parts by weight of TOTM, 10 parts by weight of DEHCH, and 10 parts by weight of CAS 68440-29-9. [Comparative Examples] [6]

[0076] TOTM is used as a trimellitate-based compound, DEHCH is used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 is used as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 20 parts by weight of TOTM, 40 parts by weight of DEHCH, and 40 parts by weight of CAS 68440-29-9. [Comparative Examples] [7]

[0077] TINTM was used as a trimellitic acid ester-based compound, DEHCH was used as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 was used as a petroleum-free compound. A plasticizer composition was prepared by mixing 80 parts by weight of TINTM, 10 parts by weight of DEHCH, and 10 parts by weight of CAS 68440-29-9. [Comparative Examples] [8]

[0078] TINTM was used as a trimellitate-based compound, DEHCH as a cyclohexane dicarboxylic acid ester-based compound, and CAS 68440-29-9 as a non-petroleum-based compound. A plasticizer composition was prepared by mixing 20 parts by weight of TINTM, 40 parts by weight of DEHCH, and 40 parts by weight of CAS 68440-29-9. [<] [Experimental Examples] [>] [ ] [Vinyl chloride resin composition] [ ]

[0079] Prepare a vinyl chloride resin composition comprising the plasticizer composition of Examples 1 to 6 and Comparative Examples 1 to 8.

[0080] 100 parts by weight of polyvinyl chloride (P-1000F, Hanwha Solutions), 50 parts by weight of plasticizer composition, 5 parts by weight of antioxidant (RUP-110, Adeka Korea), 2 parts by weight of epoxy resin-assisted heat stabilizer (E-700, Songwon Industrial), and 0.2 parts by weight of lubricant (Ca-St) were mixed. The mixture was then stirred in a Hobart mixer for 10 minutes to prepare the vinyl chloride resin composition.

[0081] The prepared vinyl chloride resin composition was rolled and kneaded on a high-temperature mixing roller at 170°C for 3 minutes, and then continuously rolled in a hot press at 180°C for 10 minutes to prepare a sample with a thickness of 2 mm for physical property evaluation. [Methods for measuring elongation, tensile strength, tensile retention, and elongation retention] [ ]

[0082] After dumbbell-shaped specimens were prepared from molded sheets, elongation and tensile strength were measured using a Universal Test Machine (UTM) at a speed of 500 mm / min, according to ASTM D638.

[0083] In addition, after heating the specimen at 113°C for 168 hours, the elongation and tensile strength were measured, and the tensile retention rate (%) and elongation retention rate (%) were calculated according to the following equations. - Tensile retention rate (%) = (Tensile strength after heat aging / Tensile strength before heat aging) × 100 - Elongation retention (%) = (Elongation after heat aging / Elongation before heat aging) × 100 [Methods for evaluating the migration resistance of plasticizers] [ ]

[0084] Refer to ISO 177:1988 (Plastics—Determination of plasticizer migration) to assess the resistance to plasticizer migration. Prepare molded specimens cut into circular shapes with a diameter of 50 mm. Sequentially stack oil paper (PP porous membrane) and glass plates on top and bottom of the specimens, allowing plasticizers migrating from the specimen to be absorbed into the oil paper. Apply a 5 kg load to the specimens and place them at 100°C for 1 hour. Subsequently, measure the rate of change in weight (%) of the specimens to analyze the degree of plasticizer migration.

[0085] The rate of change in sample weight was calculated as [(sample weight change / sample weight before test) × 100], and the rate of change in oil paper weight was calculated as [(oil paper weight change / oil paper weight before test) × 100]. Since the decrease in sample weight is the same as the increase in oil paper weight, in this experiment, the plasticizer migration rate was assessed solely by the rate of change in sample weight. [Methods for measuring extrusion output and torque] [ ]

[0086] Using a Brabender mixer extruder, the resin composition was extruded for 1 minute at a screw speed of 30 rpm and a temperature of 140°C to 160°C. The extrusion output was measured by measuring its weight (g). The torque was measured by measuring the load applied to the device during this process. The assessment data are shown in Tables 1 and 2 below. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Phthalate endocrine disruptor issues X X X X X X Extrusion output (g) 46.7 47.4 48.6 49.4 45.9 46.1 Torque (Nm) 18.6 16.1 19.1 18.9 17.6 17.7 Tensile strength (kgf / cm2) 177.7 181.3 183.2 186.4 176.9 178.1 Elongation (%) 352.1 348.4 350.9 348.2 365.4 371.1 Stretch retention rate (%) 101 101 101 102 104 103 Elongation retention (%) 98 95 98 97 95 98 Plasticizer migration rate (%) 100℃, 1 h 0.32 0.38 0.48 0.51 0.27 0.31 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Phthalate endocrine disruptor issues O O X X X X X X Extrusion output (g) 44.1 44.4 44.8 46.5 49.8 46.8 49.6 47.3 Torque (Nm) 18.8 16.1 16.9 21.8 22.7 18.5 23.1 18.6 Tensile strength (kgf / cm2) 168 172.9 169.4 173.7 187.9 181.5 189.1 178.6 Elongation (%) 318.4 329.5 324.4 331.8 345.1 369.2 343.4 368.8 Stretch retention rate (%) 99 101 104 103 103 107 103 107 Elongation retention (%) 95 97 91 94 97 92 96 91 Plasticizer migration rate (%) 100℃, 1 h 0.18 0.16 0.6 0.19 0.43 0.28 0.46 0.31

[0087] In Comparative Examples 1 and 2, DINP and DIDP were used as plasticizers, respectively. These are common phthalate plasticizers currently used in electrical wire compounds and have endocrine disruptor issues. Furthermore, it was confirmed that Comparative Examples 1 and 2 exhibited poorer tensile strength and elongation compared to the examples.

[0088] Comparative Example 3 contained only BIO-DEHCH, i.e., a compound based on cyclohexane dicarboxylic acid ester, as a plasticizer, and exhibited poor tensile strength and elongation.

[0089] Comparative Example 4 contained only TEHCH, a compound based on cyclohexane tricarboxylic acid ester, as a plasticizer. It was confirmed that TEHCH had poor plasticizing efficiency, thus placing a heavier load on the machine.

[0090] Comparative Examples 5 and 7 show cases where the proportion of trimellitate-based compounds in the plasticizer composition is higher. It was confirmed that, due to the larger molecular weight of the trimellitate-based compounds, the torque increases, thus placing a heavier load on the processing machine.

[0091] Comparative Examples 6 and 8 show cases where the proportion of non-petroleum-based compounds in the plasticizer composition is higher. Since non-petroleum-based compounds have poorer anti-volatility, the plasticizer evaporates and disappears, resulting in a lower plasticizer content. Therefore, an increase in tensile strength retention and a decrease in elongation retention are confirmed.

[0092] Therefore, it was confirmed that the vinyl chloride resin composition containing the plasticizer composition of Examples 1 to 6 exhibits physical properties suitable for use in wire compounds, while not causing problems with endocrine disruptors.

[0093] none

Claims

1. A plasticizer composition comprising: i) a trimellitic acid ester-based compound represented by the following Chemical Formula 1; ii) a cyclohexane dicarboxylic acid ester-based compound represented by the following Chemical Formula 2; and iii) a petroleum-based compound, wherein the petroleum-based compound is present in an amount greater than 10 parts by weight and less than 40 parts by weight, based on 100 parts by weight of the plasticizer composition, and wherein the petroleum-based compound has 14 to 22 carbon atoms and 3 to 8 chlorine atoms: [Chemical Formula 1], in Chemical Formula 1, R1 to R3 are each independently a straight-chain or branched alkyl group having 4 to 12 carbon atoms; [Chemical Formula 2], in Chemical Formula 2, R4 and R5 are each independently a straight-chain or branched alkyl group having 4 to 12 carbon atoms.

2. The plasticizer composition of claim 1, wherein the trimellitate-based compound is present in an amount greater than 20 parts by weight and less than 80 parts by weight, based on 100 parts by weight of the plasticizer composition.

3. The plasticizer composition of claim 1, wherein the non-petroleum-based compound is a chlorinated bio-based oil.

4. The plasticizer composition of claim 1, wherein R1 to R3 in chemical formula 1 are each independently butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, 2-propylheptyl, decyl or isodecyl.

5. The plasticizer composition of claim 1, wherein the trimellitate-based compound comprises at least one of the following groups: tri(2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), and mixtures thereof.

6. The plasticizer composition of claim 1, wherein the compound based on cyclohexane dicarboxylate is represented by any one of the following chemical formulas 2-1 to 2-3: [Chemical Formula 2-1], [Chemical Formula 2-2], [Chemical Formula 2-3], wherein in chemical formulas 2-1 to 2-3, R6 to R11 are each independently butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, 2-propylheptyl, decyl, or isodecyl.

7. The plasticizer composition of claim 1, wherein the cyclohexane dicarboxylate-based compound comprises at least one of the following groups: di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, di(isononyl)cyclohexane-1,4-dicarboxylate, di(2-propylheptyl)cyclohexane-1,4-dicarboxylate, di(decyl)cyclohexane-1,4-dicarboxylate, and di(isodecyl)cyclohexane-1,4-dicarboxylate.

8. A vinyl chloride resin composition comprising polyvinyl chloride and a plasticizer composition as claimed in any one of claims 1 to 7.

9. The vinyl chloride resin composition of claim 8, wherein the plasticizer composition is present in an amount of 10 to 200 parts by weight based on 100 parts by weight of the polyvinyl chloride.

10. The vinyl chloride resin composition of claim 8, wherein the vinyl chloride resin further comprises at least one of the following components selected from the group consisting of: stabilizer, filler and foaming agent.

11. A vinyl chloride resin molding article comprising the vinyl chloride resin composition as claimed in claim 8.

12. A vinyl chloride resin molded article as claimed in claim 11, wherein the vinyl chloride resin molded article is an electrical wire covering, flooring material, mat, wallpaper, food packaging or medical device.