Plasticizer composition and vinyl chloride resin composition comprising same

Abstract

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

Description

Plasticizer composition and vinyl chloride resin composition containing the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2024-0191749 filed December 19, 2024, and all contents disclosed in the literature of said Korean patent applications are incorporated herein as part of this specification.

[0003]

[0004] The present invention relates to a plasticizer composition and a vinyl chloride resin composition containing the same. Specifically, the present invention relates to a plasticizer composition with improved physical properties, such as tensile strength, elongation, and migration resistance, and a vinyl chloride resin composition containing the same.

[0005]

[0006] Vinyl chloride resin (PVC resin) is widely applied in various fields due to its high utility, resulting from its excellent cost competitiveness, and its ability to be molded in diverse ways due to its rigid and flexible properties. Additives are commonly used as auxiliary materials to facilitate the processing of vinyl chloride resin and improve the performance of the final product. These additives include plasticizers, stabilizers, fillers, and blowing agents, and they are mixed during the resin manufacturing process to produce the final resin. Among these, plasticizers enable the production of various products by increasing the flexibility of the resin.

[0007] Plasticizers are classified into phthalate, epoxy, and polyester types according to their molecular structural formulas. Among them, phthalate plasticizers are the most commonly used representative plasticizers due to their excellent compatibility with vinyl chloride resin and high plasticization efficiency. Phthalate plasticizers are substances in which various alkyl groups are substituted into a phthalate structure. Examples of phthalate plasticizers include DEHP (di-2-ethylhexyl phthalate), DINP (di-isononyl phthalate), DIDP (di-isodecyl phthalate), and DBP (di-butyl phthalate).

[0008] Despite the aforementioned advantages, research has shown that phthalate plasticizers are endocrine disruptors harmful to the human body; as they have been classified as hazardous substances, alternative components have been required. Research on eco-friendly plasticizers was initiated to replace phthalate plasticizers. Representative examples include terephthalate plasticizers, epoxide plasticizers, vegetable oil plasticizers, cyclohexane plasticizers, and mixtures thereof. Among eco-friendly plasticizers, a general-purpose product is DOTP (di-octyl terephthalate), which is based on terephthalic acid. However, its harmfulness remains an issue, and it cannot replace phthalate plasticizers in terms of quality.

[0009] Therefore, there is a need to develop an eco-friendly plasticizer that is free from endocrine disruptors, is environmentally friendly, and does not impair the physical properties of vinyl chloride resin.

[0010]

[0011] One embodiment of the present disclosure aims to provide a plasticizer composition and a vinyl chloride resin composition comprising the same.

[0012] Specifically, the first embodiment of the present disclosure aims to provide a plasticizer composition having excellent physical properties such as tensile strength, elongation, and migration resistance, and a vinyl chloride resin composition containing the same.

[0013]

[0014] One embodiment of the present disclosure provides a plasticizer composition comprising a trimellitate-based compound; a cyclohexane dicarboxylate-based compound; and a non-petroleum-based compound.

[0015] In addition, another embodiment of the present disclosure provides a vinyl chloride resin composition comprising the plasticizer composition.

[0016] In addition, another embodiment of the present disclosure provides a vinyl chloride resin molded article comprising the vinyl chloride resin composition.

[0017]

[0018] The terms used in this specification are used merely to describe exemplary embodiments and are not intended to limit the invention.

[0019] A singular expression includes a plural expression unless the context clearly indicates otherwise.

[0020] In this specification, terms such as “comprising,” “comprising,” or “having” are used to describe the features, numbers, steps, components, or combinations thereof that are implemented, and do not exclude one or more other features, numbers, steps, components, combinations thereof, or the possibility of addition.

[0021] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0022] The present invention will be described in detail below.

[0023]

[0024] The plasticizer composition according to the present invention comprises trimellitate-based compounds, cyclohexane dicarboxylate-based compounds, and non-petroleum-based compounds.

[0025] The above trimellitate-based compound can be represented by the following chemical formula 1.

[0026] [Chemical Formula 1]

[0027]

[0028] In the above chemical formula 1,

[0029] R1 to R3 can each be independently selected from straight-chain or branched-chain alkyl groups having 4 to 12 carbon atoms.

[0030] In the above chemical formula 1, R1 to R3 are each a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, an isononyl group, a 2-propylheptyl group, a decyl group, or an isodecyl group.

[0031] According to one embodiment of the present invention, among the components of the plasticizer composition, the mellitate-based compound may be a compound in which R1 to R3 are all 2-ethylhexyl groups. This compound has the structure of [Chemical Formula 1-1] below and is tris(2-ethylhexyl)trimellitate (TOTM).

[0032] [Chemical Formula 1-1]

[0033]

[0034] According to one embodiment of the present invention, among the components of the plasticizer composition, the melitate-based compound may be a compound in which R1 to R3 are all isononyl groups. This compound has the structure of [Chemical Formula 1-2] below and is triisononyl melitate (TINTM).

[0035] [Chemical Formula 1-2]

[0036]

[0037] According to one embodiment of the present invention, the mellitate-based compound may include tris(2-ethylhexyl)trimellitate (TOTM), triisononyl trimellitate (TINTM), or a combination thereof.

[0038]

[0039] The above cyclohexane dicarboxylate-based compound can be represented by the following chemical formula 2.

[0040] [Chemical Formula 2]

[0041]

[0042] In the above chemical formula 2,

[0043] R4 and R5 can each be independently selected from straight-chain or branched-chain alkyl groups having 4 to 12 carbon atoms.

[0044] The compound represented by the above [Chemical Formula 2] may be represented by the following [Chemical Formula 2-1] to [Chemical Formula 2-3] depending on the position of the carboxylate group substitution on cyclohexane.

[0045] [Chemical Formula 2-1]

[0046]

[0047] [Chemical Formula 2-2]

[0048]

[0049] [Chemical Formula 2-3]

[0050]

[0051] The above [Chemical Formula 2-1] is a cyclohexane-1,4-dicarboxylate-based compound, the above [Chemical Formula 2-2] is a cyclohexane-1,3-dicarboxylate-based compound, and the above [Chemical Formula 2-3] is a cyclohexane-1,2-dicarboxylate-based compound.

[0052] In addition, in the above chemical formulas 2-1 to 2-3, R6 to R11 Each is a butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, isononyl group, 2-propylheptyl group, decyl group, or isodecyl group.

[0053] For example, in a cyclohexane-1,4-dicarboxylate-based compound, if R6 and R7 are the same, it may be di(butyl)cyclohexane-1,4-dicarboxylate, di(isononyl)cyclohexane-1,4-dicarboxylate, etc.; if R6 and R7 are different, it may be butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, butyl(isononyl)cyclohexane-1,4-dicarboxylate, etc.

[0054] According to one embodiment of the present invention, among the components of the plasticizer composition, the cyclohexane dicarboxylate-based compound may be a compound in which both R6 and R7 are 2-ethylhexyl groups in the cyclohexane-1,4-dicarboxylate-based compound. This compound has the structure of [Chemical Formula 2-4] below and is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, DEHCH).

[0055] [Chemical Formula 2-4]

[0056]

[0057] According to one embodiment of the present invention, in the plasticizer composition, the cyclohexane dicarboxylate-based compound is selected from the group consisting of 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. It may include one or more types.

[0058]

[0059] One of the components of the plasticizer composition according to the present invention, a non-petroleum compound, may be a compound having 14 to 22 carbon atoms and 3 to 8 chlorine atoms.

[0060] Specifically, the non-petroleum compound may be a chlorinated bio-oil. The chlorinated bio-oil may include chlorinated vegetable oil, chlorinated animal oil, or chlorinated discarded bio-oil. Specifically, the non-petroleum compound may be a chlorinated alkyl ester compound. For example, it may be a compound such as Bio-based chlorinated paraffin; Methyl 3-octyloxiraneoctanoate (CAS # 2566-91-8); or chlorinated Fatty acids, tallow, Me esters (CAS # 68440-29-9).

[0061] The above-mentioned chlorinated vegetable oil may include chlorinated vegetable oils such as soybean oil, castor oil, linseed oil, palm oil, tall oil, tung oil, grapeseed oil, olive oil, jojoba oil, poppyseed oil, cottonseed oil, canola oil, wheat germ oil, peanut oil, and walnut oil. The above-mentioned animal oil may include chlorinated tallow, lard, lamb fat, poultry oil, butter, whale oil, etc. Additionally, discarded bio-oil refers to oil that is discarded after being used in food preparation, whether vegetable, animal, or both; for example, it may include waste cooking oil, which may be recycled and chlorinated for use.

[0062]

[0063] Chlorinated bio-oil can be obtained by chlorinating ester compounds known in the art.

[0064]

[0065] Currently, phthalate-based plasticizers such as DINP (diisononyl phthalate) and DIDP (diisodecyl phthalate) are mainly used in wire compounds, and accordingly, there is a need in the industry to use eco-friendly plasticizers. The above-mentioned non-petroleum compounds have superior compatibility compared to BIO-DEHCH, an eco-friendly plasticizer previously used, and trimellitate-based compounds have a higher molecular weight compared to phthalate-based plasticizers, which have environmental hormone issues, resulting in relatively lower toxicity and excellent volatility resistance when used in wire compounds.

[0066] Accordingly, the plasticizer composition according to the first embodiment of the present disclosure may have improved physical properties such as tensile strength, elongation, and migration resistance by including a trimellitate-based compound and the non-petroleum-based compound together with a cyclohexane dicarboxylate-based compound.

[0067]

[0068] A plasticizer composition according to one embodiment of the present invention may include the non-petroleum compound 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 compound may be included in an amount greater than 10 parts by weight, 15 parts by weight or more, 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.

[0069] If an excessive amount of non-petroleum compounds is included, the volatility is inferior. Consequently, plasticizers volatilize due to aging caused by heat generated during processing or use, which is a critical property of wire compounds. This can lead to an increase in tensile retention and a significant decrease in elongation retention. Therefore, the inclusion of excessive non-petroleum compounds can result in severe degradation of physical properties during the processing or use stages of the wire compound.

[0070] On the other hand, if non-petroleum compounds are included in too small a quantity, the content of trimellitate compounds in the plasticizer composition increases, and since trimellitate compounds have a high molecular weight, more energy must be used during processing, which may lead to problems such as inferior migration resistance.

[0071]

[0072] In addition, a plasticizer composition according to one embodiment of the present invention may contain the trimellitate-based compound 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 trimellitate-based compound may be contained in an amount greater than 20 parts by weight, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more but 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.

[0073] If the composition contains an excessive amount of trimellitate compounds, the high molecular weight of these compounds increases extrusion volume and torque, which can place a heavy load on the processing machinery. This may necessitate higher processing temperatures and result in reduced migration resistance. Conversely, if the composition contains too little trimellitate compounds, the proportion of DEHCH and non-petroleum compounds, which have inferior volatility, increases. This can lead to a deterioration in physical properties due to aging caused by the heat generated during processing or use of the wire compound.

[0074]

[0075] Specifically, the plasticizer composition of the first embodiment of the present disclosure may be a ternary composition comprising only a trimellitate-based compound, a cyclohexane dicarboxylate-based compound, and a non-petroleum-based compound.

[0076] That is, when the non-petroleum compound is included in an amount of 5 to 35 parts by weight and the trimellitate compound is included in an amount of 5 to 70 parts by weight per 100 parts by weight of the plasticizer composition, the remainder may be a cyclohexane dicarboxylate compound.

[0077] For example, 100 parts by weight of the plasticizer composition may consist of 50 parts by weight of the trimellitate-based plasticizer, 25 parts by weight of the cyclohexane dicarboxylate-based compound, and 25 parts by weight of the non-petroleum-based compound. Alternatively, 100 parts by weight of the plasticizer composition may consist of 70 parts by weight of the trimellitate-based plasticizer, 15 parts by weight of the cyclohexane dicarboxylate-based compound, and 15 parts by weight of the non-petroleum-based compound.

[0078]

[0079] According to one embodiment of the present invention, the plasticizer composition can be prepared by mixing and blending the trimellitate-based compound, the cyclohexane dicarboxylate-based compound, and the non-petroleum-based compound.

[0080]

[0081] In addition, the present invention provides a vinyl chloride resin composition comprising polyvinyl chloride and the plasticizer composition. A vinyl chloride composition comprising the plasticizer composition according to one embodiment of the present invention may have improved physical properties such as tensile strength, elongation, and resistance to migration.

[0082] Throughout this disclosure, the term "vinyl chloride resin composition" refers to a vinyl chloride-based monomer alone, or a (co)polymer formed by copolymerizing a vinyl chloride-based monomer and a comonomer copolymerizable therefrom, or polyvinyl chloride. In addition, it may be prepared by polymerization methods such as suspension polymerization, micro-suspension polymerization, emulsion polymerization, or miniemulsion polymerization by mixing a suspending agent, a buffering agent, and a polymerization initiator.

[0083] In addition, the vinyl chloride resin composition according to one embodiment of the present invention may contain, with respect to 100 parts by weight of the polyvinyl chloride, 10 parts by weight or more to 200 parts by weight or less of the plasticizer composition, 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 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. If the plasticizer composition is included in a relatively small amount, it may be difficult to achieve the desired physical properties, and if the plasticizer composition is included in a relatively large amount, there may be problems such as low viscosity, making processing difficult, and tackiness appearing on the surface of the product.

[0084] Additionally, the vinyl chloride resin composition may further include other additives such as stabilizers, fillers, and foaming agents.

[0085] The above stabilizer is added for the purpose of preventing changes in the physical properties of the resin composition and comprises one or more selected from the group consisting of Ca-Zn compounds, K-Zn compounds, Ba-Zn compounds, organic tin compounds; metallic soap compounds, phenol compounds, phosphate ester compounds, and phosphite ester compounds.

[0086] In addition, the above filler is used for the purpose of improving the productivity and dryness texture of the resin composition, and includes one or more selected from the group consisting of calcium carbonate, silica, alumina kaolin, and magnesium hydroxide.

[0087] In addition, the above-mentioned blowing agent is used to lighten the resin composition and may be a chemical or physical blowing agent. Examples of chemical blowing agents include azodicarbonamide, azodiisobutyronitrile, benzenesulfonylhydrazide, p-toluenesulfonyl semi-carbazide, sodium bicarbonate, ammonium bicarbonate, etc. Examples of physical blowing agents include carbon dioxide, nitrogen, cyclohexane, toluene, 1,2-dichloroethane, acetone, methyl ethyl ketone, etc.

[0088] The above other additives may be used in addition to the examples provided, provided that they do not impede the purpose of the present invention, and may be selected in appropriate proportions depending on the purpose of the vinyl chloride resin composition.

[0089] The above vinyl chloride resin composition may have a degree of polymerization of 700 to 1,700, preferably 800 to 1,500. When having a degree of polymerization within the above range, dispersibility is excellent, compatibility with plasticizers is good, and the processability of plastisol can be improved.

[0090]

[0091] Meanwhile, the present invention may provide a vinyl chloride resin molded article comprising a vinyl chloride resin composition. Specifically, the vinyl chloride resin molded article may include a plasticizer composition.

[0092] The above vinyl chloride resin molded product can be used for wire insulation, flooring, mats, wallpaper, food packaging wrap, medical devices, etc.

[0093]

[0094] The plasticizer composition disclosed herein has improved overall physical properties, such as tensile strength, elongation, and migration resistance, compared to existing eco-friendly plasticizer compositions, making it highly valuable as an eco-friendly plasticizer.

[0095] Furthermore, the vinyl chloride resin composition containing the plasticizer composition according to the present disclosure is free from endocrine disruptor issues, is eco-friendly, and has improved physical properties, making it highly versatile.

[0096]

[0097] Preferred embodiments are presented below to aid in understanding the invention. However, the following embodiments are intended only to illustrate the invention and do not limit the invention to these embodiments.

[0098]

[0099] <Example>

[0100] Example 1

[0101] TOTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was 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 compound.

[0102]

[0103] Example 2

[0104] TINTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was used as a non-petroleum-based 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 CAS 68440-29-9 compound.

[0105]

[0106] Example 3

[0107] TOTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was 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 compound.

[0108]

[0109] Example 4

[0110] TINTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was used 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 compound.

[0111]

[0112] Example 5

[0113] TOTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-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 TOTM, 35 parts by weight of DEHCH, and 35 parts by weight of CAS 68440-29-9 compound.

[0114]

[0115] Example 6

[0116] TINTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-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 CAS 68440-29-9 compound.

[0117]

[0118] <Comparative Example>

[0119]

[0120] Comparative Example 1

[0121] 100 parts by weight of diisononyl phthalate (DINP) was used alone as a plasticizer composition.

[0122]

[0123] Comparative Example 2

[0124] 100 parts by weight of diisodecyl phthalate (DIDP) was used alone as a plasticizer composition.

[0125]

[0126] Comparative Example 3

[0127] 100 parts by weight of BIO-DEHCH, a cyclohexane dicarboxylate-based compound, was used alone as a plasticizer composition.

[0128]

[0129] Comparative Example 4

[0130] 100 parts by weight of TEHCH (tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate), a cyclohexane tricarboxylate compound, was used alone as a plasticizer composition.

[0131]

[0132] Comparative Example 5

[0133] TOTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was 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 compound.

[0134]

[0135] Comparative Example 6

[0136] TOTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was 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 compound.

[0137]

[0138] Comparative Example 7

[0139] TINTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was used as a non-petroleum-based 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 compound.

[0140]

[0141] Comparative Example 8

[0142] TINTM was used as a trimellitate-based compound, DEHCH was used as a cyclohexane dicarboxylate-based compound, and CAS 68440-29-9 was used 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 compound.

[0143]

[0144] <Experimental Example>

[0145] Vinyl chloride resin composition

[0146] A vinyl chloride resin composition comprising the plasticizer compositions of Examples 1 to 6 and Comparative Examples 1 to 8 was prepared.

[0147] 100 parts by weight of polyvinyl chloride (P-1000F, Hanwha Solution), 50 parts by weight of a plasticizer composition, 5 parts by weight of an antioxidant (RUP-110, Adeka Korea), 2 parts by weight of an epoxy auxiliary heat stabilizer (E-700, Songwon Industrial), and 0.2 parts by weight of a lubricant (Ca-St) were mixed. Subsequently, the mixture was mixed in a Hobart mixer for 10 minutes to prepare a vinyl chloride resin composition.

[0148] The vinyl chloride resin composition prepared above was rolled and kneaded at 170°C for 3 minutes in a high-temperature mixing roll, and then rolled at 180°C for 10 minutes in a hot press to produce a specimen for evaluating physical properties with a thickness of 2 mm.

[0149]

[0150] Methods for measuring elongation, tensile strength, tensile retention, and elongation retention

[0151] Elongation and tensile strength were measured by preparing a molding sheet into a dumbbell-shaped specimen according to ASTM D638 and then measuring it on a Universal Test Machine (UTM) at a speed of 500 mm / min.

[0152] In addition, after heat-aging the specimen at 113℃ 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 formula.

[0153]

[0154] - Tensile Retention Rate (%) = Tensile Strength After Thermal Aging / Tensile Strength Before Thermal Aging * 100

[0155] - Remaining elongation rate (%) = Elongation rate after thermal aging / Elongation rate before thermal aging * 100

[0156]

[0157] Method for evaluating plasticizer migration

[0158] The plasticizer migration resistance was determined by referring to the ISO 177:1988 (Plastics - Determination of migration of Plasticizer) method. A molding sheet specimen cut into a circular shape with a diameter of 50 mm was prepared, and a sheet of parchment paper (PP porous film) and a glass plate were placed sequentially on top and bottom of the specimen to allow the plasticizer migrated from the specimen to be absorbed into the parchment paper. A load of 5 kg was applied to the specimen, and after leaving it at 100°C for 1 hour, the percentage change in weight of the specimen was measured to analyze the degree of plasticizer migration.

[0159] The weight change rate of the specimen was calculated as [(weight change of specimen / weight of specimen before test) * 100], and the weight change rate of the tracing paper was calculated as [(weight change of tracing paper / weight of tracing paper before test) * 100]. Since the weight loss of the specimen was equal to the weight increase of the tracing paper, the plasticizer migration was evaluated based solely on the weight change rate of the specimen in this experiment.

[0160]

[0161] Extrusion volume and torque measurement method

[0162] The extrusion amount was measured as the weight (g) of the resin composition extruded for 1 minute using a Brabender Mixer extruder at a screw rpm of 30 rpm and a temperature of 140 to 160 ℃. The torque was measured as the load applied to the machine at that time.

[0163]

[0164] The data evaluated above is shown in Tables 1 and 2 below.

[0165]

[0166] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Phthalate Endocrine Disruptor Issue XXXXXX Extrusion Amount (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) 2)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 Retention tensile strength (%) 101 101 101 102 104 103 Retention tensile strength (%) 98 95 98 97 95 98 Plasticizer migration (%) 100°C, 1 hour 0.3 20.3 80.4 80.5 10.2 70.31

[0167] 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 Issue OOXXXXXX Extrusion Amount (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 2 )168 172.9 169.4 173.7 187.9 181.5 189.1 178.6 Elongation (%) 3 18.4 329.5 324.4 331.8 345.1 369.2 343.4 368.8 Remaining Tensile Ratio (%) 9 9 101 104 103 103 107 103 107 Remaining Elongation (%) 9 5 9 7 91 9 4 9 7 92 9 6 91 Plasticizer Migration (%) 100°C, 1 hr 0.1 8 0.1 6 0.6 0.1 9 0.4 3 0.2 8 0.4 6 0.31

[0168] Comparative Examples 1 and 2 used DINP and DIDP, respectively, as plasticizers. These are common phthalate plasticizers currently used in wire compounds, and there are issues regarding endocrine disruptors. Furthermore, it was confirmed that Comparative Examples 1 and 2 exhibited inferior tensile strength and elongation compared to the Examples.

[0169] Comparative Example 3 contained only BIO-DEHCH, a cyclohexane dicarboxylate-based compound, as a plasticizer, and showed inferior tensile strength and elongation.

[0170] Comparative Example 4 contains only TEHCH, a cyclohexane tricarboxylate-based compound, as a plasticizer, and it was confirmed that TEHCH has poor plasticizing efficiency, which places a heavy load on the equipment.

[0171] Comparative Examples 5 and 7 are cases where the proportion of trimellitate-based compounds in the plasticizer composition is high, and it was confirmed that the torque increased due to the trimellitate-based compounds with large molecular weights, causing a heavy load on the processing machine.

[0172] Comparative Examples 6 and 8 are cases where the proportion of non-petroleum compounds in the plasticizer composition is high. Since non-petroleum compounds have inferior volatility, the plasticizer volatilizes and evaporates, causing the plasticizer content to decrease. Consequently, it was confirmed that the tensile strength increased and the elongation strength decreased.

[0173] Therefore, it was confirmed that the vinyl chloride resin composition containing the plasticizer compositions of Examples 1 to 6 exhibits properties suitable for use in wire compounds without the problem of generating endocrine disruptors.

Claims

1. i) A trimellitate compound represented by the following chemical formula 1; ii) a cyclohexane dicarboxylate-based compound represented by the following chemical formula 2; and iii) Non-petroleum compounds; As a plasticizer composition comprising, The non-petroleum compound is included in an amount of more than 10 parts by weight and less than 40 parts by weight per 100 parts by weight of the plasticizer composition, and The above non-petroleum compound has 14 to 22 carbon atoms and 3 to 8 chlorine atoms, Plasticizer composition: [Chemical Formula 1] In the above chemical formula 1, R1 to R3 are each independently a straight-chain or branched-chain alkyl group having 4 to 12 carbon atoms, and [Chemical Formula 2] In the above chemical formula 2, R4 and R5 are each independently straight-chain or branched-chain alkyl groups having 4 to 12 carbon atoms.

2. In Paragraph 1, The trimellitate-based compound is included in an amount of more than 20 parts by weight and less than 80 parts by weight per 100 parts by weight of the above plasticizer composition, Plasticizer composition.

3. In Paragraph 1, The above-mentioned non-petroleum compound is a chlorinated bio-oil, Plasticizer composition.

4. In Paragraph 1, R1 to R3 of Chemical Formula 1 are each independently a butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, isononyl group, 2-propylheptyl group, decyl group, or isodecyl group, Plasticizer composition.

5. In Paragraph 1, A plasticizer composition comprising one or more selected from the group consisting of the trimellitate-based compounds tris(2-ethylhexyl)trimellitate (TOTM), triisononyl trimellitate (TINTM), or mixtures thereof.

6. In Paragraph 1, The above-mentioned cyclohexane dicarboxylate-based compound is a plasticizer composition that is any one of the following chemical formulas 2-1 to 2-3: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] In the above chemical formulas 2-1 to 2-3, R6 to R 11 Each is independently a butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, isononyl group, 2-propylheptyl group, decyl group, or isodecyl group.

7. In Paragraph 1, A plasticizer composition comprising one or more compounds selected from the group consisting of 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 according to any one of claims 1 to 7.

9. In Paragraph 8, A vinyl chloride resin composition comprising 10 to 200 parts by weight of the plasticizer composition per 100 parts by weight of polyvinyl chloride.

10. In Paragraph 8, The above vinyl chloride resin composition further comprises one or more selected from the group consisting of stabilizers, fillers, and foaming agents.

11. A vinyl chloride resin molded article comprising the vinyl chloride resin composition of claim 8.

12. In Paragraph 11, The above vinyl chloride resin molded article is a vinyl chloride resin molded article that is a wire insulation, flooring material, mat, wallpaper, food packaging wrap, or medical device.

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