Plasticizer composition and vinyl chloride resin composition containing the same

Abstract

The present invention relates to an environmentally friendly plasticizer composition comprising a cyclohexanedicarboxylate-based compound, a vegetable oil and an epoxidized vegetable oil, and a vinyl chloride resin composition comprising the plasticizer composition. The vinyl chloride resin composition prepared according to the present invention has improved low temperature stability, viscosity, odor, etc.

Description

Technical Field

[0001] The present invention relates to a plasticizer composition having improved low temperature stability and viscosity properties, and a vinyl chloride resin composition comprising the plasticizer composition. Background Art

[0002] Vinyl chloride resin (PVC resin) is being used in various application fields because of its hard and soft properties, various moldings, excellent price competitiveness and high practicality. In order to promote the processing of vinyl chloride resin and improve the performance of the final product, additives are often used as auxiliary materials. These additives include plasticizers, stabilizers, fillers, foaming agents, etc., and in the preparation process of the resin, they are mixed to prepare the final resin. Among them, the plasticizer increases the flexibility of the resin, thereby enabling the preparation of various products.

[0003] According to the molecular structural formula, plasticizers are divided into plasticizers based on phthalates, plasticizers based on epoxy, and plasticizers based on polyester. Among them, plasticizers based on phthalates are a representative plasticizer that has excellent compatibility with vinyl chloride resins and has high plasticizing efficiency, and are therefore most commonly used. Plasticizers based on phthalates are materials in which the phthalate structure is substituted by various alkyl groups. As plasticizers based on phthalates, EHP (di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), DBP (dibutyl phthalate), etc. can be mentioned.

[0004] Despite the above advantages, previous studies have shown that the plasticizer based on phthalate is an environmental hormone and harmful to the human body, so it is specified as a harmful substance and requires its alternative material. In order to replace the plasticizer based on phthalate, the research on environmentally friendly plasticizers has been started. Representatively, plasticizers based on terephthalate, plasticizers based on epoxides, plasticizers based on vegetable oils, plasticizers based on cyclohexane and their mixed plasticizers can be mentioned. In environmentally friendly plasticizers, as commercial products, DOTP (dioctyl terephthalate) based on terephthalic acid can be mentioned. However, harmfulness is still a problem, and it cannot replace the plasticizer based on phthalate in quality, so recently, the research on the plasticizer based on cyclohexane is underway.

[0005] As a representative cyclohexane-based plasticizer, DEHCH (cyclohexanedicarboxylic acid di (2-ethylhexyl) ester) can be mentioned. DEHCH has excellent hardness characteristics and a fast gelling speed, and unlike phthalate-based plasticizers, there are almost no environmental problems. However, DEHCH has problems in terms of low temperature stability, volatility, and thermal stability. In order to compensate for the properties of DEHCH, plasticizer compositions in which various materials are additionally mixed with DEHCH have been previously studied. However, due to problems in low temperature stability and viscosity properties, as well as the fatal disadvantage of odor, its versatility is low and additional research is required. Summary of the invention

[0006] Technical issues

[0007] An object of the present invention is to provide an environmentally friendly plasticizer composition having improved thermal stability, improved low temperature stability and viscosity properties.

[0008] Another object of the present invention is to provide an environmentally friendly vinyl chloride resin composition having high versatility using the plasticizer composition.

[0009] Technical Solution

[0010] According to the present invention, there is provided a plasticizer composition comprising a cyclohexanedicarboxylate-based compound, a vegetable oil and an epoxidized vegetable oil.

[0011] According to the present invention, a vinyl chloride resin composition comprising the plasticizer composition is also provided.

[0012] The terminology used herein is for explaining particular embodiments only and is not intended to be limiting of the invention.

[0013] Unless it is clearly stated or obvious from the context that it is not, a singular expression includes a plural expression.

[0014] As used herein, the terms "comprising", "equipped" or "having" and the like are intended to indicate the presence of practical features, quantities, steps, structural elements or a combination thereof, and they are not intended to exclude the possibility of the presence or addition of one or more other features, quantities, steps, structural elements or a combination thereof.

[0015] Although various modifications can be made to the present invention, and the present invention can have various forms, specific embodiments will be described and explained in detail below. However, it should be understood that these are not intended to limit the present invention to specific disclosures, but the present invention includes all modifications, equivalents or replacements thereof without departing from the spirit and technical scope of the present invention.

[0016] Hereinafter, the present invention will be explained in detail.

[0017] According to the present invention, there is provided a plasticizer composition comprising a cyclohexanedicarboxylate-based compound, a vegetable oil and an epoxidized vegetable oil.

[0018] The cyclohexanedicarboxylate-based compound has a structure of Chemical Formula 1 below.

[0019] [Chemical formula 1]

[0020]

[0021] In Chemical Formula 1,

[0022] R1 and R2 are each independently a C4-12 straight or branched chain alkyl group.

[0023] The compound represented by [Chemical Formula 1] may be represented by the following [Chemical Formula 1-1] to [Chemical Formula 1-3] according to the substitution position of the carboxylate group on cyclohexane.

[0024] [Chemical formula 1-1]

[0025]

[0026] [Chemical formula 1-2]

[0027]

[0028] [Chemical formula 1-3]

[0029]

[0030] [Chemical Formula 1-1] is a compound based on cyclohexane-1,4-dicarboxylate, [Chemical Formula 1-2] is a compound based on cyclohexane-1,3-dicarboxylate, and [Chemical Formula 1-3] is a compound based on cyclohexane-1,2-dicarboxylate.

[0031] Also, in Chemical Formulae 1-1 to 1-3, R3 to R8 are each independently butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, 2-propylheptyl, decyl or isodecyl.

[0032] For example, the cyclohexane-1,4-dicarboxylate-based compound in which R3 and R4 are the same can be cyclohexane-1,4-dicarboxylic acid di(butyl) ester, cyclohexane-1,4-dicarboxylic acid di(isononyl) ester, etc.; and the cyclohexane-1,4-dicarboxylate-based compound in which R3 and R4 are different can be cyclohexane-1,4-dicarboxylic acid butyl (2-ethylhexyl) ester, cyclohexane-1,4-dicarboxylic acid butyl (isononyl) ester, etc.

[0033] According to one embodiment of the present invention, among the constituent elements of the plasticizer composition, the cyclohexane dicarboxylate-based compound may be a cyclohexane-1,4-dicarboxylate-based compound in which both R3 and R4 are 2-ethylhexyl. The compound has the structure of the following [Chemical Formula 1-4] and is cyclohexane-1,4-dicarboxylic acid di(2-ethylhexyl) ester (DEHCH).

[0034] [Chemical formula 1-4]

[0035]

[0036] According to one embodiment of the present invention, in the plasticizer composition, the cyclohexane dicarboxylate-based compound may include one or more selected from cyclohexane-1,4-dicarboxylic acid di(2-ethylhexyl) ester, cyclohexane-1,4-dicarboxylic acid di(isononyl) ester, cyclohexane-1,4-dicarboxylic acid di(2-propylheptyl) ester, cyclohexane-1,4-dicarboxylic acid di(decyl) ester and cyclohexane-1,4-dicarboxylic acid di(isodecyl) ester.

[0037] The cyclohexane dicarboxylate-based compound has low viscosity at room temperature and low temperature, and thus can achieve excellent coating properties, and has a fast gelation speed, small plasticizer migration, and excellent hardness properties. However, in the case of using the cyclohexane dicarboxylate-based compound alone, the volatility, thermal stability, and elongation may be inferior compared to the existing commercial plasticizer DOTP.

[0038] One of the constituent elements of the plasticizer composition according to the present invention, the vegetable oil, may include, for example, a compound having the structure of the following [Chemical Formula 2].

[0039] [Chemical formula 2]

[0040]

[0041] Vegetable oils may have a triglyceride structure in which glycerol and fatty acids are ester-bonded. 21 To R 23 R are each independently a C1-20 straight or branched alkenyl or alkyl group, provided that they do not include an epoxy group. 21 To R 23 The unsaturation degree can affect the color, texture, mechanical properties of the final resin composition. This unsaturation degree can be measured by an iodine value measurement method in which the unsaturated bonds are iodinated.

[0042] And, vegetable oil can include soybean oil, castor oil, linseed oil, palm oil, tall oil, tung oil, grape seed oil, olive oil, jojoba oil, poppy seed oil, cottonseed oil, rapeseed oil, wheat germ oil, peanut oil, walnut oil and their derivatives. The derivative of vegetable oil can be a mixture of vegetable oil, fatty acid and halogenated compound etc.

[0043] The epoxidized vegetable oil as one of the constituent elements of the plasticizer composition of the present invention may include a compound having a structure containing an epoxy group on a fatty acid chain of the vegetable oil, for example, [Chemical Formula 3].

[0044] [Chemical formula 3]

[0045]

[0046] The epoxidized vegetable oil may be a compound in which an epoxy group is introduced into the unsaturated bond of the vegetable oil by an epoxidation reaction. 31 To R 33 It may be a C1-20 straight or branched alkenyl or alkyl group containing an epoxy group. The epoxidized vegetable oil can be obtained by subjecting the vegetable oil to an epoxidation reaction. Formic acid can be used for the epoxidation reaction.

[0047] Specifically, the epoxidized vegetable oil can be epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized tall oil, epoxidized tung oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized jojoba oil, epoxidized poppy seed oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized wheat germ oil, epoxidized peanut oil, epoxidized walnut oil or a mixture thereof.

[0048] Plasticizer compositions containing epoxidized vegetable oils have improved volatility and thermal stability. However, due to the epoxy structure, they have low stability at low temperatures, so if the temperature is low, there may be freezing problems, especially in winter, and their use is limited due to high viscosity.

[0049] The plasticizer composition according to one embodiment of the present invention maintains transparency, gelling properties and weather resistance, which are advantages of cyclohexane dicarboxylate-based compounds, as well as volatility and thermal stability, which are advantages of epoxidized vegetable oils. In addition, by including vegetable oils at a specific ratio, low temperature stability and viscosity properties, which are disadvantages of plasticizers having epoxy structures, can be improved.

[0050] The plasticizing composition according to one embodiment of the present invention may include 50 to 70 parts by weight of a cyclohexanedicarboxylate-based compound, 10 to 35 parts by weight of a vegetable oil, and 10 to 30 parts by weight of an epoxidized vegetable oil, based on 100 parts by weight of the plasticizer composition.

[0051] Specifically, the content of the cyclohexane dicarboxylate-based compound may be about 50 to about 70 parts by weight, preferably about 60 to 70 parts by weight, based on 100 parts by weight of the plasticizer composition. If the amount of the cyclohexane dicarboxylate-based compound is less than about 50 parts by weight based on the plasticizer composition, the plasticizer may freeze in winter, thereby causing problems with the flow of the plasticizer (pipeline transportation, etc.), and the color may turn yellow, making it difficult to color the product, and the product may be damaged during construction due to low elongation. If the amount is greater than about 70 parts by weight, thermal stability and tensile strength may be poor.

[0052] And, the content of the vegetable oil may be about 10 to about 35 parts by weight, preferably about 15 to 30 parts by weight, based on 100 parts by weight of the plasticizer composition. If the amount of the vegetable oil is less than about 10 parts by weight based on the plasticizer composition, the elongation may be low and the viscosity may be high, while if it is greater than about 35 parts by weight, the volatilization loss may be high and the thermal stability may be poor.

[0053] And, the content of the epoxidized vegetable oil may be about 10 to about 30 parts by weight, preferably about 15 to about 25 parts by weight, based on 100 parts by weight of the plasticizer composition. If the amount of the epoxidized vegetable oil is less than about 10 parts by weight based on the plasticizer composition, thermal stability may be poor and volatility loss may be high, while if it is greater than about 30 parts by weight, viscosity may increase and elongation may be poor.

[0054] According to one embodiment of the present invention, the plasticizer composition may be prepared by mixing and blending the cyclohexanedicarboxylate-based material, the vegetable oil, and the epoxidized vegetable oil.

[0055] According to one embodiment of the present invention, the plasticizer composition may not freeze at -20° C. to -10° C. The term "freezing" used herein means that the liquid plasticizer composition forms crystals and turns into a solid state without fluidity when observed with the naked eye.

[0056] Furthermore, a vinyl chloride resin composition comprising the plasticizer composition is also provided herein. According to one embodiment of the present invention, the vinyl chloride composition comprising the plasticizer composition may have improved low temperature stability, volatility, thermal stability, and the like.

[0057] Throughout the specification, the vinyl chloride resin composition refers to a (co)polymer obtained by copolymerizing a vinyl chloride-based monomer alone or a vinyl chloride-based monomer and a comonomer copolymerizable therewith. In addition, it can be prepared by a polymerization method such as suspension polymerization, microsuspension polymerization, emulsion polymerization or microemulsion polymerization, by mixing a suspending agent, a buffer and a polymerization initiator, etc.

[0058] And, the vinyl chloride composition according to one embodiment of the present invention comprises about 10 to about 200 parts by weight, preferably about 10 to 120 parts by weight of the plasticizer composition, based on 100 parts by weight of the vinyl chloride resin composition. If the plasticizer composition is included in a relatively small content, the flexibility of the resin composition may be low, and therefore, it may be difficult to achieve the properties of the final product, and if it is included in a relatively large content, the viscosity may be low, making processing difficult, and may show stickiness on the surface of the product.

[0059] In addition, the vinyl chloride resin composition may further include other additives such as stabilizers, fillers, foaming agents, etc. The stabilizer is added to prevent the properties of the resin composition from changing, and the stabilizer includes one or more selected from the following: Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based mixtures, organic tin-based compounds; metal soap-based compounds, phenol-based compounds, phosphate-based compounds, and phosphite-based compounds.

[0060] And, the filler is used to improve the productivity and dry feel of the resin composition, and includes one or more selected from calcium carbonate, silicon dioxide, aluminum oxide, kaolin, magnesium hydroxide and the like.

[0061] Also, the foaming agent is used to make the resin composition light in weight, and it may be a chemical or physical foaming agent. As the chemical foaming agent, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, p-toluenesulfonylsemicarbazide, sodium bicarbonate, ammonium bicarbonate, etc. may be exemplified. As the physical foaming agent, carbon dioxide, nitrogen, cyclohexane, toluene, 1,2-dichloroethane, acetone, methyl ethyl ketone, etc. may be mentioned.

[0062] In addition to the above-described exemplary materials, other additives may be used within the range not hindering the purpose of the present invention, and may be selected in an appropriate ratio according to the purpose of the vinyl chloride resin composition.

[0063] Meanwhile, according to the present invention, a vinyl chloride resin molded article including the plasticizer composition can be provided.

[0064] Vinyl chloride resin molded products can be used in various extrusion, injection, calendering and composite fields, such as wallpaper, flooring, interior decoration (such as decorative panels), packaging materials (such as food packaging packaging), wires, automotive interior materials, films, hoses or pipes, but are not limited to these.

[0065] Beneficial Effects

[0066] Compared with existing environmentally friendly plasticizer compositions, the ternary plasticizer composition according to the present invention is excellent in general properties such as thermal stability, volatility loss, mechanical properties, and low temperature stability and viscosity, and is therefore very useful as an environmentally friendly plasticizer.

[0067] Therefore, the vinyl chloride resin composition including the plasticizer composition according to the present invention is environmentally friendly and has improved low temperature stability, viscosity and odor, and thus has high versatility. DETAILED DESCRIPTION

[0068] Hereinafter, the functions and effects of the present invention will be explained in more detail through specific embodiments of the present invention. However, these embodiments are presented only as illustrations of the present invention, and the scope of rights of the present invention is not determined thereby.

[0069] <Example>

[0070] Example 1

[0071] Preparation of plasticizer compositions

[0072] A plasticizer composition was prepared using DEHCH as a cyclohexanedicarboxylate-based compound, fatty acid, vegetable oil, Me ester, chlorinated (Cas No.: 95009-45-3) as a vegetable oil, and epoxidized soybean oil (Songwon Industry, E-700) as an epoxidized vegetable oil.

[0073] Example 2, Example 3, Comparative Examples 1 to 10

[0074] A plasticizer composition was prepared by the same method as in Example 1, except that the composition of the plasticizer in Example 1 was adjusted as shown in Table 1.

[0075] The compositions of the prepared plasticizer compositions are summarized in Table 1 below.

[0076]

Table 1

[0077] The following compositions are expressed as weight ratios of the main components in the plasticizer composition.

[0078]

[0079]

[0080] Vinyl chloride resin composition

[0081] Examples 1-1 and 1-2

[0082] Using the plasticizer composition prepared in Example 1, two vinyl chloride resin compositions were prepared.

[0083] Suspension: 100 parts by weight of PVC (Hanwha Solutions P-1000F), 40 parts by weight of the plasticizer composition of Example 1, 1.5 parts by weight of a Ba / Zn-based heat stabilizer, and 2 parts by weight of E-700 were mixed to prepare a vinyl chloride resin composition (Example 1-1).

[0084] Emulsion PVC (Plastic Sol): 100 parts by weight of PSR (Hanwha Solutions EL-103) and 60 parts by weight of the plasticizer composition of Example 1 were mixed to prepare a vinyl chloride resin composition (Example 1-2).

[0085] Examples 2-1 to 3-2 and Comparative Examples 1-1 to 9-2

[0086] Vinyl chloride resin compositions were prepared by the same methods as Examples 1-1 and 1-2, except that the plasticizer compositions of Example 2, Example 3, and Comparative Examples 1 to 9 were used instead of the plasticizer composition of Example 1 in Example 1-1, respectively.

[0087] <Experimental Example>

[0088] (1) Volatilization loss

[0089] The plasticizer composition was left at 200° C. for 1 hour, and then its before / after weight change was measured.

[0090] Volatilization loss (%) = [(initial weight of plasticizer composition - weight of plasticizer composition after standing) / initial weight of plasticizer composition] * 100

[0091] (2) Low temperature stability

[0092] In order to indirectly evaluate the outdoor storage stability in winter, the mixed plasticizer composition was placed in a refrigerator at -20°C to -10°C, and the frozen shape was observed.

[0093] (3) Viscosity

[0094] To measure the viscosity, each plastisol prepared above was aged in a 25° C. constant temperature drying oven for 1 hour, and then the initial viscosity was measured using a Brookfield viscometer (spindle #6, 20 RPM), and the results are shown in Table 1 below.

[0095] (4) Gel properties

[0096] 54 g of the mixed resin was introduced into a 95° C. Brabender mixer and mixed at 30 rpm for 10 minutes. The gel time of the resin was analyzed by the torque change during the mixer processing.

[0097] (5) Plasticizer migration

[0098] The migration of plasticizers was evaluated with reference to ISO 177:1988 (Plastics--Determination of migration ofPlasticizer). A circular molded sheet sample cut into a diameter of 50 mm was prepared, and oil paper (PP porous film) and a glass plate were overlapped on / under the sample in sequence so that the migrated plasticizer was absorbed by the oil paper. A load of 5 kg was applied to the sample, and the sample was placed in a 70°C oven for 5 days, and then the weight change rate (%) of the sample was measured to analyze the degree of migration of the plasticizer.

[0099] The weight change rate of the sample is calculated as [(change in sample weight / weight of sample before test)*100], and the weight change of the oil paper is calculated as [(change in oil paper weight / weight of oil paper before test)*100]. The weight loss of the sample is the same as the weight increase of the oil paper, so in this experiment, the migration of the plasticizer is evaluated only by the weight change rate of the sample.

[0100] (6) Hardness properties

[0101] Each of the above-prepared suspension vinyl chloride compositions was processed by a roll mill (170° C.) and a press (180° C.) to prepare a 2 mm sheet, and the hardness was measured with a Shore A durometer.

[0102] (7) Initial coloring

[0103] The yellowness index of the rolled sheet was measured using a Konica Minolta (CR 400) colorimeter according to ASTM E313.

[0104] (8) Thermal stability

[0105] The rolled sheet was cut into a strip shape of 15 mm × 480 mm and installed in a Mathis oven at 190°C. The setting was such that the sample installed in the oven was discharged out of the oven at a rate of 15 mm / 5 minutes. After the test was completed, the heat resistance time (minutes) was calculated by the length to the starting point of discoloration (non-carbonized length, mm).

[0106] (9) Tensile strength and elongation

[0107] The molded sheet was prepared into a dumbbell-shaped test specimen according to ASTM D638, and then the tensile strength and elongation were measured in a UTM (Universal Testing Machine) at a rate of 500 mm / min.

[0108]

Table 2

[0109]

[0110] *1: Emulsion PVC (plastisol) vinyl chloride composition

[0111]

Table 3

[0112]

[0113]

[0114] *2: Suspended PVC vinyl chloride composition

[0115] Referring to Tables 2 and 3, it can be confirmed that, in the examples, the low temperature stability is improved compared to commercial plasticizers (DINP, DOTP), in particular, the viscosity property is improved compared to DINP, and the thermal stability is improved compared to DOTP. It can also be confirmed that the other properties are similar to those of commercial plasticizers.

[0116] It can be confirmed that the volatilization loss, low temperature stability and thermal stability are particularly improved compared with DEHCH single material, and other mechanical properties have reached similar levels. Comparing DEHCH with Comparative Examples 3 to 8 in which either vegetable oil or epoxidized vegetable oil is mixed, it can be seen that in the case of mixing only vegetable oil, although low temperature stability is ensured, viscosity, volatilization loss and thermal stability are very poor, and in the case of mixing only epoxidized vegetable, although thermal stability is ensured, low temperature stability, viscosity properties, tensile strength and elongation, etc. are very poor.

[0117] Therefore, it can be confirmed that in the case of the plasticizer composition of the present invention, which is a ternary mixture of DEHCH, vegetable oil and epoxidized vegetable oil, the properties are uniformly improved, and thus the plasticizer properties are improved compared with a single material or a binary mixture.

Claims

1. A plasticizer composition comprising i) a cyclohexanedicarboxylate-based compound represented by the following Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, R 1 and R 2 Each is independently a C4-12 straight or branched chain alkyl; ii) vegetable oils; as well as iii) epoxidized vegetable oils, Wherein, based on 100 parts by weight of the plasticizer composition, the plasticizer composition comprises: 50 to 70 parts by weight of the cyclohexanedicarboxylate-based compound; 10 to 35 parts by weight of the vegetable oil; and 10 to 30 parts by weight of the epoxidized vegetable oil.

2. The plasticizer composition according to claim 1, in, The cyclohexanedicarboxylate-based compound is one of the following Chemical Formulas 1-1 to 1-3: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] In Chemical Formulas 1-1 to 1-3, R 3 To R 8 Each is independently butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, 2-propylheptyl, decyl or isodecyl.

3. The plasticizer composition according to claim 1, in, The cyclohexane dicarboxylate-based compound comprises one or more 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.

4. The plasticizer composition according to claim 1, in, The vegetable oil comprises one or more selected from soybean oil, castor oil, linseed oil, palm oil, tall oil, tung oil, grape seed oil, olive oil, jojoba oil, poppy seed oil, cottonseed oil, rapeseed oil, wheat germ oil, peanut oil, walnut oil and their derivatives.

5. The plasticizer composition according to claim 1, in, The epoxidized vegetable oil comprises one or more selected from epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized tall oil, epoxidized tung oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized jojoba oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized wheat germ oil, epoxidized peanut oil and epoxidized walnut oil.

6. The plasticizer composition according to claim 1, in, Based on 100 parts by weight of the plasticizer composition, the plasticizer composition comprises: 60 to 70 parts by weight of the cyclohexanedicarboxylate-based compound; 15 to 30 parts by weight of the vegetable oil; and 15 to 25 parts by weight of the epoxidized vegetable oil.

7. The plasticizer composition according to claim 1, in, The plasticizer composition does not freeze at -20°C to -10°C.

8. A vinyl chloride resin composition comprising the plasticizer composition according to any one of claims 1 to 7.

9. The vinyl chloride resin composition according to claim 8, in, The vinyl chloride resin composition includes 10 to 200 parts by weight of the plasticizer composition based on 100 parts by weight of the vinyl chloride resin.

10. A vinyl chloride resin molded product comprising the vinyl chloride resin composition according to claim 8.

11. The vinyl chloride resin molded product according to claim 10, in, The vinyl chloride resin molded product is wallpaper, flooring, decorative board, packaging for food packaging, packaging material, electric wire, automobile interior material, film, hose or pipe.

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