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 excellent physical properties such as gelling speed, mechanical strength, optical properties, unwindability, and adhesion properties, and 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. 10-2024-0191748 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 having improved gelling speed, excellent mechanical strength and optical properties, and improved releaseability and tackiness, 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 harmful to the human body as endocrine disruptors; they have been classified as hazardous substances, such as endocrine disruptors, leading to a demand for alternative components. 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, DOTP (di-octyl terephthalate), based on terephthalic acid, is a general-purpose product. However, as toxicity remains an issue and it cannot replace phthalate plasticizers in terms of quality, research on cyclohexane plasticizers has recently been underway.

[0009] A representative cyclohexane-based plasticizer is DEHCH (di(2-ethylhexyl)cyclohexane dicarboxylate). DEHCH exhibits excellent hardness properties and poses fewer environmental issues compared to phthalate-based plasticizers. However, DEHCH presents challenges regarding low-temperature stability, volatility, and thermal stability. To address these issues, research is being conducted on plasticizer compositions in which various additional substances are mixed with DEHCH.

[0010] In addition to the aforementioned compounds, the use of palm oil or coconut oil-based vegetable oils is also being considered. However, these vegetable plasticizers have the problem of inferior processability, mechanical properties, and bleeding characteristics compared to chemical plasticizers.

[0011]

[0012] One embodiment of the present disclosure aims to provide a plasticizer composition and a vinyl chloride resin composition comprising the same.

[0013] Specifically, the first embodiment of the present disclosure aims to provide a plasticizer composition having excellent physical properties such as gelling speed, mechanical strength, optical properties, releaseability, and tackiness, and a vinyl chloride resin composition containing the same.

[0014]

[0015] One embodiment of the present disclosure provides a plasticizer composition comprising a cyclohexane dicarboxylate-based compound, a terephthalate-based compound or a mixture thereof; and a non-petroleum-based compound.

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

[0017] In addition, another embodiment of the present disclosure provides a vinyl chloride resin molded article comprising the vinyl chloride resin composition.

[0018]

[0019] The terms used in this specification are used merely to describe exemplary embodiments and are not intended to limit the invention.

[0020] A singular expression includes a plural expression unless the context clearly indicates otherwise.

[0021] 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.

[0022] 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.

[0023] The present invention will be described in detail below.

[0024]

[0025] The plasticizer composition according to the present invention comprises a cyclohexane dicarboxylate-based compound, a terephthalate-based compound, or a mixture thereof, and a non-petroleum-based compound.

[0026] The above cyclohexane dicarboxylate-based compound can be represented by the following chemical formula 1.

[0027] [Chemical Formula 1]

[0028]

[0029] In the above chemical formula 1,

[0030] R1 and R2 can each be independently selected from straight-chain or branched-chain alkyl groups having 4 to 12 carbon atoms.

[0031] The compound represented by the above [Chemical Formula 1] may be represented by the following [Chemical Formula 1-1] to [Chemical Formula 1-3] depending on the position of the carboxylate group substitution on cyclohexane.

[0032] [Chemical Formula 1-1]

[0033]

[0034] [Chemical Formula 1-2]

[0035]

[0036] [Chemical Formula 1-3]

[0037]

[0038] The above [Chemical Formula 1-1] is a cyclohexane-1,4-dicarboxylate-based compound, the above [Chemical Formula 1-2] is a cyclohexane-1,3-dicarboxylate-based compound, and the above [Chemical Formula 1-3] is a cyclohexane-1,2-dicarboxylate-based compound.

[0039] In addition, in the above chemical formulas 1-1 to 1-3, R5 to R 10 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.

[0040] For example, in a cyclohexane-1,4-dicarboxylate-based compound, if R5 and R6 are the same, it may be di(butyl)cyclohexane-1,4-dicarboxylate, di(isononyl)cyclohexane-1,4-dicarboxylate, etc.; if R5 and R6 are different, it may be butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, butyl(isononyl)cyclohexane-1,4-dicarboxylate, etc.

[0041] 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 R5 and R6 are both 2-ethylhexyl groups in the cyclohexane-1,4-dicarboxylate-based compound. This compound has the structure of [Chemical Formula 1-4] below and is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, DEHCH).

[0042] [Chemical Formula 1-4]

[0043]

[0044] According to one embodiment of the present invention, the cyclohexane dicarboxylate-based compound in the plasticizer composition 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.

[0045]

[0046] The above terephthalate-based compound can be represented by the following chemical formula 2.

[0047] [Chemical Formula 2]

[0048]

[0049] In the above chemical formula 2, R3 and R4 are each independently straight-chain or branched-chain alkyl groups having 4 to 12 carbon atoms.

[0050] In addition, in the above chemical formula 2, R3 and R4 are each a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, or an isodecyl group.

[0051] The terephthalate compound represented by the above chemical formula 2 may be one or more selected from the group consisting of dibutyl terephthalate (DBTP; dibutyl terephthalate), dioctyl terephthalate (DOTP; dioctyl terephthalate, or di(2-ethylhexyl)terephthalate), diisononyl terephthalate (DINTP; diisononyl terephthalate), and diisodecyl terephthalate (DIDTP; diisodecyl terephthalate). Specifically, the terephthalate compound represented by the above chemical formula 2 may be dioctyl terephthalate represented by the following chemical formula 2-1.

[0052] [Chemical Formula 2-1]

[0053]

[0054]

[0055] Conventional palm oil and coconut oil-based vegetable oil plasticizers, which were used by mixing them into plasticizer compositions, pose environmental problems as previously described. Furthermore, due to bleeding issues that limit the amount that can be added, it has been difficult to manufacture soft products mixed with bioplasticizers.

[0056] However, in the present invention, a non-petroleum compound produced by chlorination is intended to be used in the plasticizer composition to replace conventionally used palm oil and coconut oil-based vegetable oils.

[0057] Specifically, a non-petroleum compound, which 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.

[0058] Specifically, the non-petroleum compound may be a chlorinated bio-oil. The chlorinated bio-oil may include chlorinated vegetable oil, chlorinated animal oil, chlorinated biodiesel byproduct, or chlorinated waste 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).

[0059] 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.

[0060] Chlorinated bio-oil can be obtained by chlorinating ester compounds known in the industry.

[0061]

[0062] The above-mentioned non-petroleum compound exhibits improved bleeding properties, specifically migration resistance, making it easy to add to polymers to impart flexibility. Furthermore, since adding the above-mentioned non-petroleum compound to a resin results in flexibility while maintaining transparency, it can be applied to various uses requiring transparent, flexible polymer characteristics.

[0063] Therefore, when using a plasticizer blended with a cyclohexane dicarboxylate-based compound or a terephthalate-based compound and the non-petroleum-based compound of the present invention, the processing time for film / wrap applications is shortened due to the improved gelling speed, and a resin product with improved physical properties such as mechanical strength and optical properties (transmittance, haze) and excellent unwindability and improved tackiness can be obtained.

[0064]

[0065] The plasticizer composition according to the first embodiment of the present disclosure includes the non-petroleum compound together with the cyclohexane dicarboxylate-based compound and / or terephthalate-based compound, thereby having excellent compatibility with resins such as PVC compared to existing eco-friendly plasticizers, and when applied to resins, mechanical strength, releaseability, permeability, haze, migration resistance, and tackiness are improved, and the gelling speed is increased so that processing time can be shortened.

[0066]

[0067] A plasticizer composition according to one embodiment of the present invention may include 10 to 90 parts by weight of the non-petroleum compound with respect to 100 parts by weight of the plasticizer composition. Specifically, with respect to 100 parts by weight of the plasticizer composition, the non-petroleum compound may be included in an amount of 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more to 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, or 50 parts by weight or less.

[0068] If too much non-petroleum (bio) compound is included, compatibility with the resin is poor, which may lead to excessive migration, and there may be problems with processing due to low plasticization efficiency and slow gelling speed. In addition, when used as a wrap, the adhesive strength is low and it becomes sticky during long-term storage, making it inconvenient to use.

[0069] On the other hand, if too little non-petroleum compound is included, the unsalvageability becomes poor and the adhesiveness is too strong, which may lead to reduced workability when performing a lot of manual packaging with the manufactured finished product.

[0070]

[0071] The plasticizer composition of one embodiment of the present invention may be included as a primary plasticizer in a vinyl chloride resin composition for wrap. That is, the plasticizer composition of one embodiment of the present invention may be used as a primary plasticizer in a vinyl chloride resin composition for wrap, such as for food. The vinyl chloride resin composition for wrap may further include a primary plasticizer, a secondary plasticizer, and additives, etc., in polyvinyl chloride. The secondary plasticizer of the vinyl chloride resin composition for wrap may serve as both a plasticizer and an auxiliary stabilizer.

[0072] The above secondary plasticizer is a plant-derived plasticizer, and can be used as an epoxidized vegetable oil 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, walnut oil, etc. Specifically, epoxidized soybean oil can be used. The secondary plasticizer can impart a thermal stabilization effect to the vinyl chloride resin composition together with the heat stabilizer described later.

[0073] A plasticizer composition of one embodiment of the present invention, which can be used as a primary plasticizer in a vinyl chloride resin composition for wrap, may be a two-component system comprising a cyclohexane dicarboxylate-based compound and a non-petroleum-based compound, or a terephthalate-based compound and a non-petroleum-based compound.

[0074] That is, when a non-petroleum compound is included in an amount of 10 to 90 parts by weight per 100 parts by weight of a plasticizer composition, the remainder is a cyclohexane dicarboxylate-based compound or a terephthalate-based compound.

[0075]

[0076] According to one embodiment of the present invention, the plasticizer composition may be prepared by mixing and blending the cyclohexane dicarboxylate-based material and / or terephthalate-based compound with the non-petroleum-based compound.

[0077]

[0078] 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 mechanical strength, optical properties, releaseability, adhesiveness, and gelling speed.

[0079] 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.

[0080] 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.

[0081] A vinyl chloride resin composition comprising a plasticizer composition of one embodiment of the present invention has a hardness (Shore A) of 90 or less, a transmittance of 80% or more, a haze of 5% or less, an initial colorability (initial Yellow Index) of 30 or less, a migration resistance of 2% or less, preferably a migration resistance of 1% or less, and a tensile strength of 150 kgf / cm² 2 Ideally, the tensile strength is 180 kgf / cm² 2 Above, the elongation rate may be 250% or more, and the gelling speed may be 140 seconds or less.

[0082] The measurement method for each of the above physical properties is as described in the experimental examples below.

[0083]

[0084] Additionally, the vinyl chloride resin composition may further include other additives such as antifogging agents, heat stabilizers, fillers, and foaming agents. Specifically, the vinyl chloride resin composition may further include one or more selected from the group consisting of antifogging agents, heat stabilizers, fillers, and foaming agents.

[0085] The above anti-fog agent is intended to prevent the formation of water droplets caused by the condensation of vapor on the film surface, and polyhydric alcohol fatty acid esters such as monoglycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene fatty acid esters, particularly polyglycerol monooleate, may be used. Since the anti-fog agent may cause a decrease in transparency if added in excess, it is preferable to add it in an appropriate amount. Specifically, it may be added in an amount of 1 to 2 parts by weight per 100 parts by weight of polyvinyl chloride.

[0086] The above-mentioned heat stabilizer is a component intended to prevent thermal decomposition of vinyl chloride resin under high-temperature processing conditions and to suppress the generation of hydrogen chloride caused by heating; a non-lead heat stabilizer, in particular a calcium-zinc organic complex heat stabilizer, is used. The calcium-zinc organic complex heat stabilizer may be a mixture of fatty acid salts of calcium and zinc having one or more fatty acids selected from the group consisting of lauric acid, oleic acid, benzoic acid, behenic acid, stearic acid, and ricinoleic acid. The heat stabilizer may preferably be added in an amount of 0.1 to 2 parts by weight per 100 parts by weight of polyvinyl chloride.

[0087] 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.

[0088] In addition, the 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.

[0089] 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.

[0090] 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.

[0091] The above vinyl chloride resin molded article may be molded into a film or a wrap. For example, the above vinyl chloride resin molded article may be used in food packaging wrap.

[0092]

[0093] The plasticizer compositions disclosed herein have improved overall physical properties, such as mechanical strength, optical properties, releaseability, adhesiveness, and gelling speed, compared to existing eco-friendly plasticizer compositions, and thus have high utility value as eco-friendly plasticizers.

[0094] In addition, the vinyl chloride resin composition comprising the plasticizer composition according to the present disclosure is flexible while maintaining transparency, so it can be widely applied to applications requiring transparent soft polymer properties.

[0095]

[0096] 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.

[0097]

[0098] <Example>

[0099] Example 1

[0100] DEHCH was used as a cyclohexane dicarboxylate compound, and Biobased Chlorinated Methyl Tallow Ester (CAS 68440-29-9) was used as a non-petroleum compound. A plasticizer composition was prepared by mixing 30 parts by weight of DEHCH and 70 parts by weight of the non-petroleum compound.

[0101]

[0102] Example 2

[0103] DEHCH was used as a cyclohexane dicarboxylate compound, and Biobased Chlorinated Methyl Tallow Ester (CAS 68440-29-9) was used as a non-petroleum compound. A plasticizer composition was prepared by mixing 50 parts by weight of DEHCH and 50 parts by weight of the non-petroleum compound.

[0104]

[0105] Example 3

[0106] DEHCH was used as a cyclohexane dicarboxylate compound, and Biobased Chlorinated Methyl Tallow Ester (CAS 68440-29-9) was used as a non-petroleum compound. A plasticizer composition was prepared by mixing 70 parts by weight of DEHCH and 30 parts by weight of the non-petroleum compound.

[0107]

[0108] Example 4

[0109] DOTP was used as the terephthalate-based compound, and Biobased Chlorinated Methyl Tallow Ester (CAS 68440-29-9) was used as the non-petroleum-based compound. A plasticizer composition was prepared by mixing 50 parts by weight of DOTP and 50 parts by weight of the non-petroleum-based compound.

[0110]

[0111] Example 5

[0112] DOTP was used as the terephthalate-based compound, and Biobased Chlorinated Methyl Tallow Ester (CAS 68440-29-9) was used as the non-petroleum-based compound. A plasticizer composition was prepared by mixing 30 parts by weight of DOTP and 70 parts by weight of the non-petroleum-based compound.

[0113]

[0114] <Comparative Example>

[0115] Comparative Example 1

[0116] 100 parts by weight of Biobased Chlorinated Methyl Tallow Ester (CAS 68440-29-9) was used alone as a non-petroleum compound.

[0117]

[0118] Comparative Example 2

[0119] 100 parts by weight of Almax-5000, an acetylated monoglyceride compound from Ilshin Wells, was used alone as a plasticizer composition.

[0120]

[0121] Comparative Example 3

[0122] 100 parts by weight of dioctyl adipate (DOA) was used alone as a plasticizer composition.

[0123]

[0124] Comparative Example 4

[0125] 100 parts by weight of DEHCH, a cyclohexane dicarboxylate-based compound, was used alone as a plasticizer composition.

[0126]

[0127] Comparative Example 5

[0128] Ilshin Wells' Ecocizer 7000 series, an acetylated monoglyceride-based compound, was used alone as a plasticizer composition in an amount of 100 parts by weight.

[0129]

[0130] Comparative Example 6

[0131] DEHCH, a cyclohexane dicarboxylate compound, and Ilshin Wells' Almax-5000, an acetylated monoglyceride compound, were each mixed and used in an amount of 50 parts by weight.

[0132]

[0133] <Experimental Example>

[0134] Vinyl chloride resin composition

[0135] A vinyl chloride resin composition comprising the plasticizer compositions of Examples 1 to 5 and Comparative Examples 1 to 6 was prepared.

[0136] 100 parts by weight of polyvinyl chloride (P-1000F, Hanwha Solution), 40 parts by weight of a plasticizer composition, 1 part by weight of a calcium-zinc-based organic stabilizer (LTX, KD Chem), and 10 parts by weight of epoxy oil (E-700, Songwon Industrial) were mixed. Subsequently, the mixture was mixed in a Hobart mixer for 10 minutes to prepare a vinyl chloride resin composition.

[0137] 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 specimens for physical property evaluation with a thickness of 2 mm or 6 mm.

[0138]

[0139] Hardness measurement method

[0140] Specimens for evaluating physical properties were prepared with dimensions of 5 cm x 5 cm x 4 cm, and their hardness was measured using a Shore A durometer. The durometer needle was fully lowered into one spot on the specimen, and the hardness value was read after 5 seconds. For each specimen, three spots were tested, and the average value was taken. A lower hardness value was evaluated as indicating superior flexibility of the product.

[0141]

[0142] Transmittance and Haze Measurement Method

[0143] The transmittance and haze of a specimen prepared with a thickness of 2 mm according to ASTM D1003 standards were measured using a BYK-Gardner instrument.

[0144]

[0145] Evaluation method for initial coloration (Yellow Index)

[0146] Product color was evaluated by manufacturing 6 mm thick sheets according to ASTM E313 standards using the Yellow Index (YI). A lower Yellow Index value was evaluated as indicating superior physical properties. Additionally, initial coloring refers to the yellowness measured after specimen preparation and before evaluating other physical properties.

[0147]

[0148] Plasticizer migration assessment method

[0149] Plasticizer migration was determined by referring to the ISO 177:1988 (Plastics - Determination of migration of Plasticizer) method. Molding sheet specimens were prepared by cutting a 6 mm thick sheet into a 50 mm diameter circle. Parchment paper (PP porous film) and a glass plate were placed sequentially on top and bottom of the specimens to allow the plasticizer migrated from the specimens to be absorbed into the parchment paper. After applying a 5 kg load to the specimens and leaving them at 70°C for 5 days, the percentage change in weight of the specimens was measured to analyze the degree of plasticizer migration.

[0150] 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.

[0151]

[0152] Method for measuring elongation and tensile strength

[0153] Elongation and tensile strength were measured by preparing a molding sheet into a dumbbell-shaped specimen with a thickness of 2 mm according to ASTM D638, and then using a Universal Test Machine (UTM) at a speed of 500 mm / min.

[0154]

[0155] Gelling speed measurement method

[0156] 54g of the blended resin was placed into a 95℃ Brabender Mixer and mixed at 30 rpm for 10 minutes. The gelling time of the resin was analyzed through changes in torque during the mixing time.

[0157]

[0158] Unravelability evaluation method

[0159] The unwindability of the wrap film was measured using a universal testing machine (UTM). The degree of increase or decrease in unwindability of other examples and comparative examples was compared based on Comparative Example 2.

[0160]

[0161] Adhesion strength evaluation method

[0162] The adhesive strength of the wrap film was measured using a universal testing machine (UTM). The degree of increase or decrease in adhesive strength of other examples and comparative examples was compared based on Comparative Example 2.

[0163]

[0164] The data evaluated above is shown in Table 1 below.

[0165]

[0166] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Hardness (Shore A) 8585828786858379818380 Transmittance 898989898989898888889888 Haze (%) 2.12.0 2.42.5 2.5 2.8 3.42.2 2.5 3.42.5 Initial Color (YI) 28.0 27.5 27.0 27.5 27.0 28.9 25.8 25 25.9 26.4 26.0 Migration (%) 0.9 10.8 20.6 30.8 40.7 51.1 00.7 31.4 00.5 71.0 10.60 Tensile Strength (kgf / cm²) 2 )180 194 189 187 188 184 187 172 179 183 185 Elongation (%) 350 378 370 364 360 361 352 399 346 398 373 Gelling Speed ​​(sec, @100℃) 125 115 109 130 136 130 246 240 90 125 118 Unfoldability 3% Increase 1% Decrease 2% Increase 2% Increase 1% Increase 5% Increase Baseline 8% Increase 6% Increase 4% Increase 5% Increase Tack (180°) 8% Decrease 3% Decrease 12% Increase 3% Increase 4% Decrease 11% Decrease Baseline 5% Increase 27% Increase 7% Increase 10% Increase Bio-compound content in 100 parts by weight of plasticizer (parts by weight) 70 50 30 50 70 100 100 00 50~70 50 Deforestation ConcernsXXXXXXOXX△△

[0167] According to Table 1 above, Comparative Example 1, which contains only non-petroleum-based compounds as plasticizers, showed inferior migration performance compared to the Example. In the case of Comparative Example 2, although the plasticizer consists entirely of bio-derived compounds, it can be confirmed that compared to the Example, there is a concern regarding deforestation, and the haze value, elongation rate, and gelling speed are inferior.

[0168] In addition, Comparative Example 3 does not include any bio-derived compounds in the plasticizer composition, which contradicts the goal of providing an eco-friendly plasticizer composition. It was confirmed that Comparative Example 3 had lower hardness, greater migration, slower gelling speed, and lower tensile strength compared to the example.

[0169] It was confirmed that Comparative Example 4 had a slightly lower tensile strength and a slightly lower elongation compared to the Example.

[0170] Comparative Example 5 had a higher haze value compared to the Example, resulting in inferior optical properties, and Comparative Example 5 had lower hardness compared to the Example. In addition, although Comparative Examples 5 and 6 both included eco-friendly compounds in the plasticizer composition, they were not suitable due to concerns about deforestation.

Claims

1. i) a cyclohexane dicarboxylate compound represented by the following chemical formula 1, a terephthalate compound represented by the following chemical formula 2, or a mixture thereof; and ii) Non-petroleum compounds; As a plasticizer composition comprising, The non-petroleum compound is included in an amount of 10 to 90 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 and R2 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, R3 and R4 are each independently straight-chain or branched-chain alkyl groups having 4 to 12 carbon atoms.

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

3. In Paragraph 2, The above-mentioned chlorinated bio-oil comprises chlorinated vegetable oil, chlorinated animal oil, chlorinated biodiesel byproduct, or chlorinated discarded bio-oil. Plasticizer composition.

4. In Paragraph 1, The above-mentioned cyclohexane dicarboxylate-based compound is any one of the following chemical formulas 1-1 to 1-3, a plasticizer composition: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the above chemical formulas 1-1 to 1-3, R5 to R 10 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.

5. 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.

6. In Paragraph 1, In the above chemical formula 2, R3 and R4 are each independently an n-butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, or an isodecyl group, Plasticizer composition.

7. In Paragraph 1, The terephthalate compound represented by the above chemical formula 2 comprises one or more selected from the group consisting of dibutyl terephthalate (DBTP; dibutyl terephthalate), dioctyl terephthalate (DOTP; dioctyl terephthalate, or di(2-ethylhexyl)terephthalate), diisononyl terephthalate (DINTP; diisononyl terephthalate), and diisodecyl terephthalate (DIDTP; diisodecyl terephthalate). Plasticizer composition.

8. Polyvinyl chloride; and A vinyl chloride resin composition comprising 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 the polyvinyl chloride.

10. In Paragraph 8, The above vinyl chloride resin composition further comprises one or more selected from the group consisting of anti-fogging agents, heat 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 formed into a film or wrap.

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