Plasticizer Composition

Abstract

The present invention relates to a plasticizer composition that contains recycled raw materials, can reduce carbon emissions, is environmentally friendly, and has excellent gelling properties, plasticizing efficiency, and weather resistance.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0186411 dated December 29, 2020 and Korean Patent Application No. 10-2021-0174063 dated December 7, 2021, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to plasticizer compositions containing recycled raw materials. [Background technology]

[0003] Recently, in order to protect the environment and recycle resources, research has been conducted into recovering useful resources from waste synthetic resins and by-products generated during the synthetic resin manufacturing process. Research is also being actively conducted into reducing carbon emissions generated during the production of synthetic resin products.

[0004] Many techniques for recycling waste synthetic resins, particularly methods for recycling waste polyesters, are known. One known method is to depolymerize waste polyesters in the presence of a catalyst and regenerate them with the raw materials terephthalic acid, dimethyl terephthalate, and ethylene glycol. The regenerated terephthalic acid and dimethyl terephthalate can be regenerated into dioctyl terephthalate, a substance useful as a plasticizer, through an esterification reaction or an ester exchange reaction. In addition, Chinese Patent Publication Nos. 104230714 and 104496819 disclose a method for recovering dioctyl terephthalate from wastewater from a polyester weight reduction process.

[0005] Dioctyl terephthalate is a widely used plasticizer, and the dioctyl terephthalate recovered by the regeneration process can also be used as a plasticizer for polymer resins. However, the regenerated dioctyl terephthalate has the disadvantages of being yellow in color and having a strong odor compared to pure dioctyl terephthalate due to impurities mixed in during the recycling process. Therefore, there is a problem that the regenerated dioctyl terephthalate can only be used when manufacturing relatively low-quality products.

[0006] Therefore, there is a demand for the development of a plasticizer composition containing a phthalate compound such as dioctyl terephthalate, which can achieve resource recycling and reduce carbon emissions in the production process and also exhibits excellent quality. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] China Patent Publication No. 104230714 [Patent Document 2] China Patent Publication No. 104496819 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a plasticizer composition which contains a recycled phthalate compound obtained from waste polyester or wastewater generated in the polyester production process and which exhibits excellent physical properties. [Means for solving the problem]

[0009] According to one embodiment of the present invention, A recycled phthalate compound as a first plasticizer; and A plasticizer composition comprising as a second plasticizer a pure cyclohexanedicarboxylate-based compound and / or a recycled cyclohexanedicarboxylate-based compound; A plasticizer composition is provided that includes less than 95 parts by weight of the first plasticizer, based on 100 parts by weight of the plasticizer composition.

[0010] In this case, 100 parts by weight of the plasticizer may include 20 to 85 parts by weight of the first plasticizer and 5 to 70 parts by weight of the second plasticizer.

[0011] The first plasticizer may be one or more selected from the group consisting of regenerated dibutyl phthalate, regenerated dihexyl phthalate, regenerated dioctyl phthalate, regenerated di-n-octyl phthalate, regenerated diisononyl phthalate, regenerated diisodecyl phthalate, regenerated dibutyl isophthalate, regenerated dioctyl isophthalate, regenerated diisononyl isophthalate, regenerated diisodecyl isophthalate, regenerated dibutyl terephthalate, regenerated dioctyl terephthalate, regenerated diisononyl terephthalate, and regenerated diisodecyl terephthalate.

[0012] The first plasticizer may have an acid value in the range of 0.05 KOH mg / g to 0.25 KOH mg / g.

[0013] The cyclohexane dicarboxylate compound may be one or more selected from the group consisting of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclohexane-1,4-dicarboxylate.

[0014] As an example, the first plasticizer can be recycled dioctyl terephthalate and the second plasticizer can be pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and / or recycled di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate.

[0015] The plasticizer composition may further include one or more compounds selected from the group consisting of phthalate-based compounds; polyol ester-based compounds; trimellitate-based compounds; aliphatic ester-based compounds; phosphate-based compounds; vegetable oils; epoxidized oils; and acylated monoglyceride compounds.

[0016] The plasticizer composition may have a carbon emission reduction rate of 5% or more.

[0017] The plasticizer composition may have an acid value of 0.25 KOH mg / g or less and a Yellow index (YI) of 120 or less as measured according to ASTM E313.

[0018] According to another embodiment of the present invention, there is provided a resin composition comprising the plasticizer composition; and one or more resins selected from the group consisting of polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin, polyketone, polyvinyl butyral, acrylic, synthetic rubber resin, and thermoplastic elastomer.

[0019] The resin composition may contain 1 part by weight to 200 parts by weight of the plasticizer composition relative to 100 parts by weight of the resin.

[0020] The resin composition may have a Yellow Index (YI) of 10 to 25 as measured according to the ASTM E313 standard and / or a Yellow Index (YI) of 10 to 65 as measured after 300 hours of UV aging according to the ASTM G154 method.

[0021] According to yet another embodiment of the present invention, there is provided a molded article comprising the resin composition. Effect of the Invention

[0022] The plasticizer composition of the present invention contains recycled phthalate compounds, and has little yellow color and odor that are characteristic of recycled raw materials, and has excellent gelling properties, plasticizing efficiency, and weather resistance, so that it can be used as a general-purpose plasticizer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless a different meaning is clearly indicated in the context.

[0024] Since the present invention can be modified in various ways and can have various forms, specific examples are exemplified and described in detail below, but it is not intended to limit the present invention to the specific disclosed form, and it should be understood that the present invention includes all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0025] The plasticizer composition of the present invention, the resin composition containing the same, and the molded article will be described in more detail below.

[0026] Plasticizer Composition

[0027] First Plasticizer The plasticizer composition of the present invention includes a recycled phthalate-based compound as a first plasticizer.

[0028] In the present invention, the recycled phthalate-based compound means a phthalate-based compound that is not synthesized from a pure raw material but is recovered from waste through reprocessing.

[0029] In this case, the phthalate compound refers to a compound represented by the following formula 1: [ka] In the above Chemical Formula 1, R 1 and R 2are each independently a linear or branched alkyl group having 4 to 12 carbon atoms.

[0030] Preferably, R 1 and R 2 may each independently be n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, isononyl, or isodecyl.

[0031] The phthalate compound of the formula 1 is represented by the following formulas 1-1 to 1-3 depending on the position of the substituent.

[0032] [ka]

[0033] In the above chemical formulas 1-1 to 1-3, R 1 and R 2 is as defined in Chemical Formula 1.

[0034] The compound represented by Chemical Formula 1-1 is a phthalate compound, the compound represented by Chemical Formula 1-2 is an isophthalate compound, and the compound represented by Chemical Formula 1-3 is a terephthalate compound.

[0035] Specific examples of the phthalate compound represented by Chemical Formula 1-1 include dibutyl phthalate (DBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP, or di(2-ethylhexyl)phthalate), di-n-octyl phthalate (DnOP), diisononyl phthalate, and diisodecyl phthalate (DIDP).

[0036] Specific examples of the isophthalate compound represented by Chemical Formula 1-2 include dibutyl isophthalate (DBIP), dioctyl isophthalate (DOIP, or di(2-ethylhexyl)isophthalate), diisononyl isophthalate (DINIP), and diisodecyl isophthalate (DIDIP).

[0037] Specific examples of the terephthalate compound represented by Chemical Formula 1-3 include dibutyl terephthalate (DBTP), dioctyl terephthalate (DOTP, or di(2-ethylhexyl)terephthalate), diisononyl terephthalate (DINTP), and diisodecyl terephthalate (DIDTP).

[0038] The regenerated phthalate-based compound of the present invention may be a single or mixture of the above-mentioned phthalate compounds, isophthalate compounds, and terephthalate compounds. In one embodiment, the regenerated phthalate-based compound may be one or more selected from the group consisting of regenerated dibutyl phthalate, regenerated dihexyl phthalate, regenerated dioctyl phthalate, regenerated di-n-octyl phthalate, regenerated diisononyl phthalate, regenerated diisodecyl phthalate, regenerated dibutyl isophthalate, regenerated dioctyl isophthalate, regenerated diisononyl isophthalate, regenerated diisodecyl isophthalate, regenerated dibutyl terephthalate, regenerated dioctyl terephthalate, regenerated diisononyl terephthalate, and regenerated diisodecyl terephthalate. Preferably, the regenerated phthalate-based compound may be regenerated dioctyl terephthalate.

[0039] The regenerated phthalate compounds used in the present invention are commercially available or can be obtained from waste materials using known methods.

[0040] For example, the recycled phthalate-based compound may be obtained by depolymerizing waste polyester to obtain aromatic dicarboxylic acid or its ester, and reacting the aromatic dicarboxylic acid or its ester with a suitable alcohol.

[0041] Alternatively, phthalic acid can be extracted from waste materials such as wastewater discharged during alkaline weight reduction processing of polyester fibers, wastewater generated in the process of producing pure terephthalate compounds, and residues after filtration, and then reacted with alcohol to obtain regenerated phthalate compounds.

[0042] In the present invention, the recycled phthalate-based compound is contained in an amount of less than 95 parts by weight based on 100 parts by weight of the total plasticizer composition.

[0043] Recycled phthalate compounds contain impurities that are mixed in during the process of recycling waste materials, and they tend to be yellowish and have a foul odor, such as an oily smell. In addition, recycled phthalate compounds often have a high acid value. These issues make it difficult to use recycled phthalate compounds in the manufacture of high-quality products where color and odor are important.

[0044] Therefore, in the present invention, the content of recycled phthalate compounds is controlled to less than 95 parts by weight per 100 parts by weight of the plasticizer composition, and pure or recycled cyclohexanedicarboxylate compounds are used as a second plasticizer together with the recycled phthalate compounds, thereby solving the color and odor problems caused by the recycled phthalate compounds.

[0045] Preferably, the recycled phthalate-based compound is present in an amount of 85 parts by weight or less, or 70 parts by weight or less, and 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, based on 100 parts by weight of the plasticizer composition.

[0046] Meanwhile, as described above, the recycled phthalate-based compound has a higher acid value than the pure plasticizer. Specifically, the acid value of the recycled phthalate-based compound may be 0.05 KOH mg / g or more, 0.1 KOH mg / g or more, or 0.15 KOH mg / g or more, and 0.25 KOH mg / g or less, 0.2 KOH mg / g or less, or 0.18 KOH mg / g or less.

[0047] Thus, recycled phthalate compounds have the disadvantages of having a higher acid value than conventional plasticizers, being yellow in color, and having a somewhat strong odor, but their thermal stability and gelation speed are about 5% higher than those of pure phthalate compounds.The plasticizer composition of the present invention mainly uses recycled phthalate compounds instead of pure phthalate compounds, and also contains pure or recycled cyclohexanedicarboxylate compounds as a second plasticizer, thereby compensating for the color characteristics and odor issues caused by the inclusion of recycled raw materials, and further improving the gelation speed.

[0048] However, if the acid value of the recycled phthalate compound is excessively high, exceeding 0.25 KOH mg / g, the color of the plasticizer composition will be excessively yellow, the odor will be strong, and the resistance to plasticizer migration will be poor, so it is preferable to maintain the acid value within the above range.

[0049] In this case, the acid value is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1 g of sample, and can be determined by titrating the sample solution with a 0.1N alcoholic KOH solution.

[0050] Second Plasticizer The plasticizer composition of the present invention includes a cyclohexanedicarboxylate compound as a second plasticizer. The cyclohexanedicarboxylate compound may be a pure cyclohexanedicarboxylate compound produced from pure raw materials, a recycled cyclohexanedicarboxylate compound recovered from waste through reprocessing, or a combination thereof.

[0051] Cyclohexanedicarboxylate-based compounds can be used together with recycled phthalate-based compounds to improve the plasticizing efficiency and gelling rate of the plasticizer composition. Moreover, both pure cyclohexanedicarboxylate-based compounds and recycled cyclohexanedicarboxylate-based compounds have lighter colors and better odors than recycled phthalate-based compounds, so they can be used as second plasticizers to complement the color and odor characteristics of the first plasticizer.

[0052] The cyclohexanedicarboxylate compound is represented by the following Chemical Formula 2: [ka] In the above Chemical Formula 2, R' 1 and R' 2 are each independently a linear or branched alkyl group having 4 to 12 carbon atoms.

[0053] Preferably, R' 1 and R' 2 are each independently 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, a isononyl group, a 2-propylheptyl group, a decyl group, or an isodecyl group. 1 and R' 2 are each independently a butyl group, a 2-ethylhexyl group, or an isononyl group.

[0054] The cyclohexanedicarboxylate compound represented by the above formula 2 is represented by the following formulas 2-1 to 2-3 depending on the position of the substituent. [ka] In the above chemical formulas 2-1 to 2-3, R' 1 and R' 2 is as defined in Chemical Formula 2.

[0055] The compound represented by Chemical Formula 2-1 is a cyclohexane-1,2-dicarboxylate compound, the compound represented by Chemical Formula 2-2 is a cyclohexane-1,3-dicarboxylate compound, and the compound represented by Chemical Formula 2-3 is a cyclohexane-1,4-dicarboxylate compound.

[0056] In one embodiment, the cyclohexane dicarboxylate compound may be at least one selected from the group consisting of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclohexane-1,4-dicarboxylate.

[0057] Preferably, the cyclohexanedicarboxylate compound may be di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) represented by the following formula 2-4: [ka]

[0058] DEHCH is transparent, odorless, has low viscosity at room temperature and low temperature, and therefore can realize excellent workability, has a fast gelation rate, and has excellent plasticization efficiency and plasticizer migration resistance compared to other cyclohexanedicarboxylate compounds. Therefore, when DEHCH is used, the physical properties of the plasticizer composition can be further improved.

[0059] The pure cyclohexanedicarboxylate compounds can be obtained from commercially available materials or can be prepared from pure raw materials using known synthetic methods.

[0060] When a pure cyclohexanedicarboxylate-based compound is used as the second plasticizer, the color and odor problems of the first plasticizer, the recycled phthalate-based compound, can be more effectively compensated for. Therefore, a plasticizer composition using a pure cyclohexanedicarboxylate-based compound as the second plasticizer can be more suitably used for the production of high-quality products.

[0061] The regenerated cyclohexanedicarboxylate compound can be obtained from a commercially available material or from waste materials using a known method. As an example, after the regenerated phthalate compound, which is the first plasticizer, is obtained by the above-mentioned method, the regenerated cyclohexanedicarboxylate compound can be obtained by hydrogenating the regenerated phthalate compound. In this process, the energy consumed in the production of a pure phthalate compound and the amount of greenhouse gas emitted can be reduced, so that when a regenerated cyclohexanedicarboxylate compound is used as the second plasticizer, the carbon emissions of the plasticizer composition can be significantly reduced. In addition, since impurities are partially removed in the hydrogenation reaction and the subsequent purification process, the regenerated cyclohexanedicarboxylate compound has excellent color and less odor compared to the regenerated phthalate compound, and therefore can complement the properties of the first plasticizer.

[0062] The recycled cyclohexanedicarboxylate compound exhibits the characteristics of a fast gelation rate and high plasticization efficiency similar to the pure cyclohexanedicarboxylate compound, but differs from the pure cyclohexanedicarboxylate compound in that it is relatively yellowish in color due to impurities and has a higher acid value.

[0063] Specifically, the acid value of the regenerated cyclohexanedicarboxylate compound may be more than 0.05 KOH mg / g and not more than 0.3 KOH mg / g. The pure cyclohexanedicarboxylate compound has an acid value of not more than 0.1 KOH mg / g or not more than 0.05 KOH mg / g, and the lower the acid value, the better, and theoretically may be 0 KOH mg / g.

[0064] The acid value is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1 g of a sample, and is determined by titrating a sample solution with a 0.1 N alcoholic KOH solution.

[0065] The second plasticizer is preferably contained in an amount of 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 30 parts by weight or more, and 70 parts by weight or less, 60 parts by weight or less, or 50 parts by weight or less, based on 100 parts by weight of the plasticizer composition.

[0066] If the content of the second plasticizer is less than 5 parts by weight per 100 parts by weight of the plasticizer composition, it may be insufficient to complement the properties of the recycled phthalate-based compound. Also, if the content of the second plasticizer is more than 70 parts by weight per 100 parts by weight of the plasticizer composition, the content of the recycled phthalate-based compound is relatively small, and the properties of a plasticizer containing a phthalate-based compound cannot be secured, making it difficult to expect the effect of reducing carbon generation by using the recycled phthalate-based compound.

[0067] In one embodiment of the present invention, the first plasticizer may be recycled dioctyl terephthalate and the second plasticizer may be di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, which may be pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, recycled di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, or a combination thereof.

[0068] On the other hand, the plasticizer composition of the present invention does not contain any other plasticizers besides the first plasticizer and the second plasticizer. Specifically, the plasticizer composition may contain 20 to 85 parts by weight of the first plasticizer and 5 to 70 parts by weight of the second plasticizer. Alternatively, the plasticizer composition may contain 50 to 70 parts by weight of the first plasticizer and 30 to 50 parts by weight of the second plasticizer.

[0069] Preferably, the plasticizer composition may contain 20 to 85 parts by weight of recycled dioctyl terephthalate as the first plasticizer and 5 to 70 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate as the second plasticizer. More preferably, the plasticizer composition may contain 50 to 70 parts by weight of recycled dioctyl terephthalate as the first plasticizer and 30 to 50 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate as the second plasticizer. In this case, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate may be pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, recycled di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, or a combination thereof.

[0070] Additional plasticizer The plasticizer composition of the present invention may further comprise an additional plasticizer in addition to the first and second plasticizers.

[0071] The additional plasticizer may be any substance commonly used as a plasticizer for polymer resins, without limitation, and may be, for example, one or more selected from the group consisting of phthalate-based compounds; polyol ester-based compounds; trimellitate-based compounds; aliphatic ester-based compounds; phosphate-based compounds; vegetable oils; epoxidized oils; and acylated monoglyceride compounds.

[0072] The phthalate-based compound is a compound represented by Chemical Formula 1, and specifically may be at least one selected from the group consisting of dibutyl phthalate, dinormal hexyl phthalate, diisoheptyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diheptyl nonyl phthalate, dinormal octyl decyl phthalate, diheptyl nonyl undecyl phthalate, diisononyl phthalate, dinonyl phthalate, dinormal nonyl phthalate, diisodecyl phthalate, dinormal nonyl decyl undecyl phthalate, dinonyl undecyl phthalate, diundecyl phthalate, diisonoundecyl dodecyl phthalate, ditridecyl phthalate, dibutyl terephthalate, butyl octyl terephthalate, di(2-ethylhexyl) terephthalate, and butyl benzyl phthalate.

[0073] The polyol ester compound is a compound obtained by esterification of a polyol with a carboxylic acid.

[0074] The polyol is a polyol having 3 to 8 carbon atoms, and examples of the polyol that can be used include propane-1,3-diol, propylene glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitan, sorbitol, isosorbide, erythritol, threitol, pentaerythritol, arabitol, xylitol, ribitol, fucitol, mannitol, galactitol, iditol, inositol, volemitol, and glucose.

[0075] Examples of the carboxylic acid include, but are not limited to, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, oleic acid, or valeric acid.

[0076] Specifically, pentaerythritol tetravalerate (Pevalen (registered trademark)) can be used as the polyol ester compound.

[0077] Examples of the trimellitate-based compound include one or more selected from the group consisting of tri-(2-ethylhexyl) trimellitate, trimethyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, tri-(n-octyl, n-decyl) trimellitate, and tri-(heptyl, nonyl) trimellitate.

[0078] The aliphatic ester compound may be an ester compound derived from an aliphatic carboxylic acid compound such as adipic acid, sebacic acid, azelaic acid, maleic acid, etc. Examples of the aliphatic ester compound include one or more selected from the group consisting of dimethyl adipate, monomethyl adipate, dioctyl adipate, diheptylnonyl adipate, di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, di(2-ethylhexyl) sebacate, dibutyl sebacate, di(2-ethylhexyl) azelate, dibutyl maleate, and diisobutyl maleate.

[0079] The phosphate compound may be one or more selected from the group consisting of triethyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, tritolyl phosphate, and trixylyl phosphate.

[0080] Examples of the vegetable oil include one or more oils selected from the group consisting of soybean oil, castor oil, linseed oil, palm oil, canola oil, and linseed oil.

[0081] The epoxidized oil is an epoxidized fatty acid alkyl ester prepared by epoxidizing a fatty acid alkyl ester, and may be at least one selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid, epoxidized oleate, epoxidized tall oil, and epoxidized linoleic acid.

[0082] The acylated monoglyceride compound can be prepared by acylation of a monoglyceride prepared by reacting glycerol with a fatty acid. In this case, the fatty acid can be the above-mentioned aliphatic carboxylic acid, vegetable oil, etc.

[0083] The additional plasticizers may be used alone or in combination of two or more.

[0084] When the additional plasticizer is included, the content of the additional plasticizer may be 1 part by weight or more, or 5 parts by weight or more, and 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, based on 100 parts by weight of the plasticizer composition. If the content of the additional plasticizer is too high, the contents of the first plasticizer and the second plasticizer are relatively reduced, and the above-mentioned effects of reducing carbon emissions and improving thermal stability and gelation speed cannot be sufficiently obtained, so it is preferable to satisfy the above range.

[0085] The plasticizer composition of the present invention can reduce carbon emissions by using recycled phthalate-based compounds, and contains a cyclohexanedicarboxylate-based compound together with the recycled phthalate-based compound. Even when used as a recycled raw material, the plasticizer composition has excellent color, little odor, and a relatively low acid value.

[0086] Specifically, the plasticizer composition may have an acid value of 0.25 KOH mg / g or less, 0.22 KOH mg / g or less, or 0.2 KOH mg / g or less. The lower the acid value, the better the quality, and there is no lower limit, and theoretically the acid value may be 0 KOH mg / g. In particular, a high acid value of the plasticizer composition means that there are many impurities other than the plasticizer, and if there are many impurities, the color of the plasticizer changes from colorless transparent to yellow or brown, the odor becomes strong, or the migration resistance of the finished product using the plasticizer with a high acid value becomes poor. Therefore, it is preferable that the plasticizer composition maintains the above acid value range.

[0087] The plasticizer composition may also have a Yellow Index of 120 or less, 100 or less, or 92 or less, as measured by ASTM standards D1209 and E313.

[0088] The plasticizer composition may have a carbon emission reduction rate of 5% or more, or 5% to 40%. The carbon emission reduction rate of the plasticizer composition is a value calculated for a plasticizer composition containing a pure phthalate compound and / or a pure cyclohexanedicarboxylate compound instead of the recycled phthalate compound and / or recycled cyclohexanedicarboxylate compound, and corresponds to the carbon emission reduction rate due to the use of recycled raw materials instead of pure raw materials.

[0089] Specifically, the carbon emission reduction rate (%) of the plasticizer composition can be calculated according to the following formula 1.

[0090] [Formula 1] Carbon emissions reduction rate (%)=100-[(A1 / A2)×100] In the above formula 1, A1 is the carbon footprint (tCO 2 eq / MT), A2 is the carbon footprint of the control plasticizer composition (tCO 2 eq / MT) are shown.

[0091] Specifically, in the above formula 1, A1 is the carbon emission (tCO 2 A2 is the total carbon emissions (tCO eq / MT) according to the composition ratio of each component of the plasticizer composition of the control group, which has the same composition as the plasticizer composition calculated in A1, but uses pure raw materials (pure phthalate compounds and / or pure cyclohexanedicarboxylate compounds) instead of recycled raw materials (recycled phthalate compounds and / or recycled cyclohexanedicarboxylate compounds). 2 eq / MT), where the carbon emissions units are total CO eq / MT per metric ton. 2 It is expressed as the amount of emissions by weight equivalent (eq).

[0092] For example, the carbon emission amount A1 of a plasticizer composition containing R-DOTP and DEHCH in a 50:50 ratio is calculated as the sum of the carbon emission amounts of each component according to the composition ratio, that is, the carbon emission amount of R-DOTP x 0.5 + the carbon emission amount of DEHCH x 0.5, which is 0.568 tCO 2 The control plasticizer composition for the plasticizer composition is a plasticizer composition containing DOTP and DEHCH in a ratio of 50:50, and its carbon emission A2 is calculated as the carbon emission of DOTP x 0.5 + the carbon emission of DEHCH x 0.5, which is 0.611 tCO 2 eq / MT. Therefore, according to the above formula 1, the carbon emission reduction rate of the plasticizer composition containing R-DOTP and DEHCH in a ratio of 50:50 is 7.04%. The carbon emission of each component used in the above plasticizer composition was calculated using the following values: -Regenerated dioctyl terephthalate (R-DOTP): 0.485tCO 2 eq / MT -Pure dioctyl terephthalate (DOTP, or Pure-DOTP): 0.571tCO 2 eq / MT -Pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, or Pure-DEHCH): 0.651 tCO 2 eq / MT

[0093] The carbon emission of each component used in the plasticizer composition may be calculated by referring to the value provided by the manufacturer or by calculating based on the manufacturing process and chemical reaction of each component. A specific method for calculating the carbon emission reduction rate may be referred to the experimental examples described below.

[0094] Preferably, the carbon emission reduction rate of the plasticizer composition may be 5% or more, 5.5% or more, 6% or more, 6.5% or more, or 7% or more, and 40% or less, 30% or less, or 20% or less.

[0095] When the above-mentioned plasticizer composition is added to a resin, it has excellent physical properties such as gelling properties, plasticizing efficiency, and weather resistance. Therefore, the plasticizer composition of the present invention can be used as a plasticizer for various polymer resins.

[0096] resin composition Therefore, according to another embodiment of the present invention, there is provided a resin composition comprising the above-mentioned plasticizer composition; and one or more resins selected from the group consisting of polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin, polyketone, polyvinyl butyral, acrylic, synthetic rubber resin, and thermoplastic elastomer.

[0097] The contents of the resin and the plasticizer in the resin composition are not limited and may be appropriately adjusted depending on the resin used and the desired physical properties. For example, the resin composition may contain 1 to 200 parts by weight, 30 to 200 parts by weight, or 50 to 150 parts by weight of the plasticizer composition per 100 parts by weight of the resin.

[0098] The resin composition may further include an additive, such as one or more selected from the group consisting of a stabilizer, a filler, and a pigment. The additive may be suitably selected depending on the physical properties to be improved in the resin composition.

[0099] The stabilizer is added to prevent changes in the physical properties of the resin, and includes at least one selected from the group consisting of Ca-Zn based compounds, K-Zn based compounds, Ba-Zn based compounds, organic Tin based compounds, matallic soap based compounds, phenol based compounds, phosphate based compounds, and phosphite based compounds.

[0100] More specific examples of the stabilizer used in the present invention include, but are not limited to, Ca-Zn compounds; K-Zn compounds; Ba-Zn compounds; organic Tin compounds such as mercaptide compounds, maleic acid compounds, and carboxylic acid compounds; matallic soap compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, and Ba-stearate; phenol compounds; phosphate compounds; and phosphite compounds.

[0101] The filler is used for the purpose of improving the productivity, dry touch, flame retardancy, etc. of the resin composition, and includes at least one selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, aluminum hydroxide, phosphorus-based compounds, melamine-based compounds, phosphorus-melamine composite compounds, boron-based flame retardant treatment agents, carbon black, carbon nanotubes, nano-clay, and clay.

[0102] The pigments can be titanium dioxide, carbon black, cadmium-based pigments, and the like.

[0103] The resin composition according to the present invention can be produced by any method known in the art using a resin, a plasticizer composition and optional additives, and the method is not particularly limited.

[0104] In one embodiment, the resin composition may be a vinyl chloride resin composition containing a vinyl chloride resin. The vinyl chloride resin composition contains the plasticizer composition according to the present invention and can exhibit excellent color, gelling properties, and weather resistance.

[0105] The vinyl chloride resin is a homopolymer in which vinyl chloride monomer is polymerized alone, or a copolymer in which vinyl chloride monomer and a comonomer copolymerizable therewith are polymerized, and any one or a mixture of two of them can be used in the preparation of the vinyl chloride resin composition.

[0106] Specific examples of the comonomer copolymerizable with the vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; vinyl ethers having an alkyl group such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; vinylidene halides such as vinylidene chloride; unsaturated carboxylic acids and acid anhydrides thereof such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; olefins such as ethylene and propylene; and crosslinkable monomers such as diallyl phthalate. Any one of these or a mixture of two or more of them can be used. Among these, it is more preferable that the comonomer contains vinyl acetate or the like, since this has excellent compatibility with vinyl chloride monomer and can improve compatibility with the plasticizer that constitutes the resin composition after polymerization.

[0107] As described above, the vinyl chloride resin can be prepared by polymerizing vinyl chloride monomer alone or vinyl chloride monomer and a comonomer copolymerizable therewith. At this time, the polymerization method is not particularly limited, and can be carried out by a conventional polymerization method known in the technical field to which the present invention belongs, such as suspension polymerization, bulk polymerization, emulsion polymerization, or seed emulsion polymerization.

[0108] The average particle size and uniformity of the vinyl chloride resin can be controlled by adjusting the polymerization conditions. Specifically, straight vinyl chloride resin produced by suspension polymerization or bulk polymerization has an average particle size D 50 The average particle size D of the paste polyvinyl chloride resin produced by emulsion polymerization or fine suspension polymerization is in the range of 50 to 400 μm. 50 The average particle size D of the vinyl chloride resin may be less than 100 μm, preferably 0.1 to 40 μm. 50 can be measured by a conventional particle size distribution measuring method such as optical microscope observation or light scattering measurement.

[0109] The bulk density of the polyvinyl chloride resin measured according to ASTM D1895 is 0.30 to 0.70 g / cm 3 , or 0.40~0.60g / cm 3 When the bulk density is in the above range, the plasticizing effect and mechanical properties are more excellent.

[0110] The degree of polymerization and weight average molecular weight of the vinyl chloride resin can affect the components constituting the vinyl chloride resin composition, particularly the compatibility with the plasticizer, and the processability of the vinyl chloride resin composition, and can be appropriately adjusted by controlling the polymerization conditions during polymerization.

[0111] Specifically, the vinyl chloride resin may have a degree of polymerization of 500 to 3,000 or a weight average molecular weight (Mw) of 25,000 to 300,000 g / mol. When the vinyl chloride resin has a degree of polymerization and a weight average molecular weight within such ranges, the vinyl chloride resin has excellent dispersibility and good compatibility with plasticizers, and can improve the processability of the vinyl chloride resin composition.

[0112] If the degree of polymerization of the vinyl chloride resin is less than 500 or the weight average molecular weight is less than 25,000 g / mol, the physical properties may be insufficient, resulting in reduced processability and durability of the processed product, whereas if the degree of polymerization exceeds 3,000 or the weight average molecular weight exceeds 300,000 g / mol, the molecular weight is too high, making molding or processing difficult. More specifically, the vinyl chloride resin may have a degree of polymerization of 700 or more but less than 1,700, or a weight average molecular weight (Mw) of 45,000 to 250,000 g / mol.

[0113] The weight average molecular weight (Mw) of the vinyl chloride resin is a value calculated as a standard polystyrene by gel permeation chromatography. The degree of polymerization of the vinyl chloride resin can be measured according to JIS K 6720-2.

[0114] In one embodiment, the vinyl chloride resin may be a straight vinyl chloride resin.

[0115] In one embodiment, PVC scrap can be used as the polyvinyl chloride resin. PVC scrap is produced in powder form by processing waste PVC products such as flooring, tarpaulin, and calendar, such as crushing, and can further reduce carbon emissions compared to the use of pure PVC. The PVC scrap can be a commercially available product, or can be produced from waste PVC through crushing. In this case, the PVC scrap is suitable for producing environmentally friendly products if it does not contain heavy metals and toxic substances, and specifically, it is preferable to use PVC scrap obtained by crushing waste chassis or decorative tiles. As an example, the PVC scrap may have a content of four heavy metals (Pb, Cd, Hg, and hexavalent chromium) of 90 mg / kg or less, 50 mg / kg or less, or 25 mg / kg or less, and preferably 0 mg / kg.

[0116] The resin composition may have a Yellow index (YI) measured according to ASTM E313 of 10 to 25, or 22 or less, or 20 or less, and 15 or more, or 18 or more.

[0117] The resin composition has a Yellow index (YI) measured after 300 hours of UV aging according to the ASTM G154 method of 10 to 65, preferably 64 or less, 63 or less, or 62.5 or less, and may be 20 or more, 30 or more, or 40 or more.

[0118] The resin composition may have a carbon emission reduction rate of 1.5% or more, or 1.5% to 60%. The carbon emission reduction rate of the resin composition is a value calculated for a vinyl chloride resin composition using a plasticizer composition containing a pure phthalate compound and / or a pure cyclohexanedicarboxylate compound instead of the recycled phthalate compound and / or recycled cyclohexanedicarboxylate compound, and corresponds to the carbon emission reduction rate due to the use of recycled raw materials instead of pure raw materials.

[0119] Specifically, the carbon emission reduction rate (%) of the resin composition can be calculated according to the following formula 2. [Formula 2] Carbon emission reduction rate (%) = 100-[(A3 / A4) x 100] In the above formula 2, A3 is the carbon emission (tCO 2 eq / MT), A4 is the carbon emission (tCO 2 eq / MT) are shown.

[0120] Specifically, in the above formula 2, A3 is the carbon emission (tCO 2 A4 is the carbon emission (tCO eq / MT) according to the composition ratio of each component of the resin composition that has the same composition as the resin composition calculated in A3, but uses pure raw materials (pure phthalate compounds and / or pure cyclohexanedicarboxylate compounds) instead of recycled raw materials (recycled phthalate compounds and / or recycled cyclohexanedicarboxylate compounds). 2 eq / MT), where the carbon emissions units are total CO eq / MT per metric ton. 2 It is expressed as the amount of emissions by weight equivalent (eq).

[0121] As an example, in the case of a vinyl chloride resin composition comprising 100 parts by weight of polyvinyl chloride (PVC, Hanwha Solutions P-1000), 30 parts by weight of a plasticizer containing R-DOTP and DEHCH in a 50:50 ratio, and 2 parts by weight of a heat stabilizer, the components PVC, R-DOTP, DEHCH, and Ba / Zn-based heat stabilizer contained in the vinyl chloride resin composition have weight ratios of 0.758, 0.114, 0.114, and 0.015, respectively. In this case, excluding the carbon emission of the heat stabilizer, which is contained in a small amount in the composition, and considering only the carbon emission of PVC, R-DOTP, and DEHCH, the carbon emission A3 of the resin composition is calculated based on the weight ratios of the components PVC, R-DOTP, and DEHCH contained in the resin composition of 0.758, 0.114, and 0.114, and is calculated by adding up the carbon emission of each component according to such composition ratio (i.e., the carbon emission of PVC). * Carbon emissions of 0.758+R-DOTP * Carbon emissions of 0.114+DEHCH * 0.114) to give 0.267tCO 2 The control resin composition for the polyvinyl chloride resin composition was a mixture of PVC, DOTP, and DEHCH in weight ratios of 0.758, 0.114, and 0.114, respectively, and its carbon emissions (A4, i.e., the carbon emissions of PVC) were * Carbon emissions of 0.758+DOTP * Carbon emissions of 0.114+DEHCH * 0.114) is 0.277tCO 2 eq / MT. Therefore, according to the above formula 2, the carbon emission reduction rate of the above vinyl chloride resin composition is 3.53%. The carbon emission of each component used in the above resin composition was calculated using the following values: - Polyvinyl chloride (PVC, Hanwha Solutions P-1000): 0.182tCO 2 eq / MT -Regenerated dioctyl terephthalate (R-DOTP): 0.485tCO 2 eq / MT -Pure dioctyl terephthalate (DOTP, or Pure-DOTP): 0.571tCO2 eq / MT -Pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, or Pure-DEHCH): 0.651 tCO 2 eq / MT

[0122] The carbon emission amount of each component used in the resin composition may be calculated by referring to the value provided by the manufacturer or by calculating based on the manufacturing process and chemical reaction of each component.

[0123] For a specific method of calculating such a carbon emission reduction rate, reference can be made to the experimental examples described below.

[0124] The carbon emission reduction rate varies depending on the composition of the plasticizer composition and the type of resin used. For example, the carbon emission reduction rate of the resin composition may be 1.8% or more, or 2% or more, or 3% or more, or 3.5% or more, or 4.2% or more, or 5% or more. If a resin made from pure raw materials is used, the carbon emission reduction rate of the resin composition may be 28% or less, or 25% or less, or 22% or less, or 20% or less, or 18% or less, or 16% or less, or 11% or less. If a recycled resin such as PVC scrap is used, the carbon emission reduction rate may be 60% or less, or 55% or less.

[0125] The resin composition has excellent color and odor properties as described above, and has a fast gelation rate along with excellent thermal stability.

[0126] On the other hand, according to another aspect of the present invention, there is provided a molded article containing the resin composition.

[0127] The molded article can be used for the manufacture of food packaging films (e.g., wraps), industrial films, compounds, deco sheets, deco tiles, soft sheets, hard sheets, electric wires and cables, wallpaper, foam mats, leather, flooring materials, tarpaulins, gloves, sealants, gaskets for refrigerators, hoses, medical devices, geogrids, mesh tarpaulins, toys, stationery, insulating tapes, clothing coatings, labels used for clothing or stationery, bottle cap liners, stoppers for industrial or other uses, artificial feed, internal parts of electronic devices (e.g., sleeves), automotive interior materials, adhesives, coatings, etc., but is not limited thereto.

[0128] The present invention will be described in more detail with reference to the following examples, however, the following examples are merely for the purpose of illustrating the present invention and do not limit the scope of the invention.

[0129] [Example] Example 1 A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP, acid value 0.175 KOH mg / g) from Runzenengyuan Co., Ltd., China, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, Hanwha Solutions, Eco-DEHCH) in a weight ratio of 50:50.

[0130] Polyvinyl chloride (Hanwha Solutions, P-1000F, Degree of polymerization 1000±50, Bulk Density 0.55±0.04g / cm 3 To 100 parts by weight of the resin composition, 30 parts by weight of the plasticizer composition and 2 parts by weight of a Ba / Zn-based heat stabilizer were added, and the mixture was kneaded in a roll mill to produce a vinyl chloride resin composition.

[0131] Example 2 A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP) from Runzenengyuan Co., Ltd., China, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) in a weight ratio of 60:40.

[0132] To 100 parts by weight of polyvinyl chloride (Hanwha Solutions, P-1000F), 30 parts by weight of the plasticizer composition and 2 parts by weight of a Ba / Zn-based heat stabilizer were added, and then kneaded in a roll mill to prepare a vinyl chloride resin composition.

[0133] Example 3 A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP) from Runzenengyuan Co., Ltd., China, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) in a weight ratio of 70:30.

[0134] To 100 parts by weight of polyvinyl chloride (Hanwha Solutions, P-1000F), 30 parts by weight of the plasticizer composition and 2 parts by weight of a Ba / Zn-based heat stabilizer were added, and then kneaded in a roll mill to prepare a vinyl chloride resin composition.

[0135] Example 4 A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP, acid value 0.175 KOH mg / g) from Runzenengyuan Co., Ltd. of China and recycled di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH, acid value 0.250 KOH mg / g) produced by hydrogenating the R-DOTP in a weight ratio of 50:50.

[0136] Polyvinyl chloride (Hanwha Solutions, P-1000F, Degree of polymerization 1000±50, Bulk Density 0.55±0.04g / cm 3 To 100 parts by weight of the resin composition, 60 parts by weight of the plasticizer composition and 3 parts by weight of a Ba / Zn-based heat stabilizer were added, and the mixture was kneaded in a roll mill to produce a vinyl chloride resin composition.

[0137] Example 5 To 100 parts by weight of recycled polyvinyl chloride (PVC scrap: waste PVC flooring, tarpaulin, and calendar products processed into powder form by crushing or other processing), 60 parts by weight of the plasticizer composition of Example 4 and 3 parts by weight of a Ba / Zn-based heat stabilizer were added, and the mixture was kneaded in a roll mill to produce a vinyl chloride resin composition.

[0138] Example 6 A plasticizer composition was prepared in the same manner as in Example 4, except that the weight ratio of R-DOTP and R-DEHCH was 70:30. Then, a vinyl chloride resin composition was prepared in the same manner as in Example 4 using the plasticizer composition.

[0139] Comparative Example 1 A vinyl chloride resin composition was produced in the same manner as in Example 1, using recycled dioctyl terephthalate (R-DOTP) from Runzenengyuan Co., Ltd., China, as a plasticizer.

[0140] Comparative Example 2 A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP) from Runzenengyuan Co., Ltd., China, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) in a weight ratio of 95:5.

[0141] Thereafter, a vinyl chloride resin composition was produced in the same manner as in Example 1 using the plasticizer composition.

[0142] Comparative Example 3 A plasticizer composition and a polyvinyl chloride resin composition were prepared in the same manner as in Example 1, except that pure dioctyl terephthalate (DOTP, Hanwha Solutions, SP-390) was used instead of the recycled dioctyl terephthalate.

[0143] [Experimental Example] The plasticizer compositions and vinyl chloride resin compositions of the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1.

[0144] (1) Carbon emission reduction rate (%) The carbon emission reduction rate (%) for the plasticizer compositions of the Examples and Comparative Examples was calculated according to the following Equation 1. [Formula 1] Carbon emissions reduction rate (%)=100-[(A1 / A2)×100] In the above formula 1, A1 is the carbon footprint (tCO 2 eq / MT), A2 is the carbon footprint of the control plasticizer composition (tCO 2 eq / MT) are shown.

[0145] Specifically, in the above formula 1, A1 is the carbon emission (tCO 2 A2 is the total carbon emissions (tCO eq / MT) according to the composition ratio of each component of the plasticizer composition of the control group, which has the same composition as the plasticizer composition calculated in A1, but uses pure raw materials (pure phthalate compounds and / or pure cyclohexanedicarboxylate compounds) instead of recycled raw materials (recycled phthalate compounds and / or recycled cyclohexanedicarboxylate compounds). 2 eq / MT), where the carbon emissions units are total CO eq / MT per metric ton. 2 It is expressed as the amount of emissions by weight equivalent (eq).

[0146] In addition, the carbon emission reduction rate (%) was calculated for each of the vinyl chloride resin compositions of the Examples and Comparative Examples according to the following formula 2. [Formula 2] Carbon emission reduction rate (%) = 100-[(A3 / A4) x 100] In the above formula 2, A3 is the carbon emission (tCO 2 eq / MT), A4 is the carbon emission (tCO 2 eq / MT) are shown.

[0147] Specifically, in the above formula 2, A3 is the carbon emission (tCO 2 A4 is the carbon emission (tCO eq / MT) according to the composition ratio of each component of the resin composition that has the same composition as the resin composition calculated in A3, but uses pure raw materials (pure phthalate compounds and / or pure cyclohexanedicarboxylate compounds) instead of recycled raw materials (recycled phthalate compounds and / or recycled cyclohexanedicarboxylate compounds). 2 eq / MT), where the carbon emissions units are total CO eq / MT per metric ton. 2 It is expressed as the amount of emissions by weight equivalent (eq).

[0148] As an example, the plasticizer composition of Example 1 contains R-DOTP and DEHCH in a ratio of 50:50. The total carbon emissions of each component according to this composition ratio (A1, i.e., the carbon emissions of R-DOTP) * Carbon emissions of 0.5+DEHCH * 0.5) is 0.568tCO 2 eq / MT. The control group was the plasticizer of Comparative Example 3, whose carbon emissions A2 was 0.611 tCO 2 eq / MT. Therefore, according to the above formula 1, the carbon emission reduction rate of the plasticizer composition of Example 1 is 7.04%. The carbon emission and the carbon emission reduction rate of the plasticizer composition of Example 4 can also be obtained in the same manner as above, using the plasticizer composition of Comparative Example 3 as a control.

[0149] In addition, the vinyl chloride resin composition of Example 1 uses 30 parts by weight of a plasticizer containing R-DOTP and DEHCH in a 50:50 ratio to 100 parts by weight of polyvinyl chloride (PVC), and the components PVC, R-DOTP, DEHCH, and Ba / Zn-based heat stabilizer contained in the vinyl chloride resin composition have weight ratios of 0.758, 0.114, 0.114, and 0.015, respectively. In this case, excluding the carbon emissions of the heat stabilizer, which is contained in a relatively small amount in the composition, and considering only the carbon emissions of PVC, R-DOTP, and DEHCH, the total carbon emissions A3 of each component according to the composition ratio is 0.267 tCO 2 eq / MT. In comparison, the carbon emission A4 of the vinyl chloride resin composition of Comparative Example 3, which is the control group, is 0.277 tCO 2 Since the carbon emission reduction rate is eq / MT, according to Equation 2, the carbon emission reduction rate of the vinyl chloride resin composition of Example 1 is 3.53%.

[0150] Here, the carbon emissions of each component used in the plasticizer composition and the vinyl chloride resin composition of the examples and comparative examples are as follows: -Polyvinyl chloride (PVC, Hanwha Solutions, P-1000): 0.182tCO 2 eq / MT -Recycled polyvinyl chloride (PVC scrap): 0tCO 2 eq / MT -Regenerated dioctyl terephthalate (R-DOTP): 0.485tCO 2 eq / MT -Pure dioctyl terephthalate (DOTP, or Pure-DOTP): 0.571tCO 2 eq / MT - Regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH): 0.520tCO 2 eq / MT -Pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, or Pure-DEHCH): 0.651 tCO 2 eq / MT

[0151] The carbon emissions of polyvinyl chloride (PVC) and pure dioctyl terephthalate (DOTP, or Pure-DOTP) were calculated based on values ​​provided by the manufacturers. The carbon emissions of regenerated dioctyl terephthalate (R-DOTP) were calculated by dividing the carbon emissions of the regenerated PTA (purified terephthalic acid) used in R-DOTP by 70% of that of pure PTA, and the carbon emissions of PTA and 2-EH (2-ethylhexanol) were calculated in the same way. PTA and 2-EH are the raw materials used to manufacture DOTP.

[0152] (2) Plasticizers Composition APHA Color Plasticizer Composition The color of was measured using an APHA measuring instrument according to ASTM D1209 and E313.

[0153] (3) Plasticizers Composition Acid value of Plasticizer Composition The acid value was calculated using 0.1N KOH aqueous solution and an indicator according to the following formula: [Formula 3] Acid Value = (Titer x 5.6 x factor) / Sample size In the above formula 2, "titer amount" is the consumption amount (ml) of 0.1N KOH aqueous solution used in titrating the plasticizer, "factor" is the correction coefficient of the KOH aqueous solution (in the case of 0.1N KOH aqueous solution, the factor is 1), and "sample amount" is the weight (g) of the plasticizer sample.

[0154] (4) Gelation speed 54 g of the vinyl chloride resin composition was placed in a Brabender Mixer at 95° C. and mixed at 30 rpm for 10 minutes. The gel time of the resin was analyzed based on the change in torque during processing in the mixer.

[0155] (5) Hardness (plasticization efficiency) The polyvinyl chloride resin composition was subjected to a roll mill process (170°C, 3 minutes) and a press process (180°C, 8 minutes) in sequence to produce a flat plate having a thickness of 6 mm. Based on the ASTM D2240 method, the needle of the hardness tester (Shore D Type) was lowered completely to one point on the test piece, and the hardness value was read after 5 seconds. After testing three points on each test piece, the average value was taken and used as an index of plasticization efficiency.

[0156] (6) Color of the vinyl chloride resin composition The polyvinyl chloride resin composition was subjected to a roll mill process (170°C, 3 minutes) and a press process (180°C, 8 minutes) in sequence to produce a flat plate having a thickness of 6 mm.

[0157] The yellow index (YI) of the test specimen thus prepared was measured according to the standard of ASTM E313. The test specimen was then placed in an accelerated weathering tester (QUV, Q-Lab) and subjected to the method of ASTM G154 (1 cycle: temperature 60°C, illuminance 0.8 W / m using a UVB 313 nm lamp). 2 After 300 hours of exposure (8 hours of UV irradiation at 1000 nm / nm and 4 hours of condensation at 50°C), the YI was measured again.

[0158] From the viewpoint of realizing an excellent hue during the production of the final resin product, the lower the initial colorability (color, YI) of the vinyl chloride resin composition, the better.

[0159] [Table 1]

[0160] [Table 2]

[0161] Referring to Table 1 above, it has been confirmed that the plasticizer composition of the present invention contains recycled raw materials, can reduce carbon emissions, and by using both pure cyclohexanedicarboxylate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds, has a good odor, excellent hue and acid value, and exhibits gelation speed, hardness and hue properties equal to or greater than those of conventional plasticizers.

Claims

1. a recycled phthalate-based compound as a first plasticizer; and A plasticizer composition comprising as a second plasticizer a pure cyclohexanedicarboxylate-based compound and / or a recycled cyclohexanedicarboxylate-based compound, The first plasticizer is contained in an amount of less than 95 parts by weight based on 100 parts by weight of the plasticizer composition; The acid value is 0.25 KOH mg / g or less. Plasticizer composition.

2. 100 parts by weight of the plasticizer composition 20 to 85 parts by weight of the first plasticizer, and 2. The plasticizer composition of claim 1 comprising 5 to 70 parts by weight of the second plasticizer.

3. The plasticizer composition according to claim 1, wherein the first plasticizer is one or more selected from the group consisting of regenerated dibutyl phthalate, regenerated dihexyl phthalate, regenerated dioctyl phthalate, regenerated di-n-octyl phthalate, regenerated diisononyl phthalate, regenerated diisodecyl phthalate, regenerated dibutyl isophthalate, regenerated dioctyl isophthalate, regenerated diisononyl isophthalate, regenerated diisodecyl isophthalate, regenerated dibutyl terephthalate, regenerated dioctyl terephthalate, regenerated diisononyl terephthalate, and regenerated diisodecyl terephthalate.

4. 2. The plasticizer composition of claim 1, wherein the first plasticizer has an acid value of 0.05 KOH mg / g to 0.25 KOH mg / g.

5. The plasticizer composition according to claim 1, wherein the cyclohexane dicarboxylate compound is at least one selected from the group consisting of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclohexane-1,4-dicarboxylate.

6. the first plasticizer is recycled dioctyl terephthalate; 2. The plasticizer composition of claim 1, wherein the second plasticizer is pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and / or recycled di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate.

7. 2. The plasticizer composition of claim 1, further comprising one or more compounds selected from the group consisting of phthalate-based compounds; polyol ester-based compounds; trimellitate-based compounds; aliphatic ester-based compounds; phosphate-based compounds; vegetable oils; epoxidized oils; and acylated monoglyceride compounds.

8. The plasticizer composition according to claim 1, which has a carbon emission reduction rate of 5% or more.

9. The plasticizer composition according to claim 1, having a Yellow Index (YI) of 120 or less as measured according to the ASTM E313 standard.

10. The plasticizer composition according to any one of claims 1 to 9; and A resin composition comprising one or more resins selected from the group consisting of polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin, polyketone, polyvinyl butyral, acrylic, synthetic rubber resin, and thermoplastic elastomer.

11. The resin composition according to claim 10, comprising 1 to 200 parts by weight of the plasticizer composition per 100 parts by weight of the resin.

12. The resin composition according to claim 10, having a yellow index (YI) of 10 to 25 as measured according to the ASTM E313 standard.

13. The resin composition according to claim 10, having a yellow index (YI) of 10 to 65, measured after 300 hours of UV aging by the method of ASTM G154.

14. A molded article comprising the resin composition according to claim 10.

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