Plasticizer composition

Abstract

The present disclosure relates to an environmentally friendly plasticizer composition, which can reduce carbon emissions by including recycled raw materials, and has excellent gelling properties, plasticizing efficiency, and weather resistance.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2020-0186411 filed with the Korean Intellectual Property Office on December 29, 2020, and Korean Patent Application No. 10-2021-0174063 filed with the Korean Intellectual Property Office on December 7, 2021, the disclosure of which is incorporated herein by reference in its entirety.

[0003] This disclosure relates to plasticizer compositions comprising recycled raw materials. Background Technology

[0004] Recently, for environmental protection and resource recycling considerations, research has been conducted on recovering useful resources from waste synthetic resins or byproducts generated during the synthetic resin production process. In addition, research is actively underway to reduce carbon emissions generated during the production of synthetic resin products.

[0005] Recycling technologies for waste synthetic resins, particularly waste polyesters, are widely known. For example, it is known to depolymerize waste polyester in the presence of a catalyst to recover it as raw materials such as terephthalic acid, dimethyl terephthalate, and ethylene glycol. The recovered terephthalic acid and dimethyl terephthalate can be recycled to dioctyl terephthalate (DTB) via esterification or transesterification, which is a useful material for use as a plasticizer. Furthermore, Chinese Patent Publications 104230714 and 104496819 disclose a method for recovering DTB from wastewater during a polyester weight reduction process.

[0006] Dioctyl terephthalate (DTP) is a widely used plasticizer, and DTP recovered through recycling processes can also be used as a plasticizer for polymer resins. However, due to impurities introduced during the recycling process, recovered DTP has disadvantages compared to pure DTP, such as a yellowish color and an unpleasant odor. Therefore, the problem is that recovered DTP can only be used to manufacture relatively low-quality products.

[0007] Therefore, for plasticizer compositions containing phthalate-based compounds such as dioctyl terephthalate, there is a need to develop a plasticizer composition that can achieve carbon emission reduction effects with excellent quality during resource recycling and manufacturing processes.

[0008] [Existing Technical Documents]

[0009] Chinese Patent Publication No. 104230714

[0010] Chinese Patent Publication No. 104496819 Summary of the Invention

[0011] Technical issues

[0012] In this disclosure, a plasticizer composition with excellent physical properties is provided, which also comprises a recycled phthalate-based compound obtained from waste polyester or wastewater generated in polyester production.

[0013] Technical solution

[0014] According to one embodiment of this disclosure, a plasticizer composition is provided, comprising a recycled phthalate-based compound as a first plasticizer; and a pure cyclohexane dicarboxylate-based compound and / or a recycled cyclohexane dicarboxylate-based compound as a second plasticizer.

[0015] In this composition, based on 100 parts by weight of plasticizer, the content of the first plasticizer is 95 parts by weight or less.

[0016] Here, 100 parts by weight of the plasticizer composition may include 20 to 85 parts by weight of a first plasticizer and 5 to 70 parts by weight of a second plasticizer.

[0017] The first plasticizer may be selected from at least one of the following: recycled dibutyl phthalate, recycled dihexyl phthalate, recycled dioctyl phthalate, recycled di-n-octyl phthalate, recycled diisononyl phthalate, recycled diisodecyl phthalate, recycled dibutyl isophthalate, recycled dioctyl isophthalate, recycled diisononyl isophthalate, recycled diisodecyl isophthalate, recycled dibutyl terephthalate, recycled dioctyl terephthalate, recycled diisononyl terephthalate, and recycled diisodecyl terephthalate.

[0018] The first plasticizer may have an acid value of 0.05 KOH mg / g to 0.25 KOH mg / g.

[0019] The compound based on cyclohexane dicarboxylic acid ester can be at least one selected from 1,4-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester, 1,2-cyclohexane dicarboxylic acid diisononyl ester, 1,2-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester, 1,4-cyclohexane dicarboxylic acid butyl(2-ethylhexyl) ester and 1,4-cyclohexane dicarboxylic acid dibutyl ester.

[0020] For example, the first plasticizer may be recycled dioctyl terephthalate, and the second plasticizer may be pure di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate and / or recycled di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate.

[0021] The plasticizer composition may further comprise at least one compound selected from the following: phthalate-based compounds; polyol ester-based compounds; trimellitate-based compounds; aliphatic ester-based compounds; phosphate ester-based compounds; vegetable oils; epoxidized oils; and acylated glycerol monoester compounds.

[0022] Plasticizer compositions can achieve carbon emission reduction rates of 5% or more.

[0023] The plasticizer composition may have an acid value of less than 0.25 KOH mg / g and a yellow index (YI, yellowness) of less than 120 as measured according to ASTM E313.

[0024] According to another embodiment of this disclosure, a resin composition is provided comprising a plasticizer composition; and at least one resin selected from polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin, polyketone, polyvinyl butyral, acrylic resin, synthetic rubber resin and thermoplastic elastomer.

[0025] Based on 100 parts by weight of resin, the resin composition may contain 1 to 200 parts by weight of plasticizer composition.

[0026] The resin composition may have a yellow index (YI, yellowness) of 10 to 25 as measured according to ASTM E313, and / or a yellow index (YI, yellowness) of 10 to 65 as measured according to ASTM G154 after 300 hours of UV aging.

[0027] According to another embodiment of this disclosure, a molding article comprising a resin composition is provided.

[0028] Beneficial effects

[0029] The plasticizer compositions according to this disclosure comprise recycled phthalate-based compounds, but with less of the yellow color and odor characteristic of recycled raw materials, and have excellent gelling properties, plasticizing efficiency and weather resistance, thus they can be used as plasticizers for general purposes. Detailed Implementation

[0030] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. Singular forms are also intended to include plural forms unless the context clearly indicates otherwise.

[0031] While the present invention can be modified and take many forms, its specific embodiments will be shown by way of example and will be described in detail. However, it is not intended to limit the invention to the specific forms disclosed, and it should be understood that the invention includes all modifications, equivalents, and substitutions within the spirit and scope of the invention.

[0032] The plasticizer compositions, resin compositions comprising the plasticizer compositions, and molding articles of the present invention will be described in more detail below.

[0033] Plasticizer Composition

[0034] First plasticizer

[0035] The plasticizer compositions disclosed herein include recycled phthalate-based compounds as a first plasticizer.

[0036] In this disclosure, the term "recovered phthalate-based compound" refers to a phthalate-based compound that is not synthesized from pure raw materials but is recovered from waste through reprocessing.

[0037] In this article, phthalate-based compounds refer to compounds represented by the following chemical formula 1:

[0038] [Chemical Formula 1]

[0039]

[0040] In chemical formula 1,

[0041] R1 and R2 are each independently C4 to C12 straight-chain or branched alkyl groups.

[0042] Preferably, R1 and R2 can each be independently n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, isononyl, or isodecyl.

[0043] Depending on the position of the substituents, phthalate-based compounds of formula 1 can be represented by the following formulas 1-1 to 1-3.

[0044] [Chemical Formula 1-1]

[0045]

[0046] [Chemical Formula 1-2]

[0047]

[0048] [Chemical Formulas 1-3]

[0049]

[0050] In chemical formulas 1-1 to 1-3, R1 and R2 are as defined in chemical formula 1.

[0051] Chemical formula 1-1 is a phthalate compound, chemical formula 1-2 isophthalate compound, and chemical formula 1-3 is a terephthalate compound.

[0052] Specific examples of phthalic acid ester compounds represented by chemical formula 1-1 may be dibutyl phthalate (DBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP; or di(2-ethylhexyl) phthalate), di-n-octyl phthalate (DnOP), diisononyl phthalate, or diisodecyl phthalate (DIDP).

[0053] Specific examples of phthalate compounds represented by chemical formulas 1-2 may be dibutyl isophthalate (DBIP), dioctyl isophthalate (DOIP; or di(2-ethylhexyl) isophthalate), diisononyl isophthalate (DINIP) or diisodecyl isophthalate (DIDIP).

[0054] Specific examples of terephthalic acid ester compounds represented by chemical formulas 1-3 may be dibutyl terephthalate (DBTP), dioctyl terephthalate (DOTP; or di(2-ethylhexyl) terephthalate), diisononyl terephthalate (DINTP) or diisodecyl terephthalate (DIDTP).

[0055] The recovered phthalate-based compounds disclosed herein can be any one or a mixture thereof of the aforementioned phthalate compounds, isophthalate compounds, and terephthalate compounds. In one embodiment, at least one selected from recovered dibutyl phthalate, recovered dihexyl phthalate, recovered dioctyl phthalate, recovered di-n-octyl phthalate, recovered diisononyl phthalate, recovered diisodecyl phthalate, recovered dibutyl isophthalate, recovered dioctyl isophthalate, recovered diisononyl isophthalate, recovered diisodecyl isophthalate, recovered dibutyl terephthalate, recovered dioctyl terephthalate, recovered diisononyl terephthalate, and recovered diisodecyl terephthalate can be used as the recovered phthalate-based compound. Preferably, recovered dioctyl terephthalate can be used as the recovered phthalate-based compound.

[0056] The recycled phthalate-based compounds used in this disclosure may be commercially available products or may be obtained from waste using known methods.

[0057] For example, recycled phthalate-based compounds can be obtained by depolymerizing waste polyester to obtain aromatic dicarboxylic acids or their esters, and then reacting them with suitable alcohols.

[0058] Alternatively, phthalic acid can be extracted from wastewater discharged during the alkali reduction processing of polyester fibers, wastewater generated during the production of pure terephthalate-based compounds, and filtered residues, and then reacted with alcohols to obtain recovered terephthalate-based compounds.

[0059] In this disclosure, based on 100 parts by weight of total plasticizer composition, there are up to 95 parts by weight of recycled phthalate-based compounds.

[0060] Due to impurities introduced during the waste recycling process, recovered phthalate-based compounds are yellow in color and emit an unpleasant, oily odor. Furthermore, they typically have high acid values. Because of these issues, recovered phthalate-based compounds are difficult to use in the manufacture of high-quality products where color or odor is important.

[0061] Accordingly, based on 100 parts by weight of the plasticizer composition, the present invention controls the content of the recycled phthalate-based compound to be less than 95 parts by weight, and uses pure or recycled cyclohexane dicarboxylate-based compound as a second plasticizer together with the recycled phthalate-based compound, thereby solving the color and odor problems caused by the recycled phthalate-based compound.

[0062] Preferably, based on 100 parts by weight of the plasticizer composition, the content of the recovered phthalate-based compound can be less than 85 parts by weight, less than 70 parts by weight, or more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, or more than 50 parts by weight.

[0063] Meanwhile, the recovered phthalate-based compounds have higher acid values ​​than the pure plasticizers. Specifically, the recovered phthalate-based compounds may have acid values ​​of ≥0.05 KOH mg / g, ≥0.1 KOH mg / g, ≥0.15 KOH mg / g and ≤0.25 KOH mg / g, ≤0.2 KOH mg / g, or ≤0.18 KOH mg / g.

[0064] Therefore, recycled phthalate-based compounds have higher acid values ​​than conventional plasticizers and suffer from drawbacks such as yellowing and unpleasant odors. However, they are characterized by approximately 5% improvement in thermal stability and gelation rate compared to pure phthalate-based compounds. Since the plasticizer composition of this disclosure primarily uses recycled phthalate-based compounds instead of pure phthalate-based compounds, and also includes pure or recycled cyclohexane dicarboxylate-based compounds as a secondary plasticizer, the color and odor issues are resolved, and the gelation rate can be further improved.

[0065] However, when the acid value of the recycled phthalate-based compound is too high, exceeding 0.25 KOH mg / g, the plasticizer composition may become too yellow or have a strong odor, and the plasticizer's migration resistance may be poor. Therefore, it is desirable for the acid value to be within the aforementioned range.

[0066] Here, the acid value is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1g of sample, which can be obtained by titrating the sample solution with a 0.1N KOH alcohol solution.

[0067] Second plasticizer

[0068] The plasticizer compositions disclosed herein include a cyclohexane dicarboxylate-based compound as a second plasticizer. As the cyclohexane dicarboxylate-based compound, pure cyclohexane dicarboxylate-based compounds prepared from pure raw materials, recycled cyclohexane dicarboxylate-based compounds recovered from waste through reprocessing, or combinations thereof can be used.

[0069] Compounds based on cyclohexane dicarboxylate can be used in conjunction with recycled phthalate-based compounds to improve the plasticizing efficiency and gelation rate of plasticizer compositions. Furthermore, since both pure and recycled cyclohexane dicarboxylate-based compounds have lighter colors and better odors than recycled phthalate-based compounds, they can be used as secondary plasticizers to compensate for the color and odor of the primary plasticizer.

[0070] Compounds based on cyclohexane dicarboxylic acid esters are represented by the following chemical formula 2:

[0071] [Chemical Formula 2]

[0072]

[0073] In chemical formula 2,

[0074] R'1 and R'2 are each independently C4 to C12 straight-chain or branched alkyl groups.

[0075] Preferably, R'1 and R'2 are each independently butyl, isobutyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, isononyl, 2-propylheptyl, decyl, or isodexyl. Preferably, R'1 and R'2 are each independently butyl, 2-ethylhexyl, or isononyl.

[0076] Depending on the position of the substituents, compounds based on cyclohexane dicarboxylic acid esters of chemical formula 2 can be represented by the following chemical formulas 2-1 to 2-3.

[0077] [Chemical Formula 2-1]

[0078]

[0079] [Chemical Formula 2-2]

[0080]

[0081] [Chemical Formula 2-3]

[0082]

[0083] In chemical formulas 2-1 to 2-3, R'1 and R'2 are as defined in chemical formula 2.

[0084] Chemical formula 2-1 is a compound based on cyclohexane-1,2-dicarboxylic acid ester, chemical formula 2-2 is a compound based on cyclohexane-1,3-dicarboxylic acid ester, and chemical formula 2-3 is a compound based on cyclohexane-1,4-dicarboxylic acid ester.

[0085] In one embodiment, the compound based on cyclohexane dicarboxylic acid ester may be at least one selected from 1,4-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester, 1,2-cyclohexane dicarboxylic acid diisononyl ester, 1,2-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester, 1,4-cyclohexane dicarboxylic acid butyl(2-ethylhexyl) ester and 1,4-cyclohexane dicarboxylic acid dibutyl ester.

[0086] Preferably, the compound based on cyclohexane dicarboxylic acid ester can be 1,4-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester (DEHCH) represented by the following chemical formulas 2-4:

[0087] [Chemical Formula 2-4]

[0088]

[0089] Compared to other compounds based on cyclohexane dicarboxylic acid esters, DEHCH is transparent and odorless, has low viscosity at both room and low temperatures, exhibits excellent workability, fast gelation rate, and demonstrates superior plasticizing efficiency and resistance to plasticizer migration. Therefore, the use of DEHCH can further improve the physical properties of plasticizer compositions.

[0090] Pure compounds based on cyclohexane dicarboxylic acid esters can be commercially available products or can be obtained from pure materials using known methods.

[0091] When pure cyclohexane dicarboxylic acid ester-based compounds are used as the second plasticizer, the color and odor problems of recycled phthalate-based compounds used as the first plasticizer can be more effectively compensated for. Therefore, plasticizer compositions using pure cyclohexane dicarboxylic acid ester-based compounds as the second plasticizer are more suitable for manufacturing high-quality products.

[0092] The recovered cyclohexane dicarboxylate-based compounds can be commercially available products or obtained from waste using known methods. For example, after obtaining a recovered phthalate-based compound as a first plasticizer using the methods described above, it can be hydrogenated to obtain a recovered cyclohexane dicarboxylate-based compound. In this process, the energy consumed and greenhouse gas emissions for producing pure phthalate-based compounds are reduced. Therefore, when the recovered cyclohexane dicarboxylate-based compound is used as a second plasticizer, the carbon emissions of the plasticizer composition can be significantly reduced. Furthermore, due to the removal of some impurities during the hydrogenation reaction and subsequent purification process, the recovered cyclohexane dicarboxylate-based compound has better color and less odor compared to the recovered phthalate-based compound, thus compensating for the characteristics of the first plasticizer.

[0093] The recovered cyclohexane dicarboxylate-based compound exhibited the same properties as the pure cyclohexane dicarboxylate-based compound, with a rapid gelation rate and high plasticizing efficiency. However, due to impurities, it was relatively yellow and had a higher acid value compared to the pure cyclohexane dicarboxylate-based compound.

[0094] Specifically, the recovered cyclohexane dicarboxylic acid ester-based compounds can have an acid value greater than 0.05 KOH mg / g and less than 0.3 KOH mg / g. Pure cyclohexane dicarboxylic acid ester-based compounds have an acid value less than 0.1 KOH mg / g or less than 0.05 KOH mg / g. Since lower acid values ​​are better, the lower limit can theoretically be 0 KOH mg / g.

[0095] The acid value is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1g of sample, which can be obtained by titrating the sample solution with a 0.1N KOH alcohol solution.

[0096] The content of the second plasticizer is preferably 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 less than 70 parts by weight, less than 60 parts by weight, or less than 50 parts by weight.

[0097] When 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 compensate for the physical properties of the recycled phthalate-based compounds. Furthermore, when the content of the second plasticizer exceeds 70 parts by weight per 100 parts by weight of the plasticizer composition, the relatively low content of the recycled phthalate-based compounds makes it difficult to ensure the physical properties of the plasticizer containing phthalate-based compounds, and the effect of reducing carbon emissions through the use of recycled phthalate-based compounds is difficult to anticipate.

[0098] In one embodiment of the invention, the first plasticizer may be recycled dioctyl terephthalate, and the second plasticizer may be di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate. In this case, the di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate may be pure di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate, recycled di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate, or a combination thereof.

[0099] Meanwhile, the plasticizer composition disclosed herein may not contain any plasticizers other than the first and second plasticizers described above. 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.

[0100] Preferably, the plasticizer composition may comprise 20 to 85 parts by weight of recycled dioctyl terephthalate as a first plasticizer and 5 to 70 parts by weight of di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate as a second plasticizer. More preferably, the plasticizer composition may comprise 50 to 70 parts by weight of recycled dioctyl terephthalate as a first plasticizer and 30 to 50 parts by weight of di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate as a second plasticizer. In this case, the di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate may be pure di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate, recycled di(2-ethylhexyl) 1,4-cyclohexanedicarboxylate, or a combination thereof.

[0101] Other plasticizers

[0102] In addition to the first and second plasticizers, the plasticizer compositions disclosed herein may also contain other plasticizers.

[0103] As an additional plasticizer, materials commonly used as plasticizers for polymer resins can be used without restriction. For example, at least one selected from phthalate-based compounds; polyol ester-based compounds; trimellitate-based compounds; aliphatic ester-based compounds; phosphate ester-based compounds; vegetable oils; epoxidized oils; and acylated glycerol monoester compounds can be used.

[0104] Compounds based on phthalates are those represented by chemical formula 1. Specifically, it can be selected from at least one of dibutyl phthalate, di-n-hexyl phthalate, diisoheptyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diheptylnonyl phthalate, di-n-octyldecyl phthalate, diheptylnonylundecyl phthalate, diisononyl phthalate, dinonyl phthalate, di-n-nonyl phthalate, diisodecyl phthalate, di-n-nonyldecylundecyl phthalate, dinonylundecyl phthalate, dodecyl phthalate, diisoundecyl dodecyl phthalate, trialkyl phthalate, dibutyl terephthalate, butyl octyl terephthalate, di(2-ethylhexyl) terephthalate, and butyl benzyl phthalate.

[0105] Compounds based on polyol esters are obtained by esterification of polyols and carboxylic acids.

[0106] The polyol is a polyol with 3 to 8 carbon atoms, such as 1,3-propanediol, propylene glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitol, isosorbide, erythritol, threitol, pentaerythritol, arabinitol, xylitol, ribitol, fucitol, mannitol, galactitol, idoteol, inositol, heptaheptanol, or glucose.

[0107] Examples of carboxylic acids include butyric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benzyl acid, ceramide, palmitoleic acid, oleic acid, and valeric acid, but this disclosure is not limited thereto.

[0108] Specifically, pentaerythritol tetravalerate (Pevalen TM It can be used as a compound based on polyol esters.

[0109] Specific examples of compounds based on trimellitic esters may be at least one selected from tri-(2-ethylhexyl) trimellitate, trimethyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, tri-(n-octyl, n-decyl) trimellitate and tri-(heptyl, nonyl) trimellitate.

[0110] Compounds based on aliphatic esters can be ester compounds derived from aliphatic carboxylic acid compounds such as adipic acid, sebacic acid, azelaic acid, and maleic acid. Specific examples of aliphatic ester compounds may be at least one selected from dimethyl adipic acid, monomethyl adipic acid, dioctyl adipic acid, diheptylnonyl adipic acid, di(2-ethylhexyl) adipic acid, diisononyl adipic acid, diisodecyl adipic acid, di(2-ethylhexyl) sebacic acid, dibutyl sebacic acid, di(2-ethylhexyl) azelaic acid, dibutyl maleate, and diisobutyl maleate.

[0111] The phosphate-based compound may be at least one selected from triethyl phosphate, trimethylol phosphate, tri-2-ethylhexyl phosphate, tritolyl phosphate, and tridimethylol phosphate.

[0112] Vegetable oil may be selected from at least one of soybean oil, castor oil, flaxseed oil, palm oil, rapeseed oil, and linseed oil.

[0113] Epoxidized oils are epoxidized fatty acid alkyl esters obtained by epoxidizing fatty acid alkyl esters. Specific examples of epoxidized vegetable oils may be at least one selected from epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized tall oil, and epoxidized linoleate.

[0114] Acylated monoglyceride compounds can be prepared by acylation of monoglycerides prepared by the reaction of glycerol with fatty acids, in which case the aforementioned aliphatic carboxylic acids, vegetable oils, etc., can be used as fatty acids.

[0115] Other plasticizers can be used alone or in combination of two or more.

[0116] When additional plasticizers are included, the content of the additional plasticizer based on 100 parts by weight of the plasticizer composition 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. When the content of the additional plasticizer is too high, the content of the first and second plasticizers is relatively reduced. Therefore, the aforementioned carbon emission reduction effect and the improvement effect of thermal stability and gelation rate cannot be sufficiently obtained, and it is preferable to satisfy the above ranges.

[0117] The plasticizer composition disclosed herein can reduce carbon emissions by using recycled phthalate-based compounds. Furthermore, it comprises both cyclohexane dicarboxylate-based compounds and recycled phthalate-based compounds, thus exhibiting excellent color, less odor, and a relatively low acid value even when using recycled raw materials.

[0118] Specifically, the plasticizer composition may have an acid value of less than 0.25 mg / g, less than 0.22 mg / g, or less than 0.2 mg / g. There is no specific lower limit, as a lower acid value is generally preferred. Theoretically, the lower limit could be 0 mg / g. In particular, a high acid value in the plasticizer composition indicates the presence of many impurities besides the plasticizer. When there are many impurities, the color of the plasticizer may change from colorless and transparent to yellow or brown, or it may have a stronger odor. Alternatively, the migration resistance of the final product using a plasticizer with a high acid value may deteriorate. Therefore, it is preferable to maintain the acid value of the plasticizer composition within the above-mentioned range.

[0119] In addition, when measured according to ASTM D1209 and E313, the plasticizer composition may have a yellow index of less than 120, less than 100, or less than 92.

[0120] Furthermore, the plasticizer composition may have a carbon emission reduction rate of 5% or more, or 5% or more and less than 40%. The carbon emission reduction rate of the plasticizer composition is a value calculated compared with a plasticizer composition comprising pure phthalate-based compounds and / or pure cyclohexanedicarboxylate-based compounds instead of recycled phthalate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds, and corresponds to the carbon emission reduction rate of using recycled materials instead of pure raw materials.

[0121] Specifically, the carbon emission reduction rate (%) of the plasticizer composition can be calculated as shown in Equation 1 below.

[0122] [Equation 1]

[0123] Carbon emission reduction rate (%) = 100 - [(A1 / A2) × 100]

[0124] In equation 1,

[0125] A1 represents the carbon emissions (tCO2 eq / MT) of the plasticizer composition, and

[0126] A2 represents the carbon emissions (tCO2 eq / MT) of the control plasticizer composition.

[0127] Specifically, A1 in the equation corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components contained in the plasticizer composition to be measured. A2 corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components in a control plasticizer composition, wherein the control plasticizer composition uses the same composition as the plasticizer composition measured in A1, but contains pure materials (pure phthalate-based compounds and / or pure cyclohexanedicarboxylate-based compounds) instead of recycled materials (recycled phthalate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds). Here, the unit of carbon emissions is weight equivalent (eq) of total CO2 emissions per metric tonne.

[0128] For example, the carbon emission (A1) of a plasticizer composition containing R-DOTP and DEHCH in a 50:50 ratio is 0.568 tCO2 eq / MT, calculated as the sum of the carbon emissions of each component at that ratio, i.e., carbon emission of R-DOTP × 0.5 + carbon emission of DEHCH × 0.5. The control plasticizer composition for the above plasticizer composition is a plasticizer composition containing DOTP and DEHCH in a 50:50 ratio, with a carbon emission (A2) of 0.611 tCO2 eq / MT, calculated as carbon emission of DOTP × 0.5 + carbon emission of DEHCH × 0.5. Therefore, according to Equation 1, the carbon emission reduction rate of the plasticizer composition containing R-DOTP and DEHCH in a 50:50 ratio is 7.04%. The carbon emission of each component used in the above plasticizer composition is calculated as follows:

[0129] -Recovered dioctyl terephthalate (R-DOTP): 0.485 tCO2 eq / MT

[0130] - Pure dioctyl terephthalate (DOTP, or pure -DOTP): 0.571 tCO2 eq / MT

[0131] - Pure 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester (DEHCH, or pure DEHCH): 0.651 tCO2 eq / MT

[0132] The carbon emissions of each component used in the plasticizer composition can be referenced from the values ​​provided by the manufacturer, or calculated based on the manufacturing process and chemical reactions of each component. The method for calculating the carbon emission reduction rate can be specified in the experimental examples described later.

[0133] Preferably, the carbon emission reduction rate of the plasticizer composition is 5% or more, 5.5% or more, 6% or more, 6.5% or more, 7% or more, and less than 40%, less than 30%, or less than 20%.

[0134] Furthermore, when used with resins, the plasticizer composition exhibits 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 in various polymer resins.

[0135] Resin Composition

[0136] Therefore, according to another embodiment of the present invention, a resin composition is provided comprising a plasticizer composition; and at least one resin selected from the following: polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin, polyketone, polyvinyl butyral, acrylic resin, synthetic rubber resin and thermoplastic elastomer.

[0137] There are no limitations on the content of resin and plasticizer in the resin composition, and it can be appropriately adjusted according to the resin used and the desired physical properties. For example, based on 100 parts by weight of resin, 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 aforementioned plasticizer composition.

[0138] The resin composition may further include at least one additive selected from stabilizers, fillers, and pigments. The additive can be appropriately selected based on the physical properties to be improved in the resin composition.

[0139] The purpose of adding stabilizers is to prevent changes in the physical properties of the resin, and they include at least one selected from Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organotin-based compounds, metal soap-based compounds, phenol-based compounds, phosphate ester-based compounds, and phosphite-based compounds.

[0140] More specific examples of stabilizers that can be used in this disclosure may include Ca-Zn based compounds; K-Zn based compounds; Ba-Zn based compounds; organotin based compounds (e.g., thiol-based compounds, maleic acid-based compounds, or carboxylic acid-based compounds); metal soap-based compounds (e.g., magnesium stearate, calcium stearate, lead stearate, cadmium stearate, or barium stearate); phenol-based compounds; phosphate ester-based compounds; phosphite-based compounds, etc., but the invention is not limited thereto.

[0141] The filler is used to improve the productivity, dry touch and flame retardant properties of the resin composition, and includes at least one selected from calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, aluminum hydroxide, phosphorus-based compounds, melamine-based compounds, phosphorus-melamine complexes, boron-based flame retardants, carbon black, carbon nanotubes, nanoclay, and clay.

[0142] Pigments can be titanium dioxide, carbon black, cadmium-based pigments, etc.

[0143] The resin compositions according to this disclosure can be prepared using methods known in the art, employing a resin, a plasticizer composition, and optional additives. There are no particular limitations to this method.

[0144] In one embodiment, the resin composition may be a vinyl chloride resin composition comprising vinyl chloride resin. The vinyl chloride resin composition contains a plasticizer composition according to the present disclosure, thereby exhibiting excellent color, gelling properties, and weather resistance.

[0145] Vinyl chloride resin can be a homopolymer formed by homopolymerization of vinyl chloride monomer, or a copolymer formed by polymerization of vinyl chloride monomer and comonomers that can copolymerize therewith. Either or a mixture thereof can be used to prepare vinyl chloride resin compositions.

[0146] Examples of comonomers capable of copolymerizing with vinyl chloride monomers include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; vinylidene dihaloethylene compounds such as vinylidene chloride; unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, or itaconic anhydride; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butyl benzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; olefins such as ethylene or propylene; or crosslinkable monomers such as diallyl phthalate. Any one or a mixture of two or more of these monomers may be used. From the viewpoint of excellent compatibility with vinyl chloride monomers and improved compatibility with plasticizers constituting the resin composition after polymerization, the comonomer is more preferably vinyl acetate or the like.

[0147] As described above, vinyl chloride resins can be prepared by polymerizing vinyl chloride monomer alone, or by polymerizing vinyl chloride monomer and a comonomer that can copolymerize with it. In this case, there are no particular limitations on the polymerization method, and polymerization can be carried out according to conventional polymerization methods known in the art, such as suspension polymerization, bulk polymerization, emulsion polymerization, or seed emulsion polymerization.

[0148] The average particle size and uniformity of vinyl chloride resin can be controlled by adjusting the polymerization conditions. Specifically, linear vinyl chloride resins prepared by suspension polymerization or bulk polymerization can have an average particle size (Dsize) of 50 to 400 μm. 50 The paste-like vinyl chloride resin prepared by emulsion polymerization or fine suspension polymerization can have an average particle size (D) of less than 100 μm, preferably 0.1 to 40 μm. 50The average particle size (D) of vinyl chloride resin 50 It can be measured using conventional particle size distribution measurement methods such as optical microscopy or light scattering measurement.

[0149] The bulk density of vinyl chloride resin, measured according to ASTM D 1895, can range from 0.30 to 0.70 g / cm³. 3 Or 0.40 to 0.60 g / cm³ 3 Within the above range, the plasticizing effect and mechanical properties can be better when the bulk density is within the above range.

[0150] The degree of polymerization and weight-average molecular weight of vinyl chloride resins may affect their compatibility with the components constituting the vinyl chloride resin composition, especially plasticizers, as well as the processing properties of the vinyl chloride resin composition, and can be appropriately adjusted by controlling the polymerization conditions during the polymerization process.

[0151] 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 g / mol to 300,000 g / mol. When the degree of polymerization and weight-average molecular weight are within the above ranges, the dispersibility is excellent, the compatibility with plasticizers is good, and the processability of the vinyl chloride resin composition can be improved.

[0152] If the degree of polymerization of vinyl chloride resin is less than 500 or the weight-average molecular weight is less than 25,000 g / mol, there are concerns that processing performance and the durability of the processed product may deteriorate due to insufficient physical properties. When the degree of polymerization is greater than 3,000 or the weight-average molecular weight is greater than 300,000 g / mol, the molecular weight is too high, making it difficult to mold or process. More specifically, vinyl chloride resins can have a degree of polymerization of 700 or more but less than 1,700 or a weight-average molecular weight (Mw) of 45,000 g / mol to 250,000 g / mol.

[0153] The weight-average molecular weight (Mw) of vinyl chloride resin is a value converted from standard polystyrene using gel permeation chromatography. Additionally, the degree of polymerization of vinyl chloride resin can be determined according to JIS K 6720-2.

[0154] In one embodiment, the vinyl chloride resin may be pure vinyl chloride resin.

[0155] In one embodiment, PVC waste can be used as vinyl chloride resin. PVC waste is manufactured by processing waste PVC products such as flooring materials, waterproof tarpaulins, and calendering machines into powder form, which further reduces carbon emissions compared to using pure PVC. PVC waste can be commercially available products or obtained by crushing waste PVC. In this case, PVC waste free of heavy metals and toxic substances is suitable for producing environmentally friendly products; specifically, PVC waste obtained by crushing waste chassis or decorative bricks is preferred. For example, PVC waste may contain four major heavy metals (Pb, Cd, Hg, hexavalent Cr) in amounts of less than 90 mg / kg, less than 50 mg / kg, or less than 25 mg / kg, preferably 0 mg / kg.

[0156] The yellowness index (YI, yellowness) of the resin composition, as measured according to ASTM E313, can be 10 to 25; or less than 22, or less than 20, or more than 15, or more than 18.

[0157] In addition, the yellowness index (YI) of the resin composition, measured according to ASTM G154 after 300 hours of UV aging, can be from 10 to 65; preferably below 64, below 63, or below 62.5, and above 20, above 30, or above 40.

[0158] Furthermore, the resin composition may have a carbon emission reduction rate of 1.5% or more, or 1.5% or more and less than 60%. The carbon emission reduction rate of the resin composition is a value calculated compared to a vinyl chloride resin composition using a plasticizer composition containing pure phthalate-based compounds and / or pure cyclohexanedicarboxylate-based compounds instead of recycled phthalate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds, and corresponds to the carbon emission reduction rate of using recycled materials instead of pure materials.

[0159] Specifically, the carbon emission reduction rate (%) of the resin composition can be calculated as shown in Equation 2 below.

[0160] [Equation 2]

[0161] Carbon emission reduction rate (%) = 100 - [(A3 / A4) × 100]

[0162] In equation 2,

[0163] A3 represents the carbon emissions (tCO2 eq / MT) of the resin composition, and

[0164] A4 represents the carbon emissions (tCO2 eq / MT) of the control resin composition.

[0165] Specifically, A3 in Equation 2 corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components contained in the resin composition to be measured. A4 corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components in a resin composition, wherein the resin composition uses the same composition as the plasticizer composition measured in A3, but contains pure materials (pure phthalate-based compounds and / or pure cyclohexanedicarboxylate-based compounds) instead of recycled materials (recycled phthalate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds). Here, the unit of carbon emissions is weight equivalent (eq) of total CO2 emissions per metric tonne.

[0166] For example, when the resin composition is a vinyl chloride resin composition containing 100 parts by weight of polyvinyl chloride (PVC, Hanwha Solutions P-1000), 30 parts by weight of a plasticizer comprising R-DOTP and DEHCH in a 50:50 ratio, and 2 parts by weight of a heat stabilizer, the weight ratios of PVC, R-DOTP, DEHCH, and the Bn / Zn-based heat stabilizer in the vinyl chloride resin composition are 0.758, 0.114, 0.114, and 0.015, respectively. Considering only the carbon emissions of PVC, R-DOTP, and DEHCH, and ignoring the negligible carbon emissions of the heat stabilizer in the composition, the carbon emissions (A3) of the resin composition are calculated as the sum of the carbon emissions of each component in the weight ratios of PVC, R-DOTP, and DEHCH of 0.758, 0.114, and 0.114, respectively, and is 0.267tCO2 eq / MT (i.e., carbon emissions of PVC × 0.758 + carbon emissions of R-DOTP × 0.114 + carbon emissions of DEHCH × 0.114). The control resin composition relative to the above-mentioned vinyl chloride resin composition is a resin composition containing PVC, DOTP, and DEHCH in weight ratios of 0.758, 0.114, and 0.114, with a carbon emission (A4) of 0.277 tCO2 eq / MT, calculated as carbon emission of PVC × 0.758 + carbon emission of DOTP × 0.114 + carbon emission of DEHCH × 0.114. Therefore, according to Equation 2, the carbon emission reduction rate of the vinyl chloride resin composition is 3.53%. The carbon emissions of each component used in the above plasticizer composition are calculated as follows:

[0167] - Polyvinyl chloride (PVC, Hanwha Solution P-1000): 0.182tCO2 eq / MT

[0168] -Recovered dioctyl terephthalate (R-DOTP): 0.485 tCO2 eq / MT

[0169] - Pure dioctyl terephthalate (DOTP, or pure -DOTP): 0.571 tCO2 eq / MT

[0170] - Pure 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester (DEHCH, or pure -DEHCH): 0.651 tCO2 eq / MT

[0171] The carbon emissions of each component used in the plasticizer composition can be referenced from the values ​​provided by the manufacturer, or calculated based on the manufacturing process and chemical reactions of each component. The method for calculating the carbon emission reduction rate can be specified in the experimental examples described later.

[0172] The carbon emission reduction rate can vary 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 can be 1.8% or more, 2% or more, 3% or more, 3.5% or more, 4.2% or more, or 5% or more. If resin produced from pure raw materials is used, the carbon emission reduction rate of the resin composition can be 28% or less, 25% or less, 22% or less, 20% or less, 18% or less, 16% or less, or 11% or less. If recycled resin such as PVC waste is used, the carbon emission reduction rate can be 60% or less, or 55% or less.

[0173] In addition, the resin composition has the excellent color and odor properties described above, and also has excellent thermal stability and rapid gelation rate.

[0174] According to another aspect of this disclosure, a molding article comprising the above-described resin composition is provided.

[0175] Molded articles can be used to manufacture food packaging films (e.g., packaging films), industrial films, compounds, decorative panels, decorative bricks, flexible boards, rigid boards, wires and cables, wallpaper, foam pads, artificial leather, flooring, tarpaulins, gloves, sealants, refrigerator gaskets, hoses, medical devices, geogrids, mesh tarpaulins, toy products, stationery, insulating tapes, clothing coatings, labels for clothing or stationery, bottle cap liners, stoppers for industrial or other purposes, artificial baits, electronic components (such as sleeves), automotive interior materials, adhesives, sealants, coatings, etc., but the invention is not limited thereto.

[0176] The present invention will be described in more detail below through the following embodiments. However, the following embodiments are for illustrative purposes only, and the scope of the invention is not limited thereto.

[0177] [Example]

[0178] Example 1

[0179] A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP, acid value 0.175 KOH mg / g) produced by China Runze Energy with di(2-ethylhexyl) 1,4-cyclohexanedicarboxylic acid (DEHCH) at a weight ratio of 50:50.

[0180] Based on 100 parts by weight of polyvinyl chloride (Hanwha Solution P-1000F, degree of polymerization 1000±50, bulk density 0.55±0.04 g / cm³). 3 Add 30 parts by weight of a plasticizer composition and 2 parts by weight of a Ba / Zn-based heat stabilizer, and then knead using a roller mill to prepare a vinyl chloride resin composition.

[0181] Example 2

[0182] A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP) produced by China Runze Energy with di(2-ethylhexyl) 1,4-cyclohexanedicarboxylic acid (DEHCH) at a weight ratio of 60:40.

[0183] Based on 100 parts by weight of polyvinyl chloride (Hanwha Solution P-1000F), 30 parts by weight of a plasticizer composition and 2 parts by weight of a Ba / Zn-based heat stabilizer were added, and then kneaded using a roller mill to prepare a vinyl chloride resin composition.

[0184] Example 3

[0185] A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP) produced by China Runze Energy with di(2-ethylhexyl) 1,4-cyclohexanedicarboxylic acid (DEHCH) at a weight ratio of 70:30.

[0186] Based on 100 parts by weight of polyvinyl chloride (Hanwha Solution P-1000F), 30 parts by weight of a plasticizer composition and 2 parts by weight of a Ba / Zn-based heat stabilizer were added, and then kneaded using a roller mill to prepare a vinyl chloride resin composition.

[0187] Example 4

[0188] A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP, acid value 0.175 KOH mg / g) produced by China Runze Energy with recycled 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester (R-DEHCH, acid value 0.250 KOH mg / g) prepared by hydrogenation of R-DOTP in a weight ratio of 50:50.

[0189] Based on 100 parts by weight of polyvinyl chloride (Hanwha Solution P-1000F, degree of polymerization 1000±50, bulk density 0.55±0.04 g / cm³). 3 Add 60 parts by weight of a plasticizer composition and 3 parts by weight of a Ba / Zn-based heat stabilizer, and then knead using a roller mill to prepare a vinyl chloride resin composition.

[0190] Example 5

[0191] Based on 100 parts by weight of recycled polyvinyl chloride (PVC waste: flooring materials, waterproof tarpaulins, calendering machines and other waste PVC products that have been crushed into powder), 60 parts by weight of the plasticizer composition of Example 4 and 3 parts by weight of the Ba / Zn-based heat stabilizer were added, and then the mixture was kneaded using a roller mill to prepare a vinyl chloride resin composition.

[0192] Example 6

[0193] The plasticizer composition was prepared in the same manner as in Example 4, except that the weight ratio of R-DOTP to R-DEHCH was 70:30. Then, using this plasticizer composition, a vinyl chloride resin composition was prepared in the same manner as in Example 4.

[0194] Comparative Example 1

[0195] The plasticizer composition was prepared in the same manner as in Example 1, using recycled dioctyl terephthalate (R-DOTP) produced by China Runze Energy as a plasticizer.

[0196] Comparative Example 2

[0197] A plasticizer composition was prepared by mixing recycled dioctyl terephthalate (R-DOTP) produced by China Runze Energy with di(2-ethylhexyl) 1,4-cyclohexanedicarboxylic acid at a weight ratio of 95:5.

[0198] Then, using the plasticizer composition, a vinyl chloride resin composition was prepared in the same manner as in Example 1.

[0199] Comparative Example 3

[0200] The plasticizer composition and the vinyl 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 recycled dioctyl terephthalate.

[0201]

Experimental Example

[0202] The plasticizer compositions and vinyl chloride resin compositions of each embodiment and comparative example were evaluated by the following methods, and the results are shown in Table 1.

[0203] (1) Carbon emission reduction rate (%)

[0204] The carbon emission reduction rate (%) of the plasticizer compositions of the Examples and Comparative Examples is calculated according to Equation 1 below.

[0205] [Equation 1]

[0206] Carbon emission reduction rate (%) = 100 - [(A1 / A2) × 100]

[0207] In equation 1,

[0208] A1 represents the carbon emissions (tCO2 eq / MT) of the plasticizer composition, and

[0209] A2 represents the carbon emissions (tCO2 eq / MT) of the control plasticizer composition.

[0210] Specifically, A1 in the equation corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components contained in the plasticizer composition to be measured. A2 corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components in a control plasticizer composition, wherein the control plasticizer composition uses the same composition as the plasticizer composition measured in A1, but contains pure materials (pure phthalate-based compounds and / or pure cyclohexanedicarboxylate-based compounds) instead of recycled materials (recycled phthalate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds). Here, the unit of carbon emissions is weight equivalent (eq) of total CO2 emissions per metric tonne.

[0211] In addition, the carbon emission reduction rate (%) of the vinyl chloride resin compositions of the Examples and Comparative Examples is calculated according to Equation 2 below.

[0212] [Equation 2]

[0213] Carbon emission reduction rate (%) = 100 - [(A3 / A4) × 100]

[0214] In equation 2,

[0215] A3 represents the carbon emissions (tCO2 eq / MT) of the resin composition, and

[0216] A4 represents the carbon emissions (tCO2 eq / MT) of the control resin composition.

[0217] Specifically, A3 in Equation 2 corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components contained in the resin composition to be measured. A4 corresponds to the total carbon emissions (tCO2 eq / MT) based on the composition ratio of the components in a resin composition, wherein the resin composition uses the same composition as the plasticizer composition measured in A3, but contains pure materials (pure phthalate-based compounds and / or pure cyclohexanedicarboxylate-based compounds) instead of recycled materials (recycled phthalate-based compounds and / or recycled cyclohexanedicarboxylate-based compounds). Here, the unit of carbon emissions is weight equivalent (eq) of total CO2 emissions per metric tonne.

[0218] For example, the plasticizer composition of Example 1 contains R-DOTP and DEHCH in a 50:50 ratio, and the sum of the carbon emissions of each component calculated according to the composition ratio is 0.568 tCO2 eq / MT (A1, i.e., carbon emissions of R-DOTP × 0.5 + carbon emissions of DEHCH × 0.5). Its control group is the plasticizer composition of Comparative Example 3, whose carbon emissions (A2) are 0.611 tCO2 eq / MT. Therefore, according to Equation 1, the carbon emission reduction rate of the plasticizer composition of Example 1 is 7.04%. The carbon emissions and carbon emission reduction rate of the plasticizer composition of Example 4 can be obtained in the same manner as described above using the plasticizer composition of Comparative Example 3 as a control group.

[0219] Furthermore, the vinyl chloride resin composition of Example 1 comprises 100 parts by weight of polyvinyl chloride (PVC) and 30 parts by weight of a plasticizer containing R-DOTP and DEHCH in a 50:50 ratio. The weight ratios of PVC, R-DOTP, DEHCH, and the Bn / Zn-based heat stabilizer in the vinyl chloride resin composition are 0.758, 0.114, 0.114, and 0.015, respectively. Considering only the carbon emissions of PVC, R-DOTP, and DEHCH, and ignoring the negligible carbon emissions of the heat stabilizer in the composition, the sum of the carbon emissions of each component at this composition ratio (A3) is 0.267 tCO2 eq / MT. Since the carbon emissions (A4) of the vinyl chloride resin composition of Comparative Example 3 (the control group) are 0.277 tCO2 eq / MT, the carbon emission reduction rate of the vinyl chloride resin composition of Example 1 is 3.53% when calculated according to Equation 2.

[0220] Here, the carbon emissions of each component used in the plasticizer composition and the vinyl chloride resin composition are calculated as follows:

[0221] - Polyvinyl chloride (PVC, Hanwha Solution P-1000): 0.182tCO2 eq / MT

[0222] - Recycled polyvinyl chloride (PVC waste): 0tCO2 eq / MT

[0223] -Recovered dioctyl terephthalate (R-DOTP): 0.485 tCO2 eq / MT

[0224] - Pure dioctyl terephthalate (DOTP, or pure -DOTP): 0.571 tCO2 eq / MT

[0225] -Recovered 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester (R-DEHCH): 0.520 tCO2 eq / MT

[0226] - Pure 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester (DEHCH, or pure -DEHCH): 0.651 tCO2 eq / MT

[0227] The carbon emissions for polyvinyl chloride (PVC) and pure dioctyl terephthalate (DOTP, or pure -DOTP) are based on figures provided by the manufacturers. Additionally, the carbon emissions for recycled dioctyl terephthalate (R-DOTP) are calculated by assuming that the carbon emissions from recycled PTA (pure terephthalic acid) used for R-DOTP are 70% of those from pure PTA, while the carbon emissions from PTA and 2-EH (2-ethylhexanol) are the same. PTA and 2-EH are raw materials for the manufacture of DOTP.

[0228] (2) Plasticizer Color (APHA Color)

[0229] The color of plasticizers was measured using an APHA colorimeter according to ASTM D1209 and E313.

[0230] (3) Acid value of plasticizer

[0231] The acid value of the plasticizer is calculated using a 0.1N KOH aqueous solution and an indicator by the following formula.

[0232] [Equation 3]

[0233] Acid value = (Titration amount × 5.6 × Coefficient) / Sample amount

[0234] In Formula 3, 'titering amount' represents the amount (ml) of 0.1N KOH aqueous solution consumed in titrating the plasticizer, 'coefficient' is the correction coefficient of KOH aqueous solution (the coefficient of 0.1N KOH aqueous solution is 1), and 'sample amount' represents the weight (g) of the plasticizer sample.

[0235] (4) Gelation rate

[0236] 54g of the vinyl chloride resin composition was placed in a Brabender mixer at 95°C and mixed at 30 rpm for 10 minutes. The gelation time of the resin was analyzed by measuring the change in torque during processing in the mixer.

[0237] (5) Hardness (plasticization efficiency)

[0238] The vinyl chloride resin composition was subjected to rolling (170°C, 3 minutes) and pressure processing (180°C, 8 minutes) in sequence to produce a plate with a thickness of 6 mm.

[0239] According to ASTM D2240, the needle of the hardness tester (Shore Type D) is fully lowered into a portion of the specimen, and the hardness value is read after 5 seconds. After testing three portions of each sample, the average value is taken and used as an indication of plasticizing efficiency.

[0240] (6) Color of the vinyl chloride resin composition

[0241] The vinyl chloride resin composition was subjected to rolling (170°C, 3 minutes) and pressure processing (180°C, 8 minutes) in sequence to produce a plate with a thickness of 6 mm.

[0242] For the samples prepared above, the yellow index (YI, yellowness) was measured according to ASTM E313. The samples were then placed in an accelerated aging test chamber (QUV, manufactured by Q-Lab) and exposed for 300 hours according to ASTM G154 (1 cycle: at 60°C using a UVB 313nm lamp at 0.8W / m²). 2 / nm UV irradiation for 8 hours, followed by condensation at 50℃ for 4 hours, and then YI was measured again.

[0243] When preparing the final resin product, it is evaluated that the lower the initial color (color, YI) of the vinyl chloride resin composition, the better in terms of color quality.

[0244] Table 1

[0245]

[0246]

[0247] Table 2

[0248]

[0249] Referring to Table 1, it is confirmed that the plasticizer compositions of this disclosure can reduce carbon emissions by incorporating recycled raw materials. Furthermore, by using pure cyclohexane dicarboxylic acid ester-based compounds and / or recycled cyclohexane dicarboxylic acid ester-based compounds, which possess favorable odor, excellent color, and acid value, the gelation rate, hardness, and color characteristics are equal to or higher than those of conventional plasticizers.

Claims

1. A plasticizer composition comprising: Recycled phthalate-based compounds are used as the first plasticizer; and Pure cyclohexane dicarboxylic acid ester-based compounds and / or recycled cyclohexane dicarboxylic acid ester-based compounds are used as secondary plasticizers. in, Based on 100 parts by weight of the plasticizer composition, the content of the first plasticizer is 95 parts by weight or less. The recovered phthalate-based compounds have an acid value of 0.05 KOH mg / g to 0.25 KOH mg / g. The recovered cyclohexane dicarboxylic acid ester-based compound has an acid value greater than 0.05 KOH mg / g and less than 0.3 KOH mg / g. The plasticizer composition has an acid value of less than 0.25 KOH mg / g, and The plasticizer composition has a yellow index (YI, yellowness) of less than 120 as measured according to ASTM E313.

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

3. The plasticizer composition as described in claim 1, in, The first plasticizer is selected from at least one of the following: recycled dibutyl phthalate, recycled dihexyl phthalate, recycled dioctyl phthalate, recycled di-n-octyl phthalate, recycled diisononyl phthalate, recycled diisodecyl phthalate, recycled dibutyl isophthalate, recycled dioctyl isophthalate, recycled diisononyl isophthalate, recycled diisodecyl isophthalate, recycled dibutyl terephthalate, recycled dioctyl terephthalate, recycled diisononyl terephthalate, and recycled diisodecyl terephthalate.

4. The plasticizer composition according to claim 1, in, The compound based on cyclohexane dicarboxylic acid ester is selected from at least one of 1,4-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester, 1,2-cyclohexane dicarboxylic acid diisononyl ester, 1,2-cyclohexane dicarboxylic acid di(2-ethylhexyl) ester, 1,4-cyclohexane dicarboxylic acid butyl(2-ethylhexyl) ester and 1,4-cyclohexane dicarboxylic acid dibutyl ester.

5. The plasticizer composition of claim 1, in, The first plasticizer is recycled dioctyl terephthalate, and The second plasticizer is pure 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester and / or recycled 1,4-cyclohexanedicarboxylic acid di(2-ethylhexyl) ester.

6. The plasticizer composition according to claim 1, It further comprises at least one compound selected from the following: phthalate-based compounds; polyol ester-based compounds; trimellitate-based compounds; aliphatic ester-based compounds; phosphate ester-based compounds; vegetable oils; epoxidized oils; and acylated glycerol monoester compounds.

7. The plasticizer composition according to claim 1, in, The carbon emission reduction rate is over 5%.

8. A resin composition comprising a plasticizer composition as described in any one of claims 1 to 7; and at least one resin selected from polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin, polyketone, polyvinyl butyral, acrylic resin, synthetic rubber resin and thermoplastic elastomer.

9. The resin composition according to claim 8, in, The content of the plasticizer composition is from 1 part by weight to 200 parts by weight, based on 100 parts by weight of the resin.

10. The resin composition according to claim 8, in, The yellowness index (YI, yellowness) measured according to ASTM E313 is 10 to 25.

11. The resin composition according to claim 8, in, The yellowness index (YI, yellowness) measured after 300 hours of UV aging according to ASTM G154 is 10 to 65.

12. A molding article comprising the resin composition of claim 8.

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