Resin composition

Abstract

The present invention relates to a resin composition comprising a polyester copolymer and a plasticizer. Particularly, according to an embodiment of the present invention, the resin composition comprises: an eco-friendly polyester copolymer; and 0.1-50 parts by weight of a plasticizer with respect to 100 parts by weight of the polyester copolymer, and thus, a specimen manufactured using the resin composition has a Shore A hardness of less than 95 while having excellent moldability and processability, and thus liquid-form plasticizer's migration does not occur on the surface of the specimen, enabling easy application in various fields.

Description

resin composition

[0001] The present invention relates to a resin composition that is environmentally friendly and has excellent formability and processability.

[0002] Polyvinyl chloride (PVC) is colorless and transparent, has excellent strength, and its properties can be easily adjusted depending on the type of additives mixed in during processing, making it widely used in various industries. For example, by adding a certain amount of plasticizer, a softening agent, to PVC, soft PVC can be produced, making it suitable for flexible products such as packaging films and shower curtains. By adding less than 10% by weight of plasticizer, rigid PVC can be produced, making it suitable for use in plumbing materials. Thus, PVC boasts excellent productivity and processability, as its softness and hardness can be easily controlled simply by adjusting the plasticizer content, without the need for additional processing.

[0003] However, the plasticizers used to control the softness and hardness of PVC can reduce its moldability and processability. Specifically, the large amount of plasticizer used to achieve sufficient hardness can lead to migration (the movement or extraction of the liquid plasticizer from the product surface during the extrusion process), limiting its potential applications. Furthermore, PVC produces toxic dioxins when burned, making landfill disposal the only option. Therefore, there is a pressing need to develop materials that can replace PVC while still offering superior moldability and processability, even when using plasticizers.

[0004] Meanwhile, polyester boasts excellent mechanical properties, such as durability and heat resistance, and optical properties, such as transparency. This makes it widely used as a raw material for fibers, films, packaging materials, molded products, building materials, interior and exterior finishes, and various industrial materials, such as display devices. Furthermore, polyester is more environmentally friendly than PVC, as it can be recycled through mechanical and chemical recycling methods. Furthermore, it boasts superior mechanical and optical properties, making it a promising alternative to PVC. However, controlling flexibility and rigidity remains challenging. Therefore, research into polyesters that can effectively control flexibility and rigidity continues.

[0005] For example, Korean Patent Publication No. 2013-0122746 discloses a copolyester resin capable of controlling softness or hardness by attaching soft segments or hard segments.

[0006] [Prior Art Literature]

[0007] [Patent Document]

[0008] (Patent Document 1) Korean Patent Publication No. 2013-0122746

[0009] Accordingly, the present invention aims to provide a resin composition that is environmentally friendly, can effectively control softness and hardness, contains a plasticizer, and has excellent moldability and processability, making it easy to apply to various purposes.

[0010] A resin composition according to one embodiment of the present invention is a resin composition comprising a polyester copolymer and a plasticizer, wherein the plasticizer is included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyester copolymer, and a Shore A hardness of a specimen manufactured from the resin composition measured according to ASTM D2240 is less than 95.

[0011] A molded article according to another embodiment of the present invention is manufactured by molding the resin composition.

[0012] A resin composition according to one embodiment of the present invention comprises an environmentally friendly polyester copolymer and a plasticizer in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyester copolymer, thereby having excellent moldability and processability and being easily applicable to various fields.

[0013] Specifically, a specimen manufactured using the resin composition can secure softness with a Shore A hardness of less than 95, and has excellent formability and processability while including a plasticizer, so that the surface of the strand is smooth and uniform during the extrusion process, and liquid plasticizer migration does not occur on the surface of the specimen, thereby having excellent quality.

[0014] In addition, the polyester copolymer comprises a residue of a first dicarboxylic acid component including terephthalic acid or a derivative thereof; a residue of a second dicarboxylic acid component including cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate, or a derivative thereof; and a residue of a diol component including ethylene glycol or a derivative thereof, and comprises 30 mol% or more of the second dicarboxylic acid component based on the total dicarboxylic acid component, thereby being environmentally friendly and also having excellent mechanical properties such as softness and elasticity, and optical properties such as transparency and UV stability.

[0015] The present invention is described in detail below. The present invention is not limited to the details disclosed below and may be modified in various ways without altering the spirit of the invention.

[0016] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0017] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification should be understood to be modified by the term “about” in all cases unless otherwise specified.

[0018] In this specification, the terms "first," "second," etc. are used to describe various components, and the components are not limited by the terms. The terms are used only to distinguish one component from another.

[0019] The term “derivative thereof” as used herein means a compound that has been modified by introducing a functional group, oxidation, reduction, substitution of atoms, etc., without significantly changing the structure and properties of the parent compound.

[0020]

[0021] resin composition

[0022] A resin composition according to one embodiment of the present invention is a resin composition comprising a polyester copolymer and a plasticizer, wherein the plasticizer is included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyester copolymer, and a Shore A hardness of a specimen manufactured from the resin composition measured according to ASTM D2240 is less than 95.

[0023] For example, a flat specimen having a thickness of 1 mm is manufactured using the resin composition, and the Shore A hardness of the specimen measured according to ASTM D2240 may be 93 or less, 90 or less, 85 or less, 80 or less, 78 or less, 77 or less, 76 or less, 75 or less, 72 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, or 40 or less. The resin composition according to one embodiment of the present invention can secure softness that can be applied to processes and various fields by having the Shore A hardness satisfying the above range.

[0024]

[0025] polyester copolymer

[0026] According to one embodiment of the present invention, the resin composition comprises a polyester copolymer.

[0027] Specifically, the polyester copolymer is a copolymer of a first dicarboxylic acid component, a second dicarboxylic acid component, and a diol component including ethylene glycol or a derivative thereof, and may be a block copolymer or a random copolymer including a residue of the first dicarboxylic acid component, a residue of the second dicarboxylic acid component, and a residue of a diol component including ethylene glycol or a derivative thereof.

[0028] The first dicarboxylic acid component comprises terephthalic acid (TPA) or a derivative thereof. Specifically, the first dicarboxylic acid component may comprise 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol% of terephthalic acid or a derivative thereof.

[0029] Additionally, the polyester copolymer may contain the first dicarboxylic acid component in an amount of 5 mol% to 70 mol%, 8 mol% to 65 mol%, 10 mol% to 60 mol%, 13 mol% to 55 mol%, or 15 mol% to 50 mol% based on the total dicarboxylic acid component.

[0030] According to one embodiment of the present invention, the second dicarboxylic acid component includes cyclohexane dicarboxylic acid (CHDA), dimethyl cyclohexane dicarboxylate (DMCD), or a derivative thereof. More specifically, the second dicarboxylic acid component may be 1,4-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, or a derivative thereof.

[0031] A polyester copolymer according to one embodiment of the present invention comprises a first dicarboxylic acid component including terephthalic acid or a derivative thereof as a dicarboxylic acid component, and a second dicarboxylic acid component including cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate or a derivative thereof, thereby improving mechanical properties such as softness and elasticity, optical properties such as transparency and UV stability, and processability while being environmentally friendly. In particular, since the softness can be effectively controlled by adjusting the content of the second dicarboxylic acid component, productivity and processability are very excellent.

[0032] Specifically, the second dicarboxylic acid component comprises cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate, or a derivative thereof. Specifically, the second dicarboxylic acid component may comprise cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate, or a derivative thereof in an amount of 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol%.

[0033] In addition, the polyester copolymer may contain the second dicarboxylic acid component in an amount of 20 mol% or more, 25 mol% or more, 30 mol% or more, 50 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more, and may contain 100 mol% or less, 95 mol% or less, or 90 mol% or less, based on the total dicarboxylic acid component. By satisfying the above range, the softness of the polyester copolymer can be further improved.

[0034] More specifically, the second dicarboxylic acid component may be dimethyl cyclohexane dicarboxylate, and the polyester copolymer may contain the dimethyl cyclohexane dicarboxylate in an amount of 20 mol% or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, 45 mol% or more, 50 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more, based on the total dicarboxylic acid component, and may contain it in an amount of 100 mol% or less, 95 mol% or less, or 90 mol% or less. When the content of dimethyl cyclohexane dicarboxylate or a derivative thereof satisfies the above range, the softness of the polyester copolymer can be further improved.

[0035] Alternatively, the second dicarboxylic acid component may be cyclohexane dicarboxylic acid, and the polyester copolymer may contain cyclohexane dicarboxylic acid in an amount of 20 mol% or more, 25 mol% or more, or 30 mol% or more, and 100 mol% or less, 95 mol% or less, or 90 mol% or less, based on the total dicarboxylic acid component.

[0036] According to another embodiment of the present invention, the polyester copolymer may comprise residues of a third dicarboxylic acid component.

[0037] Specifically, the third dicarboxylic acid component may be a dicarboxylic acid component different from the first and second dicarboxylic acid components. More specifically, the third dicarboxylic acid may include at least one selected from the group consisting of succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanoic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate.

[0038] Additionally, the polyester copolymer may contain the third dicarboxylic acid component in an amount of 30 mol% or less, 25 mol% or less, 15 mol% or less, 10 mol% or less, 5 mol% or less, 3 mol% or less, or 1 mol% or less based on the total dicarboxylic acid component.

[0039] The above diol component comprises ethylene glycol or a derivative thereof. Specifically, the diol component may comprise 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol% of ethylene glycol or a derivative thereof.

[0040] According to another embodiment of the present invention, the polyester copolymer may include a residue of a first diol component comprising ethylene glycol or a derivative thereof, and a residue of a second diol component different from the first diol component.

[0041] Specifically, the second diol component may include at least one selected from the group consisting of propanediol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, neopentylglycol, diethylene glycol, and triethylene glycol. For example, the second diol component may include at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 2,6-hexanediol, 3,4-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol.

[0042] Additionally, the polyester copolymer may contain the first diol in an amount of 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol% based on the total diol component.

[0043] Additionally, the polyester copolymer may contain the second diol in an amount of 30 mol% or less, 25 mol% or less, 15 mol% or less, 10 mol% or less, 5 mol% or less, 3 mol% or less, 2 mol% or less, or 1 mol% or less based on the total diol component.

[0044] According to another embodiment of the present invention, the polyester copolymer may be a copolymer additionally comprising an elastomer or resin.

[0045] For example, the elastomer may be at least one selected from the group consisting of a polyvinyl chloride elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyester elastomer, a polyamide elastomer, and a polybutadiene elastomer, and the resin may be at least one selected from the group consisting of polyethylene, polyethylene terephthalate, polybutylene terephthalate, and glycol-modified polyethylene terephthalate.

[0046] Additionally, the polyester copolymer may contain 0.1 wt% to 50 wt% of the elastomer or resin. For example, the content of the elastomer or resin may be 0.1 wt% to 50 wt%, 1 wt% to 40 wt%, or 5 wt% to 25 wt%, based on the total weight of the polyester copolymer and the elastomer or resin.

[0047] As a specific example, the polyester copolymer may additionally include polybutylene terephthalate (PBT) or polyester elastomer (TPEE).

[0048] The elastomer or resin may be melt-blended and added at the end of the polycondensation step during the manufacturing process of the polyester copolymer. The elastomer or resin may be melt-blended and added to the polyester copolymer to impart crystallinity to the polyester copolymer, thereby providing advantageous effects in terms of improving heat resistance, dimensional stability, and chemical resistance.

[0049] The polyester copolymer may have a glass transition temperature (Tg) of 10°C to 70°C as measured by differential scanning calorimetry (DSC). For example, the polyester copolymer may have a glass transition temperature (Tg) of 13°C to 68°C or 15°C to 65°C as measured by differential scanning calorimetry (DSC).

[0050] The polyester copolymer may have an intrinsic viscosity (IV) of 0.5 dl / g to 1.3 dl / g. For example, the intrinsic viscosity (IV) of the polyester copolymer may be 0.5 dl / g to 1.3 dl / g, 0.55 dl / g to 1.2 dl / g, or 0.6 dl / g to 1.15 dl / g.

[0051] The polyester copolymer may have a specific gravity of 1.2 or greater. For example, the specific gravity of the polyester copolymer may be 1.2 or greater, 1.21 or greater, or 1.22 or greater.

[0052] The above polyester copolymer may have a heat of fusion of 0.01 J / g to 80 J / g. For example, the heat of fusion of the crystallization peak of the polyester copolymer may be 0.01 J / g to 75 J / g, 0.01 J / g to 60 J / g, 0.1 J / g to 55 J / g, 0.5 J / g to 50 J / g, 0.1 J / g to 40 J / g, or 1 J / g to 20 J / g. Since sufficient crystallinity can be secured when the heat of fusion of the polyester copolymer satisfies the above range, there is a more advantageous effect in terms of improving heat resistance, shape stability, and chemical resistance.

[0053]

[0054] plasticizer

[0055] According to one embodiment of the present invention, the resin composition includes a plasticizer.

[0056] Specifically, the plasticizer may include at least one selected from the group consisting of phthalate, terephthalate, adipate, carboxylate, citric acid, trimellitate, phosphite, epoxy, ester, polyester, aliphatic, anti-chlorine, vegetable oil derivatives, petroleum, hydrocarbon, acid, and alcohol.

[0057] For example, the plasticizer may be di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, dioctyl terephthalate, tributyl citrate, diisononyl adipate, dioctyl adipate, adipic acid polyester, hexanoic acid polymer, 1,3-butanediol, 1,2-propnediol, isononyl ester, dioctyl maleate, tri-isononyl trimellitate, trioctyl trimellitate, dioctyl It may include at least one selected from the group consisting of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, diisodecyl phthalate, di(2-propylheptyl) phthalate, and di-branched alkyl ester.

[0058] More specifically, the plasticizer may include at least one selected from the group consisting of dioctyl terephthalate, tributyl citrate, diisononyl adipate, and di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate.

[0059] The resin composition contains the plasticizer in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyester copolymer. For example, the content of the plasticizer may be 0.2 to 50 parts by weight, 0.5 to 50 parts by weight, 1 to 50 parts by weight, 3 to 50 parts by weight, 5 to 50 parts by weight, 5 to 40 parts by weight, 10 to 50 parts by weight, 15 to 30 parts by weight, or 30 to 50 parts by weight based on 100 parts by weight of the polyester copolymer.

[0060]

[0061] elastomer

[0062] According to another embodiment of the present invention, the resin composition may further include an elastomer.

[0063] Specifically, the resin composition may further include at least one selected from the group consisting of polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, and polybutadiene elastomers.

[0064] For example, the elastomer may be a thermoplastic elastomer (TPE), and may include at least one selected from the group consisting of a thermoplastic polyether block amide (TPA), a thermoplastic polyurethane elastomer (TPU), a thermoplastic copolyester elastomer (TPC), a styrene block copolymer-based thermoplastic elastomer (TPS), a thermoplastic elastomer (TPV) made of a thermoplastic plastic and a vulcanized elastomer, and a polyolefin-based elastomer (TPO).

[0065] More specifically, the elastomer may be a styrene ethylene / butylene block copolymer or methacrylate butadiene styrene.

[0066] The resin composition may contain the elastomer in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the polyester copolymer. For example, the content of the elastomer may be 0.2 to 90 parts by weight, 0.5 to 80 parts by weight, 1 to 65 parts by weight, 3 to 50 parts by weight, 5 to 45 parts by weight, 10 to 35 parts by weight, 10 to 30 parts by weight, 15 to 30 parts by weight, or 20 to 30 parts by weight based on 100 parts by weight of the polyester copolymer.

[0067]

[0068] additives

[0069] According to another embodiment of the present invention, the resin composition may further include an additive. The additive is not limited in type as long as it does not impede the purpose of the present invention, but may further include, for example, one or more selected from the group consisting of rubber, inorganic filler, antioxidant, stabilizer, heat stabilizer, plasticizer, release agent, colorant, lubricant, weather stabilizer, foaming agent, rust inhibitor, wax, nucleating agent, fiber reinforcing agent, and compatibilizer.

[0070] The above-mentioned lubricant may include at least one selected from the group consisting of silicone-based lubricants, wax-based lubricants, fluorine-based lubricants, surfactant-based lubricants, metal-based lubricants, metal salt-based lubricants, phosphorus-based lubricants, amide-based lubricants, ethylene-based lubricants, ester-based lubricants, alcohol-based lubricants, fatty acid-based lubricants, mineral-based lubricants, petroleum-based lubricants, and mixed-based lubricants. In addition, the above-mentioned lubricant may include at least one selected from the group consisting of stearic acid, glycerol stearate, zinc stearate, calcium stearate, magnesium acetate, magnesium stearate, and sodium stearate.

[0071] The above heat stabilizer can be used to prevent the resin from being decomposed due to the action of heat and light during the manufacturing process or use of the resin, and can effectively control the physical properties by improving the compatibility of the polyester copolymer with other additives or other resins, thereby minimizing side reactions that may occur at high temperatures during processes such as molding.

[0072] The above heat stabilizer may include, but is not limited to, metal heat stabilizers such as calcium magnesium zinc heat stabilizers, calcium zinc heat stabilizers, organotin heat stabilizers, metal tin heat stabilizers, barium zinc heat stabilizers, epoxy zinc heat stabilizers, magnesium aluminum carbonate heat stabilizers, zinc heat stabilizers, and lead heat stabilizers; and non-metal heat stabilizers such as epoxy heat stabilizers and organophosphite heat stabilizers.

[0073] The above antioxidant is an additive that prevents thermal oxidation and may include phenol-based, phosphorus-based, sulfur-based, amine-based antioxidants, etc.

[0074] The resin composition may contain the additive in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyester copolymer. For example, the content of the additive may be 0.2 to 30 parts by weight, 0.5 to 15 parts by weight, 0.8 to 10 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the polyester copolymer.

[0075] According to another embodiment of the present invention, the resin composition may further include an additional resin. For example, the resin composition may further include an additional resin in addition to the polyester copolymer, and may include a homopolymer or copolymer of monomers such as ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth)acrylonitrile, etc.; a polyester such as polyurethane, polybutylene terephthalate (PBT), polyethylene terephthalate (PET); a polyacetal; a polycarbonate; a polysulfone; a polyallyl sulfone; a polyethersulfone; a polyphenylene ether; a polyether ketone; a polyether ether ketone; a polyimide; a polyamideimide; a polyetherimide; a silicone resin; an epoxy resin; a phenoxy resin; a liquid crystal polymer; Polyaryl ether; may include at least one selected from the group consisting of a homopolymer, a random copolymer, a block copolymer, a graft copolymer, etc., but is not limited thereto.

[0076] Specifically, the resin composition may further include at least one selected from the group consisting of polyethylene, polyethylene terephthalate, polybutylene terephthalate, and glycol-modified polyethylene terephthalate, and may be included in an amount of 0.1 to 50 parts by weight, 0.5 to 25 parts by weight, 1 to 20 parts by weight, 5 to 40 parts by weight, 10 to 30 parts by weight, or 5 to 10 parts by weight, based on 100 parts by weight of the polyester copolymer.

[0077]

[0078] Method for producing polyester copolymer

[0079] According to another embodiment of the present invention, a method for producing a polyester copolymer comprises the steps of mixing a first dicarboxylic acid component comprising terephthalic acid or a derivative thereof, a second dicarboxylic acid component comprising cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate, or a derivative thereof, and a diol component comprising ethylene glycol or a derivative thereof; subjecting the mixture to an esterification reaction; and subjecting a product of the esterification reaction to a polycondensation reaction, wherein the polyester copolymer contains 30 mol% or more of the second dicarboxylic acid component based on the total dicarboxylic acid component.

[0080] A polyester copolymer manufactured according to the above method for manufacturing a polyester copolymer has substantially the same composition and properties as the polyester copolymer described above.

[0081] In addition, the polyester copolymer finally manufactured according to the method for manufacturing the polyester copolymer can have its composition and process conditions adjusted so as to satisfy the mechanical properties such as softness and elasticity described above, optical properties such as transparency and UV stability, and processability.

[0082]

[0083] First, a first dicarboxylic acid component including terephthalic acid or a derivative thereof, a second dicarboxylic acid component including cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate, or a derivative thereof, and a diol component including ethylene glycol or a derivative thereof are mixed.

[0084] The description of the first dicarboxylic acid component, the second dicarboxylic acid component, and the diol component is as described above. Specifically, the first dicarboxylic acid component, the second dicarboxylic acid component, and the diol component are mixed to produce a mixture.

[0085] According to another embodiment of the present invention, one or more additives selected from the group consisting of a coloring agent, a crystallizing agent, an oxidation stabilizer, and a branching agent may be additionally added to the mixture of the first dicarboxylic acid component, the second dicarboxylic acid component, and the diol component.

[0086] The above coloring agent is an additive for improving the color characteristics of the polyester copolymer. As long as the coloring agent does not impede the effects of the present invention, a commonly used coloring agent such as cobalt acetate or cobalt propionate can be used.

[0087] Specifically, the coloring agent may be cobalt acetate, cobalt propionate, anthraquionone-based compound, perinone-based compound, azo-based compound, methine-based compound, etc., and commercially available products include toners such as Clarient's Polysynthren Blue RLS or Clarient's Solvaperm Red BB.

[0088] In addition, the polyester copolymer may contain the coloring agent in an amount of 0.1 ppm to 30 ppm based on the total weight of the polyester copolymer. For example, the coloring agent may be added in an amount of 0.2 ppm to 30 ppm, 0.5 ppm to 25 ppm, 0.6 ppm to 23 ppm, or 0.8 ppm to 20 ppm based on the total weight of the mixture. By satisfying the content of the coloring agent in the above range, the color characteristics can be sufficiently improved without deteriorating the mechanical properties of the polyester copolymer.

[0089] The above oxidation stabilizer may include at least one selected from the group consisting of phosphorus-based, hindered phenol-based, phosphite-based, and thioether-based.

[0090] In addition, the polyester copolymer may contain the oxidation stabilizer in an amount of 50 ppm to 2,500 ppm based on the total weight of the polyester copolymer. For example, the oxidation stabilizer may be added in an amount of 50 ppm to 2,300 ppm, 60 ppm to 2,200 ppm, 80 ppm to 2,100 ppm, 100 ppm to 2,000 ppm, or 100 ppm to 1,500 ppm based on the total weight of the mixture. By satisfying the content of the oxidation stabilizer in the above range, not only can a decrease in intrinsic viscosity that may occur during subsequent processing or the like be effectively prevented, but also a decrease in physical properties such as impact strength can be prevented.

[0091] The above-mentioned branching agent may include at least one selected from the group consisting of trimellitic anhydride, trimellitic propane, trimellitic acid, and glycerol.

[0092] In addition, the polyester copolymer may contain the branching agent in an amount of 10 ppm to 5000 ppm based on the total weight of the polyester copolymer. For example, the branching agent may be added in an amount of 20 ppm to 4000 ppm or 30 ppm to 3000 ppm based on the total weight of the mixture. By satisfying the content of the branching agent within the above range, the intrinsic viscosity can be more effectively controlled within a specific range, thereby improving physical properties such as impact strength.

[0093]

[0094] Afterwards, the mixture is subjected to an esterification reaction.

[0095] Specifically, a mixture of the first dicarboxylic acid component, the second dicarboxylic acid component, and the diol component is subjected to an esterification reaction.

[0096] The above esterification reaction is carried out at atmospheric pressure or 0.1 kg / cm compared to atmospheric pressure. 2 3.0 kg / cm 2 It can be performed for 2 to 12 hours under high pressure conditions and temperature conditions of 245°C to 275°C.

[0097] Specifically, the pressurized state is 0.1 kg / cm compared to normal pressure. 2 3.0 kg / cm 2 , 0.2 kg / cm 2 2.5 kg / cm 2 or 0.3 kg / cm 2 2.0 kg / cm 2 It can be as high as that. In addition, the esterification reaction can be performed at a temperature condition of 150°C to 275°C, 155°C to 275°C, or 160°C to 270°C for 2 to 12 hours, 2 to 11 hours, or 2.5 to 10 hours.

[0098] For example, the above esterification reaction is carried out at atmospheric pressure or 0.1 kg / cm compared to atmospheric pressure.2 3.0 kg / cm 2 The temperature can be increased from room temperature to 150°C to 275°C or from 155°C to 270°C over 30 to 110 minutes or 30 to 100 minutes under high pressure, maintained for 0.5 to 3 hours or 0.5 to 2.5 hours, and then continuously or stepwise increased from room temperature to 150°C to 275°C or from 155°C to 270°C over 2 to 12 hours.

[0099] When the above esterification reaction is completed, the pressure of the pressurized reactor can be lowered to room temperature and the following polycondensation reaction can be performed.

[0100]

[0101] Finally, the product of the above esterification reaction is subjected to a polycondensation reaction.

[0102] The polycondensation reaction may be carried out under conditions of a pressure of 0.00001 mmHg to 400 mmHg and a temperature of 240°C to 300°C for 1 to 12 hours. For example, the polycondensation reaction may be carried out under conditions of a pressure of 0.00001 mmHg to 200 mmHg, 0.0001 mmHg to 100 mmHg, 0.001 mmHg to 50 mmHg, 0.002 mmHg to 10 mmHg, 0.005 mmHg to 3 mmHg, 0.01 mmHg to 1.5 mmHg, or 0.01 mmHg to 1.2 mmHg, and a temperature of 240°C to 300°C or 245°C to 295°C for 1 to 12 hours or 1 to 10 hours.

[0103] For example, the polycondensation reaction may be performed by reducing the pressure of the product of the esterification reaction to 4.0 mmHg to 6.0 mmHg or 4.5 mmHg to 5.5 mmHg over 20 to 40 minutes or 25 to 35 minutes, and then heating the product to 240°C to 300°C or 245°C to 295°C over 0.5 to 2 hours or 0.7 to 1.2 hours, and then maintaining the pressure of 0.01 mmHg to 400 mmHg.

[0104] At the beginning of the polycondensation reaction, the stirring speed is set to high, and as the polycondensation reaction progresses, the stirring force becomes weak due to the increase in the viscosity of the reactants, or the temperature of the reactants rises above the set temperature, the stirring speed can be appropriately adjusted accordingly.

[0105] The intrinsic viscosity (IV) of the melt produced by the polycondensation reaction may be 0.5 dl / g to 1.3 dl / g. For example, the polycondensation reaction may be performed until the intrinsic viscosity (IV) of the melt produced by the polycondensation reaction becomes 0.5 dl / g to 1.2 dl / g, or 0.6 dl / g to 1.15 dl / g.

[0106] Additionally, a catalyst and / or stabilizer may be additionally added in the esterification reaction and the polycondensation reaction.

[0107] For example, the esterification reaction catalyst may be a methylate of sodium or magnesium; an acetate, borate, fatty acid salt, or carbonate of Zn, Cd, Mn, Co, Ca, Ba, etc.; an oxide of metal Mg; an oxide of Pb, Zn, Sb, Ge, etc.

[0108] In addition, the polycondensation reaction catalyst may be, for example, a titanium-based catalyst such as tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, etc.; a germanium-based catalyst such as germanium dioxide and copolymers using the same; or a tin-based catalyst such as monobutyl tin oxide, dibutyl tin oxide, monobutyl hydroxy tin oxide, etc.

[0109] Additionally, the stabilizer may be a phosphorus compound such as phosphoric acid, trimethyl phosphate, or triethyl phosphate, but is not limited thereto.

[0110] The stabilizer may be added in an amount of 10 ppm to 2,500 ppm based on the total weight of the polycondensation reactant. For example, the stabilizer may be added in an amount of 150 ppm to 2,300 ppm, 200 ppm to 2,000 ppm, 300 ppm to 1,500 ppm, 50 ppm to 400 ppm, 70 ppm to 350 ppm, or 100 ppm to 300 ppm based on the total weight of the polycondensation reactant.

[0111] According to another embodiment of the present invention, the method for producing the polyester copolymer may include a melt blending step.

[0112] Specifically, after the polycondensation reaction, an elastomer or resin may be added and melt blended. More specifically, after the polycondensation reaction, the vacuum may be broken using nitrogen gas, and then an elastomer or resin may be additionally added and melt blended.

[0113] As a specific example, the elastomer introduced in the melt blending step may be at least one selected from the group consisting of polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, and polybutadiene elastomers, and the resin may be at least one selected from the group consisting of polyethylene, polyethylene terephthalate, polybutylene terephthalate, and glycol-modified polyethylene terephthalate.

[0114] Additionally, the melt blending step may be performed at 250°C to 290°C, 255°C to 285°C, or 260°C to 280°C for 1 minute to 60 minutes, 2 minutes to 40 minutes, 2 minutes to 20 minutes, or 3 minutes to 10 minutes.

[0115] By performing the above melt blending step, there is an advantageous effect in terms of improving heat resistance, shape stability, and chemical resistance due to imparting crystallinity.

[0116]

[0117] Method for producing a resin composition

[0118] According to another embodiment of the present invention, a resin composition can be prepared by mixing a polyester copolymer and a plasticizer.

[0119] As a specific example, a polyester copolymer and a plasticizer are mixed to prepare a primary composition, and the primary composition is automatically metered and fed into a hopper of a twin-screw extruder (40 mm Extruder, L / D: 40), and then volatile gas is depressurized and removed, and a pellet-shaped resin is prepared using a chip cutter.

[0120]

[0121] molded products

[0122] A molded article according to another embodiment of the present invention is manufactured by molding the resin composition.

[0123] For example, the molded product may be manufactured by extruding or kneading the resin composition, and may be molded through calendaring, extrusion, or injection, but is not limited thereto.

[0124] The above-mentioned molded article may be in the form of a sheet, film, or fiber. For example, the above-mentioned molded article may be, but is not limited to, various food / beverage containers, packaging materials, sheets for soundproofing or sound-absorbing materials, tarpaulin, silk wallpaper, artificial leather, wrap, medical devices, decorative sheets, filament for 3D printers, or films such as decorative films or mulching films. In addition, the above-mentioned resin composition may also be used as a binder for fibers, a coating agent, an adhesive, etc.

[0125] The above contents are explained in more detail with the following examples. However, the following examples are only intended to illustrate the present invention, and the scope of the examples is not limited to these examples.

[0126]

[0127] [Example]

[0128] Preparation of polyester copolymers

[0129] Manufacturing Example 1

[0130] (1) Esterification reaction

[0131] In a 10 L reactor connected to a column and a condenser that can be cooled by water, 569 g (3.425 mol) of terephthalic acid (TPA), 1,600 g (7.992 mol) of dimethyl cyclohexane dicarboxylate (DMCD), and 1,417 g (22.834 mol) of ethylene glycol (EG) were charged. At this time, G / A (total diol / total diacid, molar ratio of the diol component to the dicarboxylic acid or its derivative component) was 2.0.

[0132] Afterwards, 0.853 g of tetrabutyl titanate (TBT) as a catalyst, 0.235 g of phosphoric acid as a stabilizer, and 1.47 g of trimellitic anhydride as a branching agent were added and stirred.

[0133] Afterwards, nitrogen was injected into the reactor containing the above composition so that the pressure of the reactor was 1.0 kgf / cm compared to the atmospheric pressure. 2 The reactor was pressurized to a high pressure (absolute pressure: 1495.6 mmHg). Then, the temperature of the reactor was increased from room temperature to 200°C over 60 minutes, maintained at 200°C for 2 hours, and then increased again to 245°C over 5 hours. Afterwards, the esterification reaction was carried out at 245°C for 0.5 hours. During this process, by-products were discharged through the column and condenser. When the esterification reaction was completed, the nitrogen inside the pressurized reactor was purged to the outside to lower the pressure of the reactor to ambient pressure, and the product of the esterification reaction inside the reactor was transferred to a 7 L reactor capable of vacuum reaction.

[0134] (2) Polycondensation reaction

[0135] Afterwards, the pressure of the reactor containing the product of the esterification reaction was reduced from atmospheric pressure to 5.0 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was increased to 270°C over 1 hour. Then, the pressure of the reactor was maintained at 1.0 Torr (absolute pressure: 1.0 mmHg) or less to perform the polycondensation reaction. At this time, the stirring speed was set to be fast in the early stage of the polycondensation reaction, but as the polycondensation reaction progressed, if the stirring force weakened due to the increase in the viscosity of the reactants or the temperature of the reactants rose above the set temperature, the stirring speed was appropriately adjusted accordingly. The polycondensation reaction was performed until the intrinsic viscosity (IV) of the mixture (melt) in the reactor became 0.8 dl / g or more. After the above polycondensation reaction was completed, the vacuum was broken using nitrogen gas, 750 g of poly(butylene terephthalate) (PBT) was added, melt blended at 270°C for 10 minutes, the mixture was discharged outside the reactor, solidified with a cooling liquid, and then granulated to an average weight of about 10 mg to 20 mg to produce a polyester copolymer.

[0136]

[0137] Manufacturing Example 2

[0138] (1) Esterification reaction

[0139] In a 10 L reactor connected to a column and a condenser that can be cooled by water, 569 g (3.425 mol) of terephthalic acid (TPA), 1,600 g (7.992 mol) of dimethyl cyclohexane dicarboxylate (DMCD), and 1,417 g (22.834 mol) of ethylene glycol (EG) were charged. At this time, G / A (total diol / total diacid, molar ratio of the diol component to the dicarboxylic acid or its derivative component) was 2.0.

[0140] Afterwards, 0.853 g of tetrabutyl titanate (TBT) as a catalyst, 0.235 g of phosphoric acid as a stabilizer, and 1.47 g of trimellitic anhydride as a branching agent were added and stirred.

[0141] Afterwards, nitrogen was injected into the reactor containing the above composition so that the pressure of the reactor was 1.0 kgf / cm compared to the atmospheric pressure. 2 The reactor was pressurized to a high pressure (absolute pressure: 1,495.6 mmHg). Then, the temperature of the reactor was increased from room temperature to 200°C over 60 minutes, maintained at 200°C for 2 hours, and then increased again to 245°C over 5 hours. Afterwards, the esterification reaction was carried out at 245°C for 0.5 hours. During this process, by-products were discharged through the column and condenser. When the esterification reaction was completed, the nitrogen inside the pressurized reactor was purged to the outside to lower the pressure of the reactor to ambient pressure, and the product of the esterification reaction inside the reactor was transferred to a 7 L reactor capable of vacuum reaction.

[0142] (2) Polycondensation reaction

[0143] Afterwards, the pressure of the reactor containing the product of the esterification reaction was reduced from atmospheric pressure to 5.0 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was increased to 270°C over 1 hour. Then, the pressure of the reactor was maintained at 1.0 Torr (absolute pressure: 1.0 mmHg) or less to perform the polycondensation reaction. At this time, the stirring speed was set to be fast in the early stage of the polycondensation reaction, but as the polycondensation reaction progressed, if the stirring force weakened due to the increase in the viscosity of the reactants or the temperature of the reactants rose above the set temperature, the stirring speed was appropriately adjusted accordingly. The polycondensation reaction was performed until the intrinsic viscosity (IV) of the mixture (melt) in the reactor became 0.8 dl / g or more. After the above polycondensation reaction was completed, the vacuum was broken using nitrogen gas, 250 g of a polyester elastomer (thermoplastic polyester elastomer, TPEE) was added, melt blended at 270°C for 10 minutes, the mixture was discharged outside the reactor, solidified with a cooling liquid, and then granulated to an average weight of about 10 mg to 20 mg to prepare a polyester copolymer.

[0144]

[0145] Manufacturing Example 3

[0146] (1) Esterification reaction

[0147] In a 10 L reactor connected to a column and a condenser that can be cooled by water, 569 g (3.425 mol) of terephthalic acid (TPA), 1,600 g (7.992 mol) of dimethyl cyclohexane dicarboxylate (DMCD), and 1,417 g (22.834 mol) of ethylene glycol (EG) were charged. At this time, G / A (total diol / total diacid, molar ratio of the diol component to the dicarboxylic acid or its derivative component) was 2.0.

[0148] Afterwards, 0.853 g of tetrabutyl titanate (TBT) as a catalyst, 0.235 g of phosphoric acid as a stabilizer, and 1.47 g of trimellitic anhydride as a branching agent were added and stirred.

[0149] Afterwards, nitrogen was injected into the reactor containing the above composition so that the pressure of the reactor was 1.0 kgf / cm compared to the atmospheric pressure. 2 The reactor was pressurized to a high pressure (absolute pressure: 1,495.6 mmHg). Then, the temperature of the reactor was increased from room temperature to 200°C over 60 minutes, maintained at 200°C for 2 hours, and then increased again to 245°C over 5 hours. Afterwards, the esterification reaction was carried out at 245°C for 0.5 hours. During this process, by-products were discharged through the column and condenser. When the esterification reaction was completed, the nitrogen inside the pressurized reactor was purged to the outside to lower the pressure of the reactor to ambient pressure, and the product of the esterification reaction inside the reactor was transferred to a 7 L reactor capable of vacuum reaction.

[0150] (2) Polycondensation reaction

[0151] Afterwards, the pressure of the reactor containing the product of the esterification reaction was reduced from atmospheric pressure to 5.0 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was increased to 270°C over 1 hour. Then, the pressure of the reactor was maintained at 1.0 Torr (absolute pressure: 1.0 mmHg) or less to carry out the polycondensation reaction. At this time, the stirring speed was set fast in the early stage of the polycondensation reaction, but as the polycondensation reaction progressed, the stirring force weakened due to the increase in the viscosity of the reactants or the temperature of the reactants rose above the set temperature, and the stirring speed was appropriately adjusted accordingly. The polycondensation reaction was carried out until the intrinsic viscosity (IV) of the mixture (melt) inside the reactor became 0.8 dl / g or more, and then the mixture was discharged outside the reactor, solidified with a cooling liquid, and then granulated to an average weight of about 10 mg to 20 mg to manufacture a polyester copolymer.

[0152]

[0153] Preparation of resin composition

[0154] Examples 1 to 13 and Comparative Examples 1 to 5

[0155] The components described in Table 1 below were uniformly mixed as described in Tables 2 to 4 below to prepare a resin composition. The resin composition was automatically metered and fed into the hopper of a twin-screw extruder (40 mm Extruder, L / D: 40), volatile gases were removed under reduced pressure, and pellets were prepared using a chip cutter. At this time, information on the components used in the examples and comparative examples is shown in Table 1 below, and the values ​​described in Tables 2 to 4 below represent parts by weight.

[0156]

[0157] Item Characteristics Polyester copolymer (A-1) Manufacturing example 1 (DMCD 70 mol% + PBT) Polyester copolymer (A-2) Manufacturing example 2 (DMCD 70 mol% + TPEE) Polyester copolymer (A-3) Manufacturing example 3 (DMCD 70 mol%) Plasticizer (B-1) dioctyl terephthalate (67% to 72%) Plasticizer (B-2) adipic acid polyester Plasticizer (B-3) di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate Elastomer (C-1) styrene ethylene / butylene block copolymer Elastomer (C-2) methacrylate butadiene styrene Polyester elastomer (C-3) TPEE Polyethylene (D-1) PE, Manufacturer: Hanwha Solutions Polyethylene terephthalate (D-2) PET, Manufacturer: Lotte Chemical Polybutylene terephthalate (D-3) PBT, Manufacturer: CHANG CHUN PLASTICS Glycol-modified polyethylene terephthalate (D-4) PETG, Manufacturer: SK Chemical Activator (E) stearic acid

[0158]

[0159] ClassificationEmbodiment 1Embodiment 2Embodiment 3Embodiment 4Embodiment 5Embodiment 6Embodiment 7Embodiment 8A-1100100100100100100100100B-15305030--3030B-2----30---B-3-----30--C-1-2030-20202020C-2---20----C-3------1010E-------1

[0160]

[0161] Classification Example 9 Example 10 Example 11 Example 12 Example 13A-2100100100100-A-3----100B-13030303030C-12020202030D-130----D-2-10---D-3--30--

[0162]

[0163] Classification Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 A-1100----A-2-100---A-3--100--B-1---3030C-1---2020D-2----100D-4---100-

[0164]

[0165] [Experimental Example]

[0166] Experimental Example 1: Strand compatibility after extrusion

[0167] The compatibility was evaluated based on the state of the strand coming out of the extruder when manufacturing pellets using the resin compositions of Examples 1 to 13, Comparative Examples 4 and 5. If the surface of the strand was smooth and there was no problem with the process, and thus there was no problem with pellet formation, it was marked with ○, and if the surface of the strand was rough or pellet formation was difficult through the process, it was marked with X. Since no plasticizer was used in Comparative Examples 1 to 3, the compatibility of the strand after extrusion was not evaluated.

[0168]

[0169] Experimental Example 2: Plasticizer Migration

[0170] Flat specimens having a thickness of 1 mm were prepared using the resin compositions of Examples 1 to 13, Comparative Examples 4 and 5, and a polyimide film was placed between the specimens. It was then confirmed whether migration, in which a liquid plasticizer moved or was extracted, occurred on the surface of the film. If migration of the plasticizer occurred on the surface of the film, it was marked with ○, and if migration of the plasticizer did not occur on the surface of the film, it was marked with X. Since no plasticizer was used in Comparative Examples 1 to 3, plasticizer migration was not evaluated.

[0171]

[0172] Experimental Example 3: Shore A Hardness

[0173] Flat specimens having a thickness of 1 mm were prepared using the resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5. Six identical specimens were placed overlapping each other, and then the Shore A hardness was measured according to ASTM D2240.

[0174]

[0175] ClassificationExample 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8Extrusion strand compatibility○○○○○○○○Plasticizer migrationXXXXXXXXShore A hardness9075657785957776

[0176]

[0177] Classification Example 9 Example 10 Example 11 Example 12 Example 13 Extrusion strand compatibility ○○○○○ Plasticizer migration XXXXX Shore A hardness 7073754038

[0178]

[0179] Classification Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Extrusion strand compatibility---XX Plasticizer migration N / AN / AN / A○○ Shore A hardness >959595>95>95

[0180]

[0181] As shown in Tables 5 to 7 above, the resin compositions of Examples 1 to 13 were able to form pellets with smooth surfaces of extruded strands and without any process problems, and the Shore A hardness of the specimens manufactured using the resin compositions was less than 95, and no liquid-like plasticizer migration occurred on the surface of the specimens.

[0182] On the other hand, Comparative Examples 1 to 5 had Shore A hardnesses of 95 or higher. In particular, Comparative Examples 4 and 5 had rough surfaces of extruded strands, and the physical properties were not sufficient to allow the process of manufacturing pellets to be performed without problems, making it difficult to form pellets. In addition, migration of a liquid-like plasticizer also occurred on the surface manufactured using the strands.

Claims

1. A resin composition comprising a polyester copolymer and a plasticizer, The plasticizer is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyester copolymer, A resin composition, wherein a Shore A hardness of a specimen manufactured from the resin composition is less than 95 as measured according to ASTM D2240.

2. In paragraph 1, The above polyester copolymer, A residue of a first dicarboxylic acid component comprising terephthalic acid or a derivative thereof; A residue of a second dicarboxylic acid component comprising cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylate, or a derivative thereof; and Containing a residue of a diol component including ethylene glycol or a derivative thereof, A resin composition comprising 30 mol% or more of the second dicarboxylic acid component based on the total dicarboxylic acid component.

3. In paragraph 2, A resin composition comprising 50 mol% or more of the second dicarboxylic acid component based on the total dicarboxylic acid component.

4. In paragraph 2, The second dicarboxylic acid component comprises dimethyl cyclohexane dicarboxylate or a derivative thereof, A resin composition comprising dimethyl cyclohexane dicarboxylate or a derivative thereof in an amount of 60 mol% or more based on the total dicarboxylic acid component.

5. In paragraph 2, A resin composition comprising a residue of a third dicarboxylic acid component comprising at least one selected from the group consisting of succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanoic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate.

6. In paragraph 2, Containing a residue of a first diol component comprising ethylene glycol or a derivative thereof, A resin composition comprising a residue of a second diol component comprising at least one selected from the group consisting of propanediol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, neopentyl glycol, diethylene glycol, and triethylene glycol.

7. In paragraph 6, A resin composition wherein the molar ratio of the first diol component is 80 mol% or more.

8. In paragraph 1, A resin composition wherein the above polyester copolymer is a block copolymer or a random copolymer.

9. In paragraph 1, A resin composition wherein the polyester copolymer further comprises polybutylene terephthalate (PBT) or polyester elastomer (TPEE).

10. In paragraph 1, A resin composition, wherein the plasticizer comprises at least one selected from the group consisting of phthalate, terephthalate, adipate, carboxylate, citric acid, trimellitate, phosphite, epoxy, ester, polyester, aliphatic, anti-chlorine, vegetable oil derivatives, petroleum, hydrocarbon, acid, and alcohol.

11. In paragraph 1, A resin composition, wherein the resin composition further comprises at least one selected from the group consisting of a polyvinyl chloride-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, and a polybutadiene-based elastomer.

12. In paragraph 1, A resin composition, wherein the resin composition further comprises at least one selected from the group consisting of polyethylene, polyethylene terephthalate, polybutylene terephthalate, and glycol-modified polyethylene terephthalate.

13. In paragraph 1, A resin composition, wherein the resin composition further comprises at least one selected from the group consisting of rubber, inorganic filler, antioxidant, stabilizer, heat stabilizer, plasticizer, release agent, colorant, lubricant, weather stabilizer, foaming agent, rust inhibitor, wax, nucleating agent, fibrous reinforcing agent, and compatibilizer.

14. A molded product manufactured by molding the resin composition of any one of claims 1 to 13.

15. In paragraph 14, A molded product, wherein the molded product is molded through calendaring, extrusion or injection.

16. In paragraph 14, A molded product, wherein the molded product is in the form of a sheet, film or fiber.

17. In paragraph 14, A molded product, wherein the molded product is a film such as various food / beverage containers, packaging materials, sheets for soundproofing or sound-absorbing materials, tarpaulin, silk wallpaper, artificial leather, wrap, medical devices, decorative sheets, filament for 3D printers, or decorative films or mulching films.