Resin composition

Abstract

The present invention relates to a resin composition with reduced plasticizer migration.

Description

Resin composition

[0001] The present invention relates to a resin composition in which the migration phenomenon of a plasticizer is reduced.

[0002] Polyvinyl chloride (PVC) is colorless, transparent, and has excellent strength. It is used in various industrial fields because it is easy to control desired physical properties depending on the type of additives used during processing. For example, by adding a certain amount of plasticizer, which is a softening component of PVC, flexible PVC can be manufactured to produce products such as packaging films and shower curtains. Conversely, by adding 10 weight percent or less of plasticizer, rigid PVC can be manufactured to produce products such as plumbing materials. As such, PVC has excellent productivity and processability in that its flexibility and rigidity can be easily controlled simply by adjusting the content of the plasticizer without additional processes.

[0003] However, the plasticizers used to control the flexibility and rigidity of PVC can reduce its moldability and processability. In particular, since a large amount of plasticizer is used to ensure sufficient hardness, migration—where liquid plasticizer moves or is extracted from the product surface during the extrusion process—can occur, thereby limiting its applicable uses. Furthermore, because PVC generates dioxins, which are toxic substances, upon combustion, there is no disposal method other than landfilling. Therefore, there is a need to develop materials that can replace PVC while maintaining excellent moldability and processability even when plasticizers are used.

[0004] Meanwhile, polyester is widely used not only as a raw material for fibers, films, packaging materials, molded products, building materials, and interior / exterior finishes, but also as a material for various industries such as display devices, due to its excellent mechanical properties, such as durability and heat resistance, and optical properties, such as transparency. Furthermore, polyester is attracting attention as a material that can replace PVC because it is more eco-friendly than PVC—allowing for resource reuse through mechanical and chemical recycling—while possessing superior mechanical and optical properties; however, controlling its flexibility or rigidity is not easy. Therefore, research on polyesters capable of effectively controlling flexibility and rigidity is ongoing.

[0005] However, since plasticizer migration occurs in polyester, research is being conducted on resin compositions that can reduce this phenomenon.

[0006] [Prior Art Literature]

[0007] [Patent Literature]

[0008] (Patent Document 1) Republic of Korea Registered Patent No. 10-1233372

[0009] Accordingly, the present invention aims to provide a resin composition in which the migration phenomenon of a plasticizer is reduced.

[0010] According to one aspect of the present invention, a resin composition is provided comprising a base composition (A) comprising a polyester copolymer (Aa) and a plasticizer (B), wherein the polyester copolymer (Aa) comprises a residue of a dicarboxylic acid component and a residue of a diol component, and the dicarboxylic acid component comprises a first dicarboxylic acid component comprising terephthalic acid, dimethyl terephthalate or a combination thereof, and a second dicarboxylic acid component comprising dimethyl isophthalate, dimethylcyclohexanedicarboxylate or a combination thereof, and the second dicarboxylic acid component comprises 10 mol% or more based on 100 mol% of the dicarboxylic acid component.

[0011] The resin composition according to the present invention has excellent moldability and processability, and can effectively control softness and hardness, as well as provide a resin composition in which the migration phenomenon of plasticizers is reduced.

[0012] The present invention will be described in detail below.

[0013] In this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0014] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification should be understood as being modified by the term "about" in all cases unless otherwise specified.

[0015] In the following description, the statement that one component is formed above or below another component, or is connected or combined with one another, includes both direct formation, connection, or combination between these components and indirect formation, connection, or combination through the interposition of another component.

[0016] In this specification, terms such as "first," "second," etc. are used to describe various components, and said components are not limited by said terms. These terms are used solely for the purpose of distinguishing one component from another.

[0017] Where a numerical range with a limited upper limit and a numerical range with a limited lower limit are described in this specification to exemplify the size, physical properties, etc. of a component, it should be understood that a numerical range combining these upper and lower limits is also included within the exemplary scope of the present invention.

[0018] In this specification, singular expressions should be interpreted to include the singular or plural as interpreted in context unless otherwise specified.

[0019] The present invention is not limited to the contents disclosed below, but can be modified in various forms as long as the essence of the invention is not altered.

[0020]

[0021] Resin composition

[0022] A resin composition according to one embodiment of the present invention comprises a base composition (A) comprising a polyester copolymer (Aa) and a resin composition comprising a plasticizer (B), wherein the polyester copolymer (Aa) comprises a residue of a dicarboxylic acid component and a residue of a diol component, and the dicarboxylic acid component comprises a first dicarboxylic acid component comprising terephthalic acid (TPA), dimethyl terephthalate (DMT), or a combination thereof, and a second dicarboxylic acid component comprising dimethyl isophthalate (DMI), dimethyl cyclohexane dicarboxylate (DMCD), or a combination thereof, and the second dicarboxylic acid component comprises 10 mol% or more of the second dicarboxylic acid component based on 100 mol% of the dicarboxylic acid component, so that the migration of the plasticizer is below a certain standard.

[0023] It is preferable that the resin composition has a residual amount of the plasticizer (B) measured according to a plasticizer migration induction residual amount measurement experiment, in which plasticizer migration is induced under certain conditions and the residual amount of the plasticizer is measured at the time of elapsed for a certain period, of 50% by weight or more relative to the input amount. For example, the residual amount of the plasticizer (B) measured according to a plasticizer migration induction residual amount measurement experiment, in which plasticizer migration is induced at 60°C to 90°C for the resin composition and the residual amount of the plasticizer is measured at the time of elapsed for 4 days to 10 days, may be 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more relative to the initial input amount. A composition according to one embodiment of the present invention is useful for manufacturing various molded articles as the residual amount of plasticizer (B) measured according to a plasticizer migration-inducing residual amount measurement experiment is 50% by weight or more compared to the initial input amount.

[0024]

[0025] Base composition (A)

[0026] According to one embodiment of the present invention, the resin composition comprises a base composition (A).

[0027] According to one embodiment of the present invention, the base composition (A) comprises a polyester copolymer (Aa).

[0028] Specifically, the polyester copolymer (Aa) is copolymerized with a first dicarboxylic acid component, a second dicarboxylic acid component, and a first diol component comprising one or more selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), cyclohexanedimethanol (CHDM), and 1,4-butanediol (1,4-BD), and may be a block copolymer or a random copolymer comprising a residue of the first dicarboxylic acid component, a residue of the second dicarboxylic acid component, and a residue of a diol component comprising one or more selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), cyclohexanedimethanol (CHDM), and 1,4-butanediol (1,4-BD).

[0029] The first dicarboxylic acid component comprises terephthalic acid (TPA), dimethyl terephthalate (DMT), and combinations thereof. Specifically, the terephthalic acid (TPA), dimethyl terephthalate (DMT), and combinations thereof may be included in an amount of 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 25 mol% or more, or 30 mol% or more, and may be included in an amount of 99 mol% or less, 95 mol% or less, 90 mol% or less, or 85 mol% or less. For example, the polyester copolymer (Aa) may include the first dicarboxylic acid component in an amount of 1 mol% to 90 mol% or 30 mol% to 85 mol% based on the total dicarboxylic acid component.

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

[0031] A polyester copolymer (Aa) according to one embodiment of the present invention comprises a first dicarboxylic acid component comprising terephthalic acid (TPA), dimethyl terephthalate (DMT), and combinations thereof as a dicarboxylic acid component, and a second dicarboxylic acid component comprising dimethyl isophthalate (DMI), dimethyl cyclohexane dicarboxylate (DMCD), or combinations thereof, thereby being environmentally friendly and capable of improving mechanical properties such as softness and elasticity, optical properties such as transparency and UV stability, and processability. In particular, since the migration of the plasticizer can be effectively controlled by adjusting the content of the second dicarboxylic acid component, it is very easy to apply to various products.

[0032] Specifically, the second dicarboxylic acid component comprises dimethyl isophthalate (DMI), dimethyl cyclohexane dicarboxylate (DMCD), or a derivative thereof. Specifically, the second dicarboxylic acid component may comprise dimethyl isophthalate (DMI), dimethyl cyclohexane dicarboxylate (DMCD), or a derivative thereof.

[0033] In addition, the polyester copolymer (Aa) may contain the second dicarboxylic acid component in an amount of 10 mol% or more, 15 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, based on the total dicarboxylic acid component, and may contain 99 mol% or less, 90 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less. For example, the polyester copolymer (Aa) may also contain the second dicarboxylic acid component in an amount of 10 mol% to 99 mol% or 15 mol% to 70 mol% based on the total dicarboxylic acid component. By satisfying the above range for the content of the second dicarboxylic acid component, the physical properties of the resin composition and the molded article manufactured by molding the same can be improved, and the migration of the plasticizer can be effectively controlled.

[0034] More specifically, the second dicarboxylic acid component may include dimethyl isophthalate (DMI), and the polyester copolymer (Aa) may include the dimethyl isophthalate (DMI) in an amount of 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, or 5 mol% or more based on the total dicarboxylic acid component, and may include 60 mol% or less, 50 mol% or less, 40 mol% or less, 35 mol% or less, or 30 mol% or less. For example, the polyester copolymer (Aa) may also include the dimethyl isophthalate (DMI) in an amount of 1 mol% to 60 mol%, 1 mol% to 35 mol%, or 5 mol% to 30 mol% based on the total dicarboxylic acid component.

[0035] Alternatively, the second dicarboxylic acid component may include dimethylcyclohexane dicarboxylate (DMCD), and the polyester copolymer (Aa) may include the dimethylcyclohexane dicarboxylate (DMCD) in an amount of 1 mol% or more, 5 mol% or more, 10 mol% or more, or 15 mol% or more based on the total dicarboxylic acid component, and may include 75 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 35 mol% or less. For example, the polyester copolymer (Aa) may also include the dimethylcyclohexane dicarboxylate (DMCD) in an amount of 1 mol% to 75 mol% or 15 mol% to 70 mol% based on the total dicarboxylic acid component.

[0036] More specifically, the second dicarboxylic acid component may be a combination of dimethyl isophthalate (DMI) and dimethyl cyclohexane dicarboxylate (DMCD), and the polyester copolymer (Aa) may contain the combination of dimethyl isophthalate (DMI) and dimethyl cyclohexane dicarboxylate (DMCD) in an amount of 10 mol% or more, 15 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 60 mol% or more based on the total dicarboxylic acid component, and may contain 70 mol% or less, 65 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less. For example, the polyester copolymer (Aa) may also contain the combination of dimethyl isophthalate (DMI) and dimethyl cyclohexane dicarboxylate (DMCD) in an amount of 10 mol% to 70 mol%, 10 mol% to 65 mol%, or 15 mol% to 60 mol% based on the total dicarboxylic acid component.

[0037] According to another embodiment of the present invention, the polyester copolymer (Aa) may include a residue of a third dicarboxylic acid component.

[0038] 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 one or more selected from the group consisting of succinic acid, adipic acid, sebacic acid, azeraic acid, dodecanoic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate.

[0039] In addition, the polyester copolymer (Aa) 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.

[0040] Meanwhile, the above diol component may include one or more selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), cyclohexanedimethanol (CHDM), and 1,4-butanediol (1,4-BD) as the first diol component.

[0041] Specifically, the diol component may contain ethylene glycol (EG) in an amount of 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more based on the total diol component, and may contain 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, or 58 mol% or less. For example, the polyester copolymer (Aa) may also contain ethylene glycol (EG) in an amount of 1 mol% to 99 mol% or 40 mol% to 70 mol% based on the total dicarboxylic acid component.

[0042] Specifically, the diol component may contain diethylene glycol (EG) in an amount of 1 mol% or more, 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more based on the total diol component, and may contain 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, 50 mol% or less, 45 mol% or less, or 40 mol% or less. For example, the polyester copolymer (Aa) may also contain the diethylene glycol (EG) in an amount of 1 mol% to 99 mol% or 15 mol% to 45 mol% based on the total dicarboxylic acid component.

[0043] Specifically, the diol component may contain cyclohexanedimethanol (CHDM) in an amount of 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, or 5 mol% or more based on the total diol component, and may contain 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 25 mol% or less, 20 mol% or less, or 15 mol% or less. For example, the polyester copolymer (Aa) may also contain cyclohexanedimethanol (CHDM) in an amount of 1 mol% to 99 mol% or 5 mol% to 15 mol% based on the total dicarboxylic acid component.

[0044] Specifically, the diol component may contain 1,4-butanediol (1,4-BD) in an amount of 1 mol% or more, 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, or 30 mol% or more based on the total diol component, and may contain 100 mol% or less, 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 25 mol% or less, 20 mol% or less, or 15 mol% or less. For example, the polyester copolymer (Aa) may also contain 1,4-butanediol (1,4-BD) in an amount of 1 mol% to 99 mol%, 25 mol% to 90 mol%, or 100 mol% based on the total dicarboxylic acid component.

[0045] According to another embodiment of the present invention, the polyester copolymer (Aa) comprises a residue of one or more first diol components selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), cyclohexanedimethanol (CHDM), and 1,4-butanediol (1,4-BD), and may also comprise a residue of a second diol component different from the first diol component.

[0046] Specifically, the second diol component may include one or more selected from the group consisting of propanediol, pentanediol, hexanediol, neopentyl glycol, triethylene glycol, and polytetramethylene glycol. For example, the second diol component may include one or more selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-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.

[0047] In addition, the polyester copolymer (Aa) may contain the first diol component in an amount of 1 mol% or more, 10 mol% or more, 20 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 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.

[0048] In addition, the polyester copolymer (Aa) may contain the second diol component in an amount of 35 mol% or less, 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.

[0049] The above base composition (A) may additionally include a blending component (Ab).

[0050] For example, the elastomer may be one or more selected from the group consisting of polyvinyl chloride-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and polybutadiene-based elastomers, and the resin may be one or more selected from the group consisting of polyethylene, polyethylene terephthalate, polybutylene terephthalate, and glycol-modified polyethylene terephthalate.

[0051] Additionally, the base composition (A) may contain the blending component (Ab) in an amount of 0.1% to 50% by weight. For example, the content of the blending component (Ab) may be 0.1% to 99% by weight, 0.1% to 50% by weight, 1% to 40% by weight, or 5% to 25% by weight based on the total weight of the polyester copolymer (Aa) and the blending component (Ab).

[0052] As a specific example, the base composition (A) may additionally include polybutylene terephthalate (PBT) or a polyester elastomer (TPEE).

[0053] The blending component (Ab) may be introduced at the end of the polycondensation step during the manufacturing process of the base composition (A) and melt-blended. The blending component (Ab) is melt-blended to the polyester copolymer (Aa) to form the base composition (A).

[0054]

[0055] Plasticizer (B)

[0056] According to one embodiment of the present invention, the resin composition includes a plasticizer (B).

[0057] Specifically, the plasticizer may include one or more selected from the group consisting of phthalate-based, terephthalate-based, adipate-based, carboxylate-based, citric acid-based, trimellitate-based, phosphite-based, epoxy-based, ester-based, polyester-based, aliphatic-based, anti-chlorine-based, vegetable oil derivatives, petroleum-based, hydrocarbon-based, acid-based, and alcohol-based plasticizers.

[0058] For example, the above plasticizer is 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-propanediol, isononyl ester, dioctyl maleate, tri-isononyl trimellitate, trioctyl trimellitate, dioctyl It may include one or more selected from the group consisting of phthalates (dioctyl phthalate), dibutyl phthalate, diisononyl phthalate, diisodecyl phthalate, di(2-propylheptyl) phthalate, and di-branched alkyl esters.

[0059] More specifically, the plasticizer may include one or more selected from the group consisting of dioctyl terephthalate, tributyl citrate, adipic acid polyester, diisononyl adipate, and di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate.

[0060] The resin composition comprises the plasticizer in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the base composition (A). 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, 1 to 45 parts by weight, 5 to 35 parts by weight, or 10 to 30 parts by weight per 100 parts by weight of the base composition (A).

[0061]

[0062] Shock absorber (C)

[0063] According to another embodiment of the present invention, the resin composition may further include an impact inhibitor (C). The impact inhibitor (C) may include styrene ethylene / butadiene (SEBS), methacrylate butadiene styrene (MBS), or a combination thereof.

[0064] The resin composition comprises an impact inhibitor (C) in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the base composition (A). For example, the content of the impact inhibitor (C) may be 0.2 to 50 parts by weight, 0.5 to 50 parts by weight, 1 to 50 parts by weight, 1 to 45 parts by weight, 1 to 40 parts by weight, 1 to 35 parts by weight, 5 to 30 parts by weight, 5 to 20 parts by weight, or 5 to 15 parts by weight per 100 parts by weight of the base composition (A).

[0065]

[0066] Additional mixed ingredients (D)

[0067] According to another embodiment of the present invention, the resin composition may further include an additional mixing component (D). For example, the resin composition may further include additional resins in addition to the base composition (A), and one or more selected from the group consisting of polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, and polybutadiene elastomers, or 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; polyesters such as polyurethane, polybutylene terephthalate (PBT), and polyethylene terephthalate (PET); polyacetal; polycarbonate; and polysulfone. It may include one or more selected from the group consisting of homopolymers, random copolymers, block copolymers, graft copolymers, etc., such as polyallylsulfone; polyethersulfone; polyphenylene ether; polyether ketone; polyether ether ketone; polyimide; polyamideimide; polyetherimide; silicone resin; epoxy resin; phenoxy resin; liquid crystal polymer; polyaryl ether; etc., but is not limited thereto.

[0068] Specifically, the resin composition may further include one or more additional mixed components (D) selected from the group consisting of a polyester elastomer, polyethylene, polybutylene terephthalate, glycol-modified polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, and a low-melting point polyethylene terephthalate.

[0069] The above additional mixed component (D) may be included in an amount of 0.1 to 90 parts by weight or 10 to 30 parts by weight per 100 parts by weight of the base composition (A). As an example, the above additional mixed component (D) may be included in an amount of 1 to 80 parts by weight, 5 to 35 parts by weight, or 10 to 30 parts by weight per 100 parts by weight of the base composition (A).

[0070] additives

[0071] According to another embodiment of the present invention, the resin composition may further include other additives. The types of the additives are not limited as long as they do 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 fillers, antioxidants, stabilizers, heat stabilizers, release agents, colorants, lubricants, weather stabilizers, foaming agents, rust inhibitors, waxes, nucleating agents, fibrous reinforcing agents, and compatibilizers.

[0072] The above lubricant may include one or more 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. Additionally, the above lubricant may include one or more selected from the group consisting of stearic acid, glycerol stearate, zinc stearate, calcium stearate, magnesium acetate, magnesium stearate, and sodium stearate.

[0073] The above-mentioned heat stabilizer can be used to prevent the resin from decomposing due to the action of heat and light during the manufacturing process or use of the resin, and can effectively control physical properties by improving the compatibility between the resin composition and other additives or other resins, thereby minimizing side reactions that may occur at high temperatures during processes such as molding.

[0074] The above heat stabilizers may include metal-based heat stabilizers such as calcium magnesium zinc-based heat stabilizers, calcium zinc-based heat stabilizers, organotin-based heat stabilizers, metal-tin-based heat stabilizers, barium zinc-based heat stabilizers, epoxy zinc-based heat stabilizers, magnesium aluminum carbonate-based heat stabilizers, zinc-based heat stabilizers, lead-based heat stabilizers, etc., and non-metal-based heat stabilizers such as epoxy-based heat stabilizers and organophosphorus-based heat stabilizers, but are not limited thereto.

[0075] The above antioxidant may include phenolic, phosphorus-based, sulfur-based, amine-based antioxidants, etc., as an additive that prevents thermal oxidation.

[0076] The resin composition may contain the additive in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the base composition (A). 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 per 100 parts by weight of the base composition (A).

[0077]

[0078] Method for preparing a base composition

[0079] A method for preparing a base composition according to another embodiment of the present invention comprises the steps of: mixing a first dicarboxylic acid component comprising terephthalic acid (TPA), dimethyl terephthalate (DMT), or a combination thereof; a second dicarboxylic acid component comprising dimethyl isophthalate (DMI), dimethyl cyclohexane dicarboxylate (DMCD), or a combination thereof; and a diol component comprising one or more selected from the group consisting of ethylene glycol (EG) or a derivative thereof and 1,4-butanediol (butane diol) or a derivative thereof; esterifying the mixture; and polycondensing the product of the esterification reaction, wherein the polyester copolymer of the base composition comprises the second dicarboxylic acid component in an amount of 50 mol% or more based on the total dicarboxylic acid component.

[0080] The base composition (A) prepared according to the method of preparing the base composition above has substantially the same composition and characteristics as the base composition (A) described above.

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

[0082]

[0083] First, a first dicarboxylic acid component comprising terephthalic acid (TPA), dimethyl terephthalate (DMT), or a combination thereof; a second dicarboxylic acid component comprising dimethyl isophthalate (DMI), dimethyl cyclohexane dicarboxylate (DMCD), or a combination thereof; and a diol component comprising one or more selected from the group consisting of ethylene glycol (EG) or its derivatives and 1,4-butanediol (butane diol) or its derivatives 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 colorant, 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-mentioned colorant is an additive for improving the color characteristics of the base composition (A). As long as it does not impede the effects of the present invention, commonly used colorants such as cobalt acetate, cobalt propionate, etc. may be used as the colorant.

[0087] Specifically, the above-mentioned colorant may be cobalt acetate, cobalt propionate, anthraquinone-based compounds, perinone-based compounds, azo-based compounds, methine-based compounds, etc., and commercially available products may include toners such as Clarient’s Polysynthren Blue RLS or Clarient’s Solvaperm Red BB.

[0088] In addition, the base composition (A) may contain the colorant in an amount of 0.1 ppm to 30 ppm based on the total weight of the base composition (A). For example, the colorant 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 above ranges for the content of the colorant, color characteristics can be sufficiently improved without deteriorating the mechanical properties of the base composition (A).

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

[0090] In addition, the base composition (A) may contain the oxidation stabilizer in an amount of 50 ppm to 2,500 ppm based on the total weight of the base composition (A). 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 above ranges for the content of the oxidation stabilizer, not only can the decrease in intrinsic viscosity that may occur during subsequent processing be effectively prevented, but the deterioration of physical properties such as impact strength can also be prevented.

[0091] The above branching agent may include one or more selected from the group consisting of trimellitic anhydride, trimethylol propane, trimellitic acid, and glycerol.

[0092] In addition, the base composition (A) may contain the branching agent in an amount of 10 ppm to 5000 ppm based on the total weight of the base composition (A). 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 above range, the intrinsic viscosity can be controlled more effectively within a specific range, thereby improving physical properties such as impact strength.

[0093]

[0094] Afterwards, the above mixture is subjected to an esterification reaction or an ester exchange 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 or an ester exchange reaction.

[0096] The above esterification reaction or transesterification reaction is carried out at atmospheric pressure or 0.1 kg / cm² relative to atmospheric pressure. 2 up to 3.0 kg / cm² 2 It can be performed for 2 to 12 hours under high pressure conditions and a temperature condition of 180 ℃ to 275 ℃.

[0097] Specifically, the above pressurized state is atmospheric pressure or 0.1 kg / cm² relative to atmospheric pressure. 2 up to 3.0 kg / cm² 2 , 0.2 kg / cm 2 up to 2.5 kg / cm² 2 or 0.3 kg / cm² 2 up to 2.0 kg / cm² 2 It can be as high as that. In addition, the esterification reaction or ester exchange reaction may be carried out for 2 to 12 hours, 2 to 11 hours, or 2.5 to 10 hours under temperature conditions of 150 ℃ to 275 ℃, 155 ℃ to 275 ℃, or 160 ℃ to 270 ℃.

[0098] For example, the above esterification reaction or transesterification reaction is at atmospheric pressure or 0.1 kg / cm² relative to atmospheric pressure. 2 up to 3.0 kg / cm² 2 This can be performed by increasing the temperature from room temperature to 150°C to 275°C or 155°C to 270°C over 30 minutes to 110 minutes or 30 minutes to 100 minutes under high pressure, maintaining it for 0.5 hours to 3 hours or 0.5 hours to 2.5 hours, and then increasing the temperature continuously or in steps from room temperature to 150°C to 275°C or 155°C to 270°C over 2 hours to 12 hours.

[0099] Once the above esterification reaction or ester exchange reaction is completed, the pressure of the pressurized reactor can be lowered to room temperature, and then 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 above polycondensation reaction may be carried out for 1 hour to 12 hours under pressure conditions of 0.00001 mmHg to 400 mmHg and temperature conditions of 240 ℃ to 300 ℃. For example, the above polycondensation reaction may be carried out for 1 hour to 12 hours or 1 hour to 10 hours under pressure conditions 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 temperature conditions of 240 ℃ to 300 ℃ or 245 ℃ to 295 ℃.

[0103] For example, the polycondensation reaction may be carried out by reducing the pressure of the product of the esterification reaction or ester exchange 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, increasing the temperature to 240 ℃ to 300 ℃ or 245 ℃ to 295 ℃ over 0.5 to 2 hours or 0.7 to 1.2 hours, and then maintaining a pressure of 0.01 mmHg to 400 mmHg.

[0104] In the initial stages of the polycondensation reaction, the stirring speed is set to a high speed, and as the polycondensation reaction proceeds, the stirring force may weaken due to an increase in the viscosity of the reactants or the temperature of the reactants may rise above the set temperature, at which point the stirring speed can be appropriately adjusted accordingly.

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

[0106] In addition, a catalyst and / or stabilizer may be additionally added in the above esterification reaction or ester exchange reaction and the above polycondensation reaction.

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

[0108] In addition, the polycondensation reaction catalyst may be a titanium-based catalyst such as, for example, tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic 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, monobutylhydroxy tin oxide, etc.

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

[0110] The above stabilizer may be added in an amount of 10 ppm to 2,500 ppm based on the total weight of the polycondensation reactants. For example, the above 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 reactants.

[0111] According to another embodiment of the present invention, the method for manufacturing the base composition (A) may include a melt blending step.

[0112] Specifically, after the polycondensation reaction, a blending component (Ab) can be added to perform melt blending. More specifically, after the polycondensation reaction, the vacuum can be broken using nitrogen gas, and then a blending component (Ab) can be additionally added to perform melt blending.

[0113] As a specific example, the elastomer introduced in the melt blending step may be one or more selected from the group consisting of polyvinyl chloride-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and polybutadiene-based elastomers, and the resin may be one or more selected from the group consisting of polyethylene, polyethylene terephthalate, polybutylene terephthalate, and glycol-modified polyethylene terephthalate. As a specific example, the blending component (Ab) included in the base composition (A) may include polybutylene terephthalate (PBT) or polyester-based elastomer (TPEE).

[0114] In addition, 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 the imparting of crystallinity.

[0116]

[0117] Method for manufacturing a resin composition

[0118] According to another embodiment of the present invention, a resin composition can be prepared by mixing a base composition (A) and a plasticizer (B).

[0119] As a specific example, a primary composition can be prepared by mixing a base composition (A) and a plasticizer (B), and the primary composition can be automatically metered and fed into a hopper of a twin-screw extruder (40 mm Extruder, L / D: 40), volatile gases can be removed by depressurization, and a resin in the form of pellets can be produced using a chip cutter.

[0120] Meanwhile, according to another embodiment of the present invention, a resin composition can be prepared by further mixing an impact inhibitor (C) in addition to the base composition (A) and plasticizer (B).

[0121] In addition, according to another embodiment of the present invention, a resin composition can be prepared by further mixing an additional mixing component (D) in addition to the base composition (A) and plasticizer (B).

[0122] In addition, according to another embodiment of the present invention, a resin composition can be prepared by mixing all of the base composition (A), plasticizer (B), shock absorber (C), and additional mixing component (D).

[0123]

[0124] molded product

[0125] A molded article according to another embodiment of the present invention is manufactured by molding the resin composition.

[0126] For example, the above-mentioned molded article may be manufactured by extruding or kneading the resin composition, and may be molded through calendering, extrusion, or injection, but is not limited thereto.

[0127] It is preferable that the residual amount of the plasticizer (B), measured according to a plasticizer migration induction residual amount measurement experiment in which plasticizer migration is induced under certain conditions and the residual amount of the plasticizer is measured at the time of elapsed for a certain period, is 50% by weight or more relative to the input amount. For example, for a molded product of 100 μm to 200 μm, the residual amount of the plasticizer (B), measured according to a plasticizer migration induction residual amount measurement experiment in which plasticizer migration is induced at 60°C to 90°C and the residual amount of the plasticizer is measured at the time of elapsed for 4 days to 10 days, may be 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more relative to the initial input amount.

[0128] 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 various food / beverage containers, packaging materials, sheets for sound insulation or sound absorption purposes, tarpaulins, silk wallpapers, artificial leather, wraps, medical devices, deco sheets, filaments for 3D printers, or films such as deco films or mulching films, but is not limited thereto. In addition, the above-mentioned resin composition may be used as a fiber binder, coating agent, adhesive, etc.

[0129] The above contents will be explained in more detail by the following examples. However, the following examples are merely for illustrating the present invention, and the scope of the examples is not limited to these.

[0130] [Example]

[0131] Preparation of base composition

[0132] Preparation Example 1

[0133] (1) Esterification reaction

[0134] 569 g of terephthalic acid (TPA), 1,600 g of dimethylcyclohexane dicarboxylate (DMCD), and 1,417 g of ethylene glycol (EG) were introduced into a 10 L reactor connected to a column and a condenser capable of cooling with water. At this time, the content of the second dicarboxylic acid was 70 mol% based on 100 mol% of the dicarboxylic acid component.

[0135] Subsequently, 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.

[0136] Subsequently, nitrogen is injected into the reactor containing the above composition so that the pressure in the reactor is 1.0 kgf / cm² relative to atmospheric pressure. 2 The reactor was subjected to a high pressurization state (absolute pressure: 1495.6 mmHg). The reactor temperature was then raised from room temperature to 200°C over 60 minutes, maintained at 200°C for 2 hours, and then raised again to 245°C over 5 hours. Subsequently, the esterification reaction was carried out at 245°C for 0.5 hours. During this process, byproducts were discharged through a column and a condenser. Once the esterification reaction was complete, the nitrogen inside the pressurized reactor was purged to lower the reactor pressure to atmospheric pressure, and the product of the esterification reaction was transferred to a 7L capacity reactor capable of vacuum reaction.

[0137] (2) Polycondensation reaction

[0138] Subsequently, 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 ℃ over 1 hour, after which the pressure of the reactor was maintained at 1.0 Torr (absolute pressure: 1.0 mmHg) or lower to carry out the polycondensation reaction. At this time, the stirring speed was set fast at the beginning of the polycondensation reaction, but as the polycondensation reaction progressed, the stirring force weakened due to the increase in 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 (molten material) in the reactor became 0.8 dl / g or higher. After the above polycondensation reaction was completed, the vacuum was broken using nitrogen gas, 750 g of poly(butylene terephthalate), PBT, was added as a blending component (Ab) and melt blended at 270°C for 10 minutes, and the mixture was discharged outside the reactor and solidified with a cooling liquid, then granulated to have an average weight of about 10 mg to 20 mg to prepare a base composition.

[0139]

[0140] Preparation Example 2

[0141] A base composition was prepared in the same manner as in Preparation Example 1, except that 250 g of thermoplastic polyester elastomer (TPEE) was added as the blending component (Ab) in the polycondensation reaction instead of 750 g of poly(butylene terephthalate), PBT.

[0142]

[0143] Preparation Example 3

[0144] A base composition was prepared by performing the same procedure as in Preparation Example 1, except that the blending component (Ab) was not added in the polycondensation reaction.

[0145]

[0146] Preparation Example 4

[0147] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0148]

[0149] Preparation Example 5

[0150] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0151]

[0152] Preparation Example 6

[0153] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0154]

[0155] Preparation Example 7

[0156] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0157]

[0158] Preparation Example 8

[0159] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0160]

[0161] Preparation Example 9

[0162] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0163]

[0164] Preparation Example 10

[0165] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0166]

[0167] Preparation Example 11

[0168] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0169]

[0170] Preparation Example 12

[0171] A base composition was prepared in the same manner as in Preparation Example 1, except that the raw material components and their content were applied as shown in Table 1 below, and the conditions of the ester exchange reaction (or esterification reaction) and polycondensation reaction were adjusted according to the raw material components.

[0172]

[0173] Meanwhile, the base compositions prepared in the above Preparation Examples 1 to 12 are summarized as shown in the table below.

[0174] Base composition (A) Polyester copolymer (Aa) Resin or elastomer (Ab) Dicarboxylic acid component Diol component Agent 1 Dicarboxylic acid component Agent 2 Dicarboxylic acid component Preparation Example 1 TPA ​​569g DMCD 1,600g EG 1,417g PBT 750g Preparation Example 2 TPA 569g DMCD 1,600g EG 1,417g TPEE 250g Preparation Example 3 TPA 569g DMCD 1,600g EG 1,417g -- Preparation Example 4 DMT 1200.1g DMI 218.2g EG --- DEG --- DMCD 787.5g CHDM --- 1,4-BD 1367.1g -- Preparation Example 5 TPA 74 8.2gDMI655.9gEG---DEG---DMCD676.9gCHDM---1,4-BD1369.9g--Production Example 6DMT1295.9gDMI432.0gEG---DEG236 .1g--DMCD445.4gCHDM---1,4-BD1333.1g--Production Example 7TPA439.2gDMI425.9gEG---DEG640.1g--DMCD439.2gCHDM-- -1,4-BD790.7g--Production Example 8DMT1996.4gDMI-EG621.1g--DEG---DMCD357.8gCHDM171.8g--1,4-BD536.8g--Production Example 9D MT1662.2gDMI356.2gEG569.3g--DEG---DMCD367.3gCHDM---1,4-BD661.2g--Production Example 10TPA1462.8gDMI114gEG53 9.2g--DEG---DMCD470.1gCHDM16.9g--1,4-BD634.8g--Production Example 11DMT1658.8gDMI355.5gEG568.1g--DEG---DMC D366.5gCHDM---1,4-BD659.9g--Production Example 12DMT1413.7DMI-EG---DEG---DMCD624.7CHDM1246.6--1,4-BD208.0--

[0175]

[0176] In Preparation Examples 4 to 12, the content of the second dicarboxylic acid based on 100 mol% of the dicarboxylic acid component was 45 mol% for Preparation Example 4, 60 mol% for Preparation Example 5, 40 mol% for Preparation Example 6, 40 mol% for Preparation Example 7, 15 mol% for Preparation Example 8, 30 mol% for Preparation Example 9, 25 mol% for Preparation Example 10, 30 mol% for Preparation Example 11, and 30 mol% for Preparation Example 12.

[0177]

[0178] Preparation of resin composition

[0179] Examples 1 to 24 and Comparative Example 1

[0180] A resin composition was prepared by uniformly mixing the components listed in Table 1 below as described in Tables 2 to 6 below. 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 by depressurization, and the composition was manufactured into pellets using a chip cutter. At this time, information regarding the components used in the examples and comparative examples is shown in Table 2 below, and the values ​​listed in Tables 3 to 6 below represent parts by weight.

[0181] Item Characteristics Base Composition (A-1) Preparation Example 1 Base Composition (A-2) Preparation Example 2 Base Composition (A-3) Preparation Example 3 Base Composition (A-4) Preparation Example 4 Base Composition (A-5) Preparation Example 5 Base Composition (A-6) Preparation Example 6 Base Composition (A-7) Preparation Example 7 Base Composition (A-8) Preparation Example 8 Base Composition (A-9) Preparation Example 9 Base Composition (A-10) Preparation Example 10 Base Composition (A-11) Preparation Example 11 Base Composition (A-12) Preparation Example 12 Plasticizer (B-1) Tributylene citrate (TBC) Plasticizer (B-2) Adipic acid polyester (OLICIZER) Styrene Ethylene / Butadiene Styrene (C-1) SEBS Methacrylate Butadiene Styrene (C-2) MBS Polyester Elastomer (D-1) TPEE Polyethylene (D-2) PE Polybutylene Terephthalate (D-3) PBT Glycol Modified Polyethylene Terephthalate (D-4) PETG Polyethylene Terephthalate Isophthalate Copolymer (D-5) PET-IPA Copolymer Low Melting Point Polyethylene Terephthalate (D-6) Low Melting PET Polyethylene Terephthalate (D-7) PET

[0182] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 A-1100--------A-2-100-------A-3--100------A-4---100-----A-5----100----A-6-----100---A-7------100--A-8-------100-A-9--------100B-110101010101010101010

[0183] Classification Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 A-1---100100907070A-10100-------A-11-100------A-12--100-----B-110101020-101010B-230---D-1---10--D-2----30-D-3------30

[0184] Classification Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 A-170707060609090A-5---20---A-12----20--B-11010101010101010C-1----10-C-2------10D-430------D-5-30-20---D-6--30-20--

[0185] Classification Comparison Example 1D-7100B-110

[0186]

[0187] [Experimental Example]

[0188] Experimental Example 1 Plasticizer Migration

[0189] For molded articles containing the resin compositions of Examples 1 to 24 and Comparative Example 1, a plasticizer migration induction residual amount measurement experiment was performed in which plasticizer migration was induced under certain conditions and the residual amount of plasticizer was measured at the time of elapsed for a certain period.

[0190] Specifically, a flat film having a thickness of 150 μm was prepared using the resin compositions of Examples 1 to 24 and Comparative Example 1, and the specimen was left at 80°C for 7 days to induce plasticizer migration, after which the remaining amount relative to the initial amount of plasticizer was measured by NMR.

[0191]

[0192] Experimental Example 2 Shore A Hardness

[0193] Plate specimens with a thickness of 1 mm were prepared using the resin compositions of Examples 1 to 24 and Comparative Example 1. Six identical specimens prepared were stacked on top of each other, and Shore A hardness was measured according to ASTM D2240.

[0194] Plasticizer migration Shore A Hardness Example 168.9 wt% 65 Example 275.2 wt% 60 Example 382.1 wt% 57 Example 464.9 wt% 79 Example 569.2 wt% 80 Example 677.8 wt% 87 Example 762.5 wt% 85 Example 855.7 wt% 89 Example 951.0 wt% 92 Example 1055.8 wt% 90 Example 1152.0 wt% 92 Example 1257.4 wt% 75 Example 1365.2 wt% 60 Example 1498.0 wt% 60 Example 1572.3 wt% 70 Example 1665.6 wt% 73 Example 1763.0 wt% 85 Example 1870.3 wt% 78 Example 1961.1 Weight % 77 Example 206 1.5 Weight % 77 Example 216 3.8 Weight % 74 Example 226 0.2 Weight % 72 Example 237 1.9 Weight % 75 Example 246 7.0 Weight % 78 Comparative Example 14 1.5 Weight % > 95

Claims

A base composition (A) comprising a polyester copolymer (Aa) and a plasticizer (B), and The above polyester copolymer (Aa) includes residues of a dicarboxylic acid component and residues of a diol component, and The above dicarboxylic acid component comprises a first dicarboxylic acid component comprising terephthalic acid, dimethyl terephthalate, or a combination thereof, and a second dicarboxylic acid component comprising dimethyl isophthalate, dimethylcyclohexanedicarboxylate, or a combination thereof, and A resin composition comprising 10 mol% or more of a second dicarboxylic acid component based on 100 mol% of the above dicarboxylic acid component. In Article 1, The above dicarboxylic acid component further includes a third dicarboxylic acid component, and A resin composition comprising one or more selected from the group consisting of succinic acid, adipic acid, sebacic acid, azeraic acid, dodecanoic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diethyl isophthalate, and dibutyl isophthalate, wherein the third dicarboxylic acid component comprises succinic acid, adipic acid, sebacic acid, azeraic acid, dodecanoic acid, isophthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diethyl isophthalate, and dibutyl isophthalate. In Article 1, A resin composition comprising a first diol component including one or more selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), cyclohexanedimethanol (CHDM), and 1,4-butanediol (1,4-BD). In Article 1, A resin composition comprising a second diol component, wherein the diol component comprises one or more selected from the group consisting of propanediol, pentanediol, hexanediol, neopentyl glycol, triethylene glycol, and polytetramethylene glycol. In Article 1, A resin composition comprising one or more types selected from the group consisting of phthalate-based, terephthalate-based, adipate-based, carboxylate-based, citric acid-based, trimellitate-based, phosphite-based, epoxy-based, ester-based, polyester-based, aliphatic-based, anti-chlorine-based, vegetable oil derivatives, petroleum-based, hydrocarbon-based, acid-based, and alcohol-based plasticizers. In Article 1, A resin composition in which the above plasticizer (B) is included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the above base composition (A). In Article 1, The above resin composition further includes an impact reinforcing agent (C), and The above impact modifier (C) is a resin composition comprising styrene-ethylene-butadiene-styrene (SEBS) or methacrylate butadiene styrene (MBS). In Article 7, The above impact reinforcing agent (C) is a resin composition included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the base composition (A). In Article 1, The above base composition (A) further includes a blending component (Ab), and The above blending component (Ab) is a resin composition comprising polybutylene terephthalate or a polyester-based elastomer. In Article 1, The above resin composition further includes an additional mixing component (D), and A resin composition comprising one or more additional mixed components (D) selected from the group consisting of polyester elastomer, polyethylene, polybutylene terephthalate, glycol-modified polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer and low melting point polyethylene terephthalate. In Article 10, The above additional mixed component (D) is a resin composition included in an amount of 0.1 to 90 parts by weight based on 100 parts by weight of the base composition (A). In Article 1, The above resin composition is a resin composition that induces plasticizer migration under certain conditions and measures the remaining amount of plasticizer at the time of elapsed for a certain period, wherein the remaining amount of plasticizer measured according to the plasticizer migration induction remaining amount measurement is 50% by weight or more relative to the input amount. A molded article manufactured by molding the resin composition of claim 1. In Article 13, A molded article formed by calendering, extrusion, or injection.