阅读说明：本技术 热塑性树脂组合物 (Thermoplastic resin composition ) 是由 李如达 崔正洙 李元锡 朴相厚 李宗周 于 2020-06-04 设计创作，主要内容包括：本发明提供一种热塑性树脂组合物,包含：基体树脂,该基体树脂包含重量比为70:30至90:10的第一共聚物和第二共聚物,所述第一共聚物通过平均粒径为50nm至200nm的二烯类橡胶聚合物与包含(甲基)丙烯酸烷基酯类单体和芳香族乙烯基类单体的第一单体混合物的接枝聚合形成,所述第二共聚物是包含(甲基)丙烯酸烷基酯类单体和芳香族乙烯基类单体的第二单体混合物的共聚物；和增塑剂。(The present invention provides a thermoplastic resin composition comprising: a base resin comprising a first copolymer and a second copolymer in a weight ratio of 70:30 to 90:10, the first copolymer being formed by graft polymerization of a diene-based rubber polymer having an average particle diameter of 50nm to 200nm and a first monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl-based monomer, the second copolymer being a copolymer of a second monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl-based monomer; and a plasticizer.)

1. A thermoplastic resin composition comprising:

a base resin comprising a first copolymer and a second copolymer in a weight ratio of 70:30 to 90:10, the first copolymer being formed by graft polymerization of a diene-based rubber polymer having an average particle diameter of 50nm to 200nm and a first monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl-based monomer, the second copolymer being a copolymer of a second monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl-based monomer; and

and (3) a plasticizer.

2. The thermoplastic resin composition according to claim 1, wherein the base resin is contained in an amount of 100 parts by weight, and the plasticizer is contained in an amount of 4 to 10 parts by weight.

3. The thermoplastic resin composition of claim 1, wherein said plasticizer is a polyester-based plasticizer.

4. The thermoplastic resin composition of claim 1, wherein the plasticizer has a viscosity of 1,500cps to 5,000 cps.

5. The thermoplastic resin composition of claim 1, wherein said plasticizer is selected from the group consisting of poly (di (2-ethylhexyl) glycol adipate); polymers of adipic acid with 1, 3-butanediol, 2-ethylhexyl ester; polymers of adipic acid with 1, 3-butanediol and 1, 2-propanediol, 2-ethylhexyl ester; and one or more of adipic acid, 2-dimethyl-1, 3-propanediol, 1, 2-propanediol, isononyl ester.

6. The thermoplastic resin composition of claim 1, wherein said plasticizer has a refractive index of 1.45 to 1.6.

7. The thermoplastic resin composition of claim 1, wherein the refractive indices of said first copolymer and said second copolymer differ by 0.01 or less.

8. The thermoplastic resin composition of claim 1, wherein said first monomer mixture and said second monomer mixture each further comprise a vinyl cyanide monomer.

9. A thermoplastic resin molded article made of the thermoplastic resin composition according to claim 1,

wherein the thermoplastic resin molded article has a haze of 2.0% or less and a flexural strength of 280kg/cm²To 420kg/cm²Flexural modulus of 11,000kg/cm²To 13,500kg/cm²。

Technical Field

[ Cross-reference to related applications ]

The present application claims priority and benefit from korean patent application No.10-2019-0070232 filed on 13.06.2019 and korean patent application No.10-2020-0066697 filed on 2.06.2020, the disclosures of which are incorporated herein by reference in their entirety.

[ technical field ]

The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition excellent in transparency, processability and softness.

Background

Artificial nails are mainly manufactured by injection molding. Acrylonitrile/butadiene/styrene (ABS) thermoplastic resin compositions containing ABS graft copolymers have been commonly used for artificial nails because ABS thermoplastic resin compositions allow a molded body to be easily separated from an injection machine and do not generate burrs. Meanwhile, the conventional ABS thermoplastic resin composition is hard. When a hard artificial nail is adhered to a natural nail with an adhesive, the artificial nail is likely to be detached from the natural nail due to the different curvature of the consumer's nail. Further, wearing comfort is reduced due to the force of the artificial nail to restore the original shape in a state of being adhered to the nail of the consumer. To compensate for these disadvantages, a method of manufacturing an artificial nail using ethylene vinyl acetate or styrene/butadiene copolymer is proposed. However, since the artificial nail manufactured by this method is soft, there is a disadvantage that the end of the artificial nail is easily bent by external impact when worn. To overcome this disadvantage, a method of mixing an ABS graft copolymer with an ethylene vinyl acetate or styrene/butadiene copolymer has also been proposed. Recently, it has been common to use transparent artificial nails to make various designs to satisfy individuality or taste, but when a methyl methacrylate/butadiene/styrene copolymer as a transparent graft copolymer is mixed with ethylene vinyl acetate or a styrene/butadiene copolymer, there is a limitation in maintaining transparency due to a difference in refractive index between the two materials. Meanwhile, when a methylmethacrylate/butadiene/styrene copolymer is mixed, as the rubber content increases, softness increases, but haze increases, resulting in low transparency, deterioration in color and deterioration in processability.

Therefore, research and development are being conducted on a thermoplastic resin composition for an artificial nail, which is excellent in transparency, processability and softness.

Disclosure of Invention

Technical problem

The present invention provides a thermoplastic resin composition having excellent transparency, processability and softness.

Technical scheme

One aspect of the present invention provides a thermoplastic resin composition comprising: a base resin comprising a first copolymer and a second copolymer in a weight ratio of 70:30 to 90:10, the first copolymer being formed by graft polymerization of a diene-based rubber polymer having an average particle diameter of 50nm to 200nm and a first monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl-based monomer, the second copolymer being a copolymer of a second monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl-based monomer; and a plasticizer.

Another aspect of the present invention provides a thermoplastic resin molded article which is made of the above thermoplastic resin composition and has a haze of 2.0% or less and a flexural strength of 280kg/cm²To 420kg/cm²Flexural modulus of 11,000kg/cm²To 13,500kg/cm²。

Advantageous effects

The thermoplastic resin composition according to the present invention is excellent in transparency, processability and softness. Therefore, the thermoplastic resin composition according to the present invention can be used to manufacture an artificial nail that is transparent, can realize various colors, and has excellent wearing comfort.

Detailed Description

Hereinafter, the present invention will be described in more detail to help understanding the present invention.

The terms and words used in the present specification and claims should not be construed as limited to general or dictionary meanings, and should be construed as meanings and concepts consistent with the technical idea of the present invention based on the principle that the inventor can appropriately define the concept of the term to describe their invention in the best way.

In the present invention, the average particle diameter of the diene-based rubber polymer can be measured by a dynamic light scattering method, specifically, by using a Nicomp 380 instrument (manufactured by PSS).

In the present specification, the average particle diameter may refer to an arithmetic average particle diameter in a particle diameter distribution measured by a dynamic light scattering method, that is, an average particle diameter based on a scattering intensity distribution.

In the present invention, the viscosity can be measured using a brookfield viscometer under the following conditions.

Spindle type: cone type (CPA-52Z), cone angle 3 °, cone radius 1.2cm, gap: shear rate was measured at 13 μm or less: 10/sec to 20/sec, measurement temperature: 25 deg.C

In the present invention, the refractive index refers to the absolute refractive index of a material, and is considered to be the ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material, wherein the radiation may be visible light having a wavelength of 450nm to 680nm, in particular, 589.3 nm. The refractive index can be measured by a known method, i.e., using an abbe refractometer.

In the present invention, the degree of grafting may be calculated by dissolving 1g of the first copolymer powder in 50g of acetone while stirring for 24 hours, then centrifuging in a centrifuge (Supra 30K manufactured by Hanil Science Industrial) at 16,000rpm and-10 ℃ for 4 hours to separate a supernatant and a precipitate, and drying the precipitate in a hot air drier set to 50 ℃ for 12 hours, and then weighing the resulting dried solid, after which it is calculated by the following equation 1:

[ equation 1]

Degree of grafting (%) { (grafted monomer mixture)¹⁾Weight of copolymer (2)/(diene rubber Polymer)²⁾Weight of) } × 100

1) The weight of the copolymer of the grafted monomer mixture (weight of dry solid) - (weight of diene rubber polymer)

2) Weight of diene rubber Polymer-weight of diene rubber Polymer theoretically charged (based on solid content), or weight of diene rubber Polymer measured by infrared spectroscopic analysis of the first copolymer

In the present invention, the weight average molecular weight of the shell of the first copolymer may be measured as a relative value with respect to a standard Polystyrene (PS) sample by Gel Permeation Chromatography (GPC) after dissolving a dried solid obtained by drying the supernatant as described in the measurement method of the degree of grafting in a Tetrahydrofuran (THF) solution and then filtering through a 1 μm filter.

In the present invention, the weight average molecular weight of the second copolymer can be measured by gpc (waters breeze) as a relative value to a standard PS sample using THF as a solution.

In the present invention, haze may be measured according to ASTM D1003.

In the present invention, the flexural strength and flexural modulus can be measured according to ASTM D790.

In the present invention, the alkyl (meth) acrylate monomer may be (meth) acrylic acid C₁To C₁₀Alkyl ester monomers. The (meth) acrylic acid C₁To C₁₀The alkyl ester monomer may be selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate and (meth) acrylic acidOne or more of lauryl sulfate, preferably methyl methacrylate.

In the present invention, the aromatic vinyl monomer may be one or more selected from the group consisting of styrene, α -methylstyrene, α -ethylstyrene and p-methylstyrene, and is preferably styrene.

In the present invention, the vinyl cyanide monomer may be one or more selected from acrylonitrile, methacrylonitrile, phenylacetonitrile and α -chloroacrylonitrile, and is preferably acrylonitrile.

1. Thermoplastic resin composition

The thermoplastic resin composition according to one embodiment of the present invention comprises: 1)100 parts by weight of a base resin comprising a first copolymer and a second copolymer in a weight ratio of 70:30 to 90:10, the first copolymer being formed by graft polymerization of a diene-based rubber polymer having an average particle diameter of 50nm to 200nm and a first monomer mixture comprising an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer, the second copolymer being a copolymer of a second monomer mixture comprising an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer; and 2) a plasticizer.

Hereinafter, the respective components of the thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

1) Matrix resin

The base resin comprises (1) a first copolymer and (2) a second copolymer.

Hereinafter, the respective components of the matrix resin will be described in detail.

(1) First copolymer

The first copolymer is a graft copolymer formed by graft copolymerization of a diene-based rubber polymer having an average particle diameter of 50nm to 200nm and a first monomer mixture comprising an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer.

The diene-based rubber polymer may have an average particle diameter of 50nm to 200nm, preferably, an average particle diameter of 70nm to 180 nm. When the above range is satisfied, excellent transparency can be achieved even when an excessive amount of the first copolymer is contained in the thermoplastic resin composition. Below the above range, the impact resistance of the thermoplastic resin composition may be significantly reduced, while above the above range, the transparency of the thermoplastic resin composition may be reduced.

The diene-based rubber polymer may be a synthetic rubber formed by crosslinking a conjugated diene-based monomer. The conjugated diene monomer may be one or more selected from 1, 3-butadiene, isoprene, chloroprene, piperylene, dicyclopentadiene, ethylidene norbornene and vinyl norbornene, and is preferably 1, 3-butadiene.

The alkyl (meth) acrylate monomer may impart excellent transparency to the first copolymer. The content of the alkyl (meth) acrylate-based monomer may be 64 to 75% by weight or 68 to 72% by weight, preferably in the range of 68 to 72% by weight, relative to the total weight of the first monomer mixture. When the above range is satisfied, the transparency of the first copolymer can be improved.

The aromatic vinyl monomer can impart excellent processability to the first copolymer. The aromatic vinyl monomer may be included as the remainder such that the total weight of the first monomer mixture is 100% by weight.

The first monomer mixture may further include a vinyl cyanide monomer to improve polymerization stability and chemical resistance of the first copolymer. The content of the vinyl cyanide-based monomer may be 7 wt% or less with respect to the total weight of the first monomer mixture. When the above range is satisfied, the chemical resistance of the first copolymer may be improved while minimizing the yellowing phenomenon caused by the vinyl cyanide monomer.

The weight ratio of the diene-based rubber polymer to the first monomer mixture may be 40:60 to 60:40 or 45:55 to 55:45, preferably in the range of 45:55 to 55: 45. When the above range is satisfied, the transparency and color of the first copolymer may be improved.

The degree of grafting of the first copolymer may be in the range of from 45% to 65% or from 50% to 60%, preferably in the range of from 50% to 60%. When the above range is satisfied, the transparency of the thermoplastic resin composition may be improved, and the compatibility of the first copolymer with the second copolymer may also be improved.

Meanwhile, the transparency of the first copolymer may be determined by the difference between the refractive index of the diene-based rubber polymer and the refractive index of the shell, which is a copolymer of the first monomer mixture. That is, in order for the first copolymer to achieve excellent transparency, the refractive index of the diene-based rubber polymer and the refractive index of the shell may differ by 0.01 or less, and preferably there is no difference in refractive index.

In addition, in order to achieve excellent transparency of the thermoplastic resin composition, the refractive indices of the first copolymer and the second copolymer may differ by 0.01 or less, and preferably there is no difference in refractive index.

The refractive index of the first copolymer may be 1.5 to 1.525 or 1.51 to 1.52, preferably in the range of 1.51 to 1.52. When the above range is satisfied, the first copolymer may cooperate with a second copolymer described below to improve transparency of the thermoplastic resin composition.

(2) Second copolymer

The second copolymer is a non-grafted copolymer that is a copolymer of a second monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer.

The second copolymer can impart excellent transparency and processability to the thermoplastic resin composition.

The alkyl (meth) acrylate monomer may be contained in an amount of 64 to 75% by weight or 68 to 72% by weight, preferably in a range of 68 to 87% by weight, with respect to the total weight of the second monomer mixture. When the above range is satisfied, the transparency of the second copolymer may be improved, and the compatibility of the second copolymer with the first copolymer may be improved.

The aromatic vinyl monomer can impart excellent processability to the second copolymer. The aromatic vinyl monomer may be included as the remainder such that the total weight of the second monomer mixture is 100% by weight.

The second monomer mixture may further include a vinyl cyanide monomer to improve polymerization stability and chemical resistance of the second copolymer. The content of the vinyl cyanide-based monomer may be 7 wt% or less with respect to the total weight of the second monomer mixture. When the above range is satisfied, the chemical resistance of the second copolymer may be improved while minimizing the yellowing phenomenon caused by the vinyl cyanide-based monomer.

The refractive index of the second copolymer may be 1.5 to 1.525 or 1.51 to 1.52, preferably in the range of 1.5 to 1.52. When the above range is satisfied, the transparency of the thermoplastic resin composition may be improved.

The second copolymer may be prepared by suspension polymerization or bulk polymerization of a monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer, and is preferably bulk polymerization capable of preparing a high purity copolymer.

The base resin may comprise the first and second copolymers in a weight ratio of 70:30 to 90:10, and preferably comprises the first and second copolymers in a weight ratio of 75:25 to 85: 15. When the above range is satisfied, the amount of the diene-based rubber polymer in the thermoplastic resin composition is increased, and thereby, the softness can be remarkably improved. Therefore, the force with which the artificial nail manufactured using the thermoplastic resin composition restores the original shape in the state of being adhered to the natural nail is weakened, and thus, the wearing comfort can be improved. However, below the above range, softness cannot be improved due to excessive increase in bending strength and bending modulus, and the artificial nail manufactured using the thermoplastic resin composition may have reduced wearing comfort. Beyond the above range, processability and transparency may be deteriorated.

2) Plasticizer

The plasticizer is used to improve processability and softness while maintaining transparency of the thermoplastic resin composition, and the viscosity may be 1,500cps to 5,000cps, 2,000cps to 4,000cps, or 2,000cps to 3,500 cps. The viscosity of the plasticizer is preferably 2,000cps to 4,000cps, and more preferably, the viscosity is 2,000cps to 3,500 cps. When the viscosity of the plasticizer satisfies the above range, a thermoplastic resin composition realizing excellent migration resistance, processability and transparency can be prepared.

The refractive index of the plasticizer may be 1.45 or more, 1.45 to 1.6, or 1.45 to 1.52, preferably in the range of 1.45 to 1.52. When the refractive index of the plasticizer satisfies the above conditions, the transparency of the thermoplastic resin composition can be improved. In addition, the artificial nail manufactured using such a thermoplastic resin composition may not only have excellent transparency but also realize various colors.

The plasticizer is preferably a polymer plasticizer other than a phthalate-based plasticizer causing environmental problems, and more preferably a polyester-based plasticizer. The plasticizer is preferably selected from poly (di (2-ethylhexyl) glycol adipate); polymers of adipic acid with 1, 3-butanediol, 2-ethylhexyl ester; polymers of adipic acid with 1, 3-butanediol and 1, 2-propanediol, 2-ethylhexyl ester; and one or more of adipic acid, 2-dimethyl-1, 3-propanediol, 1, 2-propanediol, isononyl ester.

As the plasticizer, among commercially available products, songcize selected from those manufactured by Songwon Industrial co^TMP-2600, SONGCIZER manufactured by Songwon Industrial Co., Ltd^TMP-3000, and manufactured by BASF corporation652.

The content of the plasticizer may be 4 to 10 parts by weight, 5 to 10 parts by weight, or 5 to 9 parts by weight, preferably in the range of 5 to 9 parts by weight, with respect to 100 parts by weight of the base resin. When the above range is satisfied, the transparency and processability of the thermoplastic resin composition may be improved, and the migration phenomenon of the plasticizer may be prevented.

2. Thermoplastic resin molded article

A thermoplastic resin molded article according to another embodiment of the present invention is made of the thermoplastic resin composition according to the embodiment of the present invention, and has a haze of 2.0% or less and a flexural strength of 280kg/cm²To 420kg/cm²Flexural modulus of 11,000kg/cm²To 13,500kg/cm². Preferably, the thermoplastic resin molded article has a haze of 1.8% or less and a flexural strength of 300kg/cm²To 400kg/cm²Flexural modulus of 11,500kg/cm²To 13,000kg/cm². When the above conditions are satisfied, excellent transparency and softness can be achieved, and thus, the thermoplastic resin molded article is suitable for use in artificial nails. When the haze exceeds the above range, the transparency is lowered. Further, when the bending strength and the bending modulus are lower than the above ranges, the thermoplastic resin molded article is easily deformed when used for manufacturing an artificial nail. When the bending strength and the bending modulus exceed the above ranges, the restoring force to restore the original shape increases, and thus, the artificial nail may easily fall off from the nail of the user, or the wearing comfort may be reduced.

Meanwhile, haze may be measured according to ASTM D1003, and flexural strength and flexural modulus may be measured according to ASTM D790.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily perform the present invention. However, it should be understood that the present invention may be embodied in various forms, and the exemplary embodiments are not intended to limit the present invention thereto.

Preparation of example 1

50 parts by weight (based on the solid content) of a butadiene rubber polymer latex (average particle diameter: 120nm, gel content: 90%), 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, 0.8 part by weight of acrylonitrile, 0.1 part by weight of divinylbenzene as a crosslinking agent, 0.2 part by weight of cumene hydroperoxide as an initiator, and 0.5 part by weight of sodium dodecylbenzenesulfonate as an emulsifier were added in portions to a nitrogen-substituted reactor and mixed for 5 hours. Subsequently, polymerization was carried out while continuously feeding 26.2 parts by weight of methyl methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 part by weight of t-dodecyl mercaptan as a molecular weight control agent, 0.05 part by weight of disodium ethylenediaminetetraacetate, 0.1 part by weight of sodium formaldehyde sulfoxylate, 0.001 part by weight of ferrous sulfate as an activator, and 0.1 part by weight of cumene hydroperoxide as an initiator to a reactor at 70 ℃ and a constant rate over 5 hours. After the termination of the continuous addition, the temperature was raised to 80 ℃ to conduct aging for one hour, and then the polymerization was terminated to obtain a graft copolymer latex. The graft copolymer latex was coagulated by adding 2 parts by weight of magnesium sulfate as a coagulant, and aged, dehydrated and dried to obtain a graft copolymer powder. In this case, the refractive index of the graft copolymer powder was 1.516, and the degree of grafting was 55%.

Preparation of example 2

50 parts by weight (based on solid content) of a butadiene rubber polymer latex (average particle diameter: 300nm, gel content: 70%), 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, 0.8 part by weight of acrylonitrile, 0.1 part by weight of divinylbenzene as a crosslinking agent, 0.2 part by weight of cumene hydroperoxide as an initiator, and 0.5 part by weight of sodium dodecylbenzenesulfonate as an emulsifier were charged into a nitrogen-substituted reactor and mixed for 3 hours. Subsequently, polymerization was carried out while continuously feeding 26.2 parts by weight of methyl methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 part by weight of t-dodecyl mercaptan as a molecular weight control agent, 0.05 part by weight of disodium ethylenediaminetetraacetate, 0.1 part by weight of sodium formaldehyde sulfoxylate, 0.001 part by weight of ferrous sulfate as an activator, and 0.1 part by weight of cumene hydroperoxide as an initiator to a reactor at 70 ℃ and a constant rate over 5 hours. After the termination of the continuous addition, the temperature was raised to 80 ℃ to conduct aging for one hour, and then the polymerization was terminated to obtain a graft copolymer latex. The graft copolymer latex was coagulated by adding 2 parts by weight of magnesium sulfate as a coagulant, and aged, dehydrated and dried to obtain a graft copolymer powder. In this case, the refractive index of the graft copolymer powder was 1.516, and the degree of grafting was 45%.

Preparation of example 3

Polymerization was carried out while continuously feeding 70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene and 0.15 part by weight of t-dodecyl mercaptan as a molecular weight controlling agent to a nitrogen-purged reactor at 148 ℃ and a constant rate over 3 hours, thereby obtaining a copolymer. The copolymer was heated in a pre-heated bath and unreacted monomer and solvent were removed in a volatilization pot. Subsequently, the copolymer from which the unreacted monomer and the like have been removed was fed into a polymer transfer pump extruder and extruded at 210 ℃ to obtain a pellet-type copolymer. The weight average molecular weight of the resulting copolymer was 90,000g/mol, and the refractive index was 1.516.

Examples and comparative examples

The specifications of the components used in the examples and comparative examples are as follows.

(A) Graft copolymers

(A-1): the graft copolymer prepared in preparation example 1 was used.

(A-2): the graft copolymer prepared in preparation example 2 was used.

(A-3): using a methylmethacrylate/acrylonitrile/butadiene/styrene graft copolymer: TR557-NP (refractive index: 1.516, average particle diameter of butadiene rubber polymer: 300nm) commercially available from LGchem Ltd.

(B) Non-grafted copolymer: the copolymer prepared in preparation example 3 was used.

(C) Plasticizer

(C-1): SONGCIZER commercially available from Songwon Industrial Co., Ltd is used^TMP-2600 (viscosity: 2,700cps to 3,500cps, refractive index: 1.462 to 1.468, poly (di (2-ethylhexyl) glycol adipate)).

(C-2): SONGCIZER commercially available from Songwon Industrial Co., Ltd is used^TMP-3000 (viscosity: 2,000cps to 3,200cps, refractive index: 1.462 to 1.468, poly (di (2-ethylhexyl) glycol adipate)).

(C-3): using a commercially available from BASF652 (viscosity: 2,000cps, refractive index: 1.465, adipic acid-adipicPolymers of acids with 2, 2-dimethyl-1, 3-propanediol and 1, 2-propanediol, isononyl ester).

(D) Styrene/butadiene copolymer: KR-03 (refractive index: 1.571) commercially available from Chevron was used.

The above components were mixed at the contents shown in tables 1 to 5 and stirred to prepare thermoplastic resin compositions.

Experimental example 1

Each of the thermoplastic resin compositions of examples and comparative examples was fed into a twin-screw extruder set to 230 ℃, and then extruded to prepare pellets. The melt flow index of the pellets was measured by the method described below, and the results thereof are shown in tables 1 to 5.

(1) Melt flow index (g/10 min): measured at 220 ℃ and 10kg according to ASTM D1238.

Experimental example 2

The pellets prepared in experimental example 1 were injection molded at 230 ℃ to prepare samples. The physical properties of the test pieces were measured by the methods described below, and the results thereof are shown in tables 1 to 5.

(2) Haze (%): measured according to ASTM D1003.

(3) Flexural Strength (kg/cm)²): measured according to ASTM D790.

(4) Flexural modulus (kg/cm)²): measured according to ASTM D790.

(5) Hardness: measured according to ASTM D785 (R-rating).

(6) Mobility: the evaluation was performed by: the sample was placed on a paper liner in an oven at 70 ℃, a weight of 10kg was applied to the sample, it was stored for one week, and then the change of the paper liner was observed. When migrating, the plasticizer wets the oiled paper, discoloring the oiled paper, and thus, discoloration indicates that the oiled paper is contaminated with the plasticizer due to migration of the plasticizer. Therefore, no discoloration is denoted by "OK" and discoloration is denoted by "NG".

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

Referring to table 1, examples 1 to 3, which include appropriate amounts of graft copolymer and non-graft copolymer, are excellent in melt flow index, haze, flexural strength, flexural modulus, hardness, and migration, and thus, are suitable for use in artificial nails. On the other hand, comparative examples 1 and 2, which contain a small amount of the graft copolymer, exhibited higher flexural strength, higher flexural modulus and higher hardness as compared to examples 1 to 3, and thus, were not suitable for use in artificial nails. In addition, comparative example 3, which includes an excessive amount of the graft copolymer, exhibits a lower melt flow index and higher haze, causing a reduction in processability, as compared to examples 1 to 3, and thus, is not suitable for artificial nails. Comparative example 4, which contained a diene-based rubber polymer having a large average particle diameter, exhibited high haze and low flexural modulus, and thus, was not suitable for use in artificial nails. Referring to table 2, it can be seen that as the plasticizer content increases within the appropriate plasticizer content range, haze is maintained and melt flow index increases. Specifically, it can be seen that examples 5 to 7 exhibited melt flow indexes of 10g/10min or more, compared to example 4, so that processability was excellent.

Referring to table 3, examples 8 to 10, which include the optimized amounts of the graft copolymer and the non-graft copolymer, are excellent in all of melt flow index, haze, flexural strength, flexural modulus, hardness, and migration, and thus, are suitable for use in artificial nails. On the other hand, comparative example 5, which contains a small amount of the graft copolymer, exhibits relatively high flexural strength, high flexural modulus and high hardness, and thus, is not suitable for use in artificial nails. Comparative example 6, which contained an excessive amount of the graft copolymer, exhibited a relatively low melt flow index, causing a reduction in processability, and also exhibited a relatively high haze and a low flexural modulus, and thus, was not suitable for use in artificial nails.

Referring to table 4, examples 11 to 13 satisfying an appropriate plasticizer content range are excellent in haze, flexural strength, flexural modulus, hardness, and migration, and thus are suitable for use in artificial nails. Specifically, it can be seen that example 12 and example 13 exhibited melt flow indexes of 10g/10min or more, compared to example 11, so that processability was excellent.

Referring to table 5, comparative example 7 consisting of only the graft copolymer exhibited relatively high flexural strength, high flexural modulus and high hardness, and thus, was not suitable for the artificial nail, while comparative example 8 consisting of the graft copolymer and the styrene/butadiene copolymer was opaque, and exhibited relatively high flexural strength and high flexural modulus, and thus, was not suitable for the artificial nail.