Title of Invention: Thermoplastic resin composition
technical field
[One]
[Citation with related applications]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2019-0070232, filed on June 13, 2019 and Korean Patent Application No. 10-2020-0066697, filed on June 2, 2020, , all contents disclosed in the literature of the corresponding Korean patent application are incorporated as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition, and to a thermoplastic resin composition having excellent transparency, processability and soft properties.
[5]
background
[6]
Artificial nails are mainly manufactured by injection molding. The ABS thermoplastic resin composition containing the acrylonitrile/butadiene/styrene graft copolymer is widely used for artificial nails because the separation operation is easy and burrs do not occur when the molded article is separated from the injection machine. . On the other hand, a general ABS thermoplastic resin composition has a hard property. When hard artificial nails are attached to natural nails using an adhesive, the curvature of the nails of consumers is different, so there is a high possibility that the artificial nails will come off when used. In addition, the wearability is deteriorated due to the force of continuing to restore the original state while attached to the consumer's nails. In order to compensate for these disadvantages, a method of manufacturing artificial nails with ethylene vinyl acetate or styrene/butadiene copolymer has been proposed. However, there is a disadvantage that the tip of the artificial nail is easily bent due to an external impact when worn because the artificial nail is soft. In order to overcome these disadvantages, a method of mixing the acrylonitrile/butadiene/styrene graft copolymer with ethylene vinyl acetate or styrene/butadiene copolymer has also been proposed. Recently, a lot of transparent artificial nails are used to create a variety of designs to suit individual personalities and tastes. A transparent graft copolymer, methyl methacrylate/butadiene/styrene copolymer, and ethylene vinyl acetate or styrene/butadiene copolymer There is a limit in that transparency cannot be maintained due to the difference in refractive index between the two materials. On the other hand, when compounding the methyl methacrylate/butadiene/styrene copolymer, there is an advantage in that the softness property increases as the rubber content increases, but the haze increases and the transparency deteriorates, the color decreases, and the processability decreases do.
[7]
Therefore, research to develop a thermoplastic resin composition for artificial nails excellent in transparency, processability and soft properties is continuing.
[8]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[9]
An object of the present invention is to provide a thermoplastic resin composition excellent in transparency, processability and soft properties.
[10]
means of solving the problem
[11]
In order to solve the above problems, the present invention is a product obtained by graft polymerization of a first monomer mixture comprising an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer to a diene-based rubber polymer having an average particle diameter of 50 to 200 nm. 1 copolymer and a second copolymer, which is a copolymer of a second monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer, in a weight ratio of 70:30 to 90:10; And it provides a thermoplastic resin composition comprising a plasticizer.
[12]
In addition, the present invention provides a thermoplastic resin molded article made of the above-described thermoplastic resin composition, having a transparency of 2.0% or less, a flexural strength of 280 to 420 kg/cm 2 , and a flexural modulus of 11,000 to 13,500 kg/cm 2 .
[13]
Effects of the Invention
[14]
The thermoplastic resin composition of the present invention has excellent transparency, processability and soft properties. For this reason, it is possible to manufacture artificial nails that are transparent, can implement various colors, and have excellent feel with the thermoplastic resin composition of the present invention.
[15]
Modes for carrying out the invention
[16]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[17]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[18]
[19]
In the present invention, the average particle diameter of the diene-based rubber polymer can be measured using a dynamic light scattering method, and in detail, it can be measured using a Nicomp 380 equipment (product name, manufacturer: PSS).
[20]
In the present specification, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, that is, an average particle diameter of scattering intensity.
[21]
[22]
In the present invention, the viscosity can be measured using a Brookfield (Brookfield) under the following conditions.
[23]
Spindle type - Cone type (CPA-52Z), cone angle = 3°, cone radius = 1.2 cm, gap: 13 μm or less, measurement shear rate: 10 to 20/sec, measurement Temperature: 25 ℃
[24]
In the present invention, the refractive index refers to the absolute refractive index of a material, and the refractive index can be recognized as the ratio of the speed of electromagnetic radiation in free space to the speed of radiation in a material, where the radiation is visible light with a wavelength of 450 nm to 680 nm. It may be a line, and specifically, it may be visible light having a wavelength of 589.3 nm. The refractive index can be measured using a known method, that is, an Abbe Refractometer.
[25]
[26]
In the present invention, the graft rate is determined by dissolving 1 g of the first copolymer powder in 50 g of acetone with stirring for 24 hours, then putting it in a centrifugal separator (trade name: SUPRA 30 K, manufacturer: Hanil Science Industrial), 16,000 rpm, -10 ℃ conditions The supernatant and the precipitate are separated by centrifugation for 4 hours under
[27]
[Equation 1]
[28]
Graft ratio (%) = {(weight 1) of copolymer of grafted monomer mixture ) / (weight of diene-based rubbery polymer 2) )}×100
[29]
[30]
1) Weight of copolymer of grafted monomer mixture = (weight of dry matter) - (weight of diene-based rubbery polymer)
[31]
2) Weight of diene-based rubbery polymer = theoretically added weight of diene-based rubbery polymer (based on solid content) or weight of diene-based rubbery polymer measured by analyzing the first copolymer by infrared spectroscopy
[32]
[33]
In the present invention, the weight average molecular weight of the shell of the first copolymer is determined by dissolving the dried supernatant of the supernatant described in the graft rate measurement method in a tetrahydrofuran (THF) solution, filtering it through a 1 μm filter, and then performing gel permeation chromatography. It can be measured relative to a standard PS (standard polystyrene) sample.
[34]
[35]
In the present invention, the weight average molecular weight of the second copolymer is measured as a relative value with respect to a standard PS (standard polystyrene) sample using tetrahydrofuran (THF) as a solution and using gel permeation chromatography (GPC, waters breeze). can do.
[36]
[37]
In the present invention, transparency may be measured according to ASTM D1003.
[38]
[39]
In the present invention, flexural strength and flexural modulus can be measured according to ASTM D790.
[40]
[41]
In the present invention, the alkyl (meth)acrylate-based monomer may be a C 1 to C 10 alkyl (meth)acrylate-based monomer. The C 1 to C 10 alkyl (meth) acrylate-based monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) may be at least one selected from the group consisting of acrylate, decyl (meth) acrylate and lauryl (meth) acrylate, of which methyl methacrylate is preferable.
[42]
[43]
In the present invention, the aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene and p-methyl styrene, among which styrene is preferable.
[44]
[45]
In the present invention, the vinyl cyanide-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is preferable.
[46]
[47]
1. Thermoplastic resin composition
[48]
The thermoplastic resin composition according to an embodiment of the present invention is 1) grafted with a first monomer mixture comprising an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer to a diene-based rubber polymer having an average particle diameter of 50 to 200 nm. A base resin comprising a polymerized first copolymer and a second copolymer, which is a copolymer of a second monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer, in a weight ratio of 70:30 to 90:10 100 parts by weight; and 2) a plasticizer.
[49]
[50]
Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[51]
[52]
1) Base resin
[53]
The base resin includes (1) a first copolymer and (2) a second copolymer.
[54]
[55]
Hereinafter, the components of the base resin will be described in detail.
[56]
[57]
(1) first copolymer
[58]
The first copolymer is a graft copolymer obtained by graft copolymerizing a first monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer to a diene-based rubbery polymer having an average particle diameter of 50 to 200 nm.
[59]
[60]
The diene-based rubbery polymer may have an average particle diameter of 50 to 200 nm, preferably 70 to 180 nm. When the above-described range is satisfied, excellent transparency may be realized even if the first copolymer is included in an excessive amount in the thermoplastic resin composition. If it is less than the above range, the impact resistance of the thermoplastic resin composition may be significantly reduced, and if it exceeds the above range, the transparency of the thermoplastic resin composition may be reduced.
[61]
[62]
The diene-based rubbery polymer may be a synthetic rubber prepared by cross-linking a conjugated diene-based monomer. The conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, piperylene, dicyclopentadiene, ethylidene norbornene and vinyl norbornene, of which 1,3-butadiene This is preferable.
[63]
[64]
The alkyl (meth)acrylate-based monomer may impart excellent transparency to the first copolymer. The alkyl (meth) acrylate-based monomer may be included in 64 to 75 wt% or 68 to 72 wt%, based on the total weight of the first monomer mixture, and preferably included in 68 to 72 wt% . When the above-described range is satisfied, transparency of the first copolymer may be further improved.
[65]
The aromatic vinyl-based monomer may impart excellent processability to the first copolymer. The aromatic vinyl-based monomer may be included in the remaining amount such that the total weight of the first monomer mixture is 100% by weight.
[66]
The first monomer mixture may further include a vinyl cyanide-based monomer to improve polymerization stability and to improve chemical resistance of the first copolymer. The vinyl cyanide-based monomer may be included in an amount of 7 wt% or less based on the total weight of the first monomer mixture. When the above-described range is satisfied, the chemical resistance of the first copolymer may be improved while minimizing yellow expression due to the vinyl cyanide-based monomer.
[67]
[68]
The weight ratio of the diene-based rubbery polymer to the first monomer mixture may be 40:60 to 60:40 or 45:55 to 55:45, of which 45:55 to 55:45 is preferable. When the above-described range is satisfied, transparency and color of the first copolymer may be improved.
[69]
[70]
The first copolymer may have a graft rate of 45 to 65% or 50 to 60%, of which 50 to 60% is preferable. When the above-described range is satisfied, transparency of the thermoplastic resin composition may be further improved, and compatibility with the second copolymer may also be improved.
[71]
[72]
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 the copolymer of the first monomer mixture. That is, in order for the first copolymer to implement excellent transparency, the difference between the refractive index of the diene-based rubber polymer and the refractive index of the shell may be 0.01 or less, and it is preferable that there is no difference in the refractive index.
[73]
In addition, in order to realize excellent transparency of the thermoplastic resin composition, the difference in refractive index between the first copolymer and the second copolymer may be 0.01 or less, and it is preferable that there is no difference in refractive index.
[74]
[75]
The first copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.51 to 1.52 is preferable. When the above-mentioned range is satisfied, the transparency of the thermoplastic resin composition can be further improved by a synergistic action with the second copolymer to be described later.
[76]
[77]
(2) second copolymer
[78]
The second copolymer is a non-graft copolymer, and is a copolymer of a second monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer.
[79]
The second copolymer may impart excellent transparency and processability to the thermoplastic resin composition.
[80]
[81]
The alkyl (meth) acrylate-based monomer may be included in an amount of 64 to 75% by weight or 68 to 72% by weight based on the total weight of the second monomer mixture, and preferably included in an amount of 68 to 87% by weight. . When the above-described range is satisfied, transparency of the second copolymer may be further improved, and compatibility with the first copolymer may be further improved.
[82]
The aromatic vinyl-based monomer may impart excellent processability to the second copolymer. The aromatic vinyl-based monomer may be included in a remaining amount such that the total weight of the second monomer mixture is 100% by weight.
[83]
The second monomer mixture may further include a vinyl cyanide monomer to improve polymerization stability and improve chemical resistance of the second copolymer. The vinyl cyanide-based monomer may be included in an amount of 7 wt% or less based on the total weight of the second monomer mixture. When the above-described range is satisfied, the chemical resistance of the second copolymer may be improved while minimizing yellow expression due to the vinyl cyanide-based monomer.
[84]
[85]
The second copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.5 to 1.52 is preferable. When the above-mentioned range is satisfied, the transparency of the thermoplastic resin composition can be further improved.
[86]
[87]
The second copolymer can be prepared by suspension polymerization or bulk polymerization of a monomer mixture comprising an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer, and among them, a bulk polymerization capable of producing a copolymer with high purity. It is preferable to manufacture
[88]
[89]
The base resin may include the first copolymer and the second copolymer in a weight ratio of 70:30 to 90:10, preferably 75:25 to 85:15. When the above-described range is satisfied, the content of the diene-based rubbery polymer in the thermoplastic resin composition may increase, so that soft properties may be remarkably improved. Accordingly, the artificial nail made of the thermoplastic resin composition has a weak force to return to the original state while attached to the natural nail, so that the wearing comfort can be improved. However, when included below the above range, the flexural strength and flexural modulus are too high, so that the soft properties are not improved, and the artificial nail made of the thermoplastic resin composition may have reduced wearing comfort. When included in excess of the above-mentioned range, processability and transparency may be reduced.
[90]
[91]
2) plasticizer
[92]
The plasticizer is intended to improve processability and soft properties while maintaining transparency of the thermoplastic resin composition, and may have a viscosity of 1,500 to 5,000 cps, 2,000 to 4,000 cps, or 2,000 to 3,500 cps. The plasticizer may preferably have a viscosity of 2,000 to 4,000 cps, and more preferably 2,000 to 3,500 cps. When the viscosity of the plasticizer satisfies the above-mentioned range, it is possible to prepare a thermoplastic resin composition implementing excellent migration resistance, processability and transparency.
[93]
[94]
The plasticizer may have a refractive index of 1.45 or more, 1.45 to 1.6, or 1.45 to 1.52, of which 1.45 to 1.52 is preferable. When the refractive index of the plasticizer satisfies the above-described conditions, transparency of the thermoplastic resin composition may be further improved. In addition, artificial nails made of such a thermoplastic resin composition can implement various colors as well as excellent transparency.
[95]
[96]
The plasticizer is preferably a polymer plasticizer rather than a phthalate-based plasticizer that causes environmental problems, and more preferably a polyester plasticizer. The plasticizer is polydi (2-ethylhexyl) glycol adipate; hexanedioic acid, polymer with 1,3-butanediol, 2-ethylhexyl ester; hexanedioic acid, polymer with 1,3-butadiol and 1,2-propanediol, 2-ethylhexyl ester; and hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, and preferably at least one selected from the group consisting of isononyl ester.
[97]
[98]
The plasticizer may use at least one selected from the group consisting of SONGCIZER TM P-2600 by Songwon Industries, SONGCIZER TM P-3000 by Songwon Industries, and Palamoll ® 652 by BASF among commercially available materials.
[99]
[100]
The plasticizer may be included in an amount of 4 to 10 parts by weight, 5 to 10 parts by weight, or 5 to 9 parts by weight based on 100 parts by weight of the base resin, of which 5 to 9 parts by weight is preferable. When the above-described range is satisfied, transparency and processability of the thermoplastic resin composition can be further improved, and migration of the plasticizer can be prevented.
[101]
[102]
2. Thermoplastic resin molded products
[103]
A thermoplastic resin molded article according to another embodiment of the present invention is made of the thermoplastic resin composition according to an embodiment of the present invention, has a transparency of 2.0% or less, a flexural strength of 280 to 420 kg/cm2, and a flexural modulus of 11,000 to 13,500 kg/cm 2 . Preferably, the transparency is 1.8% or less, the flexural strength is 300 to 400 kg/cm 2 , and the flexural modulus is 11,500 to 13,000 kg/cm 2 . If the above-mentioned conditions are satisfied, excellent transparency and soft properties can be realized, so that it can be suitable for artificial nails. When transparency exceeds the above-mentioned range, transparency will fall. In addition, if the flexural strength and the flexural modulus are less than the above-mentioned ranges, there may be a problem in that the shape is easily deformed when manufactured as an artificial nail. When the flexural strength and the flexural modulus exceed the above-described ranges, the restoring force to return to the original shape is strong, and thus the user's nail may be easily removed or the fit may be deteriorated.
[104]
[105]
Meanwhile, transparency may be measured according to ASTM D1003, and flexural strength and flexural modulus may be measured according to ASTM D790.
[106]
[107]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
[108]
[109]
Preparation Example 1
[110]
In a nitrogen-substituted reactor, 50 parts by weight of butadiene rubbery polymer latex (average particle diameter: 120 nm, gel content: 90%) (based on solid content), 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, 0.8 parts by weight of acrylonitrile, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, and 0.5 parts by weight of sodium dodecylbenzene sulfonate as an emulsifier were added together and mixed for 5 hours. Then, in the reactor, 26.2 parts by weight of methyl methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, and 0.05 parts by weight of disodium salt of ethylenediaminetetraacetic acid as an activator , 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfate, and 0.1 parts by weight of cumene hydroperoxide as an initiator were continuously added at a constant rate at 70° C. for 5 hours while polymerization was carried out. After the continuous input was completed, the temperature was raised to 80° C., and the polymerization was terminated after aging for 1 hour to prepare a graft copolymer latex. 2 parts by weight of magnesium sulfate as a coagulant was added to the graft copolymer latex for coagulation, aging, dehydration, and drying to obtain a graft copolymer powder. At this time, the refractive index of the graft copolymer powder was 1.516, and the graft rate was 55%.
[111]
[112]
Preparation 2
[113]
In a reactor substituted with nitrogen, 50 parts by weight of butadiene rubber polymer latex (average particle diameter: 300 nm, gel content: 70%) (based on solid content), 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, 0.8 parts by weight of acrylonitrile, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, and 0.5 parts by weight of sodium dodecylbenzene sulfonate as an emulsifier were added and mixed for 3 hours. Then, in the reactor, 26.2 parts by weight of methyl methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, and 0.05 parts by weight of ethylenediaminetetraacetic acid disodium salt as an activator Part, 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfate, and 0.1 parts by weight of cumene hydroperoxide as an initiator were continuously introduced at 70° C. for 5 hours at a constant rate for polymerization. After the continuous input was completed, the temperature was raised to 80° C., and the polymerization was terminated after aging for 1 hour to prepare a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate as a coagulant was added to the graft copolymer latex for coagulation, aging, dehydration, and drying to obtain a graft copolymer powder. The refractive index of the graft copolymer powder was 1.516, and the graft ratio was 45%.
[114]
[115]
Preparation 3
[116]
In a nitrogen-substituted reactor, 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 parts by weight of t-dodecyl mertaptan as a molecular weight modifier were constant at 148° C. for 3 hours. Polymerization was carried out while continuously inputting at a rate to obtain a copolymer. The copolymer was heated in a preheating tank, and unreacted monomers and solvents were removed in the volatilization tank. Then, the copolymer from which the unreacted monomers were removed was put into a polymer transfer pump extrusion machine, and extruded at 210° C. to prepare a copolymer in the form of pellets. The copolymer had a weight average molecular weight of 90,000 g/mol and a refractive index of 1.516.
[117]
[118]
Examples and Comparative Examples
[119]
[120]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[121]
[122]
(A) graft copolymer
[123]
(A-1): The graft copolymer of Preparation Example 1 was used.
[124]
(A-2): The graft copolymer of Preparation Example 2 was used.
[125]
(A-3): Methyl methacrylate/acrylonitrile/butadiene/styrene graft copolymer: TR557-NP (refractive index: 1.516, average particle diameter of butadiene rubber polymer: 300 nm) manufactured by LG Chem.
[126]
[127]
(B) Non-graft copolymer: The copolymer of Preparation Example 3 was used.
[128]
[129]
(C) plasticizer
[130]
(C-1): SONGCIZER TM P-2600 (viscosity: 2,700 to 3,500 cps, refractive index: 1.462 to 1.468, polydi(2-ethylhexyl)glycol adipate) manufactured by Songwon Industries was used.
[131]
(C-2): SONGCIZER TM P-3000 from Songwon Industries (viscosity: 2,000 to 3,200 cps, refractive index: 1.462 to 1.468, polydi(2-ethylhexyl)glycol adipate) was used.
[132]
(C-3): Palamoll ® 652 from BASF (viscosity: 2,000 cps, refractive index: 1.465, hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, isononyl ester )
[133]
[134]
(D) Styrene/butadiene copolymer: KR-03 (refractive index: 1.571) manufactured by Chevron was used.
[135]
[136]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents shown in Tables 1 to 5 below.
[137]
[138]
Experimental Example 1
[139]
The thermoplastic resin compositions of Examples and Comparative Examples were put into a twin-screw extruder set at 230° C. and extruded to prepare pellets. The flow index of the pellets was measured as follows, and the results are shown in Tables 1 to 5 below.
[140]
[141]
① Melt Flow Index (g/10min): Measured at 220 °C under 10 kg in accordance with ASTM D1238.
[142]
[143]
Experimental Example 2
[144]
A specimen was prepared by injecting the pellets prepared in Experimental Example 1 at 230 °C. And the physical properties of the specimen were measured by the method described below, and the results are shown in Tables 1 to 5 below.
[145]
[146]
② Transparency (haze, %): Transparency was measured according to ASTM D1003.
[147]
③ Flexural Strength (kg/cm2): Measured according to ASTM D790.
[148]
④ Flexural Modulus (kg/cm2): It was measured according to ASTM D790.
[149]
⑤ Hardness: It was measured according to ASTM D785 (R-scale).
[150]
⑥ Migration: After placing the specimen on oiled paper in an oven at 70°C, placing a 10 kg weight, and storing it for 1 week, the migration was evaluated by examining the change in the oiled paper. When the plasticizer is transferred, the oiled paper is wetted and the color of the oiled paper is changed, so the change in color means that the transfer occurs and the plasticizer is attached to the oiled paper. Therefore, no change was marked as OK, and change was marked as NG.
[151]
[Table 1]
division Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Comparative Example 3 Comparative Example 4
(A) graft copolymer (parts by weight) (A-1) 50 65 70 85 90 95 0
(A-2) 0 0 0 0 0 0 70
(A-3) 0 0 0 0 0 0 0
(B) ungrafted copolymer (parts by weight) 50 35 30 15 10 5 30
(C) plasticizer (parts by weight) (C-1) 5 5 5 5 5 5 5
(C-2) 0 0 0 0 0 0 0
(C-3) 0 0 0 0 0 0 0
(D) styrene/butadiene copolymer (parts by weight) 0 0 0 0 0 0 0
① Current index 19.2 15.0 13.8 11.0 10.1 4.4 15.7
② Transparency 0.9 1.0 1.0 1.4 1.5 2.2 3.8
③ Flexural strength 570 480 377 320 304 300 360
④ Flexural modulus 16,500 16,000 12,300 12,000 11,800 11,150 10,400
⑤ hardness 95 90 83 80 76 68 77
⑥ Transitionability OK OK OK OK OK OK OK
[152]
[Table 2]
division Example 4 Example 5 Example 6 Example 7
(A) graft copolymer (parts by weight) (A-1) 85 85 85 85
(A-2) 0 0 0 0
(A-3) 0 0 0 0
(B) ungrafted copolymer (parts by weight) 15 15 15 15
(C) plasticizer (parts by weight) (C-1) 4 6 9 10
(C-2) 0 0 0 0
(C-3) 0 0 0 0
(D) styrene/butadiene copolymer (parts by weight) 0 0 0 0
① Current index 7.7 11.9 14.5 15.0
② Transparency 1.4 1.3 2.0 2.0
③ Flexural strength 310 316 310 311
④ Flexural modulus 12,500 12,000 11,900 11,900
⑤ hardness 76 79 77 77
⑥ Transitionability OK OK OK OK
[153]
[Table 3]
division Comparative Example 5 Example 8 Example 9 Example 10 Comparative Example 6
(A) graft copolymer (parts by weight) (A-1) 65 70 75 90 95
(A-2) 0 0 0 0 0
(A-3) 0 0 0 0 0
(B) ungrafted copolymer (parts by weight) 35 30 25 10 5
(C) plasticizer (parts by weight) (C-1) 0 0 0 0 0
(C-2) 6 5 9 7 9
(C-3) 0 0 0 0 0
(D) styrene/butadiene copolymer (parts by weight) 0 0 0 0 0
① Current index 15.3 13.0 16.0 10.3 8.0
② Transparency 1.1 1.2 1.8 1.5 2.5
③ Flexural strength 460 370 342 305 290
④ Flexural modulus 16,000 12,400 12,100 11,800 11,200
⑤ hardness 90 81 80 76 68
⑥ Transitionability OK OK OK OK OK
[154]
[Table 4]
division Example 11 Example 12 Example 13
(A) graft copolymer (parts by weight) (A-1) 70 70 80
(A-2) 0 0 0
(A-3) 0 0 0
(B) ungrafted copolymer (parts by weight) 30 30 20
(C) plasticizer (parts by weight) (C-1) 0 0 0
(C-2) 0 0 0
(C-3) 4 5 9
(D) styrene/butadiene copolymer (parts by weight) 0 0 0
① Current index 8.5 12.6 15.2
② Transparency 1.0 1.1 1.9
③ Flexural strength 370 366 330
④ Flexural modulus 12,400 12,300 12,100
⑤ hardness 84 84 79
⑥ Transitionability OK OK OK
[155]
[Table 5]
division Comparative Example 7 Comparative Example 8
(A) graft copolymer (parts by weight) (A-1) 0 0
(A-2) 0 0
(A-3) 100 60
(B) ungrafted copolymer (parts by weight) 0 0
(C) plasticizer (parts by weight) (C-1) 0 0
(C-2) 0 0
(C-3) 0 0
(D) styrene/butadiene copolymer (parts by weight) 0 40
① Current index 23.0 53.3
② Transparency 2.0 opacity
③ Flexural strength 720 515
④ Flexural modulus 23,000 17,793
⑤ hardness 104 36
⑥ Transitionability OK OK
[156]
Referring to Table 1, Examples 1 to 3 containing the graft copolymer and the non-graft copolymer in an appropriate amount were excellent in flow index, transparency, flexural strength, flexural modulus, hardness, and transferability to artificial nails. suitable for use. However, Comparative Examples 1 and 2 containing a small amount of the graft copolymer were not suitable for artificial nails because of their high flexural strength, flexural modulus and hardness compared to Examples 1 to 3. In addition, Comparative Example 3 containing an excess of the graft copolymer had a low flow index compared to Examples 1 to 3, which lowered workability, and had high transparency, making it unsuitable for artificial nails. Comparative Example 4, in which the average particle diameter of the diene-based rubber polymer was large, had high transparency and low flexural modulus, so it was not suitable for artificial nails. It was confirmed that the liquidity index increased while maintaining it. In particular, in the case of Examples 5 to 7, compared to Example 4, it was confirmed that the flow index was 10 g/10 min or more, indicating excellent workability.
[157]
Referring to Table 3, Examples 8 to 10, including the graft copolymer and the non-graft copolymer in an optimal content, were excellent in flow index, transparency, flexural strength, flexural modulus, hardness, and transferability. Suitable for nails. However, Comparative Example 5 containing a small amount of the graft copolymer was not suitable for artificial nails due to high flexural strength, flexural modulus and hardness. Comparative Example 6 containing an excess of the graft copolymer had a low flow index, so processability was deteriorated, transparency was high, and flexural modulus was low, making it unsuitable for artificial nails.
[158]
Referring to Table 4, within the appropriate range of the plasticizer content, Examples 11 to 13 were suitable for artificial nails because they were excellent in transparency, flexural strength, flexural modulus, hardness, and transferability. In particular, in the case of Examples 12 and 13, it was confirmed that the flow index was 10 g/10 min or more compared to Example 11, indicating excellent workability.
[159]
Referring to Table 5, Comparative Example 7 made of the graft copolymer was not suitable for artificial nails due to high flexural strength, flexural modulus and hardness, and Comparative Example 8 made of the graft copolymer and styrene/butadiene copolymer was opaque and high flexural strength and flexural modulus, making it unsuitable for artificial nails.
Claims
[Claim 1]
A first copolymer obtained by graft polymerization of a first monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer to a diene rubber polymer having an average particle diameter of 50 to 200 nm, and an alkyl (meth) acrylate a base resin comprising a second copolymer that is a copolymer of a second monomer mixture including a system monomer and an aromatic vinyl monomer in a weight ratio of 70:30 to 90:10; And a thermoplastic resin composition comprising a plasticizer.
[Claim 2]
The method according to claim 1, 100 parts by weight of the base resin; and 4 to 10 parts by weight of the plasticizer.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the plasticizer is a polyester plasticizer.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the plasticizer has a viscosity of 1,500 to 5,000 cps.
[Claim 5]
The method according to claim 1, wherein the plasticizer is polydi (2-ethylhexyl) glycol adipate; hexanedioic acid, polymer with 1,3-butanediol, 2-ethylhexyl ester; hexanedioic acid, polymer with 1,3-butadiol and 1,2-propanediol, 2-ethylhexyl ester; And hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, the thermoplastic resin composition of at least one selected from the group consisting of isononyl ester.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the plasticizer has a refractive index of 1.45 to 1.6.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the difference in refractive index between the first copolymer and the second copolymer is 0.01 or less.
[Claim 8]
The thermoplastic resin composition of claim 1, wherein each of the first and second monomer mixtures further comprises a vinyl cyanide-based monomer.
[Claim 9]
A thermoplastic resin molded article prepared from the thermoplastic resin composition according to claim 1, having a transparency of 2.0% or less, a flexural strength of 280 to 420 kg/cm 2 , and a flexural modulus of 11,000 to 13,500 kg/cm 2 .