WO2020251215A1 - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition Download PDF

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Publication number
WO2020251215A1
WO2020251215A1 PCT/KR2020/007286 KR2020007286W WO2020251215A1 WO 2020251215 A1 WO2020251215 A1 WO 2020251215A1 KR 2020007286 W KR2020007286 W KR 2020007286W WO 2020251215 A1 WO2020251215 A1 WO 2020251215A1
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Prior art keywords
copolymer
weight
thermoplastic resin
resin composition
monomer
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PCT/KR2020/007286
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French (fr)
Korean (ko)
Inventor
이루다
최정수
이원석
박상후
이종주
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020200066697A external-priority patent/KR102474481B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/275,142 priority Critical patent/US11898029B2/en
Priority to CN202080005036.2A priority patent/CN112689658B/en
Priority to JP2021542507A priority patent/JP7325852B2/en
Priority to EP20821769.5A priority patent/EP3831881B1/en
Publication of WO2020251215A1 publication Critical patent/WO2020251215A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition excellent in transparency, processability and soft properties.
  • ABS thermoplastic resin composition containing acrylonitrile/butadiene/styrene graft copolymer is widely used for artificial nails because it facilitates the separation operation and does not generate burrs when separating the molded body from the injection machine.
  • a general ABS thermoplastic resin composition has hard properties. When hard artificial nails are attached to natural nails using an adhesive, the curvature of the customer's nails is different, so there is a high possibility that the artificial nails fall off when used. In addition, the fit is deteriorated due to the power to continuously restore the original condition while attached to the consumer's nails.
  • a method of manufacturing artificial nails with ethylene vinyl acetate or styrene/butadiene copolymer has been proposed.
  • the artificial fingernail is soft and there is a disadvantage that the end of the artificial fingernail is easily bent due to external impact when worn.
  • a method of blending an acrylonitrile/butadiene/styrene graft copolymer and an ethylene vinyl acetate or styrene/butadiene copolymer has also been proposed.
  • thermoplastic resin composition for artificial nails having excellent transparency, processability, and soft properties is ongoing.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in transparency, processability and soft properties.
  • the present invention is a first monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer in a diene rubber polymer having an average particle diameter of 50 to 200 nm.
  • a base resin comprising a second copolymer, which is a copolymer of a second monomer mixture including one copolymer and 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.
  • 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/cm2, and a flexural modulus of 11,000 to 13,500 kg/cm2.
  • thermoplastic resin composition of the present invention is excellent in all of transparency, processability and soft properties. For this reason, it is possible to manufacture an artificial nail that is transparent with the thermoplastic resin composition of the present invention, can implement various colors, and has excellent feeling of use.
  • 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).
  • 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 a scattering intensity.
  • the viscosity can be measured using Brookfield under the following conditions.
  • the refractive index refers to the absolute refractive index of a material, and the refractive index can be recognized as a ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material.
  • the radiation is visible light having a wavelength of 450 nm to 680 nm. It may be a line, and specifically, it may be visible light of a wavelength of 589.3 nm.
  • the refractive index can be measured using a known method, that is, an Abbe Refractometer.
  • the graft rate is 1 g of the first copolymer powder dissolved in 50 g of acetone while stirring for 24 hours, and then added to a centrifuge (brand name: SUPRA 30 K, manufacturer: Hanil Science Industrial) and 16,000 rpm, -10 °C conditions The supernatant and the precipitate were separated by centrifugation for 4 hours under, and the precipitate was dried for 12 hours with a hot air dryer at 50° C., and the weight of the obtained dried product was measured, and can be calculated based on the following equation:
  • Graft rate (%) ⁇ (weight of the copolymer of the grafted monomer mixture 1) ) / (weight of the diene rubber polymer 2) ) ⁇ ⁇ 100
  • Weight of the copolymer of the grafted monomer mixture (weight of the dried product)-(weight of the diene-based rubber polymer)
  • Weight of diene-based rubbery polymer Weight of diene-based rubbery polymer (based on solid content) or the weight of diene-based rubbery polymer measured by analyzing the first copolymer by infrared spectroscopy in theory
  • the weight average molecular weight of the shell of the first copolymer is determined by dissolving the dried supernatant described in the graft rate measurement method in a tetrahydrofuran (THF) solution, filtering through a 1 ⁇ m filter, and then gel permeation chromatography. It can be measured relative to a standard PS (standard polystyrene) sample.
  • THF tetrahydrofuran
  • the weight average molecular weight of the second copolymer is measured as a relative value to a standard PS (standard polystyrene) sample using tetrahydrofuran (THF) as a solution and gel permeation chromatography (GPC, water breeze). can do.
  • PS standard polystyrene
  • THF tetrahydrofuran
  • GPC gel permeation chromatography
  • transparency can be measured based on ASTM D1003.
  • the flexural strength and flexural modulus can be measured according to ASTM D790.
  • the alkyl (meth) acrylate monomer may be a C 1 to C 10 alkyl (meth) acrylate monomer.
  • the C 1 to C 10 alkyl (meth) acrylate monomers are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) It may be one or more selected from the group consisting of acrylate, decyl (meth) acrylate and lauryl (meth) acrylate, of which methyl methacrylate is preferred.
  • the aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, among which styrene is preferable.
  • the vinyl cyanide monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and ⁇ -chloroacrylonitrile, of which acrylonitrile is preferred.
  • thermoplastic resin composition 1) grafts a first monomer mixture including 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
  • Base resin comprising a second copolymer, which is a copolymer of a polymerized first copolymer and a second monomer mixture including an alkyl (meth)acrylate monomer and an aromatic vinyl monomer, in a weight ratio of 70:30 to 90:10 100 parts by weight;
  • a plasticizer grafts a first monomer mixture including an alkyl (meth)acrylate monomer and an aromatic vinyl monomer
  • thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
  • the base resin includes (1) a first copolymer and (2) a second copolymer.
  • the first copolymer is a graft copolymer obtained by graft copolymerization of a first monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer with a diene-based rubbery polymer having an average particle diameter of 50 to 200 nm.
  • the diene-based rubbery polymer may have an average particle diameter of 50 to 200 nm, and preferably 70 to 180 nm. If the above-described range is satisfied, even if the first copolymer is contained in an excessive amount in the thermoplastic resin composition, excellent transparency may be implemented. If it is less than the above-described range, the impact resistance of the thermoplastic resin composition may be significantly lowered, and if it exceeds the above-described range, the transparency of the thermoplastic resin composition may be lowered.
  • the diene-based rubber polymer may be a synthetic rubber prepared by crosslinking 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 desirable.
  • the alkyl (meth)acrylate-based monomer may impart excellent transparency to the first copolymer.
  • 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 first monomer mixture, of which 68 to 72% by weight is preferred. . If the above-described range is satisfied, the transparency of the first copolymer may be further improved.
  • the aromatic vinyl-based monomer may impart excellent processability to the first copolymer.
  • the aromatic vinyl-based monomer may be included in a residual amount 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 vinyl cyanide-based monomer may be included in an amount of 7% by weight or less based on the total weight of the first monomer mixture. If 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.
  • the weight ratio of the diene-based rubber polymer and the first monomer mixture may be 40:60 to 60:40 or 45:55 to 55:45, of which it is preferably 45:55 to 55:45. If the above-described range is satisfied, transparency and color of the first copolymer may be improved.
  • the first copolymer may have a graft rate of 45 to 65% or 50 to 60%, of which 50 to 60% is preferable. If the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved, and compatibility with the second copolymer may be improved.
  • the transparency of the first copolymer may be determined by a 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 exhibit excellent transparency, the difference between the refractive index of the diene 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 refractive index.
  • the first copolymer and the second copolymer may have a difference in refractive index of 0.01 or less, and it is preferable that there is no difference in refractive index.
  • 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. If the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved by synergistic action with the second copolymer to be described later.
  • the second copolymer is a non-grafted copolymer and is a copolymer of a second monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer.
  • the second copolymer may impart excellent transparency and processability to the thermoplastic resin composition.
  • 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, of which 68 to 87% by weight is preferred. . If the above-described range is satisfied, the transparency of the second copolymer may be further improved, and compatibility with the first copolymer may be further improved.
  • the aromatic vinyl-based monomer may impart excellent processability to the second copolymer.
  • the aromatic vinyl-based monomer may be included in a residual amount such that the total weight of the second monomer mixture is 100% by weight.
  • the second monomer mixture may further include a vinyl cyanide-based monomer to improve polymerization stability and chemical resistance of the second copolymer.
  • the vinyl cyanide-based monomer may be included in an amount of 7% by weight or less based on the total weight of the second monomer mixture. If 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.
  • 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. If the above-described range is satisfied, the transparency of the thermoplastic resin composition can be further improved.
  • the second copolymer may be prepared by suspension polymerization or bulk polymerization of a monomer mixture including an alkyl (meth) acrylate monomer and an aromatic vinyl monomer, of which a block polymerization capable of producing a copolymer with high purity It is desirable to manufacture.
  • the base resin may include the first copolymer and the second copolymer in a weight ratio of 70:30 to 90:10, and preferably 75:25 to 85:15. If the above-described range is satisfied, the content of the diene-based rubber polymer increases in the thermoplastic resin composition, so that the soft properties may be remarkably excellent. Accordingly, the artificial nail made of the thermoplastic resin composition has a weak force to return to the original state from the state attached to the natural nail, so that the fit can be improved. However, if it is included within the above-described range, the flexural strength and the flexural modulus are too high, so that the soft properties are not improved, and the artificial nail made of the thermoplastic resin composition may deteriorate the fit. When included in excess of the above-described range, processability and transparency may deteriorate.
  • Plasticizers are for improving processability and soft properties while maintaining transparency of the thermoplastic resin composition, and viscosity is 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-described range, a thermoplastic resin composition having excellent migration resistance, processability, and transparency can be prepared.
  • 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.
  • the refractive index of the plasticizer satisfies the above-described conditions, the transparency of the thermoplastic resin composition may be more excellent.
  • the artificial nail made of such a thermoplastic resin composition has excellent transparency and can implement various colors.
  • the plasticizer is preferably a polymer plasticizer rather than a phthalate plasticizer causing 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.
  • the plasticizer may be one or more selected from the group consisting of SONGCIZER TM P-2600 of Songwon Industries, SONGCIZER TM P-3000 of Songwon Industries, and Palamoll ® 652 of BASF among commercially available materials.
  • 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 preferred. If the above-described range is satisfied, the transparency and processability of the thermoplastic resin composition can be further improved, and migration of the plasticizer can be prevented.
  • the 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.
  • the transparency is 1.8% or less
  • the flexural strength is 300 to 400 kg/cm 2
  • the flexural modulus is 11,500 to 13,000 kg/cm 2.
  • the flexural strength and flexural modulus are less than the above-described range, there may be a problem that the shape is easily deformed when manufactured with an artificial nail.
  • the flexural strength and flexural modulus exceed the above-described range, the restoring force to return to the original shape becomes strong, so that the user's fingernails may easily fall off or the fit may deteriorate.
  • butadiene rubbery polymer latex (average particle diameter: 120 nm, gel content: 90%) 50 parts by weight (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 put together and mixed for 5 hours.
  • the temperature was raised to 80° C., aged for 1 hour, and then polymerization was terminated to prepare a graft copolymer latex.
  • 2 parts by weight of magnesium sulfate was added as a coagulant to the graft copolymer latex to aggregate, aged, dehydrated, and dried to obtain a graft copolymer powder.
  • the refractive index of the graft copolymer powder was 1.516, and the graft rate was 55%.
  • butadiene rubbery polymer latex (average particle diameter: 300 nm, gel content: 70%) 50 parts by weight (based on solid content), ion-exchanged water 50 parts by weight, methyl methacrylate 8.8 parts by weight, styrene 3 parts by weight, 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.
  • the temperature was raised to 80° C., aged for 1 hour, and then polymerization was terminated to prepare a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to aggregate, aged, dehydrated, and dried to obtain a graft copolymer powder.
  • the graft copolymer powder had a refractive index of 1.516 and a graft ratio of 45%.
  • 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 control agent were constant at 148° C. for 3 hours. Polymerization was carried out while continuously charged at a speed to obtain a copolymer. The copolymer was heated in a preheating bath, and unreacted monomers and solvent were removed in the volatilization bath.
  • the copolymer from which the unreacted monomer was removed was introduced into a polymer transfer pump extruder, and extruded at 210° C. to prepare a pellet-shaped copolymer.
  • the weight average molecular weight of the copolymer was 90,000 g/mol, and the refractive index was 1.516.
  • C-1 Songwon Industries' SONGCIZER TM P-2600 (viscosity: 2,700 to 3,500 cps, refractive index: 1.462 to 1.468, polydi(2-ethylhexyl) glycol adipate) was used.
  • C-2 Songwon Industries' SONGCIZER TM P-3000 (viscosity: 2,000 to 3,200 cps, refractive index: 1.462 to 1.468, polydi(2-ethylhexyl) glycol adipate) was used.
  • thermoplastic resin composition The above-described components were mixed according to the contents shown in Tables 1 to 5 and stirred to prepare a thermoplastic resin composition.
  • 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 by the following method, and the results are shown in Tables 1 to 5.
  • the pellet prepared in Experimental Example 1 was injected at 230° C. to prepare a specimen. And the physical properties of the specimen were measured by the method described below, and the results are shown in Tables 1 to 5.
  • 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) non-grafted 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 Flow 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 Transitability OK OK OK OK OK OK OK OK OK
  • Examples 1 to 3 containing a graft copolymer and a non-graft copolymer in an appropriate amount are excellent in flow index, transparency, flexural strength, flexural modulus, hardness and transferability. It was suitable for use. However, Comparative Examples 1 and 2 containing a small amount of the graft copolymer were inadequate for artificial nails due to their higher flexural strength, flexural modulus, and hardness compared to Examples 1 to 3. In addition, Comparative Example 3 containing an excessive amount of the graft copolymer had a lower flow index compared to Examples 1 to 3, resulting in lower processability, and high transparency, making it inappropriate for artificial nails.
  • Comparative Example 4 which had a large average particle diameter of the diene-based rubber polymer, was not suitable for artificial nails due to its high transparency and low flexural modulus.
  • Table 2 as the plasticizer content increases within an appropriate range of the plasticizer content, the transparency is increased. It was confirmed that the flow index increased while maintaining. Particularly, in the case of Examples 5 to 7, it was confirmed that the flow index was 10 g/10min or more compared to Example 4, which was excellent in processability.
  • Examples 8 to 10 containing the graft copolymer and the non-grafted copolymer in the optimal content are excellent in flow index, transparency, flexural strength, flexural modulus, hardness and transferability. It was suitable for nails. However, Comparative Example 5 containing a small amount of the graft copolymer was unsuitable for artificial nails due to its high flexural strength, flexural modulus and hardness. Comparative Example 6 containing an excessive amount of the graft copolymer had a low flow index, low processability, high transparency, and low flexural modulus, making it inappropriate for artificial nails.
  • Examples 11 to 13 were suitable for artificial nails due to excellent transparency, flexural strength, flexural modulus, hardness, and transferability. Particularly, in the case of Examples 12 and 13, it was confirmed that the flow index was 10 g/10min or more compared to Example 11, which was excellent in processability.
  • Comparative Example 7 consisting of a graft copolymer was unsuitable for artificial nails due to its high flexural strength, flexural modulus and hardness
  • Comparative Example 8 consisting of a graft copolymer and a styrene/butadiene copolymer was opaque. It was not suitable for artificial nails due to its high flexural strength and flexural modulus.

Abstract

The present invention relates to a thermoplastic resin composition comprising a base resin and a plasticizer, the base resin comprising, in a weight ratio of 70:30-90:10, a first copolymer obtained by graft polymerizing a first monomer mixture, which comprises an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer, onto a diene-based rubber polymer having an average diameter of 50-200 nm, and a second copolymer which is a copolymer of a second monomer mixture, which comprises an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer.

Description

열가소성 수지 조성물Thermoplastic resin composition
[관련출원과의 상호인용][Mutual citation with related application]
본 발명은 2019년 06월 13일에 출원된 한국 특허 출원 제10-2019-0070232호 및 2020년 06월 2일에 출원된 한국 특허 출원 제10-2020-0066697호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용을 본 명세서의 일부로서 포함한다.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 documents of the Korean patent application are included as part of this specification.
[기술분야][Technical field]
본 발명은 열가소성 수지 조성물에 관한 것으로서, 투명성, 가공성 및 연질 특성이 우수한 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition excellent in transparency, processability and soft properties.
인조손톱은 주로 사출성형으로 제조된다. 아크릴로니트릴/부타디엔/스티렌 그라프트 공중합체를 포함하는 ABS 열가소성 수지 조성물은 사출기로부터 성형체를 분리할 때, 분리작업이 용이하고, 버어(burr)가 발생하지 않기 때문에 인조손톱용으로 많이 이용되고 있다. 한편, 일반적인 ABS 열가소성 수지 조성물은 경질 특성을 갖는다. 경질의 인조손톱은 접착제를 사용하여 천연손톱에 붙일 때, 소비자의 손톱 곡률이 제각기 다르므로 사용시 인조손톱이 떨어져 나갈 가능성이 크다. 또한, 소비자의 손톱에 붙어있는 상태에서 계속 원래의 상태를 복원하려는 힘 때문에 착용감이 떨어진다. 이러한 단점을 보완하기 위하여, 에틸렌비닐아세테이트 또는 스티렌/부타디엔 공중합체로 인조손톱을 제조하는 방안이 제안되었다. 하지만, 인조손톱이 물렁물렁하여 착용시 외부 충격으로 인조손톱 끝 쪽이 쉽게 구부려지는 단점이 발생한다. 이러한 단점을 극복하고자, 아크릴로니트릴/부타디엔/스티렌 그라프트 공중합체와 에틸렌비닐아세테이트 또는 스티렌/부타디엔 공중합체를 배합하는 방안도 제안되었다. 최근에는 개인의 개성이나 취향에 맞게 다양한 디자인을 연출하기 위하여 투명한 인조손톱을 많이 이용하는데, 투명 그라프트 공중합체인 메틸 메타크릴레이트/부타디엔/스티렌 공중합체와 에틸렌비닐아세테이트 또는 스티렌/부타디엔 공중합체를 배합 시 두 소재간의 굴절률의 차이로 투명성을 유지할 수 없는 한계가 있다. 한편, 메틸 메타크릴레이트/부타디엔/스티렌 공중합체를 컴파운딩할 때, 고무함량이 증가할 수록 연질 특성이 증가하는 장점이 있으나, 헤이즈가 상승하여 투명성이 나빠지고, 색상이 저하되고, 가공성이 저하된다.Artificial nails are mainly manufactured by injection molding. ABS thermoplastic resin composition containing acrylonitrile/butadiene/styrene graft copolymer is widely used for artificial nails because it facilitates the separation operation and does not generate burrs when separating the molded body from the injection machine. . On the other hand, a general ABS thermoplastic resin composition has hard properties. When hard artificial nails are attached to natural nails using an adhesive, the curvature of the customer's nails is different, so there is a high possibility that the artificial nails fall off when used. In addition, the fit is deteriorated due to the power to continuously restore the original condition while attached to the consumer's nails. In order to compensate for these shortcomings, a method of manufacturing artificial nails with ethylene vinyl acetate or styrene/butadiene copolymer has been proposed. However, the artificial fingernail is soft and there is a disadvantage that the end of the artificial fingernail is easily bent due to external impact when worn. In order to overcome this disadvantage, a method of blending an acrylonitrile/butadiene/styrene graft copolymer and an 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 according to individual personality and taste, and a transparent graft copolymer such as methyl methacrylate/butadiene/styrene copolymer and ethylene vinyl acetate or styrene/butadiene copolymer are blended. There is a limit to maintaining transparency due to the difference in refractive index between the two materials. On the other hand, when compounding a methyl methacrylate/butadiene/styrene copolymer, there is an advantage in that the softness property increases as the rubber content increases, but the haze increases, resulting in poor transparency, lower color, and lower processability. do.
따라서, 투명성, 가공성 및 연질 특성이 모두 우수한 인조손톱용 열가소성 수지 조성물을 개발하고자 하는 연구가 계속되고 있다.Accordingly, research to develop a thermoplastic resin composition for artificial nails having excellent transparency, processability, and soft properties is ongoing.
본 발명의 목적은 투명성, 가공성 및 연질 특성이 우수한 열가소성 수지 조성물을 제공하는 것이다.An object of the present invention is to provide a thermoplastic resin composition excellent in transparency, processability and soft properties.
상술한 과제를 해결하기 위하여, 본 발명은 평균입경이 50 내지 200 ㎚인 디엔계 고무질 중합체에 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제1 단량체 혼합물을 그라프트 중합한 제1 공중합체, 및 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제2 단량체 혼합물의 공중합물인 제2 공중합체를 70:30 내지 90:10의 중량비로 포함하는 베이스 수지; 및 가소제를 포함하는 열가소성 수지 조성물을 제공한다.In order to solve the above problems, the present invention is a first monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer in a diene rubber polymer having an average particle diameter of 50 to 200 nm. A base resin comprising a second copolymer, which is a copolymer of a second monomer mixture including one copolymer and 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.
또한, 본 발명은 상술한 열가소성 수지 조성물로 제조되고, 투명도가 2.0 % 이하이고, 굴곡강도가 280 내지 420 ㎏/㎠이고, 굴곡탄성율이 11,000 내지 13,500 ㎏/㎠인 열가소성 수지 성형품을 제공한다.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/cm2, and a flexural modulus of 11,000 to 13,500 kg/cm2.
본 발명의 열가소성 수지 조성물은 투명성, 가공성 및 연질 특성이 모두 우수하다. 이로 인해 본 발명의 열가소성 수지 조성물로 투명하고, 다양한 색상 구현이 가능하고, 사용감이 우수한 인조손톱을 제조할 수 있다.The thermoplastic resin composition of the present invention is excellent in all of transparency, processability and soft properties. For this reason, it is possible to manufacture an artificial nail that is transparent with the thermoplastic resin composition of the present invention, can implement various colors, and has excellent feeling of use.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.
본 발명에서 디엔계 고무질 중합체의 평균입경은 동적 광산란(dynamic light scattering)법을 이용하여 측정할 수 있고, 상세하게는 Nicomp 380 장비(제품명, 제조사: PSS)를 이용하여 측정할 수 있다.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).
본 명세서에서 평균입경은 동적 광산란법에 의해 측정되는 입도분포에 있어서의 산술 평균입경, 즉 산란강도 평균입경을 의미할 수 있다.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 a scattering intensity.
본 발명에서 점도는 하기 조건에서 브룩필드(Brookfield)를 이용하여 측정할 수 있다.In the present invention, the viscosity can be measured using Brookfield under the following conditions.
스핀들(spindle) 종류 - Cone type (CPA-52Z), cone angle = 3°, cone radius = 1.2 cm, 갭(gap): 13 ㎛ 이하, 측정 전단 속도(shear rate): 10 내지 20/sec, 측정온도: 25 ℃Spindle type-Cone type (CPA-52Z), cone angle = 3°, cone radius = 1.2 cm, gap: 13 ㎛ or less, measurement shear rate: 10 to 20/sec, measurement Temperature: 25 ℃
본 발명에서 굴절률은 물질의 절대 굴절률을 의미하는 것으로, 굴절률은 자유 공간에서의 전자기 복사선 속도 대 물질 내에서의 복사선의 속도 비로서 인식될 수 있다, 이때 복사선은 파장이 450 nm 내지 680 nm의 가시광선일 수 있고, 구체적으로는 파장이 589.3 nm의 가시광선일 수 있다. 굴절률은 공지된 방법, 즉 아베 굴절계(Abbe Refractometer)를 이용하여 측정할 수 있다.In the present invention, the refractive index refers to the absolute refractive index of a material, and the refractive index can be recognized as a ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material. In this case, the radiation is visible light having a wavelength of 450 nm to 680 nm. It may be a line, and specifically, it may be visible light of a wavelength of 589.3 nm. The refractive index can be measured using a known method, that is, an Abbe Refractometer.
본 발명에서 그라프트율은 제1 공중합체 분말 1 g을 아세톤 50 g에 24 시간 동안 교반하면서 녹인 후, 원심 분리기(상품명: SUPRA 30 K, 제조사: Hanil Science Industrial)에 투입하고 16,000 rpm, -10 ℃ 조건 하에서 4 시간 동안 원심 분리하여 상등액과 침전물을 분리하고, 침전물을 50 ℃의 열풍 건조기로 12 시간 건조한 후, 수득된 건조물의 중량을 측정하고, 하기 수학식 1에 의거하여 계산할 수 있다:In the present invention, the graft rate is 1 g of the first copolymer powder dissolved in 50 g of acetone while stirring for 24 hours, and then added to a centrifuge (brand name: SUPRA 30 K, manufacturer: Hanil Science Industrial) and 16,000 rpm, -10 °C conditions The supernatant and the precipitate were separated by centrifugation for 4 hours under, and the precipitate was dried for 12 hours with a hot air dryer at 50° C., and the weight of the obtained dried product was measured, and can be calculated based on the following equation:
[수학식 1][Equation 1]
그라프트율(%) = {(그라프트된 단량체 혼합물의 공중합물의 중량1)) / (디엔계 고무질 중합체의 중량2))}×100Graft rate (%) = {(weight of the copolymer of the grafted monomer mixture 1) ) / (weight of the diene rubber polymer 2) )} × 100
1) 그라프트된 단량체 혼합물의 공중합물의 중량 = (건조물의 중량) - (디엔계 고무질 중합체의 중량) 1) Weight of the copolymer of the grafted monomer mixture = (weight of the dried product)-(weight of the diene-based rubber polymer)
2) 디엔계 고무질 중합체의 중량 = 이론상 투입된 디엔계 고무질 중합체의 중량(고형분 기준) 또는 제1 공중합체를 적외선 분광법으로 분석하여 측정한 디엔계 고무질 중합체의 중량2) Weight of diene-based rubbery polymer = Weight of diene-based rubbery polymer (based on solid content) or the weight of diene-based rubbery polymer measured by analyzing the first copolymer by infrared spectroscopy in theory
본 발명에서 제1 공중합체의 쉘의 중량평균분자량은 그라프트율 측정방법에서 기재된 상등액을 건조한 건조물을 테트라하이드로퓨란(THF) 용액에 녹인 후, 1 ㎛ 필터를 통해 걸러낸 뒤, 겔 투과 크로마토그래피를 통해 표준 PS(standard polystyrene) 시료에 대한 상대 값으로 측정할 수 있다.In the present invention, the weight average molecular weight of the shell of the first copolymer is determined by dissolving the dried supernatant described in the graft rate measurement method in a tetrahydrofuran (THF) solution, filtering through a 1 μm filter, and then gel permeation chromatography. It can be measured relative to a standard PS (standard polystyrene) sample.
본 발명에서 제2 공중합체의 중량평균분자량은 용액으로 테트라하이드로퓨란(THF)을 이용하고, 겔 투과 크로마토그래피(GPC, waters breeze)를 이용하여 표준 PS(standard polystyrene) 시료에 대한 상대 값으로 측정할 수 있다.In the present invention, the weight average molecular weight of the second copolymer is measured as a relative value to a standard PS (standard polystyrene) sample using tetrahydrofuran (THF) as a solution and gel permeation chromatography (GPC, water breeze). can do.
본 발명에서 투명도는 ASTM D1003에 의거하여 측정할 수 있다.In the present invention, transparency can be measured based on ASTM D1003.
본 발명에서 굴곡강도 및 굴곡탄성율은 ASTM D790에 의거하여 측정할 수 있다.In the present invention, the flexural strength and flexural modulus can be measured according to ASTM D790.
본 발명에서 알킬 (메트)아크릴레이트계 단량체는 C1 내지 C10의 알킬 (메트)아크릴레이트계 단량체일 수 있다. 상기 C1 내지 C10의 알킬 (메트)아크릴레이트계 단량체는 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 프로필 (메트)아크릴레이트, 부틸 (메트)아크릴레이트, 2-에틸헥실 (메트)아크릴레이트, 데실 (메트)아크릴레이트 및 라우릴 (메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 메틸 메타크릴레이트가 바람직하다.In the present invention, the alkyl (meth) acrylate monomer may be a C 1 to C 10 alkyl (meth) acrylate monomer. The C 1 to C 10 alkyl (meth) acrylate monomers are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) It may be one or more selected from the group consisting of acrylate, decyl (meth) acrylate and lauryl (meth) acrylate, of which methyl methacrylate is preferred.
본 발명에서 방향족 비닐계 단량체는 스티렌, α-메틸 스티렌, α-에틸 스티렌 및 p-메틸 스티렌으로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 스티렌이 바람직하다. 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.
본 발명에서 시안화 비닐계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 페닐아크릴로니트릴 및 α-클로로아크릴로니트릴로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 아크릴로니트릴이 바람직하다.In the present invention, the vinyl cyanide monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is preferred.
1. 열가소성 수지 조성물1. Thermoplastic resin composition
본 발명의 일 실시예에 따른 열가소성 수지 조성물은 1) 평균입경이 50 내지 200 ㎚인 디엔계 고무질 중합체에 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제1 단량체 혼합물을 그라프트 중합한 제1 공중합체, 및 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제2 단량체 혼합물의 공중합물인 제2 공중합체를 70:30 내지 90:10의 중량비로 포함하는 베이스 수지 100 중량부; 및 2) 가소제를 포함한다.The thermoplastic resin composition according to an embodiment of the present invention 1) grafts a first monomer mixture including 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 Base resin comprising a second copolymer, which is a copolymer of a polymerized first copolymer and a second monomer mixture including an alkyl (meth)acrylate monomer and an aromatic vinyl monomer, in a weight ratio of 70:30 to 90:10 100 parts by weight; And 2) a plasticizer.
이 하 본 발명의 일 실시예에 따른 열가소성 수지 조성물의 구성요소들에 대하여 상세하게 설명한다.Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
1) 베이스 수지1) Base resin
베이스 수지는 (1) 제1 공중합체 및 (2) 제2 공중합체를 포함한다.The base resin includes (1) a first copolymer and (2) a second copolymer.
이하, 상기 베이스 수지의 구성요소들에 대하여 상세하게 설명한다.Hereinafter, components of the base resin will be described in detail.
(1) 제1 공중합체 (1) first copolymer
제1 공중합체는 평균입경이 50 내지 200 ㎚인 디엔계 고무질 중합체에, 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제1 단량체 혼합물을 그라프트 공중합한 그라프트 공중합체이다.The first copolymer is a graft copolymer obtained by graft copolymerization of a first monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer with a diene-based rubbery polymer having an average particle diameter of 50 to 200 nm.
상기 디엔계 고무질 중합체는 평균입경이 50 내지 200 ㎚이고, 바람직하게는 70 내지 180 ㎚일 수 있다. 상술한 범위를 만족하면, 열가소성 수지 조성물 내에 제1 공중합체가 과량으로 포함되어도, 우수한 투명성을 구현할 수 있다. 상술한 범위 미만이면, 열가소성 수지 조성물의 내충격성이 현저하게 저하될 수 있고, 상술한 범위를 초과하면, 열가소성 수지 조성물의 투명성이 저하될 수 있다.The diene-based rubbery polymer may have an average particle diameter of 50 to 200 nm, and preferably 70 to 180 nm. If the above-described range is satisfied, even if the first copolymer is contained in an excessive amount in the thermoplastic resin composition, excellent transparency may be implemented. If it is less than the above-described range, the impact resistance of the thermoplastic resin composition may be significantly lowered, and if it exceeds the above-described range, the transparency of the thermoplastic resin composition may be lowered.
상기 디엔계 고무질 중합체는 공액 디엔계 단량체를 가교 반응시켜 제조한 합성고무일 수 있다. 상기 공액 디엔계 단량체는 1,3-부타디엔, 이소프렌, 클로로프렌, 피페릴렌, 디사이클로펜타디엔, 에틸리덴 노보넨 및 비닐 노보넨으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 중 1,3-부타디엔이 바람직하다. The diene-based rubber polymer may be a synthetic rubber prepared by crosslinking 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 desirable.
상기 알킬 (메트)아크릴레이트계 단량체는 제1 공중합체에 우수한 투명성을 부여해줄 수 있다. 상기 알킬 (메트)아크릴레이트계 단량체는 상기 제1 단량체 혼합물의 총 중량에 대하여, 64 내지 75 중량% 또는 68 내지 72 중량%로 포함될 수 있고, 이 중 68 내지 72 중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 제1 공중합체의 투명성이 보다 개선될 수 있다.The alkyl (meth)acrylate-based monomer may impart excellent transparency to the first copolymer. 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 first monomer mixture, of which 68 to 72% by weight is preferred. . If the above-described range is satisfied, the transparency of the first copolymer may be further improved.
상기 방향족 비닐계 단량체는 제1 공중합체에 우수한 가공성을 부여해줄 수 있다. 상기 방향족 비닐계 단량체는 상기 제1 단량체 혼합물의 총 중량이 100 중량%가 되도록 잔량 포함될 수 있다. The aromatic vinyl-based monomer may impart excellent processability to the first copolymer. The aromatic vinyl-based monomer may be included in a residual amount such that the total weight of the first monomer mixture is 100% by weight.
상기 제1 단량체 혼합물은 중합 안정성을 개선시키고, 제1 공중합체의 내화학성을 개선시키기 위하여 시안화 비닐계 단량체를 더 포함할 수 있다. 상기 시안화 비닐계 단량체는 상기 제1 단량체 혼합물의 총 중량에 대하여, 7 중량% 이하로 포함될 수 있다. 상술한 범위를 만족하면, 상기 시안화 비닐계 단량체로 인한 황색 발현을 최소화하면서, 제1 공중합체의 내화학성을 개선시킬 수 있다.The first monomer mixture may further include a vinyl cyanide monomer to improve polymerization stability and chemical resistance of the first copolymer. The vinyl cyanide-based monomer may be included in an amount of 7% by weight or less based on the total weight of the first monomer mixture. If 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.
상기 디엔계 고무질 중합체와 상기 제1 단량체 혼합물의 중량비는 40:60 내지 60:40 또는 45:55 내지 55:45일 수 있고, 이 중 45:55 내지 55:45인 것이 바람직하다. 상술한 범위를 만족하면, 제1 공중합체의 투명성 및 색상이 개선될 수 있다.The weight ratio of the diene-based rubber polymer and the first monomer mixture may be 40:60 to 60:40 or 45:55 to 55:45, of which it is preferably 45:55 to 55:45. If the above-described range is satisfied, transparency and color of the first copolymer may be improved.
상기 제1 공중합체는 그라프트율이 45 내지 65 % 또는 50 내지 60 %일 수 있고, 이 중 50 내지 60 %가 바람직하다. 상술한 범위를 만족하면, 열가소성 수지 조성물의 투명성이 보다 개선될 수 있고, 제2 공중합체와의 상용성도 개선될 수 있다. The first copolymer may have a graft rate of 45 to 65% or 50 to 60%, of which 50 to 60% is preferable. If the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved, and compatibility with the second copolymer may be improved.
한편, 상기 제1 공중합체의 투명성은 디엔계 고무질 중합체의 굴절률과 제1 단량체 혼합물의 공중합물인 쉘의 굴절률의 차이에 의해서 결정될 수 있다. 즉, 상기 제1 공중합체가 우수한 투명성을 구현하기 위해서는, 상기 디엔계 고무질 중합체의 굴절률과 쉘의 굴절률의 차이가 0.01 이하일 수 있으며, 굴절률의 차이가 없는 것이 바람직하다.Meanwhile, the transparency of the first copolymer may be determined by a 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 exhibit excellent transparency, the difference between the refractive index of the diene 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 refractive index.
또한, 열가소성 수지 조성물이 우수한 투명성을 구현하기 위하여, 상기 제1 공중합체 및 제2 공중합체는 굴절률의 차이가 0.01 이하일 수 있으며, 굴절률의 차이가 없는 것이 바람직하다.In addition, in order to realize excellent transparency of the thermoplastic resin composition, the first copolymer and the second copolymer may have a difference in refractive index of 0.01 or less, and it is preferable that there is no difference in refractive index.
상기 제1 공중합체는 굴절률이 1.5 내지 1.525 또는 1.51 내지 1.52일 수 있으며, 이 중 1.51 내지 1.52가 바람직하다. 상술한 범위를 만족하면, 후술할 제2 공중합체와의 시너지 작용으로 열가소성 수지 조성물의 투명성을 보다 개선시킬 수 있다.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. If the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved by synergistic action with the second copolymer to be described later.
(2) 제2 공중합체(2) second copolymer
제2 공중합체는 비그라프트 공중합체로서, 알킬 (메트)아크릴레이트계 단량체와 방향족 비닐계 단량체를 포함하는 제2 단량체 혼합물의 공중합물이다.The second copolymer is a non-grafted copolymer and is a copolymer of a second monomer mixture including an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer.
상기 제2 공중합체는 열가소성 수지 조성물에 우수한 투명성과 가공성을 부여해줄 수 있다.The second copolymer may impart excellent transparency and processability to the thermoplastic resin composition.
상기 알킬 (메트)아크릴레이트계 단량체는 상기 제2 단량체 혼합물의 총 중량에 대하여, 64 내지 75 중량% 또는 68 내지 72 중량%로 포함될 수 있고, 이 중 68 내지 87 중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 제2 공중합체의 투명성이 보다 개선될 수 있고, 상기 제1 공중합체와의 상용성이 보다 개선될 수 있다.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, of which 68 to 87% by weight is preferred. . If the above-described range is satisfied, the transparency of the second copolymer may be further improved, and compatibility with the first copolymer may be further improved.
상기 방향족 비닐계 단량체는 제2 공중합체에 우수한 가공성을 부여해줄 수 있다. 상기 방향족 비닐계 단량체는 상기 제2 단량체 혼합물의 총 중량이 100 중량%가 되도록 잔량 포함될 수 있다. The aromatic vinyl-based monomer may impart excellent processability to the second copolymer. The aromatic vinyl-based monomer may be included in a residual amount such that the total weight of the second monomer mixture is 100% by weight.
상기 제2 단량체 혼합물은 중합 안정성을 개선시키고, 제2 공중합체의 내화학성을 개선시키기 위하여 시안화 비닐계 단량체를 더 포함할 수 있다. 상기 시안화 비닐계 단량체는 상기 제2 단량체 혼합물의 총 중량에 대하여, 7 중량% 이하로 포함될 수 있다. 상술한 범위를 만족하면, 상기 시안화 비닐계 단량체로 인한 황색 발현을 최소화하면서, 제2 공중합체의 내화학성을 개선시킬 수 있다.The second monomer mixture may further include a vinyl cyanide-based monomer to improve polymerization stability and chemical resistance of the second copolymer. The vinyl cyanide-based monomer may be included in an amount of 7% by weight or less based on the total weight of the second monomer mixture. If 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.
상기 제2 공중합체는 굴절률이 1.5 내지 1.525 또는 1.51 내지 1.52일 수 있으며, 이 중 1.5 내지 1.52가 바람직하다. 상술한 범위를 만족하면, 열가소성 수지 조성물의 투명성을 보다 개선시킬 수 있다.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. If the above-described range is satisfied, the transparency of the thermoplastic resin composition can be further improved.
상기 제2 공중합체는 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 단량체 혼합물을 현탁 중합 또는 괴상 중합하여 제조할 수 있고, 이 중 고순도로 공중합체를 제조할 수 있는 괴상 중합으로 제조하는 것이 바람직하다.The second copolymer may be prepared by suspension polymerization or bulk polymerization of a monomer mixture including an alkyl (meth) acrylate monomer and an aromatic vinyl monomer, of which a block polymerization capable of producing a copolymer with high purity It is desirable to manufacture.
상기 베이스 수지는 상기 제1 공중합체와 제2 공중합체를 70:30 내지 90:10로 포함하고, 바람직하게는 75:25 내지 85:15의 중량비로 포함할 수 있다. 상술한 범위를 만족하면, 열가소성 수지 조성물 내에서 디엔계 고무질 중합체의 함량이 증가하여 연질 특성이 현저하게 우수해질 수 있다. 이에 따라 열가소성 수지 조성물로 제조된 인조손톱은 천연손톱에 붙어있는 상태에서 원래의 상태로 돌아가려는 힘이 약해 착용감이 개선될 수 있다. 하지만 상술한 범위 미만으로 포함되면, 굴곡강도 및 굴곡탄성율이 지나치게 높아져 연질 특성이 개선되지 않고, 열가소성 수지 조성물로 제조된 인조손톱은 착용감이 저하될 수 있다. 상술한 범위를 초과하여 포함되면, 가공성 및 투명성이 저하될 수 있다.The base resin may include the first copolymer and the second copolymer in a weight ratio of 70:30 to 90:10, and preferably 75:25 to 85:15. If the above-described range is satisfied, the content of the diene-based rubber polymer increases in the thermoplastic resin composition, so that the soft properties may be remarkably excellent. Accordingly, the artificial nail made of the thermoplastic resin composition has a weak force to return to the original state from the state attached to the natural nail, so that the fit can be improved. However, if it is included within the above-described range, the flexural strength and the flexural modulus are too high, so that the soft properties are not improved, and the artificial nail made of the thermoplastic resin composition may deteriorate the fit. When included in excess of the above-described range, processability and transparency may deteriorate.
2) 가소제2) plasticizer
가소제는 열가소성 수지 조성물의 투명성을 유지하면서도, 가공성과 연질 특성을 향상시키기 위한 것으로, 점도가 1,500 내지 5,000 cps, 2,000 내지 4,000 cps, 또는 2,000 내지 3,500 cps인 것일 수 있다. 상기 가소제는 점도가 2,000 내지 4,000 cps인 것이 바람직할 수 있고, 2,000 내지 3,500 cps인 것이 보다 바람직할 수 있다. 가소제의 점도가 상술한 범위를 만족하면, 우수한 내이행성, 가공성 및 투명성을 구현하는 열가소성 수지 조성물을 제조할 수 있다. Plasticizers are for improving processability and soft properties while maintaining transparency of the thermoplastic resin composition, and viscosity is 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-described range, a thermoplastic resin composition having excellent migration resistance, processability, and transparency can be prepared.
상기 가소제는 굴절률이 1.45 이상, 1.45 내지 1.6 또는 1.45 내지 1.52일 수 있고, 이 중 1.45 내지 1.52이 바람직하다. 가소제의 굴절률이 상술한 조건을 만족하면, 열가소성 수지 조성물의 투명성이 보다 우수해질 수 있다. 또한, 이러한 열가소성 수지 조성물로 제조된 인조손톱은 투명성이 우수할 뿐만 아니라 다양한 색상을 구현할 수 있다.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, the transparency of the thermoplastic resin composition may be more excellent. In addition, the artificial nail made of such a thermoplastic resin composition has excellent transparency and can implement various colors.
상기 가소제는 환경적인 문제를 야기하는 프탈레이트계 가소제가 아닌 고분자 가소제인 것이 바람직하고, 폴리에스터계 가소제인 것이 보다 바람직하다. 상기 가소제는 폴리디(2-에틸헥실)글리콜아디페이트; 헥산디오익산, 폴리머 위드 1,3-부탄디올, 2-에틸헥실 에스터; 헥산디오익산, 폴리머 위드 1,3-부타디올 앤드 1,2-프로판디올, 2-에틸헥실 에스터; 및 헥산디오익산, 폴리머 위드 2,2-디메틸-1,3-프로판디올 앤드 1,2-프로판디올, 이소노닐 에스터로 이루어진 군에서 선택되는 1종 이상인 것이 바람직하다.The plasticizer is preferably a polymer plasticizer rather than a phthalate plasticizer causing 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.
상기 가소제는 시판되는 물질 중에 송원산업의 SONGCIZERTM P-2600, 송원산업의 SONGCIZERTM P-3000 및 BASF의 Palamoll ® 652로 이루어진 군에서 선택되는 1종 이상을 이용할 수 있다.The plasticizer may be one or more selected from the group consisting of SONGCIZER TM P-2600 of Songwon Industries, SONGCIZER TM P-3000 of Songwon Industries, and Palamoll ® 652 of BASF among commercially available materials.
상기 가소제는 상기 베이스 수지 100 중량부에 대하여 4 내지 10 중량부, 5 내지 10 중량부 또는 5 내지 9 중량부로 포함될 수 있고, 이 중 5 내지 9 중량부로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 열가소성 수지 조성물의 투명성 및 가공성을 보다 개선시킬 수 있고, 가소제의 이행현상을 방지할 수 있다. 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 preferred. If the above-described range is satisfied, the transparency and processability of the thermoplastic resin composition can be further improved, and migration of the plasticizer can be prevented.
2. 열가소성 수지 성형품2. Thermoplastic molded product
본 발명의 다른 일 실시예에 따른 열가소성 수지 성형품은 본 발명의 일 실시예에 따른 열가소성 수지 조성물로 제조되고, 투명도가 2.0 % 이하이고, 굴곡강도가 280 내지 420 ㎏/㎠이고, 굴곡탄성율이 11,000 내지 13,500 ㎏/㎠이다. 바람직하게는 투명도가 1.8 % 이하이고, 굴곡강도가 300 내지 400 ㎏/㎠이고, 굴곡탄성율이 11,500 내지 13,000 ㎏/㎠이다. 상술한 조건을 만족하면, 우수한 투명도 및 연질 특성을 구현할 수 있어, 인조손톱용으로 적합할 수 있다. 투명도가 상술한 범위를 초과하면, 투명성이 저하된다. 또한, 굴곡강도 및 굴곡탄성율이 상술한 범위 미만이면, 인조손톱으로 제조 시 형태가 쉽게 변형되는 문제가 발생할 수 있다. 굴곡강도 및 굴곡탄성율이 상술한 범위를 초과하면, 원래 형태로 돌아가려는 복원력이 강해져서 사용자의 손톱에서 쉽게 떨어지거나 착용감이 떨어질 수 있다.The 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-described conditions are satisfied, excellent transparency and soft properties can be realized, and thus it can be suitable for artificial nails. When the transparency exceeds the above-described range, the transparency decreases. In addition, if the flexural strength and flexural modulus are less than the above-described range, there may be a problem that the shape is easily deformed when manufactured with an artificial nail. When the flexural strength and flexural modulus exceed the above-described range, the restoring force to return to the original shape becomes strong, so that the user's fingernails may easily fall off or the fit may deteriorate.
한편, 투명도는 ASTM D1003에 의거하여 측정할 수 있고, 굴곡강도 및 굴곡탄성율은 ASTM D790에 의거하여 측정할 수 있다.Meanwhile, transparency can be measured according to ASTM D1003, and flexural strength and flexural modulus can be measured according to ASTM D790.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.
제조예 1Manufacturing Example 1
질소 치환된 반응기에 부타디엔 고무질 중합체 라텍스(평균입경: 120 ㎚, 겔함량: 90 %) 50 중량부(고형분 기준), 이온교환수 50 중량부, 메틸 메타크릴레이트 8.8 중량부, 스티렌 3 중량부, 아크릴로니트릴 0.8 중량부, 가교제로 디비닐벤젠 0.1 중량부, 개시제로 큐멘하이드로퍼옥사이드 0.2 중량부, 유화제로 나트륨 도데실벤젠 설포네이트 0.5 중량부를 일괄 투입하고, 5 시간 동안 혼합하였다. 이어서, 상기 반응기에 메틸 메타크릴레이트 26.2 중량부, 스티렌 9 중량부, 아크릴로니트릴 2.2 중량부, 분자량 조절제로 t-도데실 머캅탄 0.5 중량부, 활성화제로 에틸렌디아민테트라아세트산 디나트륨염 0.05 중량부, 나트륨 포름알데히드 설폭실레이트 0.1 중량부, 황산제1철 0.001 중량부, 개시제로 큐멘하이드로퍼옥사이드 0.1 중량부를 70 ℃에서 5 시간 동안 일정한 속도로 연속 투입하면서 중합하였다. 연속 투입이 종료된 후, 80 ℃로 승온하고 1 시간 동안 숙성한 후 중합을 종료하여 그라프트 공중합체 라텍스를 제조하였다. 상기 그라프트 공중합체 라텍스에 응집제로 황산마그네슘 2 중량부를 투입하여 응집하고, 숙성하고, 탈수하고, 건조하여 그라프트 공중합체 분말을 수득하였다. 이때 그라프트 공중합체 분말의 굴절률은 1.516이었고, 그라프트율은 55 %이었다.In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 120 nm, gel content: 90%) 50 parts by weight (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 put together and mixed for 5 hours. Then, in the reactor, methyl methacrylate 26.2 parts by weight, styrene 9 parts by weight, acrylonitrile 2.2 parts by weight, t-dodecyl mercaptan 0.5 parts by weight as a molecular weight control agent, ethylenediaminetetraacetic acid disodium salt 0.05 parts by weight 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 polymerized while continuously adding at a constant rate at 70° C. for 5 hours. After the continuous addition was completed, the temperature was raised to 80° C., aged for 1 hour, and then polymerization was terminated to prepare a graft copolymer latex. 2 parts by weight of magnesium sulfate was added as a coagulant to the graft copolymer latex to aggregate, aged, dehydrated, and dried 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%.
제조예 2Manufacturing Example 2
질소 치환된 반응기에 부타디엔 고무질 중합체 라텍스(평균입경: 300 ㎚, 겔함량: 70 %) 50 중량부(고형분 기준), 이온교환수 50 중량부, 메틸 메타크릴레이트 8.8 중량부, 스티렌 3 중량부, 아크릴로니트릴 0.8 중량부, 가교제로 디비닐벤젠 0.1 중량부, 개시제로 큐멘하이드로퍼옥사이드 0.2 중량부, 유화제로 나트륨 도데실벤젠 설포네이트 0.5 중량부를 투입하고 3 시간 동안 혼합하였다. 그 후, 상기 반응기에 메틸 메타크릴레이트 26.2 중량부, 스티렌 9 중량부, 아크릴로니트릴 2.2 중량부, 분자량 조절제로 t-도데실 머캅탄 0.5 중량부, 활성화제로 에틸렌디아민테트라아세트산 디나트륨염 0.05 중량부, 나트륨 포름알데히드 설폭실레이트 0.1 중량부, 황산제1철 0.001 중량부, 개시제로 큐멘하이드로퍼옥사이드 0.1 중량부를 70 ℃에서 5 시간 동안 일정한 속도로 연속 투입하면서 중합하였다. 연속 투입이 종료된 후, 80 ℃로 승온하고 1 시간 동안 숙성한 후 중합을 종료하여 그라프트 공중합체 라텍스를 제조하였다. 그리고 그라프트 공중합체 라텍스에 응집제로 황산마그네슘 2 중량부를 투입하여 응집하고, 숙성하고, 탈수하고, 건조하여 그라프트 공중합체 분말을 수득하였다. 상기 그라프트 공중합체 분말의 굴절률은 1.516이었고, 그라프트율은 45%이었다.In a nitrogen-substituted reactor, butadiene rubbery polymer latex (average particle diameter: 300 nm, gel content: 70%) 50 parts by weight (based on solid content), ion-exchanged water 50 parts by weight, methyl methacrylate 8.8 parts by weight, styrene 3 parts by weight, 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 modifier, 0.05 parts by weight of ethylenediaminetetraacetic acid disodium salt as an activator Parts, 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 70° C. for 5 hours at a constant rate for polymerization. After the continuous addition was completed, the temperature was raised to 80° C., aged for 1 hour, and then polymerization was terminated to prepare a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to aggregate, aged, dehydrated, and dried to obtain a graft copolymer powder. The graft copolymer powder had a refractive index of 1.516 and a graft ratio of 45%.
제조예 3Manufacturing Example 3
질소 치환된 반응기에 메틸 메타크릴레이트 70.4 중량부, 스티렌 24.6 중량부, 아크릴로니트릴 5 중량부, 톨루엔 30 중량부, 및 분자량 조절제로 t-도데실 머탑탄 0.15 중량부를 148 ℃에서 3 시간 동안 일정한 속도로 연속 투입하면서 중합하고 공중합물을 수득하였다. 상기 공중합물을 예비 가열조에서 가열하였고, 휘발조에서 미반응 단량체 및 용매를 제거하였다. 이어서, 상기 미반응 단량체 등이 제거된 공중합물을 폴리머 이송 펌프 압출 가공기에 투입하고, 210 ℃에서 압출하여 펠렛 형태의 공중합체를 제조하였다. 상기 공중합체의 중량평균분자량은 90,000 g/mol이고, 굴절률은 1.516이었다.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 control agent were constant at 148° C. for 3 hours. Polymerization was carried out while continuously charged at a speed to obtain a copolymer. The copolymer was heated in a preheating bath, and unreacted monomers and solvent were removed in the volatilization bath. Subsequently, the copolymer from which the unreacted monomer was removed was introduced into a polymer transfer pump extruder, and extruded at 210° C. to prepare a pellet-shaped copolymer. The weight average molecular weight of the copolymer was 90,000 g/mol, and the refractive index was 1.516.
실시예 및 비교예Examples and Comparative Examples
하기 실시예 및 비교예에서 사용된 성분의 사양은 다음과 같다.The specifications of the components used in the following Examples and Comparative Examples are as follows.
(A) 그라프트 공중합체(A) Graft copolymer
(A-1): 제조예 1의 그라프트 공중합체를 사용하였다.(A-1): The graft copolymer of Preparation Example 1 was used.
(A-2): 제조예 2의 그라프트 공중합체를 사용하였다. (A-2): The graft copolymer of Preparation Example 2 was used.
(A-3): 메틸 메타크릴레이트/아크릴로니트릴/부타디엔/스티렌 그라프트 공중합체: 엘지화학 社의 TR557-NP(굴절률: 1.516, 부타디엔 고무질 중합체의 평균입경: 300 ㎚)를 사용하였다.(A-3): Methyl methacrylate/acrylonitrile/butadiene/styrene graft copolymer: TR557-NP (refractive index: 1.516, average particle diameter of butadiene rubbery polymer: 300 nm) manufactured by LG Chem was used.
(B) 비그라프트 공중합체: 제조예 3의 공중합체를 사용하였다.(B) Non-grafted copolymer: The copolymer of Preparation Example 3 was used.
(C) 가소제(C) plasticizer
(C-1): 송원산업의 SONGCIZERTM P-2600(점도: 2,700 내지 3,500 cps, 굴절률: 1.462 내지 1.468, 폴리디(2-에틸헥실)글리콜아디페이트)을 사용하였다.(C-1): Songwon Industries' SONGCIZER ™ P-2600 (viscosity: 2,700 to 3,500 cps, refractive index: 1.462 to 1.468, polydi(2-ethylhexyl) glycol adipate) was used.
(C-2): 송원산업의 SONGCIZERTM P-3000(점도: 2,000 내지 3,200 cps, 굴절률: 1.462 내지 1.468, 폴리디(2-에틸헥실)글리콜아디페이트)을 사용하였다.(C-2): Songwon Industries' SONGCIZER ™ P-3000 (viscosity: 2,000 to 3,200 cps, refractive index: 1.462 to 1.468, polydi(2-ethylhexyl) glycol adipate) was used.
(C-3): BASF의 Palamoll ® 652(점도: 2,000 cps, 굴절률: 1.465, 헥산디오익산, 폴리머 위드 2,2-디메틸-1,3-프로판디올 앤드 1,2-프로판디올, 이소노닐 에스터) (C-3): BASF's Palamoll ® 652 (viscosity: 2,000 cps, refractive index: 1.465, hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, isononyl ester )
(D) 스티렌/부타디엔 공중합체: Chevron 社의 KR-03(굴절률: 1.571)을 사용하였다.(D) Styrene/butadiene copolymer: Chevron's KR-03 (refractive index: 1.571) was used.
상술한 성분을 하기 표 1 내지 표 5에 기재된 함량대로 혼합하고 교반하여 열가소성 수지 조성물을 제조하였다.The above-described components were mixed according to the contents shown in Tables 1 to 5 and stirred to prepare a thermoplastic resin composition.
실험예 1Experimental Example 1
실시예 및 비교예의 열가소성 수지 조성물을 230 ℃로 설정된 이축 압출기에 투입하고 압출하여 펠렛을 제조하였다. 펠렛의 유동지수를 하기와 같은 방법으로 측정하였고, 그 결과를 하기 표 1 내지 표 5에 나타내었다.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 by the following method, and the results are shown in Tables 1 to 5.
① 유동지수(Melt Flow Index, g/10min): ASTM D1238에 의거하여 220 ℃, 10 ㎏ 하에서 측정하였다.① Melt Flow Index (g/10min): According to ASTM D1238, it was measured under 220°C and 10 kg.
실험예 2Experimental Example 2
실험예 1에서 제조된 펠렛을 230 ℃에서 사출하여 시편을 제조하였다. 그리고 그 시편의 물성을 하기에 기재된 방법으로 측정하였고, 그 결과를 하기 표 1 내지 표 5에 나타내었다.The pellet prepared in Experimental Example 1 was injected at 230° C. to prepare a specimen. And the physical properties of the specimen were measured by the method described below, and the results are shown in Tables 1 to 5.
② 투명도(haze, %): ASTM D1003에 의거하여 투명도를 측정하였다.② Transparency (haze, %): Transparency was measured according to ASTM D1003.
③ 굴곡강도(Flexural Strength. ㎏/㎠): ASTM D790에 의거하여 측정하였다.③ Flexural Strength. ㎏/㎠): It was measured according to ASTM D790.
④ 굴곡탄성율(Flexural Modulus, ㎏/㎠): ASTM D790에 의거하여 측정하였다.④ Flexural Modulus (kg/㎠): Measured according to ASTM D790.
⑤ 경도: ASTM D785(R-scale)에 의거하여 측정하였다.⑤ Hardness: It was measured according to ASTM D785 (R-scale).
⑥ 이행성(Migration): 70 ℃의 오븐에서 기름종이 위에 시편을 놓고, 10 ㎏의 중량물을 올린 후, 1 주일 동안 보관한 후, 기름종이의 변화를 살펴 이행성을 평가하였다. 가소제가 이행되면, 기름종이를 적셔서 기름종이의 색상이 변하게 되므로, 색상이 변하는 것은 이행이 발생하여 가소제가 기름종이에 묻어 나온 것이다. 따라서, 변화가 없는 것은 OK로 표기하였고, 변화가 있는 것은 NG로 표기하였다.⑥ Migration: Place the specimen on oil paper in an oven at 70 ℃, put a weight of 10 kg on it, store it for 1 week, and evaluate the migration by examining the change of the oil paper. When the plasticizer is transferred, the color of the oil paper changes due to wetting the oil paper. Therefore, the color change occurs because the plasticizer is smeared on the oil paper. Therefore, those with no change were marked as OK, and those with change were marked as NG.
구분division 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 3Comparative Example 3 비교예 4Comparative Example 4
(A) 그라프트 공중합체 (중량부)(A) Graft copolymer (parts by weight) (A-1)(A-1) 5050 6565 7070 8585 9090 9595 00
(A-2)(A-2) 00 00 00 00 00 00 7070
(A-3)(A-3) 00 00 00 00 00 00 00
(B) 비그라프트 공중합체 (중량부)(B) non-grafted copolymer (parts by weight) 5050 3535 3030 1515 1010 55 3030
(C) 가소제(중량부)(C) Plasticizer (parts by weight) (C-1)(C-1) 55 55 55 55 55 55 55
(C-2)(C-2) 00 00 00 00 00 00 00
(C-3)(C-3) 00 00 00 00 00 00 00
(D) 스티렌/부타디엔 공중합체(중량부)(D) Styrene/butadiene copolymer (parts by weight) 00 00 00 00 00 00 00
① 유동지수① Flow index 19.219.2 15.015.0 13.813.8 11.011.0 10.110.1 4.44.4 15.715.7
② 투명도② Transparency 0.90.9 1.01.0 1.01.0 1.41.4 1.51.5 2.22.2 3.83.8
③ 굴곡강도③ Flexural strength 570570 480480 377377 320320 304304 300300 360360
④ 굴곡탄성율④ Flexural modulus 16,50016,500 16,00016,000 12,30012,300 12,00012,000 11,80011,800 11,15011,150 10,40010,400
⑤ 경도⑤ hardness 9595 9090 8383 8080 7676 6868 7777
⑥ 이행성⑥ Transitability OKOK OKOK OKOK OKOK OKOK OKOK OKOK
구분division 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6 실시예 7Example 7
(A) 그라프트 공중합체 (중량부)(A) Graft copolymer (parts by weight) (A-1)(A-1) 8585 8585 8585 8585
(A-2)(A-2) 00 00 00 00
(A-3)(A-3) 00 00 00 00
(B) 비그라프트 공중합체 (중량부)(B) non-grafted copolymer (parts by weight) 1515 1515 1515 1515
(C) 가소제(중량부)(C) Plasticizer (parts by weight) (C-1)(C-1) 44 66 99 1010
(C-2)(C-2) 00 00 00 00
(C-3)(C-3) 00 00 00 00
(D) 스티렌/부타디엔 공중합체(중량부)(D) Styrene/butadiene copolymer (parts by weight) 00 00 00 00
① 유동지수① Flow index 7.77.7 11.911.9 14.514.5 15.015.0
② 투명도② Transparency 1.41.4 1.31.3 2.02.0 2.02.0
③ 굴곡강도③ Flexural strength 310310 316316 310310 311311
④ 굴곡탄성율④ Flexural modulus 12,50012,500 12,00012,000 11,90011,900 11,90011,900
⑤ 경도⑤ hardness 7676 7979 7777 7777
⑥ 이행성⑥ Transitability OKOK OKOK OKOK OKOK
구분division 비교예 5Comparative Example 5 실시예 8Example 8 실시예 9Example 9 실시예 10Example 10 비교예 6Comparative Example 6
(A) 그라프트 공중합체 (중량부)(A) Graft copolymer (parts by weight) (A-1)(A-1) 6565 7070 7575 9090 9595
(A-2)(A-2) 00 00 00 00 00
(A-3)(A-3) 00 00 00 00 00
(B) 비그라프트 공중합체 (중량부)(B) non-grafted copolymer (parts by weight) 3535 3030 2525 1010 55
(C) 가소제(중량부)(C) Plasticizer (parts by weight) (C-1)(C-1) 00 00 00 00 00
(C-2)(C-2) 66 55 99 77 99
(C-3)(C-3) 00 00 00 00 00
(D) 스티렌/부타디엔 공중합체(중량부)(D) Styrene/butadiene copolymer (parts by weight) 00 00 00 00 00
① 유동지수① Flow index 15.315.3 13.013.0 16.016.0 10.310.3 8.08.0
② 투명도② Transparency 1.11.1 1.21.2 1.81.8 1.51.5 2.52.5
③ 굴곡강도③ Flexural strength 460460 370370 342342 305305 290290
④ 굴곡탄성율④ Flexural modulus 16,00016,000 12,40012,400 12,10012,100 11,80011,800 11,20011,200
⑤ 경도⑤ hardness 9090 8181 8080 7676 6868
⑥ 이행성⑥ Transitability OKOK OKOK OKOK OKOK OKOK
구분division 실시예 11Example 11 실시예 12Example 12 실시예 13Example 13
(A) 그라프트 공중합체 (중량부)(A) Graft copolymer (parts by weight) (A-1)(A-1) 7070 7070 8080
(A-2)(A-2) 00 00 00
(A-3)(A-3) 00 00 00
(B) 비그라프트 공중합체 (중량부)(B) non-grafted copolymer (parts by weight) 3030 3030 2020
(C) 가소제(중량부)(C) Plasticizer (parts by weight) (C-1)(C-1) 00 00 00
(C-2)(C-2) 00 00 00
(C-3)(C-3) 44 55 99
(D) 스티렌/부타디엔 공중합체(중량부)(D) Styrene/butadiene copolymer (parts by weight) 00 00 00
① 유동지수① Flow index 8.58.5 12.612.6 15.215.2
② 투명도② Transparency 1.01.0 1.11.1 1.91.9
③ 굴곡강도③ Flexural strength 370370 366366 330330
④ 굴곡탄성율④ Flexural modulus 12,40012,400 12,30012,300 12,10012,100
⑤ 경도⑤ hardness 8484 8484 7979
⑥ 이행성⑥ Transitability OKOK OKOK OKOK
구분division 비교예 7Comparative Example 7 비교예 8Comparative Example 8
(A) 그라프트 공중합체 (중량부)(A) Graft copolymer (parts by weight) (A-1)(A-1) 00 00
(A-2)(A-2) 00 00
(A-3)(A-3) 100100 6060
(B) 비그라프트 공중합체 (중량부)(B) non-grafted copolymer (parts by weight) 00 00
(C) 가소제(중량부)(C) Plasticizer (parts by weight) (C-1)(C-1) 00 00
(C-2)(C-2) 00 00
(C-3)(C-3) 00 00
(D) 스티렌/부타디엔 공중합체(중량부)(D) Styrene/butadiene copolymer (parts by weight) 00 4040
① 유동지수① Flow index 23.023.0 53.353.3
② 투명도② Transparency 2.02.0 불투명opacity
③ 굴곡강도③ Flexural strength 720720 515515
④ 굴곡탄성율④ Flexural modulus 23,00023,000 17,79317,793
⑤ 경도⑤ hardness 104104 3636
⑥ 이행성⑥ Transitability OKOK OKOK
상기 표 1을 참조하면, 그라프트 공중합체와 비그라프트 공중합체를 적정량으로 포함하는 실시예 1 내지 실시예 3은 유동지수, 투명도, 굴곡강도, 굴곡탄성율, 경도 및 이행성이 모두 우수하여 인조손톱용으로 적절하였다. 하지만, 그라프트 공중합체를 소량으로 포함하는 비교예 1 및 2는, 실시예 1 내지 실시예 3 대비 굴곡강도, 굴곡탄성율 및 경도가 높아 인조손톱용으로 부적절하였다. 또한, 그라프트 공중합체를 과량으로 포함하는 비교예 3은, 실시예 1 내지 실시예 3 대비 유동지수가 낮아 가공성이 저하되었고, 투명도가 높아 인조손톱용으로 부적절하였다. 디엔계 고무질 중합체의 평균입경이 큰 비교예 4는 투명도가 높고 굴곡탄성율이 낮아 인조손톱용으로 적절하지 않았다.상기 표 2를 참조하면, 가소제 함량의 적정 범위 내에서 가소제 함량이 증가함에 따라 투명성은 유지하면서 유동지수가 증가하는 것을 확인할 수 있었다. 특히, 실시예 5 내지 7의 경우, 실시예 4 대비 유동지수가 10 g/10min 이상으로서 가공성이 우수한 것을 확인할 수 있었다. Referring to Table 1 above, Examples 1 to 3 containing a graft copolymer and a non-graft copolymer in an appropriate amount are excellent in flow index, transparency, flexural strength, flexural modulus, hardness and transferability. It was suitable for use. However, Comparative Examples 1 and 2 containing a small amount of the graft copolymer were inadequate for artificial nails due to their higher flexural strength, flexural modulus, and hardness compared to Examples 1 to 3. In addition, Comparative Example 3 containing an excessive amount of the graft copolymer had a lower flow index compared to Examples 1 to 3, resulting in lower processability, and high transparency, making it inappropriate for artificial nails. Comparative Example 4, which had a large average particle diameter of the diene-based rubber polymer, was not suitable for artificial nails due to its high transparency and low flexural modulus. Referring to Table 2, as the plasticizer content increases within an appropriate range of the plasticizer content, the transparency is increased. It was confirmed that the flow index increased while maintaining. Particularly, in the case of Examples 5 to 7, it was confirmed that the flow index was 10 g/10min or more compared to Example 4, which was excellent in processability.
상기 표 3을 참조하면, 그라프트 공중합체와 비그라프트 공중합체를 최적 함량으로 포함하는 실시예 8 내지 실시예 10은 유동지수, 투명도, 굴곡강도, 굴곡탄성율, 경도 및 이행성이 모두 우수하여 인조손톱용으로 적절하였다. 하지만, 그라프트 공중합체를 소량으로 포함하는 비교예 5는 굴곡강도, 굴곡탄성율 및 경도가 높아 인조손톱용으로 부적절하였다. 그라프트 공중합체를 과량으로 포함하는 비교예 6은 유동지수가 낮아 가공성이 저하되었고, 투명도가 높았고, 굴곡탄성율이 낮아 인조손톱용으로 부적절하였다. Referring to Table 3 above, Examples 8 to 10 containing the graft copolymer and the non-grafted copolymer in the optimal content are excellent in flow index, transparency, flexural strength, flexural modulus, hardness and transferability. It was suitable for nails. However, Comparative Example 5 containing a small amount of the graft copolymer was unsuitable for artificial nails due to its high flexural strength, flexural modulus and hardness. Comparative Example 6 containing an excessive amount of the graft copolymer had a low flow index, low processability, high transparency, and low flexural modulus, making it inappropriate for artificial nails.
상기 표 4를 참조하면, 가소제 함량의 적정 범위 내에서 실시예 11 내지 실시예 13은 투명도, 굴곡강도, 굴곡탄성율, 경도 및 이행성이 모두 우수하여 인조손톱용으로 적절하였다. 특히, 실시예 12 및 13의 경우, 실시예 11 대비 유동지수가 10 g/10min 이상으로서 가공성이 우수한 것을 확인할 수 있었다. Referring to Table 4, within an appropriate range of the plasticizer content, Examples 11 to 13 were suitable for artificial nails due to excellent transparency, flexural strength, flexural modulus, hardness, and transferability. Particularly, in the case of Examples 12 and 13, it was confirmed that the flow index was 10 g/10min or more compared to Example 11, which was excellent in processability.
상기 표 5를 참조하면, 그라프트 공중합체로 이루어진 비교예 7은 굴곡강도, 굴곡탄성율 및 경도가 높아 인조손톱용으로 부적절하였고, 그라프트 공중합체와 스티렌/부타디엔 공중합체로 이루어진 비교예 8은 불투명하고, 굴곡강도 및 굴곡탄성율이 높아 인조손톱용으로 부적절하였다.Referring to Table 5, Comparative Example 7 consisting of a graft copolymer was unsuitable for artificial nails due to its high flexural strength, flexural modulus and hardness, and Comparative Example 8 consisting of a graft copolymer and a styrene/butadiene copolymer was opaque. It was not suitable for artificial nails due to its high flexural strength and flexural modulus.

Claims (9)

  1. 평균입경이 50 내지 200 ㎚인 디엔계 고무질 중합체에 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제1 단량체 혼합물을 그라프트 중합한 제1 공중합체, 및 알킬 (메트)아크릴레이트계 단량체 및 방향족 비닐계 단량체를 포함하는 제2 단량체 혼합물의 공중합물인 제2 공중합체를 70:30 내지 90:10의 중량비로 포함하는 베이스 수지; 및 A first copolymer obtained by graft polymerization of a first monomer mixture including an alkyl (meth)acrylate monomer and an aromatic vinyl monomer on 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, which 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
    가소제를 포함하는 열가소성 수지 조성물.Thermoplastic resin composition containing a plasticizer.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 베이스 수지 100 중량부; 및 100 parts by weight of the base resin; And
    상기 가소제 4 내지 10 중량부를 포함하는 열가소성 수지 조성물.Thermoplastic resin composition comprising 4 to 10 parts by weight of the plasticizer.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 가소제는 폴리에스터계 가소제인 열가소성 수지 조성물.The thermoplastic resin composition of the plasticizer is a polyester plasticizer.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 가소제는 점도가 1,500 내지 5,000 cps인 것인 열가소성 수지 조성물.The thermoplastic resin composition that the plasticizer has a viscosity of 1,500 to 5,000 cps.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 가소제는 폴리디(2-에틸헥실)글리콜아디페이트; 헥산디오익산, 폴리머 위드 1,3-부탄디올, 2-에틸헥실 에스터; 헥산디오익산, 폴리머 위드 1,3-부타디올 앤드 1,2-프로판디올, 2-에틸헥실 에스터; 및 헥산디오익산, 폴리머 위드 2,2-디메틸-1,3-프로판디올 앤드 1,2-프로판디올, 이소노닐 에스터로 이루어진 군에서 선택되는 1종 이상인 것인 열가소성 수지 조성물.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 at least one selected from the group consisting of isononyl ester.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 가소제는 굴절률이 1.45 내지 1.6인 것인 열가소성 수지 조성물.The plasticizer is a thermoplastic resin composition having a refractive index of 1.45 to 1.6.
  7. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 공중합체와 제2 공중합체는 굴절률의 차이가 0.01 이하인 것인 열가소성 수지 조성물.The first copolymer and the second copolymer have a difference in refractive index of 0.01 or less.
  8. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 및 제2 단량체 혼합물은 각각 시안화 비닐계 단량체를 더 포함하는 것인 열가소성 수지 조성물.Each of the first and second monomer mixtures further comprises a vinyl cyanide-based monomer.
  9. 청구항 1에 따른 열가소성 수지 조성물로 제조되고,Made of the thermoplastic resin composition according to claim 1,
    투명도가 2.0 % 이하이고, 굴곡강도가 280 내지 420 ㎏/㎠이고, 굴곡탄성율이 11,000 내지 13,500 ㎏/㎠인 열가소성 수지 성형품.A thermoplastic resin molded article having 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/cm2.
PCT/KR2020/007286 2019-06-13 2020-06-04 Thermoplastic resin composition WO2020251215A1 (en)

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JP2021542507A JP7325852B2 (en) 2019-06-13 2020-06-04 Thermoplastic resin composition
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KR20120078583A (en) * 2010-12-31 2012-07-10 제일모직주식회사 Thermoplastic resin composition with improved white turbidity phenomenon at low temperature
KR20130074427A (en) * 2011-12-26 2013-07-04 제일모직주식회사 Thermoplastic resin composition with excellent flowability and transparency
WO2016052832A1 (en) * 2014-10-02 2016-04-07 (주) 엘지화학 Thermoplastic resin composition having excellent chemical resistance and transparency, method for preparing same, and molded product comprising same
KR20170069456A (en) * 2015-12-11 2017-06-21 주식회사 엘지화학 Thermoplastic resin composition and molded article comprision the same
US20170233548A1 (en) * 2014-08-19 2017-08-17 Basf Se Plasticizer composition comprising polymeric dicarboxylic esters

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Publication number Priority date Publication date Assignee Title
KR20120078583A (en) * 2010-12-31 2012-07-10 제일모직주식회사 Thermoplastic resin composition with improved white turbidity phenomenon at low temperature
KR20130074427A (en) * 2011-12-26 2013-07-04 제일모직주식회사 Thermoplastic resin composition with excellent flowability and transparency
US20170233548A1 (en) * 2014-08-19 2017-08-17 Basf Se Plasticizer composition comprising polymeric dicarboxylic esters
WO2016052832A1 (en) * 2014-10-02 2016-04-07 (주) 엘지화학 Thermoplastic resin composition having excellent chemical resistance and transparency, method for preparing same, and molded product comprising same
KR20170069456A (en) * 2015-12-11 2017-06-21 주식회사 엘지화학 Thermoplastic resin composition and molded article comprision the same

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