WO2022080822A1 - Surface-modified polylactic acid particle and preparation method therefor - Google Patents

Surface-modified polylactic acid particle and preparation method therefor Download PDF

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WO2022080822A1
WO2022080822A1 PCT/KR2021/014025 KR2021014025W WO2022080822A1 WO 2022080822 A1 WO2022080822 A1 WO 2022080822A1 KR 2021014025 W KR2021014025 W KR 2021014025W WO 2022080822 A1 WO2022080822 A1 WO 2022080822A1
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polylactic acid
acid particles
particles
modified
modified polylactic
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PCT/KR2021/014025
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French (fr)
Korean (ko)
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조혜민
김민경
강성용
최준호
송재한
공효재
김진홍
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(주)엘엑스하우시스
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to surface-modified polylactic acid particles and a method for preparing the same. Specifically, it relates to polylactic acid particles whose surface is modified with phytic acid and a method for preparing the same.
  • Polylactic acid is a kind of biomass raw material, and since it uses vegetable starch such as corn, sugar cane, and sweet potato as raw material, it is an eco-friendly thermoplastic that can replace traditional petrochemical polymers. It is in the spotlight as a polymer resin.
  • the polylactic acid is a representative biocompatible polymer resin having biodegradability and has been applied to conventional surgical sutures and prosthetic materials.
  • polylactic acid has poor heat resistance because it can easily deform under high temperature conditions, and the disadvantages are that the chemical resistance, which is enough to withstand chemical treatment, heat resistance, which is enough to withstand harsh conditions at high temperature, and impact resistance are markedly inferior.
  • polylactic acid in powder form was used as a biomass raw material for UV coating, but polylactic acid has significantly lower stability to solvents.
  • HDDA 1,6-hexanediol diacrylate
  • a swelling phenomenon in which the polylactic acid polymer absorbs the solvent and swells occurs easily. There was a problem with falling.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2000-128995, Method for Manufacturing Thermoplastic Particles
  • the present inventors completed the present invention by studying polylactic acid particles surface-modified with phytic acid and a method for preparing the same.
  • polylactic acid particles polylactic acid particles; and a coating layer located on the surface of the polylactic acid particles, wherein the coating layer includes phytic acid.
  • the coating layer may have a continuous coating form or an island coating form on the surface of the polylactic acid particles.
  • the coating layer may be formed by modifying the surface of the polylactic acid particles with phytic acid.
  • the surface-modified polylactic acid particles may have a 10% cumulative volume particle diameter (D 10 ) of 0.1 to 3 ⁇ m.
  • the surface-modified polylactic acid particles may have a cumulative volume 50% particle diameter (D 50 ) of 3.5 to 9 ⁇ m.
  • the surface-modified polylactic acid particles may have a 90% cumulative volume particle diameter (D 90 ) of 10 to 30 ⁇ m.
  • the cumulative volume of the surface-modified polylactic acid particles increases by 50% of the particle diameter (D 50 ) of 0.1 to 10%.
  • a method for producing surface-modified polylactic acid particles comprising the steps of: (1) preparing a phytic acid coating solution containing phytic acid; (2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surface with phytic acid; and (3) drying the modified polylactic acid particles.
  • step (1) may be a step of preparing a phytic acid coating solution by mixing an alcohol-based solvent and phytic acid.
  • the present invention relates to surface-modified polylactic acid particles having improved stability in various solvents, reduction in the degree of aggregation between particles, chemical resistance and heat resistance through surface treatment with phytic acid in the production of polylactic acid in powder form, and surface-modified polylactic acid particles thereof A manufacturing method is provided.
  • Example 1 shows an SEM image of the particle surface of Example 1, which is a polylactic acid particle surface-modified with phytic acid of the present invention.
  • Example 2 is a graph showing the particle size distribution (PSD) of Example 1, which is a polylactic acid particle surface-modified with phytic acid of the present invention.
  • Comparative Example 3 is a graph showing the particle size distribution (PSD) of Comparative Example 1, which is a polylactic acid particle that is not surface-modified.
  • Example 4 is a photograph showing the chemical resistance evaluation of Example 1 and Comparative Example 1 of the present invention.
  • Example 5 is a graph showing the particle size distribution (PSD) of Example 1, which is the polylactic acid particle surface-modified with phytic acid of the present invention, after heat resistance evaluation.
  • PSD particle size distribution
  • Comparative Example 6 is a graph showing a particle size distribution (PSD) after heat resistance evaluation of Comparative Example 1, which is a polylactic acid particle that has not been surface-modified.
  • PSD particle size distribution
  • the conventional polylactic acid (PLA) particles whose surface is not modified at all absorb the solvent and easily cause swelling, causing the particles to swell and have low chemical resistance. There was a problem with low heat resistance due to the severity of the problem.
  • the inventors of the present invention have modified the surface of polylactic acid particles to form a coating layer containing phytic acid on the surface of the polylactic acid particles, and surface-modified polylactic acid particles and their A manufacturing method was invented.
  • the surface-modified polylactic acid particles according to the present invention include polylactic acid particles; and a coating layer positioned on the surface of the polylactic acid particles, wherein the coating layer includes phytic acid.
  • the surface-modified polylactic acid particles include polylactic acid particles.
  • the polylactic acid particles may be included in the central portion of the particles in the form of a core with respect to the surface-modified polylactic acid particles.
  • the polylactic acid particles are thermoplastic aliphatic polyester-based polymers and preferably have a molecular weight of 30,000 to 40,000.
  • the surface-modified polylactic acid particles include a coating layer positioned on the surface of the polylactic acid particles, and the coating layer includes phytic acid.
  • the coating layer may have a continuous coating form or an island coating form on the surface of the polylactic acid particles.
  • the coating layer may have a continuous coating form covering the entire surface of the polylactic acid particles or an island coating form coated sporadically and irregularly on the surface of the particles.
  • the coating layer may preferably be in the form of an island coating, but is not particularly limited thereto.
  • the coating layer may be formed by modifying the surface of the polylactic acid particles with phytic acid.
  • a coating layer containing phytic acid particles is formed on the surface of the polylactic acid particles in the form of a continuous coating or a discontinuous island coating that covers the entire surface of the particles as described above, whereby the surface of the polylactic acid particles is modified may be in the form of
  • the coating layer may be a hydrophilic coating layer or a hydrophobic coating layer, but is not particularly limited thereto.
  • the coating layer is a hydrophilic coating layer, it is possible to increase the dispersion power of the hydrophobic polylactic acid particles in a hydrophilic solvent, so that it can be applied to application fields such as water dispersion.
  • the coating layer is a hydrophobic coating layer, there is an advantage of improving the chemical resistance of the polylactic acid particles to be applicable to application fields such as UV coating solution and thermal coating solution.
  • the surface-modified polylactic acid particles may have a cumulative volume 10% particle diameter (D 10 ) of 0.1 to 3 ⁇ m, preferably 1 to 2.5 ⁇ m, more preferably 1.5 to 2 ⁇ m, and the surface-modified polylactic acid
  • the particles may have a cumulative volume 50% particle diameter (D 50 ) of 3.5 to 9 ⁇ m, preferably 4 to 7 ⁇ m, more preferably 4.5 to 5 ⁇ m, and the surface-modified polylactic acid particles are 10 to 30 ⁇ m, preferably may have a 90% cumulative volume particle diameter (D 90 ) of 14 to 27 ⁇ m, more preferably 17 to 24 ⁇ m.
  • the increase rate of the particle diameter (D 50 ) by 50% of the cumulative volume of the surface-modified polylactic acid particles is 0.1 to 10%, preferably 0.5 to 7%, more preferably 0.75 to 4%.
  • Surface-modified polylactic acid particles satisfying the above range may have insignificant aggregation between particles even under severe high temperature conditions due to excellent heat resistance.
  • a method for producing surface-modified polylactic acid particles according to the present invention comprising the steps of: (1) preparing a phytic acid coating solution containing phytic acid; (2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surface with phytic acid; and (3) drying the modified polylactic acid particles.
  • the method for producing the surface-modified polylactic acid particles includes (1) preparing a phytic acid coating solution containing phytic acid.
  • Step (1) may be a step of preparing a phytic acid coating solution by mixing an alcohol-based solvent and phytic acid.
  • the alcohol-based solvent may have a concentration of 10 to 100%.
  • the alcohol-based solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, and combinations thereof, but preferably ethanol. However, it is not particularly limited thereto.
  • the method for preparing the surface-modified polylactic acid particles includes (2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surfaces with phytic acid.
  • step (2) polylactic acid particles in powder form are impregnated with the phytic acid coating solution prepared in step (1) to form a chemical bond between the polylactic acid particles and phytic acid by a wet coating method. It can be effective in that the bond is permanent. In order to form the above bond, it is preferable to impregnate the polylactic acid particles with the phytic acid coating solution at room temperature for 10 to 30 minutes.
  • the surface of the polylactic acid particles may be modified through a dry coating method instead of a wet coating.
  • the dry coating method may be a modification method in which a coating agent containing phytic acid is dispersed in an alcohol-based solvent and then sprayed through a spray to form a physical bond between the polylactic acid particles and phytic acid to form a coating layer on the particle surface. there is.
  • the method for producing the surface-modified polylactic acid particles includes (3) drying the modified polylactic acid particles.
  • Step (3) may be a drying step for removing the solvent remaining on the surface-modified polylactic acid particles on which the coating layer containing phytic acid is formed through step (2).
  • an oven may be used as drying equipment. By drying in the oven at 50 to 90°C, preferably at 60 to 80°C, for 2 to 3 hours, polylactic acid particles surface-modified with phytic acid can be finally prepared.
  • a coating solution was prepared by mixing phytic acid.
  • Polylactic acid particles (LUSMAPOL, LG Hausys) in powder form were impregnated with the coating solution containing phytic acid, and then dried at 70° C. for 3 hours using an oven with drying equipment, and finally the surface with phytic acid Modified polylactic acid particles were prepared.
  • polylactic acid particles that were not subjected to any surface modification treatment were prepared.
  • Example 1 For the polylactic acid particles of Example 1 and Comparative Example 1 , the particle size was measured through a particle size analyzer (Mastersizer3000, Malvern), and the particle size distribution (PSD) was measured in Table 1, FIG. 2 (Example 1) and 3 (Comparative Example 1) is shown.
  • Mastersizer3000 Malvern
  • PSD particle size distribution
  • Example 1 After dispersing the polylactic acid particles of Example 1 and Comparative Example 1 in HDDA (1,6-Hexanediol diacrylate), which is a UV coating solution monomer, an experiment was conducted to check whether swelling occurred after 1 minute.
  • HDDA 1,6-Hexanediol diacrylate
  • Example 1 in which the surface of the polylactic acid particles was modified with phytic acid, no swelling occurred, but the side and bottom surfaces of the container of Comparative Example 1 in which the unmodified polylactic acid particles were dispersed were observed. Through this, it was visually confirmed that the polylactic acid particles absorbed the solvent, resulting in swelling.
  • Example 1 the polylactic acid particles of Example 1 and Comparative Example 1 were heated at 70° C. for 24 hours, and then the particle size was measured through a particle size analyzer (Mastersizer3000, Malvern).
  • PSD particle size distribution
  • Example 1 As a result of heat resistance evaluation through particle size analysis after heating, in the case of Example 1, as compared to 4.61 ⁇ m, which is D 50 under the room temperature condition (before heating) of Experimental Example 1, by 0.05 ⁇ m (1.1% increase compared to D 50 at room temperature condition) D 50 was found to increase. Through this, it was confirmed that the degree of aggregation between the polylactic acid particles was insignificant due to the effect of improved heat resistance even under the harsh conditions of 70°C according to the surface modification of the phytic acid, and thus the degree of increase in the particle size was also insignificant.
  • the polylactic acid particles whose surface was modified with phytic acid had improved heat resistance even under harsh conditions at high temperatures.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
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Abstract

The present invention relates to a surface-modified polylactic acid particle and a preparation method therefor, the surface-modified polylactic acid including: a polylactic acid particle; and a coating layer on the surface of the polylactic acid particle wherein the coating layer contains phytic acid.

Description

표면 개질된 폴리락틱산 입자 및 이의 제조방법Surface-modified polylactic acid particles and manufacturing method thereof
본 발명은 표면 개질된 폴리락틱산 입자 및 이의 제조방법에 관한 것이다. 구체적으로는 표면을 피트산(Phytic Acid)으로 개질한 폴리락틱산 입자 및 이의 제조방법에 관한 것이다.The present invention relates to surface-modified polylactic acid particles and a method for preparing the same. Specifically, it relates to polylactic acid particles whose surface is modified with phytic acid and a method for preparing the same.
폴리락틱산(PLA, Polylactic Acid)은 바이오매스(Biomass) 원료의 일종으로, 옥수수, 사탕수수, 고구마와 같은 식물성 전분을 원료로 한다는 점에서 기존의 전통적인 석유화학계 고분자를 대체할 수 있는 친환경적인 열가소성 고분자 수지로 각광받고 있다. 또한 상기 폴리락틱산은 생분해성을 가지는 대표적인 생체적합성 고분자 수지로 종래 수술용 봉합사, 보철재료 등에 적용되어 사용되었으며 최근에는 3D 프린팅시 강도와 내구성이 우수하다는 점에서 고체 필라멘트의 재료로 까지 널리 사용되고 있다.Polylactic acid (PLA) is a kind of biomass raw material, and since it uses vegetable starch such as corn, sugar cane, and sweet potato as raw material, it is an eco-friendly thermoplastic that can replace traditional petrochemical polymers. It is in the spotlight as a polymer resin. In addition, the polylactic acid is a representative biocompatible polymer resin having biodegradability and has been applied to conventional surgical sutures and prosthetic materials.
다만, 폴리락틱산은 높은 온도조건에서 변형이 쉽게 생길 수 있어 내열성이 떨어지며, 화학적 물질 처리시 이를 견디는 정도인 내화학성, 고온의 가혹한 조건에서 견디는 정도인 내열성 그리고 내충격성이 현저히 떨어진다는 점이 단점으로 지적되어 왔다.However, polylactic acid has poor heat resistance because it can easily deform under high temperature conditions, and the disadvantages are that the chemical resistance, which is enough to withstand chemical treatment, heat resistance, which is enough to withstand harsh conditions at high temperature, and impact resistance are markedly inferior. has been
구체적으로 UV 코팅시 바이오매스 원료로써 파우더 형태의 폴리락틱산이 사용되었으나 폴리락틱산이 용매에 대한 안정성이 현저히 떨어지며. 특히 1,6-헥산디올 디아크릴레이트(HDDA, 1,6-hexanediol diacrylate)를 용매로 사용하는 경우에는 폴리락틱산 고분자가 용매를 흡수하여 팽창하는 팽윤(swelling)현상이 쉽게 나타나는 바 내화학성이 떨어지는 문제점이 있었다.Specifically, polylactic acid in powder form was used as a biomass raw material for UV coating, but polylactic acid has significantly lower stability to solvents. In particular, when 1,6-hexanediol diacrylate (HDDA, 1,6-hexanediol diacrylate) is used as a solvent, a swelling phenomenon in which the polylactic acid polymer absorbs the solvent and swells occurs easily. There was a problem with falling.
또한 폴리락틱산을 활용하는 화장품 제조 공정인 70℃ 이상의 고온 조건에서는 폴리락틱산 입자가 쉽게 응집된다는 점에서 내열성 개선의 필요성이 지적되어 왔다.In addition, the need to improve heat resistance has been pointed out in that polylactic acid particles are easily aggregated under high temperature conditions of 70° C. or higher, which is a cosmetic manufacturing process using polylactic acid.
따라서, 폴리락틱산 입자를 다양한 조건에서 활용하기 위하여 용매와의 안정성, 내화학성 및 내열성을 향상시킨, 폴리락틱산 입자 및 이의 제조방법에 대한 연구개발이 필요한 실정이다.Therefore, in order to utilize the polylactic acid particles in various conditions, there is a need for research and development on polylactic acid particles and a method for manufacturing the same, which have improved stability with a solvent, chemical resistance, and heat resistance.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 1) 일본 공개특허공보 제2000-128995호, 열가소성 입자의 제조방법(Patent Document 1) Japanese Patent Application Laid-Open No. 2000-128995, Method for Manufacturing Thermoplastic Particles
본 발명자들은 상기 문제를 해결하기 위하여, 피트산으로 표면 개질된 폴리락틱산 입자 및 이의 제조방법에 대하여 연구하여 본 발명을 완성시켰다.In order to solve the above problem, the present inventors completed the present invention by studying polylactic acid particles surface-modified with phytic acid and a method for preparing the same.
따라서, 본 발명의 목적은 다양한 용매에 대한 적용이나 급격히 변하는 온도 조건 등 다양한 환경 속에서도 폴리락틱산 입자가 안정적인 입자 크기, 우수한 내화학성 및 내열성을 갖는 표면 개질된 폴리락틱산 입자 및 이의 제조방법을 제공하는 것이다.Accordingly, it is an object of the present invention to provide surface-modified polylactic acid particles having a stable particle size, excellent chemical resistance and heat resistance in various environments such as application to various solvents or rapidly changing temperature conditions, and a method for manufacturing the same will do
본 발명의 제 1 측면에 따르면,According to a first aspect of the invention,
폴리락틱산(Polylactic Acid) 입자; 및 상기 폴리락틱산 입자의 표면상에 위치한 코팅층;을 포함하고, 상기 코팅층은 피트산(Phytic Acid)을 포함하는, 표면 개질된 폴리락틱산 입자를 제공한다.polylactic acid particles; and a coating layer located on the surface of the polylactic acid particles, wherein the coating layer includes phytic acid.
본 발명의 일 구체 예에 있어서, 상기 코팅층이 상기 폴리락틱산 입자의 표면 상에서 연속된 코팅 형태 또는 아일랜드 코팅 형태를 가질 수 있다.In one embodiment of the present invention, the coating layer may have a continuous coating form or an island coating form on the surface of the polylactic acid particles.
본 발명의 일 구체 예에 있어서, 상기 코팅층은 상기 폴리락틱산 입자의 표면이 피트산으로 개질되어 형성될 수 있다.In one embodiment of the present invention, the coating layer may be formed by modifying the surface of the polylactic acid particles with phytic acid.
본 발명의 일 구체 예에 있어서, 상기 표면 개질된 폴리락틱산 입자는 0.1 내지 3μm의 누적 부피 10% 입경(D10)을 가질 수 있다.In one embodiment of the present invention, the surface-modified polylactic acid particles may have a 10% cumulative volume particle diameter (D 10 ) of 0.1 to 3 μm.
본 발명의 일 구체 예에 있어서, 상기 표면 개질된 폴리락틱산 입자는 3.5 내지 9μm의 누적 부피 50% 입경(D50)을 가질 수 있다.In one embodiment of the present invention, the surface-modified polylactic acid particles may have a cumulative volume 50% particle diameter (D 50 ) of 3.5 to 9 μm.
본 발명의 일 구체 예에 있어서, 상기 표면 개질된 폴리락틱산 입자는 10 내지 30μm의 누적 부피 90% 입경(D90)을 가질 수 있다.In one embodiment of the present invention, the surface-modified polylactic acid particles may have a 90% cumulative volume particle diameter (D 90 ) of 10 to 30 μm.
본 발명의 일 구체 예에 있어서, 상기 표면 개질된 폴리락틱산 입자를 70℃에서 24시간 동안 가열시켰을 때, 상기 표면 개질된 폴리락틱산 입자의 누적 부피 50% 입경(D50)의 증가율이 0.1 내지 10% 일 수 있다.In one embodiment of the present invention, when the surface-modified polylactic acid particles are heated at 70° C. for 24 hours, the cumulative volume of the surface-modified polylactic acid particles increases by 50% of the particle diameter (D 50 ) of 0.1 to 10%.
본 발명의 제 2 측면에 따르면,According to a second aspect of the invention,
표면 개질된 폴리락틱산 입자의 제조방법으로서, (1) 피트산을 포함하는 피트산 코팅액을 준비하는 단계; (2) 폴리락틱산 입자를 상기 피트산 코팅액에 함침시켜 피트산으로 입자 표면을 개질하는 단계; 및 (3) 상기 개질된 폴리락틱산 입자를 건조시키는 단계;를 포함하는, 표면 개질된 폴리락틱산 입자의 제조방법을 제공한다.A method for producing surface-modified polylactic acid particles, comprising the steps of: (1) preparing a phytic acid coating solution containing phytic acid; (2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surface with phytic acid; and (3) drying the modified polylactic acid particles.
본 발명의 일 구체 예에 있어서, 상기 (1) 단계는 알코올계 용매와 피트산을 혼합하여 피트산 코팅액을 제조하는 단계일 수 있다.In one embodiment of the present invention, step (1) may be a step of preparing a phytic acid coating solution by mixing an alcohol-based solvent and phytic acid.
본 발명은, 파우더 형태의 폴리락틱산 제조 시에 피트산을 통한 표면처리를 통해 다양한 용매에서의 안정성, 입자간 응집 정도의 저하, 내화학성 및 내열성을 향상시킨 표면 개질된 폴리락틱산 입자 및 이의 제조방법을 제공한다.The present invention relates to surface-modified polylactic acid particles having improved stability in various solvents, reduction in the degree of aggregation between particles, chemical resistance and heat resistance through surface treatment with phytic acid in the production of polylactic acid in powder form, and surface-modified polylactic acid particles thereof A manufacturing method is provided.
도 1은 본 발명의 피트산으로 표면 개질된 폴리락틱산 입자인 실시예 1의 입자 표면의 SEM 이미지를 나타낸 것이다.1 shows an SEM image of the particle surface of Example 1, which is a polylactic acid particle surface-modified with phytic acid of the present invention.
도 2는 본 발명의 피트산으로 표면 개질된 폴리락틱산 입자인 실시예 1의 입도분포(PSD)를 나타낸 그래프이다.2 is a graph showing the particle size distribution (PSD) of Example 1, which is a polylactic acid particle surface-modified with phytic acid of the present invention.
도 3은 표면 개질이 되지 않은 폴리락틱산 입자인 비교예 1의 입도분포(PSD)를 나타낸 그래프이다.3 is a graph showing the particle size distribution (PSD) of Comparative Example 1, which is a polylactic acid particle that is not surface-modified.
도 4는 본 발명의 실시예 1과 비교예 1에 대하여 내화학성 평가를 실시한 사진이다.4 is a photograph showing the chemical resistance evaluation of Example 1 and Comparative Example 1 of the present invention.
도 5는 본 발명의 피트산으로 표면 개질된 폴리락틱산 입자인 실시예 1에 대하여 내열성 평가를 실시한 이후의 입도분포(PSD)를 나타낸 그래프이다.5 is a graph showing the particle size distribution (PSD) of Example 1, which is the polylactic acid particle surface-modified with phytic acid of the present invention, after heat resistance evaluation.
도 6은 표면 개질이 되지 않은 폴리락틱산 입자인 비교예 1에 대하여 내열성 평가를 실시한 이후의 입도분포(PSD)를 나타낸 그래프이다.6 is a graph showing a particle size distribution (PSD) after heat resistance evaluation of Comparative Example 1, which is a polylactic acid particle that has not been surface-modified.
본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 첨부되는 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다. 명세서 전체에 걸쳐 동일 참조 부호는 동일 구성요소를 지칭한다.Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention belongs It is provided to fully inform the possessor of the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout.
이하 첨부된 도면을 참조하여 본 발명의 바람직한 실시예에 따른 표면 개질된 폴리락틱산 입자에 관하여 상세히 설명하면 다음과 같다.Hereinafter, the surface-modified polylactic acid particles according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.
본 발명자들의 실험 결과, 표면이 전혀 개질되지 않은 종래의 폴리락틱산(PLA) 입자는 용매를 흡수하여 입자가 부푸는 팽윤현상이 쉽게 발생하여 낮은 내화학성을 가지며, 고온의 가혹한 조건에서는 입자간 응집되는 정도가 심해져 낮은 내열성을 갖는 문제점이 존재하였습니다. As a result of the experiments of the present inventors, the conventional polylactic acid (PLA) particles whose surface is not modified at all absorb the solvent and easily cause swelling, causing the particles to swell and have low chemical resistance. There was a problem with low heat resistance due to the severity of the problem.
본 발명의 발명자들은 상기와 같은 문제점을 해결하기 위하여, 폴리락틱산 입자의 표면을 개질하여, 폴리락틱산 입자의 표면에 피트산을 포함하는 코팅층을 형성한, 표면 개질된 폴리락틱산 입자 및 이의 제조방법에 대하여 발명하기에 이르렀다.In order to solve the above problems, the inventors of the present invention have modified the surface of polylactic acid particles to form a coating layer containing phytic acid on the surface of the polylactic acid particles, and surface-modified polylactic acid particles and their A manufacturing method was invented.
표면 개질된 폴리락틱산 입자Surface-modified polylactic acid particles
본 발명에 따른 표면 개질된 폴리락틱산 입자는 폴리락틱산(Polylactic Acid) 입자; 및 상기 폴리락틱산 입자의 표면상에 위치한 코팅층;을 포함하고, 상기 코팅층은 피트산(Phytic Acid)을 포함한다.The surface-modified polylactic acid particles according to the present invention include polylactic acid particles; and a coating layer positioned on the surface of the polylactic acid particles, wherein the coating layer includes phytic acid.
상기 표면 개질된 폴리락틱산 입자는 폴리락틱산 입자를 포함한다. 구체적으로, 표면 개질된 폴리락틱산 입자에 대하여 코어(core) 형태로 입자 중앙부에 폴리락틱산 입자를 포함할 수 있다.The surface-modified polylactic acid particles include polylactic acid particles. Specifically, the polylactic acid particles may be included in the central portion of the particles in the form of a core with respect to the surface-modified polylactic acid particles.
상기 폴리락틱산 입자는 열가소성의 지방족 폴리에스테르계 고분자로서, 분자량이 30,000 내지 40,000인 고분자인 것이 바람직하다. The polylactic acid particles are thermoplastic aliphatic polyester-based polymers and preferably have a molecular weight of 30,000 to 40,000.
상기 표면 개질된 폴리락틱산 입자는 상기 폴리락틱산 입자의 표면상에 위치한 코팅층을 포함하고, 상기 코팅층은 피트산(Phytic Acid)을 포함한다.The surface-modified polylactic acid particles include a coating layer positioned on the surface of the polylactic acid particles, and the coating layer includes phytic acid.
상기 피트산을 코팅층에 포함함으로써 표면 개질된 폴리락틱산 입자의 내열성과 내화학성을 개선시킬 수 있다.By including the phytic acid in the coating layer, heat resistance and chemical resistance of the surface-modified polylactic acid particles can be improved.
상기 코팅층이 상기 폴리락틱산 입자의 표면 상에서 연속된 코팅 형태 또는 아일랜드 코팅 형태를 가질 수 있다. 구체적으로, 상기 코팅층은 상기 폴리락틱산 입자의 표면 전체를 모두 덮는 연속된 코팅 형태 또는 입자의 표면에 산발적으로 불규칙적인 형태로 코팅된 아일랜드 코팅 형태를 가질 수 있다. 상기 코팅층은 바람직하게는 아일랜드 코팅 형태일 수 있으나, 다만 이에 특별히 제한되는 것은 아니다.The coating layer may have a continuous coating form or an island coating form on the surface of the polylactic acid particles. Specifically, the coating layer may have a continuous coating form covering the entire surface of the polylactic acid particles or an island coating form coated sporadically and irregularly on the surface of the particles. The coating layer may preferably be in the form of an island coating, but is not particularly limited thereto.
상기 코팅층은 상기 폴리락틱산 입자의 표면이 피트산으로 개질되어 형성될 수 있다. 상기 폴리락틱산 입자의 표면 상에 상기와 같이 입자의 표면 전체를 모두 덮는 연속적인 코팅 형태 또는 비연속적인 아일랜드 코팅 형태로 피트산 입자를 포함하는 코팅층이 형성됨으로써, 폴리락틱산 입자의 표면이 개질된 형태일 수 있다. The coating layer may be formed by modifying the surface of the polylactic acid particles with phytic acid. A coating layer containing phytic acid particles is formed on the surface of the polylactic acid particles in the form of a continuous coating or a discontinuous island coating that covers the entire surface of the particles as described above, whereby the surface of the polylactic acid particles is modified may be in the form of
상기 코팅층은 친수성(Hydrophilic) 코팅층 또는 소수성(Hydrophobic) 코팅층일 수 있으며, 이에 특별히 제한되는 것은 아니다. 다만, 상기 코팅층이 친수성 코팅층인 경우에는 소수성인 폴리락틱산 입자의 친수성 용매에 대한 분산력을 높일 수 있어 수분산 등의 응용분야에 적용이 가능하다. 반면, 상기 코팅층이 소수성 코팅층인 경우에는 폴리락틱산 입자의 내화학성을 향상시켜 UV 코팅액, 열코팅액 등의 응용분야에 적용 가능한 장점이 있다.The coating layer may be a hydrophilic coating layer or a hydrophobic coating layer, but is not particularly limited thereto. However, when the coating layer is a hydrophilic coating layer, it is possible to increase the dispersion power of the hydrophobic polylactic acid particles in a hydrophilic solvent, so that it can be applied to application fields such as water dispersion. On the other hand, when the coating layer is a hydrophobic coating layer, there is an advantage of improving the chemical resistance of the polylactic acid particles to be applicable to application fields such as UV coating solution and thermal coating solution.
상기 표면 개질된 폴리락틱산 입자는 0.1 내지 3μm, 바람직하게는 1 내지 2.5μm, 더 바람직하게는 1.5 내지 2μm의 누적 부피 10% 입경(D10)을 가질 수 있고, 상기 표면 개질된 폴리락틱산 입자는 3.5 내지 9μm, 바람직하게는 4 내지 7μm, 더 바람직하게는 4.5 내지 5μm의 누적 부피 50% 입경(D50)을 가질 수 있으며, 상기 표면 개질된 폴리락틱산 입자는 10 내지 30μm, 바람직하게는 14 내지 27μm, 더 바람직하게는 17 내지 24μm의 누적 부피 90% 입경(D90)을 가질 수 있다.The surface-modified polylactic acid particles may have a cumulative volume 10% particle diameter (D 10 ) of 0.1 to 3 μm, preferably 1 to 2.5 μm, more preferably 1.5 to 2 μm, and the surface-modified polylactic acid The particles may have a cumulative volume 50% particle diameter (D 50 ) of 3.5 to 9 μm, preferably 4 to 7 μm, more preferably 4.5 to 5 μm, and the surface-modified polylactic acid particles are 10 to 30 μm, preferably may have a 90% cumulative volume particle diameter (D 90 ) of 14 to 27 μm, more preferably 17 to 24 μm.
상기 표면 개질된 폴리락틱산 입자를 70℃에서 24시간 동안 가열시켰을 때, 상기 표면 개질된 폴리락틱산 입자의 누적 부피 50% 입경(D50)의 증가율이 0.1 내지 10%, 바람직하게는 0.5 내지 7%, 더 바람직하게는 0.75 내지 4% 일 수 있다. 상기 범위를 만족하는 표면 개질된 폴리락틱산 입자는 우수한 내열성으로 인하여 가혹한 고온의 조건에서도 입자 간 응집되는 정도가 미미할 수 있다.When the surface-modified polylactic acid particles are heated at 70° C. for 24 hours, the increase rate of the particle diameter (D 50 ) by 50% of the cumulative volume of the surface-modified polylactic acid particles is 0.1 to 10%, preferably 0.5 to 7%, more preferably 0.75 to 4%. Surface-modified polylactic acid particles satisfying the above range may have insignificant aggregation between particles even under severe high temperature conditions due to excellent heat resistance.
표면 개질된 폴리락틱산 입자의 제조방법Method for producing surface-modified polylactic acid particles
본 발명에 따른 표면 개질된 폴리락틱산 입자의 제조방법으로서, (1) 피트산을 포함하는 피트산 코팅액을 준비하는 단계; (2) 폴리락틱산 입자를 상기 피트산 코팅액에 함침시켜 피트산으로 입자 표면을 개질하는 단계; 및 (3) 상기 개질된 폴리락틱산 입자를 건조시키는 단계;를 포함한다.A method for producing surface-modified polylactic acid particles according to the present invention, comprising the steps of: (1) preparing a phytic acid coating solution containing phytic acid; (2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surface with phytic acid; and (3) drying the modified polylactic acid particles.
상기 표면 개질된 폴리락틱산 입자의 제조방법은, (1) 피트산(Phytic Acid) 을 포함하는 피트산 코팅액을 준비하는 단계;를 포함한다.The method for producing the surface-modified polylactic acid particles includes (1) preparing a phytic acid coating solution containing phytic acid.
상기 (1) 단계는 알코올계 용매와 피트산을 혼합하여 피트산 코팅액을 제조하는 단계일 수 있다. 상기 알코올계 용매는 10 내지 100% 농도를 가질 수 있다. Step (1) may be a step of preparing a phytic acid coating solution by mixing an alcohol-based solvent and phytic acid. The alcohol-based solvent may have a concentration of 10 to 100%.
또한 상기 알코올계 용매는 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올 및 이들의 조합으로 이루어진 군으로부터 선택된 것을 사용할 수 있으나, 바람직하게는 에탄올일 수 있다. 다만, 이에 특별히 제한되는 것은 아니다.In addition, the alcohol-based solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, and combinations thereof, but preferably ethanol. However, it is not particularly limited thereto.
상기 표면 개질된 폴리락틱산 입자의 제조방법은, (2) 폴리락틱산 입자를 상기 피트산 코팅액에 함침시켜 피트산으로 입자 표면을 개질하는 단계;를 포함한다. The method for preparing the surface-modified polylactic acid particles includes (2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surfaces with phytic acid.
상기 (2) 단계는 상기 (1) 단계를 통해 제조된 피트산 코팅액에 대하여 파우더 형태의 폴리락틱산 입자를 함침시켜 습식(Wetting) 코팅방법으로 폴리락틱산 입자와 피트산 간에 화학적 결합을 형성하여 결합이 영구적이라는 점에서 효과적일 수 있다. 상기의 결합을 형성하기 위하여 폴리락틱산 입자를 피트산 코팅액에 대하여 상온 조건에서 10 내지 30분 동안 함침시키는 것이 바람직하다.In step (2), polylactic acid particles in powder form are impregnated with the phytic acid coating solution prepared in step (1) to form a chemical bond between the polylactic acid particles and phytic acid by a wet coating method. It can be effective in that the bond is permanent. In order to form the above bond, it is preferable to impregnate the polylactic acid particles with the phytic acid coating solution at room temperature for 10 to 30 minutes.
상기 (2) 단계는 습식(Wetting) 코팅 대신에 건식(Dry) 코팅방법을 통해서 폴리락틱산 입자의 표면을 개질시킬 수 있다. 상기 건식 코팅방법은 알코올계 용매에 피트산을 포함하는 코팅제를 분산시킨 후 이를 스프레이를 통해 분사시켜 폴리락틱산 입자와 피트산 간에 물리적 결합을 형성하여 입자 표면상에 코팅층을 형성하는 개질 방법일 수 있다.In step (2), the surface of the polylactic acid particles may be modified through a dry coating method instead of a wet coating. The dry coating method may be a modification method in which a coating agent containing phytic acid is dispersed in an alcohol-based solvent and then sprayed through a spray to form a physical bond between the polylactic acid particles and phytic acid to form a coating layer on the particle surface. there is.
상기 표면 개질된 폴리락틱산 입자의 제조방법은, (3) 상기 개질된 폴리락틱산 입자를 건조시키는 단계;를 포함한다.The method for producing the surface-modified polylactic acid particles includes (3) drying the modified polylactic acid particles.
상기 (3) 단계는 상기 (2) 단계를 통해 피트산을 포함하는 코팅층이 형성된 표면 개질된 폴리락틱산 입자에 남아있는 용매를 제거하기 위한 건조 단계일 수 있다. 상기 폴리락틱산 입자를 건조시키기 위해서, 건조장비로 바람직하게는 오븐을 사용할 수 있다. 상기 오븐에서 50 내지 90℃, 바람직하게는 60 내지 80℃ 조건에서 2 내지 3시간 동안 건조시켜, 최종적으로 피트산으로 표면 개질된 폴리락틱산 입자를 제조할 수 있다.Step (3) may be a drying step for removing the solvent remaining on the surface-modified polylactic acid particles on which the coating layer containing phytic acid is formed through step (2). In order to dry the polylactic acid particles, preferably an oven may be used as drying equipment. By drying in the oven at 50 to 90°C, preferably at 60 to 80°C, for 2 to 3 hours, polylactic acid particles surface-modified with phytic acid can be finally prepared.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that changes and modifications fall within the scope of the appended claims.
피트산으로 표면 개질된 폴리락틱산 입자의 제조: 실시예 1 및 비교예 1Preparation of particles of polylactic acid surface-modified with phytic acid: Example 1 and Comparative Example 1
[실시예 1][Example 1]
에탄올 용액에 대하여, 피트산(Phytic Acid)을 혼합시켜 코팅액을 제조하였다.With respect to the ethanol solution, a coating solution was prepared by mixing phytic acid.
상기 피트산을 포함하는 코팅액에 대하여 파우더 형태인 폴리락틱산 입자(LUSMAPOL, LG 하우시스)를 함침시킨 후, 건조장비로 오븐을 이용하여 70℃에서 3시간 동안 건조하여, 최종적으로 피트산으로 표면 개질된 폴리락틱산 입자를 제조하였다.Polylactic acid particles (LUSMAPOL, LG Hausys) in powder form were impregnated with the coating solution containing phytic acid, and then dried at 70° C. for 3 hours using an oven with drying equipment, and finally the surface with phytic acid Modified polylactic acid particles were prepared.
[비교예 1][Comparative Example 1]
실시예 1과 달리 표면 개질 처리를 전혀 실시하지 않은, 폴리락틱산 입자를 준비하였다.Unlike Example 1, polylactic acid particles that were not subjected to any surface modification treatment were prepared.
실험예 1 : 입도분포 분석Experimental Example 1: Particle size distribution analysis
실시예 1 및 비교예 1의 폴리락틱산 입자에 대하여, 입도분석기(Mastersizer3000, Malvern)를 통하여 입도를 측정하고 입도분포(PSD, Particle Size Distribution)를 하기 표 1, 도 2(실시예 1) 및 도 3(비교예 1)과 같이 나타내었다.For the polylactic acid particles of Example 1 and Comparative Example 1 , the particle size was measured through a particle size analyzer (Mastersizer3000, Malvern), and the particle size distribution (PSD) was measured in Table 1, FIG. 2 (Example 1) and 3 (Comparative Example 1) is shown.
PSD 결과(상온)PSD result (room temperature)
D10(μm)D 10 (μm) D50(μm)D 50 (μm) D90(μm)D 90 (μm)
실시예 1Example 1 1.721.72 4.614.61 20.4420.44
비교예 1Comparative Example 1 1.561.56 4.924.92 20.520.5
실험예 2 : 내화학성 평가Experimental Example 2: Evaluation of chemical resistance
실시예 1 및 비교예 1의 폴리락틱산 입자를 UV 코팅액 모노머인 HDDA(1,6-Hexanediol diacrylate)에 분산시킨 후, 1분 경과 후 팽윤(Swelling) 현상이 발생하는지 확인하는 실험을 진행하였다.After dispersing the polylactic acid particles of Example 1 and Comparative Example 1 in HDDA (1,6-Hexanediol diacrylate), which is a UV coating solution monomer, an experiment was conducted to check whether swelling occurred after 1 minute.
그 결과, 도 4와 같이 폴리락틱산 입자의 표면을 피트산으로 개질한 실시예 1에서는 팽윤 현상이 발생하지 않았으나, 개질되지 않은 폴리락틱산 입자를 분산시킨 비교예 1의 용기 옆면 및 바닥면 관찰을 통해 폴리락틱산 입자가 용매를 흡수하여 부푸는 팽윤 현상(swelling)이 발생한 것을 육안으로 확인할 수 있었다.As a result, as shown in FIG. 4, in Example 1, in which the surface of the polylactic acid particles was modified with phytic acid, no swelling occurred, but the side and bottom surfaces of the container of Comparative Example 1 in which the unmodified polylactic acid particles were dispersed were observed. Through this, it was visually confirmed that the polylactic acid particles absorbed the solvent, resulting in swelling.
이를 통해, 피트산으로 입자 표면이 개질 됨에 따라 폴리락틱산 입자의 내화학성이 향상되어 UV코팅액 등 다양한 용매에 사용될 수 있는 것을 알 수 있었다.Through this, it was found that as the particle surface was modified with phytic acid, the chemical resistance of the polylactic acid particles was improved, so that it could be used in various solvents such as UV coating solution.
실험예 3 : 내열성 평가Experimental Example 3: Heat resistance evaluation
내열성을 평가하기 위하여 실시예 1 및 비교예 1의 폴리락틱산 입자를 70℃ 조건에서 24시간 동안 가열한 후, 입도분석기(Mastersizer3000, Malvern)를 통하여 입도를 측정하였다. 또한 측정 결과의 입도분포(PSD, Particle Size Distribution)를 분석하고 그 결과를 하기 표 2, 도 5(실시예 1) 및 도 6(비교예 1)과 같이 나타내었다.In order to evaluate the heat resistance, the polylactic acid particles of Example 1 and Comparative Example 1 were heated at 70° C. for 24 hours, and then the particle size was measured through a particle size analyzer (Mastersizer3000, Malvern). In addition, the particle size distribution (PSD) of the measurement results was analyzed, and the results are shown in Table 2, FIG. 5 (Example 1), and FIG. 6 (Comparative Example 1).
PSD 결과(70℃, 24hr)PSD result (70℃, 24hr)
D10(μm)D 10 (μm) D50(μm)D 50 (μm) D90(μm)D 90 (μm)
실시예 1Example 1 1.741.74 4.664.66 20.120.1
비교예 1Comparative Example 1 2.182.18 12.8112.81 31.9131.91
상기 가열 후 입도 분석을 통한 내열성 평가 결과, 실시예 1의 경우 실험예 1의 상온 조건(가열 전)의 D50인 4.61μm과 비교할 때 0.05μm만큼(상온 조건의 D50 대비 1.1% 증가) D50이 증가한 것을 확인할 수 있었다. 이를 통해 피트산의 표면 개질에 따라 70℃의 가혹한 조건에서도 개선된 내열성의 효과로 폴리락틱산 입자간 응집되는 정도가 미미하여, 이에 따른 입도가 증가하는 정도 역시 미미한 것을 확인할 수 있었다. As a result of heat resistance evaluation through particle size analysis after heating, in the case of Example 1, as compared to 4.61 μm, which is D 50 under the room temperature condition (before heating) of Experimental Example 1, by 0.05 μm (1.1% increase compared to D 50 at room temperature condition) D 50 was found to increase. Through this, it was confirmed that the degree of aggregation between the polylactic acid particles was insignificant due to the effect of improved heat resistance even under the harsh conditions of 70°C according to the surface modification of the phytic acid, and thus the degree of increase in the particle size was also insignificant.
반면, 표면 개질을 하지 않은 폴리락틱산 입자인 비교예 1의 경우 동일한 가혹 조건이었지만 입자간 응집되는 정도의 급격한 증가로 실험예 1의 상온 조건(가열 전)에서의 D50인 4.92μm 대비 7.89μm만큼(상온 조건의 D50 대비 160% 증가) D50이 증가하여, 상대적으로 큰 폭으로 입도가 증가한 것을 확인할 수 있었다.On the other hand, in the case of Comparative Example 1, which is a polylactic acid particle without surface modification, under the same severe conditions, but due to a sharp increase in the degree of aggregation between particles, the D 50 of 4.92 μm in Experimental Example 1 (before heating) was 7.89 μm compared to 4.92 μm. As much as (160% increase compared to D 50 at room temperature), D 50 increased, and it was confirmed that the particle size increased relatively significantly.
이를 통해, 고온의 가혹한 조건 하에서도 표면이 피트산으로 개질된 폴리락틱산 입자는 개선된 내열성을 갖는 것을 알 수 있었다.Through this, it was found that the polylactic acid particles whose surface was modified with phytic acid had improved heat resistance even under harsh conditions at high temperatures.
본 발명의 단순한 변형 내지 변경은 모두 본 발명의 영역에 속하는 것이며, 본 발명의 구체적인 보호 범위는 첨부된 특허청구범위에 의하여 명확해질 것이다.All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will become apparent from the appended claims.

Claims (9)

  1. 폴리락틱산(Polylactic Acid) 입자; 및polylactic acid particles; and
    상기 폴리락틱산 입자의 표면상에 위치한 코팅층;을 포함하고,Including; a coating layer located on the surface of the polylactic acid particles;
    상기 코팅층은 피트산(Phytic Acid)을 포함하는, 표면 개질된 폴리락틱산 입자.The coating layer comprises phytic acid (Phytic Acid), the surface-modified polylactic acid particles.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 코팅층이 상기 폴리락틱산 입자의 표면 상에서 연속된 코팅 형태 또는 아일랜드 코팅 형태를 갖는, 표면 개질된 폴리락틱산 입자.The surface-modified polylactic acid particles, wherein the coating layer has a continuous coating form or island coating form on the surface of the polylactic acid particles.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 코팅층은 상기 폴리락틱산 입자의 표면이 피트산으로 개질되어 형성된, 표면 개질된 폴리락틱산 입자.The coating layer is a surface-modified polylactic acid particle formed by modifying the surface of the polylactic acid particle with phytic acid.
  4. 제 1 항에 있어서,The method of claim 1,
    상기 표면 개질된 폴리락틱산 입자는 0.1 내지 3μm의 누적 부피 10% 입경(D10)을 가지는, 표면 개질된 폴리락틱산 입자.The surface-modified polylactic acid particles have a cumulative volume 10% particle diameter (D 10 ) of 0.1 to 3 μm, the surface-modified polylactic acid particles.
  5. 제 1 항에 있어서,The method of claim 1,
    상기 표면 개질된 폴리락틱산 입자는 3.5 내지 9μm의 누적 부피 50% 입경(D50)을 가지는, 표면 개질된 폴리락틱산 입자.The surface-modified polylactic acid particles have a cumulative volume 50% particle diameter (D 50 ) of 3.5 to 9 μm, the surface-modified polylactic acid particles.
  6. 제 1 항에 있어서,The method of claim 1,
    상기 표면 개질된 폴리락틱산 입자는 10 내지 30μm의 누적 부피 90% 입경(D90)을 가지는, 표면 개질된 폴리락틱산 입자.The surface-modified polylactic acid particles have a cumulative volume of 90% particle diameter (D 90 ) of 10 to 30 μm, the surface-modified polylactic acid particles.
  7. 제 1 항에 있어서,The method of claim 1,
    상기 표면 개질된 폴리락틱산 입자를 70℃에서 24시간 동안 가열시켰을 때,When the surface-modified polylactic acid particles were heated at 70° C. for 24 hours,
    상기 표면 개질된 폴리락틱산 입자의 누적 부피 50% 입경(D50)의 증가율이 0.1 내지 10%인, 표면 개질된 폴리락틱산 입자.The surface-modified polylactic acid particles having an increase rate of 0.1 to 10% of a particle diameter (D 50 ) of 50% of the cumulative volume of the surface-modified polylactic acid particles.
  8. 제 1 항에 기재된 표면 개질된 폴리락틱산 입자의 제조방법으로서,A method for producing the surface-modified polylactic acid particles according to claim 1, comprising:
    (1) 피트산을 포함하는 피트산 코팅액을 준비하는 단계;(1) preparing a phytic acid coating solution containing phytic acid;
    (2) 폴리락틱산 입자를 상기 피트산 코팅액에 함침시켜 피트산으로 입자 표면을 개질하는 단계; 및(2) impregnating the polylactic acid particles with the phytic acid coating solution to modify the particle surface with phytic acid; and
    (3) 상기 개질된 폴리락틱산 입자를 건조시키는 단계;를 포함하는, 표면 개질된 폴리락틱산 입자의 제조방법.(3) drying the modified polylactic acid particles; A method for producing surface-modified polylactic acid particles, comprising a.
  9. 제 8 항에 있어서,9. The method of claim 8,
    상기 (1) 단계는 알코올계 용매와 피트산을 혼합하여 피트산 코팅액을 제조하는 단계인, 표면 개질된 폴리락틱산 입자의 제조방법.The step (1) is a method for preparing surface-modified polylactic acid particles by mixing an alcohol-based solvent and phytic acid to prepare a phytic acid coating solution.
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CHENG XIAN-WEI; GUAN JIN-PING; TANG REN-CHENG; LIU KAI-QIANG: "Phytic acid as a bio-based phosphorus flame retardant for poly(lactic acid) nonwoven fabric", JOURNAL OF CLEANER PRODUCTION, vol. 124, 7 March 2016 (2016-03-07) - 7 March 2016 (2016-03-07), AMSTERDAM, NL , pages 114 - 119, XP029522938, ISSN: 0959-6526, DOI: 10.1016/j.jclepro.2016.02.113 *

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