WO2022260315A1 - Master batch composition for graphene-containing polyamide, and graphene polyamide yarn comprising composition - Google Patents

Master batch composition for graphene-containing polyamide, and graphene polyamide yarn comprising composition Download PDF

Info

Publication number
WO2022260315A1
WO2022260315A1 PCT/KR2022/007390 KR2022007390W WO2022260315A1 WO 2022260315 A1 WO2022260315 A1 WO 2022260315A1 KR 2022007390 W KR2022007390 W KR 2022007390W WO 2022260315 A1 WO2022260315 A1 WO 2022260315A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
polyamide
master batch
composition
batch composition
Prior art date
Application number
PCT/KR2022/007390
Other languages
French (fr)
Korean (ko)
Inventor
김헌상
이기주
Original Assignee
주식회사 네오엔프라
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 네오엔프라 filed Critical 주식회사 네오엔프라
Publication of WO2022260315A1 publication Critical patent/WO2022260315A1/en

Links

Images

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • the present invention relates to a master batch composition for polyamide containing graphene and to a graphene polyamide yarn containing the composition, and more particularly, far-infrared emission and antibacterial performance are added, as well as lubricity, UV blocking,
  • a master batch composition for graphene polyamide that exhibits electrical conductivity and heat dissipation characteristics and provides a polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus, and graphene containing the composition It relates to polyamide yarn.
  • a master batch is a high-concentration mixing of functional blending agents such as additives in order to impart various necessary functionalities to petrochemical-related industrial products, including chemical fibers, and to prevent the blending agent from leaning. It refers to a highly concentrated functional resin using a dispersant.
  • graphene is a monoatomic two-dimensional material in which carbon atoms form a honeycomb-shaped hexagon and are covalently connected. It has thermal, mechanical, electrical, and optical properties that can overcome the fundamental limitations of existing materials. It has infinite application possibilities in various industrial fields such as ultra-light and high-strength composite materials.
  • An object of the present invention is to provide far-infrared emission and antibacterial performance, as well as lubricity, UV blocking, electrical conductivity and heat dissipation, and improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus.
  • the object of the present invention is achieved by providing a master batch composition for graphene polyamide, characterized in that it contains a graphene oxide dispersion.
  • the master batch composition for graphene polyamide is composed of 99 to 99.9% by weight of polyamide and 0.1 to 1% by weight of a graphene oxide dispersion.
  • the graphene oxide dispersion is composed of 100 parts by weight of ionized water, 0.1 to 1 part by weight of graphene, 0.07 to 0.7 parts by weight of a neutralizer, and 0.05 to 0.5 parts by weight of a dispersing agent.
  • the neutralizing agent is made of at least one selected from the group consisting of stearin-based and amine-based.
  • the dispersant is made of at least one selected from the group consisting of amines and stearic acids.
  • the object of the present invention can be achieved by providing a graphene polyamide yarn characterized in that the master batch composition for graphene polyamide is contained.
  • the baster batch composition for graphene polyamide is to contain 50 to 2000 ppm.
  • the master batch composition for graphene polyamide according to the present invention and the graphene polyamide yarn containing the composition not only emits far-infrared rays and has antibacterial performance, but also exhibits lubricity, UV blocking, electrical conductivity and heat dissipation, It shows an excellent effect of providing a polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus.
  • 1 is a photograph showing a polyamide yarn showing 40D and 36F and a graphene polyamide yarn showing 70D and 48F.
  • FIGS. 2 and 3 are photographs showing the graphene polyamide yarn prepared in Example 1 of the present invention taken with a scanning electron microscope.
  • Example 4 is a test report showing the results of measuring the antistatic properties of the graphene polyamide fabric prepared in Example 1 of the present invention by requesting it to the FITI Testing & Research Institute.
  • Example 5 is a test report showing the results of measuring the antibacterial properties of the graphene polyamide fabric prepared in Example 1 of the present invention by requesting the FITI Test Research Institute.
  • Example 6 is a test report showing the results of measuring the far-infrared ray emission performance of the graphene polyamide fabric prepared in Example 1 of the present invention by requesting the Korea Far Infrared Application Evaluation Institute.
  • the master batch composition for graphene polyamide according to the present invention is characterized by containing a graphene oxide dispersion, and is preferably composed of 99 to 99.9 wt% of polyamide and 0.1 to 1 wt% of graphene oxide dispersion.
  • the master batch composition for graphene polyamide containing the graphene oxide dispersion is mixed with the graphene polyamide and exhibits lubricity, UV blocking, electrical conductivity and heat dissipation properties, scratch resistance, abrasion resistance, tensile strength, bending It serves to provide a graphene polyamide yarn with improved mechanical properties such as strength and flexural modulus.
  • the content of the graphene oxide dispersion is less than 0.1% by weight, the above effect is insignificant, and if the content of the graphene oxide dispersion exceeds 1% by weight, the above effect is not greatly improved and the graphene polyamide yarn Mechanical properties are deteriorated, and manufacturing costs are excessively increased.
  • the graphene oxide dispersion is composed of 100 parts by weight of ionized water, 0.1 to 1 parts by weight of graphene, 0.07 to 0.7 parts by weight of a neutralizer, and 0.05 to 0.5 parts by weight of a dispersing agent. It serves to neutralize graphene, and the dispersant serves to ensure that the graphene is evenly dispersed in the ionized water to provide a graphene oxide dispersion exhibiting homogeneous physical properties.
  • the neutralizing agent is contained in an amount of 0.07 to 0.7 parts by weight and is composed of at least one selected from the group consisting of stearin and amine, and serves to adjust the pH of the graphene oxide dispersion to 3 to 4.
  • the dispersing agent is contained in an amount of 0.05 to 0.5 parts by weight and is composed of at least one selected from the group consisting of amine-based and stearic acid-based, and serves to ensure that the plate-like graphene is evenly dispersed in the ionized water.
  • the master batch composition for graphene polyamide composed of the above components is physically mixed with polyamide pellets and then produced into graphene polyamide yarn through a melting process.
  • polyamide pellets When it is physically mixed with and subjected to a melting process, it is possible to provide a graphene polyamide yarn in which the physical properties exhibited by the master batch composition for graphene polyamide according to the present invention are evenly expressed.
  • the master batch composition for graphene polyamide according to the present invention is preferably contained in an amount of 50 to 200 ppm in the polyamide in pellet form. If the content of the master batch composition for graphene polyamide is less than 50 ppm, far-infrared radiation is emitted. , antibacterial performance, lubricity, UV blocking, electrical conductivity, heat dissipation, scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus, etc. The effect of improving physical properties is insignificant, and the master batch composition for graphene polyamide When the content exceeds 200 ppm, the above effect is not greatly improved, but the physical properties of the polyamide yarn are deteriorated and the manufacturing cost is excessively increased.
  • the graphene polyamide yarn produced through the above process may be formed to exhibit various denier (D, Denier) and filament (F, Filament). Graphene polyamide yarns showing 70D and 48F were photographed and shown.
  • a graphene oxide dispersion was prepared by mixing 100 parts by weight of ionized water, 0.5 parts by weight of graphene, 0.35 parts by weight of a neutralizer (stearin-based), and 0.25 parts by weight of a dispersing agent (amine-based).
  • a master batch composition for polyamide was prepared by mixing 99.9% by weight of polyamide and 0.5% by weight of the graphene oxide dispersion prepared in Preparation Example 1 above.
  • the graphene polyamide yarn prepared in Example 1 was photographed with a scanning electron microscope and shown in FIGS. 2 to 3 below.
  • the graphene polyamide fabric prepared in Example 1 of the present invention exhibits excellent antistatic and antibacterial properties.
  • the graphene polyamide fabric prepared in Example 1 of the present invention has an excellent far-infrared ray emission effect.
  • the master batch composition for graphene polyamide and the graphene polyamide yarn containing the composition according to the present invention not only emits far-infrared rays and has antibacterial performance, but also exhibits lubricity, UV blocking, electrical conductivity and heat dissipation.
  • a polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus.
  • polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus, as well as far-infrared emission and antibacterial performance, as well as lubricity, UV blocking, electrical conductivity and heat dissipation. It is possible to provide a master batch composition for graphene polyamide and a graphene polyamide yarn containing the composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention relates to a master batch composition for a graphene polyamide, and a graphene polyamide yarn comprising the composition, and, more specifically, is obtained by mixing a polyamide and a graphene oxide dispersion. The master batch composition for a graphene polyamide, obtained through the mixing of the graphene oxide dispersion, provides a graphene polyamide yarn to which far-infrared emission and antibacterial performance are added, which exhibits lubricity, UV protection, electrical conductivity and heat dissipation characteristics, and which has improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus.

Description

그래핀이 함유된 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사Master batch composition for polyamide containing graphene and graphene polyamide yarn containing the composition
본 발명은 그래핀이 함유된 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사에 관한 것으로, 더욱 상세하게는 원적외선 방출 및 항균성능이 부가될 뿐만 아니라, 윤활성, UV 차단성, 전기전도성 및 방열특성을 나타내며, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 기계적 물성이 향상된 폴리아미드 원사를 제공하는 그래핀 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사에 관한 것이다.The present invention relates to a master batch composition for polyamide containing graphene and to a graphene polyamide yarn containing the composition, and more particularly, far-infrared emission and antibacterial performance are added, as well as lubricity, UV blocking, A master batch composition for graphene polyamide that exhibits electrical conductivity and heat dissipation characteristics and provides a polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus, and graphene containing the composition It relates to polyamide yarn.
마스터 배치(Master batch)란, 화학섬유를 비롯한 석유화학 관련 공산품의 제조 시에 이들에 각종 필요한 기능성을 부여하기 위하여 첨가제 등의 기능성 배합제를 고농도로 혼합하고, 배합제의 쏠림 현상을 방지하기 위하여 분산제를 사용한 고농축 기능성 수지를 말한다.A master batch is a high-concentration mixing of functional blending agents such as additives in order to impart various necessary functionalities to petrochemical-related industrial products, including chemical fibers, and to prevent the blending agent from leaning. It refers to a highly concentrated functional resin using a dispersant.
합성섬유의 경우 천연섬유에 비해 기계적 물성은 우수하지만, 흡수 능력이 적기 때문에, 인체에서 분비되는 땀 및 각종 유기물이 부착되어 세균 및 곰팡이류 등의 미생물 서식에 적합한 환경을 제공하게 되고 이러한 미생물의 번식으로 악취, 섬유제품의 변색 및 오염, 심지어는 인체의 감염으로 인한 질병을 일으키기도 한다. 이러한 이유로 예전부터 섬유재료에 인체에 유해한 균의 증식을 억제하는 기능을 부여하고자 하는 많은 시도가 이루어지고 있다.In the case of synthetic fibers, they have excellent mechanical properties compared to natural fibers, but have low absorption capacity, so sweat and various organic substances secreted from the human body are attached to provide an environment suitable for the habitat of microorganisms such as bacteria and fungi. It can cause odor, discoloration and contamination of textile products, and even diseases caused by human infection. For this reason, many attempts have been made to impart a function of suppressing the proliferation of bacteria harmful to the human body to fiber materials from the past.
한편, 그래핀은 탄소원자들이 벌집모양의 육각형을 형성하며 공유결합으로 연결된 단원자층 2차원 소재로 기존의 소재들의 근본적인 한계를 극복할 수 있는 열적, 기계적, 전기적, 광학적 특성을 지녀 배리어 코팅소재, 초경량 고강도 복합재 등 다양한 산업 분야들에 무한한 응용 가능성을 가지고 있다.On the other hand, graphene is a monoatomic two-dimensional material in which carbon atoms form a honeycomb-shaped hexagon and are covalently connected. It has thermal, mechanical, electrical, and optical properties that can overcome the fundamental limitations of existing materials. It has infinite application possibilities in various industrial fields such as ultra-light and high-strength composite materials.
하지만, 무결점 그래핀은 그래핀 간의 반데르발스힘에 의해 고분자 수지 및 유기용매 안에서 균일한 분산이 어렵기 때문에 코팅소재 및 고성능 기능성 복합재를 제조하기 어렵고 실제 적용 가능한 기술에 대한 연구가 매우 제한적인 실정이다. 이러한 그래핀의 분산 문제점을 해결하고자 그래핀 산화물의 다양한 기능기을 활용한 표면개질 연구가 활발히 진행되고 있다. 그런데 이러한 연구들은 고온의 반응열, 낮은 재현성, 대량생산의 부적합등과 같은 문제점이 발생되어 이에 대한 개선이 요구되고 있다.However, since it is difficult to uniformly disperse defect-free graphene in polymer resins and organic solvents due to the van der Waals force between graphenes, it is difficult to manufacture coating materials and high-performance functional composites, and research on practically applicable technologies is very limited. to be. In order to solve the dispersion problem of graphene, research on surface modification using various functional groups of graphene oxide is being actively conducted. However, these studies have problems such as high temperature reaction heat, low reproducibility, and unsuitability for mass production, and improvement is required.
[선행기술문헌] [Prior art literature]
[특허문헌] [Patent Literature]
한국특허등록 제10-1975955호(2019.04.30)Korean Patent Registration No. 10-1975955 (2019.04.30)
한국특허등록 제10-2163232호(2020.09.29)Korean Patent Registration No. 10-2163232 (2020.09.29)
본 발명의 목적은 원적외선 방출 및 항균성능이 부가될 뿐만 아니라, 윤활성, UV 차단성, 전기전도성 및 방열특성을 나타내며, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 기계적 물성이 향상된 폴리아미드 원사를 제공하는 그래핀 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사를 제공하는 것이다.An object of the present invention is to provide far-infrared emission and antibacterial performance, as well as lubricity, UV blocking, electrical conductivity and heat dissipation, and improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus. To provide a master batch composition for graphene polyamide that provides a polyamide yarn and a graphene polyamide yarn containing the composition.
본 발명의 목적은 산화그래핀 분산액이 함유되는 것을 특징으로 하는 그래핀 폴리아미드용 마스터 배치 조성물을 제공함에 의해 달성된다.The object of the present invention is achieved by providing a master batch composition for graphene polyamide, characterized in that it contains a graphene oxide dispersion.
본 발명의 바람직한 특징에 따르면, 상기 그래핀 폴리아미드용 마스터 배치 조성물은 폴리아미드 99 내지 99.9 중량% 및 산화그래핀 분산액 0.1 내지 1 중량%로 이루어지는 것으로 한다.According to a preferred feature of the present invention, the master batch composition for graphene polyamide is composed of 99 to 99.9% by weight of polyamide and 0.1 to 1% by weight of a graphene oxide dispersion.
본 발명의 더 바람직한 특징에 따르면, 상기 산화그래핀은 분산액은 이온수 100 중량부, 그래핀 0.1 내지 1 중량부, 중화제 0.07 내지 0.7 중량부 및 분산제 0.05 내지 0.5 중량부로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the graphene oxide dispersion is composed of 100 parts by weight of ionized water, 0.1 to 1 part by weight of graphene, 0.07 to 0.7 parts by weight of a neutralizer, and 0.05 to 0.5 parts by weight of a dispersing agent.
본 발명의 더욱 바람직한 특징에 따르면, 상기 중화제는 스테아린계 및 아민계로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the neutralizing agent is made of at least one selected from the group consisting of stearin-based and amine-based.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 분산제는 아민계 및 스테아르산계로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the dispersant is made of at least one selected from the group consisting of amines and stearic acids.
또한, 본 발명의 목적은 상기 그래핀 폴리아미드용 마스터 배치 조성물이 함유되는 것을 특징으로 하는 그래핀 폴리아미드 원사를 제공함에 의해서도 달성될 수 있다.In addition, the object of the present invention can be achieved by providing a graphene polyamide yarn characterized in that the master batch composition for graphene polyamide is contained.
본 발명의 바람직한 특징에 따르면, 상기 그래핀 폴리아미드용 배스터 배치 조성물은 50 내지 2000ppm이 함유되는 것으로 한다.According to a preferred feature of the present invention, the baster batch composition for graphene polyamide is to contain 50 to 2000 ppm.
본 발명에 따른 그래핀 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사는 원적외선 방출 및 항균성능이 부가될 뿐만 아니라, 윤활성, UV 차단성, 전기전도성 및 방열특성을 나타내며, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 기계적 물성이 향상된 폴리아미드 원사를 제공하는 탁월한 효과를 나타낸다.The master batch composition for graphene polyamide according to the present invention and the graphene polyamide yarn containing the composition not only emits far-infrared rays and has antibacterial performance, but also exhibits lubricity, UV blocking, electrical conductivity and heat dissipation, It shows an excellent effect of providing a polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus.
도 1은 40D와 36F를 나타내는 폴리아미드 원사와 70D와 48F를 나타내는 그래핀 폴리아미드 원사를 촬영하여 나타낸 사진이다.1 is a photograph showing a polyamide yarn showing 40D and 36F and a graphene polyamide yarn showing 70D and 48F.
도 2 내지 3은 본 발명의 실시예 1을 통해 제조된 그래핀 폴리아미드 원사를 주사전자 현미경으로 촬영하여 나타낸 사진이다.2 and 3 are photographs showing the graphene polyamide yarn prepared in Example 1 of the present invention taken with a scanning electron microscope.
도 4는 본 발명의 실시예 1를 통해 제조된 그래핀 폴리아미드 직물의 대전방지성을 FITI 시험연구원에 의뢰하여 측정한 결과를 나타낸 시험성적서이다.4 is a test report showing the results of measuring the antistatic properties of the graphene polyamide fabric prepared in Example 1 of the present invention by requesting it to the FITI Testing & Research Institute.
도 5는 본 발명의 실시예 1를 통해 제조된 그래핀 폴리아미드 직물의 항균성을 FITI 시험연구원에 의뢰하여 측정한 결과를 나타낸 시험성적서이다.5 is a test report showing the results of measuring the antibacterial properties of the graphene polyamide fabric prepared in Example 1 of the present invention by requesting the FITI Test Research Institute.
도 6은 본 발명의 실시예 1을 통해 제조된 그래핀 폴리아미드 직물의 원적외선 방출성능을 한국원적외선응용평가연구원에 의뢰하여 측정한 결과를 나타낸 시험성적서이다.6 is a test report showing the results of measuring the far-infrared ray emission performance of the graphene polyamide fabric prepared in Example 1 of the present invention by requesting the Korea Far Infrared Application Evaluation Institute.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, but this is to be explained in detail so that a person having ordinary knowledge in the art to which the present invention belongs can easily practice the invention, This is not meant to limit the technical spirit and scope of the present invention.
본 발명에 따른 그래핀 폴리아미드용 마스터 배치 조성물은 산화그래핀 분산액이 함유되는 것을 특징으로 하며, 폴리아미드 99 내지 99.9 중량% 및 산화그래핀 분산액 0.1 내지 1 중량%로 이루어지는 것이 바람직하다.The master batch composition for graphene polyamide according to the present invention is characterized by containing a graphene oxide dispersion, and is preferably composed of 99 to 99.9 wt% of polyamide and 0.1 to 1 wt% of graphene oxide dispersion.
상기와 같이 산화그래핀 분산액이 함유된 그래핀 폴리아미드용 마스터 배치 조성물은 그래핀 폴리아미드에 혼합되어 윤활성, UV 차단성, 전기전도성 및 방열특성을 나타내며, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 기계적 물성이 향상된 그래핀 폴리아미드 원사가 제공될 수 있도록 하는 역할을 한다.As described above, the master batch composition for graphene polyamide containing the graphene oxide dispersion is mixed with the graphene polyamide and exhibits lubricity, UV blocking, electrical conductivity and heat dissipation properties, scratch resistance, abrasion resistance, tensile strength, bending It serves to provide a graphene polyamide yarn with improved mechanical properties such as strength and flexural modulus.
상기 산화그래핀 분산액의 함량이 0.1 중량% 미만이면 상기의 효과가 미미하며, 상기 산화그래핀 분산액의 함량이 1 중량%를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 그래핀 폴리아미드 원사의 기계적 물성이 저하되며, 제조비용을 지나치게 증가시키게 된다.If the content of the graphene oxide dispersion is less than 0.1% by weight, the above effect is insignificant, and if the content of the graphene oxide dispersion exceeds 1% by weight, the above effect is not greatly improved and the graphene polyamide yarn Mechanical properties are deteriorated, and manufacturing costs are excessively increased.
이때, 상기 산화그래핀 분산액은 이온수 100 중량부, 그래핀 0.1 내지 1 중량부, 중화제 0.07 내지 0.7 중량부 및 분산제 0.05 내지 0.5 중량부로 이루어지는 데, 상기 이온수는 흑연에서 박리된 나노수준의 얇은 판상형인 그래핀을 중화하는 역할을 하며, 상기 분산제는 상기 그래핀이 상기 이온수에 고르게 분산되어 균질한 물성을 나타내는 산화그래핀 분산액이 제공될 수 있도록 하는 역할을 한다.At this time, the graphene oxide dispersion is composed of 100 parts by weight of ionized water, 0.1 to 1 parts by weight of graphene, 0.07 to 0.7 parts by weight of a neutralizer, and 0.05 to 0.5 parts by weight of a dispersing agent. It serves to neutralize graphene, and the dispersant serves to ensure that the graphene is evenly dispersed in the ionized water to provide a graphene oxide dispersion exhibiting homogeneous physical properties.
또한, 상기 중화제는 0.07 내지 0.7 중량부가 함유되며, 스테아린계 및 아민계로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, 상기의 산화그래핀 분산액의 pH를 3 내지 4로 조절하는 역할을 한다.In addition, the neutralizing agent is contained in an amount of 0.07 to 0.7 parts by weight and is composed of at least one selected from the group consisting of stearin and amine, and serves to adjust the pH of the graphene oxide dispersion to 3 to 4.
또한, 상기 분산제는 0.05 내지 0.5 중량부가 함유되며, 아민계 및 스테아르산계로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, 상기 판상형의 그래핀이 상기 이온수에 고르게 분산될 수 있도록 하는 역할을 한다.In addition, the dispersing agent is contained in an amount of 0.05 to 0.5 parts by weight and is composed of at least one selected from the group consisting of amine-based and stearic acid-based, and serves to ensure that the plate-like graphene is evenly dispersed in the ionized water.
또한, 상기의 성분으로 이루어지는 그래핀 폴리아미드용 마스터 배치 조성물은 폴리아미드 펠릿과 물리적으로 혼합된 후에 용융공정을 통해 그래핀 폴리아미드 원사로 제조되는데, 상기와 같이 마스터 배치로 제조된 후에 폴리아미드 펠릿과 물리적으로 혼합되어 용융공정을 거치면, 본 발명에 따른 그래핀 폴리아미드용 마스터 배치 조성물이 나타내는 물성이 고르게 발현되는 그래핀 폴리아미드 원사를 제공할 수 있다.In addition, the master batch composition for graphene polyamide composed of the above components is physically mixed with polyamide pellets and then produced into graphene polyamide yarn through a melting process. After being prepared as a master batch as described above, polyamide pellets When it is physically mixed with and subjected to a melting process, it is possible to provide a graphene polyamide yarn in which the physical properties exhibited by the master batch composition for graphene polyamide according to the present invention are evenly expressed.
이때, 본 발명에 따른 그래핀 폴리아미드용 마스터 배치 조성물은 펠릿형태의 폴리아미드에 50 내지 200ppm의 함량으로 함유되는 것이 바람직한데, 상기 그래핀 폴리아미드용 마스터 배치 조성물의 함량이 50ppm 미만이면 원적외선 방출, 항균성능, 윤활성, UV 차단성, 전기전도성, 방열특성, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 물성의 향상효과가 미미하며, 상기 그래핀 폴리아미드용 마스터 배치 조성물의 함량이 200ppm을 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 폴리아미드 원사의 물성을 저하시키고 제조비용을 지나치게 증가시키게 된다.At this time, the master batch composition for graphene polyamide according to the present invention is preferably contained in an amount of 50 to 200 ppm in the polyamide in pellet form. If the content of the master batch composition for graphene polyamide is less than 50 ppm, far-infrared radiation is emitted. , antibacterial performance, lubricity, UV blocking, electrical conductivity, heat dissipation, scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus, etc. The effect of improving physical properties is insignificant, and the master batch composition for graphene polyamide When the content exceeds 200 ppm, the above effect is not greatly improved, but the physical properties of the polyamide yarn are deteriorated and the manufacturing cost is excessively increased.
상기의 과정을 통해 제조되는 그래핀 폴리아미드 원사는 다양한 데니어(D, Denier)와 필라멘트(F, Filament)를 나타내도록 형성될 수 있는데, 아래 도 1에는 40D와 36F를 나타내는 그래핀 폴리아미드 원사와 70D와 48F를 나타내는 그래핀 폴리아미드 원사를 촬영하여 나타내었다.The graphene polyamide yarn produced through the above process may be formed to exhibit various denier (D, Denier) and filament (F, Filament). Graphene polyamide yarns showing 70D and 48F were photographed and shown.
이하에서는, 본 발명에 따른 그래핀 폴리아미드용 마스터 배치 조성물의 제조방법 및 그 제조방법으로 제조된 마스터 배치가 함유된 그래핀 폴리아미드 원사의 물성을 실시예를 들어 설명하기로 한다.Hereinafter, the manufacturing method of the master batch composition for graphene polyamide according to the present invention and the physical properties of the graphene polyamide yarn containing the master batch manufactured by the manufacturing method will be described with examples.
<제조예 1> 산화그래핀 분산액의 제조<Preparation Example 1> Preparation of graphene oxide dispersion
이온수 100 중량부, 그래핀 0.5 중량부, 중화제(스테아린계) 0.35 중량부 및 분산제(아민계) 0.25 중량부를 혼합하여 산화그래핀 분산액을 제조하였다.A graphene oxide dispersion was prepared by mixing 100 parts by weight of ionized water, 0.5 parts by weight of graphene, 0.35 parts by weight of a neutralizer (stearin-based), and 0.25 parts by weight of a dispersing agent (amine-based).
<제조예 2><Production Example 2>
폴리아미드 99.9 중량% 및 상기 제조예 1을 통해 제조된 산화그래핀 분산액 0.5 중량%를 혼합하여 폴리아미드용 마스터 배치 조성물을 제조하였다.A master batch composition for polyamide was prepared by mixing 99.9% by weight of polyamide and 0.5% by weight of the graphene oxide dispersion prepared in Preparation Example 1 above.
<실시예 1><Example 1>
폴리아미드에 상기 실시예 2를 통해 제조된 그래핀 폴리아미드용 마스터 배치 조성물을 1000ppm 혼합하고 압출하여 폴리아미드 원사(40D, 36F)를 제조하고, 상기 원사를 직조하여 그래핀 폴리아미드 직물을 제조하였다.1000 ppm of the master batch composition for graphene polyamide prepared in Example 2 was mixed with polyamide and extruded to prepare polyamide yarns (40D, 36F), and then weaved the yarn to prepare graphene polyamide fabric. .
상기 실시예 1을 통해 제조된 그래핀 폴리아미드 원사를 주사전자 현미경으로 촬영하여 아래 도 2 내지 3에 나타내었다.The graphene polyamide yarn prepared in Example 1 was photographed with a scanning electron microscope and shown in FIGS. 2 to 3 below.
아래 도 2 내지 3에 나타낸 것처럼, 본 발명을 통해 제조되는 폴리아미드 원사는 그래핀이 분산되어 있는 것을 알 수 있다.As shown in FIGS. 2 and 3 below, it can be seen that graphene is dispersed in the polyamide yarn prepared according to the present invention.
또한, 상기 실시예 1를 통해 제조된 그래핀 폴리아미드 직물의 대전방지성, 항균성을 FITI 시험연구원에 의뢰하여 측정한 결과를 아래 도 4 내지 5에 나타내었다.In addition, the results of measuring the antistatic and antibacterial properties of the graphene polyamide fabric prepared in Example 1 by requesting the FITI Testing & Research Institute are shown in FIGS. 4 to 5 below.
아래 도 4 내지 5에 나타낸 것처럼, 본 발명의 실시예 1를 통해 제조된 그래핀 폴리아미드 직물은 우수한 대전방지성 및 항균성을 나타내는 것을 알 수 있다.As shown in FIGS. 4 to 5 below, it can be seen that the graphene polyamide fabric prepared in Example 1 of the present invention exhibits excellent antistatic and antibacterial properties.
또한, 상기 실시예 1을 통해 제조된 그래핀 폴리아미드 직물의 원적외선 방출성능을 한국원적외선응용평가연구원에 의뢰하여 측정한 결과를 아래 도 6에 나타내었다.In addition, the results of measuring the far-infrared ray emission performance of the graphene polyamide fabric prepared in Example 1 by requesting the Korea Far Infrared Application Evaluation Institute are shown in FIG. 6 below.
아래 도 6에 나타낸 것처럼, 본 발명의 실시예 1을 통해 제조된 그래핀 폴리아미드 직물은 원적외선 방출효과가 우수한 것을 알 수 있다.As shown in FIG. 6 below, it can be seen that the graphene polyamide fabric prepared in Example 1 of the present invention has an excellent far-infrared ray emission effect.
따라서, 본 발명에 따른 그래핀 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사는 원적외선 방출 및 항균성능이 부가될 뿐만 아니라, 윤활성, UV 차단성, 전기전도성 및 방열특성을 나타내며, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 기계적 물성이 향상된 폴리아미드 원사를 제공한다.Therefore, the master batch composition for graphene polyamide and the graphene polyamide yarn containing the composition according to the present invention not only emits far-infrared rays and has antibacterial performance, but also exhibits lubricity, UV blocking, electrical conductivity and heat dissipation. Provided is a polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus.
원적외선 방출 및 항균성능이 부가될 뿐만 아니라, 윤활성, UV 차단성, 전기전도성 및 방열특성을 나타내며, 내스크래치성, 내마모성, 인장강도, 굴곡강도 및 굴곡탄성율 등과 같은 기계적 물성이 향상된 폴리아미드 원사를 제공하는 그래핀 폴리아미드용 마스터 배치 조성물 및 그 조성물이 함유된 그래핀 폴리아미드 원사를 제공할 수 있다.Provides polyamide yarn with improved mechanical properties such as scratch resistance, abrasion resistance, tensile strength, flexural strength and flexural modulus, as well as far-infrared emission and antibacterial performance, as well as lubricity, UV blocking, electrical conductivity and heat dissipation. It is possible to provide a master batch composition for graphene polyamide and a graphene polyamide yarn containing the composition.

Claims (7)

  1. 산화그래핀 분산액이 함유되는 것을 특징으로 하는 그래핀 폴리아미드용 마스터 배치 조성물.A master batch composition for graphene polyamide, characterized in that it contains a graphene oxide dispersion.
  2. 청구항 1에 있어서,The method of claim 1,
    상기 그래핀 폴리아미드용 마스터 배치 조성물은 폴리아미드 99 내지 99.9 중량% 및 산화그래핀 분산액 0.1 내지 1 중량%로 이루어지는 것을 특징으로 하는 그래핀 폴리아미드용 마스터 배치 조성물.The master batch composition for graphene polyamide is a master batch composition for graphene polyamide, characterized in that consisting of 99 to 99.9% by weight of polyamide and 0.1 to 1% by weight of a graphene oxide dispersion.
  3. 청구항 1에 있어서,The method of claim 1,
    상기 산화그래핀은 분산액은 이온수 100 중량부, 그래핀 0.1 내지 1 중량부, 중화제 0.07 내지 0.7 중량부 및 분산제 0.05 내지 0.5 중량부로 이루어지는 것을 특징으로 하는 그래핀 폴리아미드용 마스터 배치 조성물.The graphene oxide dispersion comprises 100 parts by weight of ionized water, 0.1 to 1 part by weight of graphene, 0.07 to 0.7 parts by weight of a neutralizer, and 0.05 to 0.5 parts by weight of a dispersant. A master batch composition for graphene polyamide.
  4. 청구항 3에 있어서,The method of claim 3,
    상기 중화제는 스테아린계 및 아민계로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 그래핀 폴리아미드용 마스터 배치 조성물.The neutralizer is a master batch composition for graphene polyamide, characterized in that consisting of at least one selected from the group consisting of stearin-based and amine-based.
  5. 청구항 3에 있어서,The method of claim 3,
    상기 분산제는 아민계 및 스테아르산계로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 그래핀 폴리아미드용 마스터 배치 조성물.The dispersant is a graphene master batch composition for polyamide, characterized in that consisting of at least one selected from the group consisting of amine-based and stearic acid-based.
  6. 청구항 1 내지 5중 어느 한 항에 따른 그래핀 폴리아미드용 마스터 배치 조성물이 함유되는 것을 특징으로 하는 그래핀 폴리아미드 원사.A graphene polyamide yarn comprising the master batch composition for graphene polyamide according to any one of claims 1 to 5.
  7. 청구항 6에 있어서,The method of claim 6,
    상기 그래핀 폴리아미드용 배스터 배치 조성물은 50 내지 2000ppm이 함유되는 것을 특징으로 하는 그래핀 폴리아미드 원사.The graphene polyamide yarn, characterized in that the baster batch composition for graphene polyamide contains 50 to 2000ppm.
PCT/KR2022/007390 2021-06-11 2022-05-25 Master batch composition for graphene-containing polyamide, and graphene polyamide yarn comprising composition WO2022260315A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2021-0075855 2021-06-11
KR1020210075855A KR102544097B1 (en) 2021-06-11 2021-06-11 Master batch composition for polyamide containing graphene and polyamide yarn containing the composition

Publications (1)

Publication Number Publication Date
WO2022260315A1 true WO2022260315A1 (en) 2022-12-15

Family

ID=84426180

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/007390 WO2022260315A1 (en) 2021-06-11 2022-05-25 Master batch composition for graphene-containing polyamide, and graphene polyamide yarn comprising composition

Country Status (2)

Country Link
KR (1) KR102544097B1 (en)
WO (1) WO2022260315A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120049679A (en) * 2010-11-09 2012-05-17 한국전기연구원 Manufacturing method of single-layered reduced graphene oxide dispersion solution using shear stress and the single-layered reduced graphene oxide dispersion solution thereby
CN107313126A (en) * 2017-06-30 2017-11-03 福建锦江科技有限公司 A kind of method that the fiber of graphene modified nylon 6 is produced by high speed spinning
CN107459642A (en) * 2017-08-25 2017-12-12 长沙五犇新材料科技有限公司 A kind of master batch of high content graphene modification of nylon 6 and its preparation method and application
CN110437478A (en) * 2019-06-26 2019-11-12 圣华盾防护科技股份有限公司 A kind of antibacterial antistatic graphene extrusion spinning Masterbatch and preparation method thereof
CN110453302A (en) * 2019-04-19 2019-11-15 陕西金瑞烯科技发展有限公司 A kind of preparation method of graphene nylon fibre

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160082721A (en) * 2014-12-26 2016-07-11 주식회사 상보 Manufacturing method of graphene oxide and manufacturing method of polymer film using the graphene oxide
KR20170013635A (en) * 2015-07-28 2017-02-07 (재)울산테크노파크 Fabrication method of graphene nanoplate suspension and its conductive films
CN105862158A (en) * 2016-06-08 2016-08-17 上海史墨希新材料科技有限公司 Preparation method of graphene-chinlon nano-composite fibers
KR20180045746A (en) * 2016-10-26 2018-05-04 (주)비앤케이 A method for manufacturing high heat-radiating filament for three dimensional printing
JP2020045266A (en) * 2018-09-21 2020-03-26 国立研究開発法人産業技術総合研究所 Graphene oxide dispersion and method for preparing the same
KR101975955B1 (en) 2018-12-20 2019-05-08 맥섬석 지.엠. 주식회사 Manufacturing method of antimicrobial plastic masterbatch using macsumsuk granule
KR102213536B1 (en) * 2018-12-27 2021-02-10 주식회사 삼양사 Long fiber reinforced thermoplastic resin composition having excellent thermal conductivity and EMI shielding property and molded article comprising the same
KR102163232B1 (en) 2020-08-14 2020-10-08 주식회사 일송글로벌 Masterbatch having antibacterial and anti-fungal properties and its manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120049679A (en) * 2010-11-09 2012-05-17 한국전기연구원 Manufacturing method of single-layered reduced graphene oxide dispersion solution using shear stress and the single-layered reduced graphene oxide dispersion solution thereby
CN107313126A (en) * 2017-06-30 2017-11-03 福建锦江科技有限公司 A kind of method that the fiber of graphene modified nylon 6 is produced by high speed spinning
CN107459642A (en) * 2017-08-25 2017-12-12 长沙五犇新材料科技有限公司 A kind of master batch of high content graphene modification of nylon 6 and its preparation method and application
CN110453302A (en) * 2019-04-19 2019-11-15 陕西金瑞烯科技发展有限公司 A kind of preparation method of graphene nylon fibre
CN110437478A (en) * 2019-06-26 2019-11-12 圣华盾防护科技股份有限公司 A kind of antibacterial antistatic graphene extrusion spinning Masterbatch and preparation method thereof

Also Published As

Publication number Publication date
KR102544097B1 (en) 2023-06-16
KR20220166944A (en) 2022-12-20

Similar Documents

Publication Publication Date Title
DE112008003070B4 (en) Polymer with integrated acid anhydride structure, polymer composition, coated electrical wire and wiring harness
WO2012169804A2 (en) Method for manufacturing a graphene-treated fiber
Alimohammadi et al. Polyvinylpyrrolidone/carbon nanotube/cotton functional nanocomposite: preparation and characterization of properties
WO2013105749A1 (en) Continuous carbon fiber-reinforced thermoplastic composite material having superior impregnation properties and method for manufacturing same
WO2022260315A1 (en) Master batch composition for graphene-containing polyamide, and graphene polyamide yarn comprising composition
EP0605862A2 (en) Flame retardant polyamide moulding compositions
WO2019182362A1 (en) Graphene oxide-dyed fiber and manufacturing method therefor
WO2021117982A1 (en) Thermoplastic polyurethane-coated yarn having hydrophobic nano-silica blended therein
CN112574510A (en) Antibacterial ultraviolet aging resistant modified PP composite material and preparation method thereof
WO2018236023A1 (en) Method for enhancing tensile strength of carbon nanotube fiber aggregate
WO2020204599A1 (en) Antibacterial polymer coating composition and antibacterial polymer film
DE2625692A1 (en) Means for making plastics flame retardant
Hassan Enhanced thermal stability, hydrophobicity, UV radiation resistance, and antibacterial properties of wool fabric treated with p-aminobenzenesulphonic acid
WO2022203439A1 (en) Polyester master batch composition, and polyester yarn containing same
KR102534123B1 (en) Polyester yarn containing graphene oxide
WO2024043710A1 (en) Composition for use in wig comprising polyester, polybutylene terephthalate, and graphene
WO2018128436A1 (en) Deodorizing spandex and manufacturing method therefor
WO2021206472A1 (en) Near infrared-emitting polymer composite, and near infrared-emitting fiber, near infrared-emitting non-woven fabric and near infrared-emitting glasses frame which comprise same
EP2857455A1 (en) Polyamide moulding compositions containing cycloolefin copolymers
WO2019132385A1 (en) Thermoplastic resin composition and molded product manufactured therefrom
CN113718527A (en) High-strength high-conductivity ultrahigh molecular weight polyethylene composite fiber and preparation method thereof
WO2024010257A1 (en) Radiation-shielding film comprising waste plastics and manufacturing method therefor
CN111519273B (en) Moisture-absorption dyeable modified polyphenylene sulfide composite fiber and preparation method and application thereof
CN111040445A (en) Flame-retardant nylon 66/nylon 6 composite material with high mechanical property
DE602004000981T2 (en) MOISTURIZABLE POLYMERIC COMPOSITION

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22820443

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE