KR20200127090A - Tracheal tube composition for removal of biofouling - Google Patents

Tracheal tube composition for removal of biofouling Download PDF

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KR20200127090A
KR20200127090A KR1020190050587A KR20190050587A KR20200127090A KR 20200127090 A KR20200127090 A KR 20200127090A KR 1020190050587 A KR1020190050587 A KR 1020190050587A KR 20190050587 A KR20190050587 A KR 20190050587A KR 20200127090 A KR20200127090 A KR 20200127090A
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carbon black
tube
polypyrrole
polyurethane
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KR102251462B1 (en
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박진균
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한국외국어대학교 연구산학협력단
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L29/126Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/02Inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14Materials characterised by their function or physical properties, e.g. lubricating compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M16/00Devices for influencing the respiratory system of patients by gas treatment, e.g. mouth-to-mouth respiration; Tracheal tubes
    • A61M16/04Tracheal tubes
    • A61M16/0465Tracheostomy tubes; Devices for performing a tracheostomy; Accessories therefor, e.g. masks, filters
    • A61M16/0468Tracheostomy tubes; Devices for performing a tracheostomy; Accessories therefor, e.g. masks, filters with valves at the proximal end limiting exhalation, e.g. during speaking or coughing
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00Catheters; Hollow probes
    • A61M25/0017Catheters; Hollow probes specially adapted for long-term hygiene care, e.g. urethral or indwelling catheters to prevent infections
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M39/00Tubes, tube connectors, tube couplings, valves, access sites or the like, specially adapted for medical use
    • A61M39/10Tube connectors; Tube couplings
    • A61M39/16Tube connectors; Tube couplings having provision for disinfection or sterilisation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/24Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/108Elemental carbon, e.g. charcoal
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00Catheters; Hollow probes
    • A61M25/0043Catheters; Hollow probes characterised by structural features
    • A61M2025/0058Catheters; Hollow probes characterised by structural features having an electroactive polymer material, e.g. for steering purposes, for control of flexibility, for locking, for opening or closing
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M39/00Tubes, tube connectors, tube couplings, valves, access sites or the like, specially adapted for medical use
    • A61M39/10Tube connectors; Tube couplings
    • A61M39/16Tube connectors; Tube couplings having provision for disinfection or sterilisation
    • A61M2039/167Tube connectors; Tube couplings having provision for disinfection or sterilisation with energizing means, e.g. light, vibration, electricity
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00General characteristics of the apparatus
    • A61M2205/02General characteristics of the apparatus characterised by a particular materials
    • A61M2205/0233Conductive materials, e.g. antistatic coatings for spark prevention
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/001Conductive additives

Abstract

The present invention relates to a composition for a tracheal tube having a biofouling removal function, and more specifically, to a composition for a tracheal tube which provides a biofouling removal function by having conductivity even at a low voltage. The composition for a tracheal tube of the present invention has a function of preventing agglomeration of mucus by a low voltage electrical signal, thereby preventing clogging of the tube by phlegm and the like and prolonging the replacement cycle of the tube.

Description

생물오손 제거 기능성을 갖는 기관절개 튜브용 조성물{Tracheal tube composition for removal of biofouling}Composition for tracheal tube composition for removal of biofouling

본 발명은 생물오손 제거 기능성을 갖는 기관절개 튜브용 조성물에 관한 것이다. 더욱 상세하게는 낮은 전압으로도 전도성을 가져 생물오손 제거 기능을 나타내는 기관절개 튜브용 조성물에 관한 것이다.The present invention relates to a composition for a tracheostomy tube having a biological contamination removal function. More specifically, it relates to a composition for a tracheostomy tube exhibiting a function of removing biofouling by having conductivity even at a low voltage.

오늘날 중환자 치료 기술 발전에 따라 환자의 생존률이 높아지고 있으며, 여러 원인에 의하여 구호흡(mouth breathing)이 불가능한 경우 기도삽관(Orotracheal Intubation)이나 기관절개술(Tracheostomy)에 의해 호흡을 유지하는 경우가 늘어 이로 인한 기도삽관 혹은 기관절개술의 합병증도 증가하고 있다.Today, with the development of intensive care technology, the survival rate of patients is increasing, and when mouth breathing is not possible due to various causes, breathing is often maintained by orotracheal intubation or tracheostomy, resulting in airway. Complications from intubation or tracheostomy are also increasing.

또한, 폐렴과 같은 호흡기 감염으로 인하여 인공호흡이 필요한 경우에도 2주 이상의 장기간 기도삽관이 예상되는 경우 기관절개술이 시행되는데, 환자의 기도 내에 존재하는 분비물을 제때 제거해 주지 않으면 분비물에 의한 튜브의 폐색(obstruction)이 유발되며, 수분 이내 튜브 교체 및 폐색 해소가 되지 않으면 저산소증에 의하여 뇌손상을 초래하거나 사망에 이를 수 있는 문제가 있다.In addition, even when artificial respiration is required due to respiratory infections such as pneumonia, tracheostomy is performed when long-term airway intubation is expected for 2 weeks or more.If the secretions present in the patient's airways are not removed in time, the tube is blocked by the secretions ( obstruction), and if tube replacement and obstruction are not resolved within minutes, there is a problem that may lead to brain damage or death due to hypoxia.

특히 소아의 경우 기관절개 튜브의 내경이 매우 작기 때문에 약간의 점액질 부착으로도 심각한 호흡곤란을 유발하기 때문에, 점액질 부착을 원천적으로 감소시킬 수 있는 기관절개 튜브의 개발이 필요하다. 또한, 기관절개 튜브를 통해 외부의 물질이 유입될 경우 기관지 내 감염 우려가 있으며, 튜브 내부의 물리화학적 성질을 조절함으로서 감염을 막는 한편, 점액질에 의한 폐색을 방지할 수 있는 기술의 개발이 절실히 필요한 실정이다.In particular, in the case of children, since the inner diameter of the tracheostomy tube is very small, even a slight mucus adhesion causes severe breathing difficulties, so development of a tracheostomy tube that can fundamentally reduce mucus adhesion is required. In addition, there is a risk of infection in the bronchi when external substances are introduced through the tracheostomy tube, and there is an urgent need to develop a technology that can prevent infection by controlling the physicochemical properties inside the tube, while preventing obstruction by mucus. Actually.

현재 국내외에서 생산/판매되는 기관절개 튜브는 의료용 고분자 튜브이며, 특별히 분비물 제거나 폐색 예방기술은 적용되지 않은 상태이다. 기존 기관절개 튜브의 경우 표면에너지가 낮고 생체물질의 부착이 최소화되는 것으로 알려진 실리콘 소재나 폴리비닐클로라이드(PVC) 소재를 사용하는 것으로 알려져 있는데 이러한 소재를 사용함에도 불구하고 지속적으로 튜브의 폐색이 보고되는 것은 소재 자체만으로는 점액질과 같은 생체물질의 부착 또는 제거되기 어렵다.Currently, tracheostomy tubes produced and sold at home and abroad are medical polymer tubes, and no secretion removal or obstruction prevention technology has been applied. Conventional tracheostomy tubes are known to use silicone materials or polyvinyl chloride (PVC) materials, which are known to have low surface energy and minimize the adhesion of biomaterials. Despite the use of these materials, tube blockages are continuously reported. It is difficult to attach or remove biomaterials such as mucus with the material itself.

생물오손(biofouling)이란 선박의 밑부분, 발전소의 열교환기, 해양 구조물, 의료기기 등에 미생물(세균)이 부착하여 생물막을 형성하면 이어서 다양한 생물종이 부착하여 구조물에 영향을 주는 현상이다. 특히 튜브형 의료기기의 경우 생물오손에 의한 생물막 형성은 튜브의 막힘 현상, 균에 의한 2차 감염 등의 문제점을 발생시킨다.Biofouling is a phenomenon in which microorganisms (bacteria) adhere to the bottom of a ship, heat exchangers of power plants, marine structures, medical devices, etc. to form a biofilm, and then various species adhere to the structure and affect the structure. In particular, in the case of a tube-type medical device, the formation of a biofilm due to biofouling causes problems such as clogging of the tube and secondary infection by bacteria.

위와 같은 문제를 해결하기 위해 본 발명자들은 낮은 전압에도 전도성을 나타내어 생물오손 제거 기능성을 가지는 기관절개 튜브용 조성물을 발명하였다.In order to solve the above problem, the present inventors have invented a composition for a tracheostomy tube that exhibits conductivity even at a low voltage and thus has a biofouling function.

대한민국 등록특허 제10-1599426호(발명의 명칭 : 부테놀라이드계 화합물과 그의 제조방법 및 그를 포함하는 약제학적 조성물, 출원인 : 서울대학교산학협력단, 등록인자 : 2016.02.25.)Republic of Korea Patent Registration No. 10-1599426 (Name of the invention: butenolide-based compound and its manufacturing method and pharmaceutical composition containing the same, Applicant: Seoul National University Industry-Academic Cooperation Foundation, Registration: 2016.02.25.)

Lee et. al., Appl.Chem. Eng., 2012, 23, 71-76Lee et. al., Appl. Chem. Eng., 2012, 23, 71-76 Park et. al., Journal of Korean Crystal Growth and Crystal Technology, 2015, 25, 212-217Park et. al., Journal of Korean Crystal Growth and Crystal Technology, 2015, 25, 212-217

본 발명의 목적은 생물오손 제거 기능성을 갖는 기관절개 튜브용 조성물을 제공하는데에 있다. 전압을 인가하여 전류를 통해 기관절개 튜브용 조성물로부터 생물오손 물질을 제거하는 효과를 나타내는 것을 특징으로 하며, 더욱 상세하게는 보다 낮은 전압에서도 전도성을 가져 생물오손 제거 기능을 나타내는 기관절개 튜브용 조성물을 제공하는데에 있다.An object of the present invention is to provide a composition for a tracheostomy tube having a biological contamination removal function. It is characterized in that it exhibits the effect of removing biocontaminants from the composition for tracheostomy tubes through current by applying a voltage, and more specifically, a composition for tracheostomy tubes that exhibits a function of removing biofouling by having conductivity even at a lower voltage. It is in providing.

본 발명은 생물오손 제거 기능성을 갖는 기관절개 튜브용 조성물에 관한 것이다.The present invention relates to a composition for a tracheostomy tube having a biological contamination removal function.

상기 기관절개 튜브용 조성물은 폴리우레탄(Polyurethane), 카본블랙 및 폴리피롤(Polypyrrole)을 포함할 수 있다.The composition for the tracheostomy tube may include polyurethane, carbon black, and polypyrrole.

상기 카본블랙은 DBP 흡수율이 350 ~ 385 ㎖/100g인 것을 사용할 수 있다.The carbon black may have a DBP absorption rate of 350 ~ 385 ㎖/100g.

상기 상기 폴리피롤은 전도성이 10 ~ 50s/cm인 펠렛 형태의 고체시료인 것을 사용할 수 있다.The polypyrrole may be a solid sample in the form of a pellet having a conductivity of 10 to 50 s/cm.

또한, 상기 폴리우레탄, 카본블랙 및 폴리피롤은 폴리우레탄 100 중량부 기준 카본블랙 25 내지 30 중량부 및 폴리피롤 15 내지 35 중량부를 포함하는 것일 수 있다.In addition, the polyurethane, carbon black and polypyrrole may include 25 to 30 parts by weight of carbon black and 15 to 35 parts by weight of polypyrrole based on 100 parts by weight of polyurethane.

상기 폴리우레탄, 카본블랙 및 폴리피롤은 메틸피롤리돈에 60~80℃에서 녹인 후 12~24시간 동안 건조하여 제조한 것일 수 있다.The polyurethane, carbon black and polypyrrole may be prepared by dissolving in methylpyrrolidone at 60 to 80° C. and drying for 12 to 24 hours.

또한, 상기 기관절개 튜브용 조성물은 생물오손 제거 기능성을 갖는 것일 수 있다.In addition, the composition for the tracheostomy tube may have a biofouling removal function.

상기 기관절개 튜브용 조성물은 전압을 인가하여 생물오손 제거 기능성을 갖는 것일 수 있다.The composition for tracheostomy tube may have a biofouling function by applying a voltage.

또 다른 본 발명은 상기 기관절개 튜브용 조성물로 제조된 것을 특징으로 하는 생물오손 제거용 기관절개 튜브에 관한 것이다.Another invention relates to a tracheostomy tube for removing biofouling, characterized in that made of the composition for the tracheostomy tube.

이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.

상기 본 발명의 튜브용 조성물은 폴리우레탄 100 중량부 기준 카본블랙 25 내지 30 중량부 및 폴리피롤 15 내지 35 중량부를 포함할 수 있다.The composition for tubes of the present invention may include 25 to 30 parts by weight of carbon black and 15 to 35 parts by weight of polypyrrole based on 100 parts by weight of polyurethane.

상기 폴리우레탄은 이소시아네이트기와 폴리올의 결합에 의한 우레아 반응으로 생성된 고분자 물질일 수 있다. 폴리우레탄은 비중 6㎏/㎥ ~ 1220㎏/㎥의 범위에서 고경도 플라스틱에서 아주 유연한 폼에 이르기까지 다양하게 제조될 수 있다. 상기 폴리우레탄은 겔 투과 크로마토그래피(GPC)에 의해 측정한 중량평균 분자량(Mw)은 3,000 ~ 400,000인 것이 바람직하며, 보다 바람직하게는 6,000 ~ 80,000인 것 일 수 있다. 또한, 산가는 5 ~ 120 ㎎KOH/g인 것이 바람직하며, 보다 바람직하게는 10 ~ 60 ㎎KOH/g인 것이 좋다.The polyurethane may be a polymer material produced by a urea reaction by bonding of an isocyanate group and a polyol. Polyurethane can be manufactured in a wide variety from high hardness plastics to highly flexible foams in the range of specific gravity 6kg/㎥ to 1220kg/㎥. The polyurethane has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 3,000 to 400,000, and more preferably 6,000 to 80,000. Further, the acid value is preferably 5 to 120 mgKOH/g, more preferably 10 to 60 mgKOH/g.

상기 폴리우레탄은 2액형의 도료 촉매 경화형과 폴리올 경화형 도료를 포함하며, 더욱 적합하게는 상온에서 폴리올과 폴리이소이사네이트가 쉽게 반응하여 강인한 3차원 망상 구조를 형성하는 폴리올 경화형 도료를 사용하는 것이 가장 바람직하다. 또한, 2액형 폴리올 경화형 도료에서 폴리올계는 폴리에스테르, 폴리에테르, 폴리아크릴레이트의 3종류가 있는데, 분자구조, 분자량, 관능기 및 가교 밀도를 임의로 조정할 수 있고 폴리이소시아네이트와 결합하여 폴리우레탄이 제조되었을 때 도막물성을 쉽게 변환시킬 수 있는 장점을 가지고 있는 폴리에스테르를 사용하는 것이 더욱 바람직하다. 또한, 반응계의 평균 관능기도를 낮추고 분자량과 점도 등의 조절을 용이하게 하며 도막의 경도, 접착력, 색상 광택, 건조시간 및 내약품성 등의 물성을 향상시키기 위해 벤조산 변성 폴리에스테르를 사용한다. 벤조산의 함량은 폴리에스테르 총량에 대해 5~30중량% 정도가 적정하며, 바람직하게는 15~20중량%가 적정하다. 벤조산의 함량이 증가함에 따라 고형분의 함량이 증가하는 장점이 있지만, 적정 수준 이상에서는 상대적인 점도 저하의 수준이 감소하는 것을 알 수 있다.The polyurethane includes a two-component coating catalyst curing type and a polyol curing type coating. More suitably, it is best to use a polyol curing type coating that forms a strong three-dimensional network structure by easily reacting polyol and polyisocyanate at room temperature. desirable. In addition, in the two-component polyol curable paint, there are three types of polyols: polyester, polyether, and polyacrylate. The molecular structure, molecular weight, functional group and crosslinking density can be arbitrarily adjusted, and polyurethane can be produced by combining with polyisocyanate. It is more preferable to use polyester, which has the advantage of easily converting the properties of the coating film. In addition, benzoic acid-modified polyester is used to lower the average functional degree of the reaction system, facilitate control of molecular weight and viscosity, and improve physical properties such as hardness, adhesion, color gloss, drying time and chemical resistance of the coating film. The content of benzoic acid is appropriate about 5 to 30% by weight, preferably 15 to 20% by weight, based on the total amount of polyester. There is an advantage in that the solid content increases as the benzoic acid content increases, but it can be seen that the level of relative viscosity decrease decreases above an appropriate level.

또한, 폴리우레탄의 합성을 위한 폴리올은 벤조산 변성 폴리에스테르를 사용하며, 그 함량은 20~40중량%가 적당하며, 바람직하게는 25~35중량%가 적당하다. 이소시아네이트로는 통상적으로 많이 사용되는 이소포론 디이소시아네이트(IPDI, isophorone diisocyanate)를 사용하는 것이 좋으며, 그 함량은 5~20중량%를 사용할 수 있으며 5~15중량%가 가장 바람직하다. 한편, 친수성기를 도입하기 위해 2,2-비스(히드록시메틸)프로피온산(DMPA)을 사용할 수 있다. DMPA의 함량이 증가할수록 초기 입도 크기는 감소하며, 연속상의 이온성 그룹의 농도가 증가함에 따라 최종 입도 크기는 증가하고, 안정화 가능한 친수성기의 농도를 증가하지만, 최적 사슬연장 정도는 감소한다. DMPA의 함량이 적을 경우, 저장성이 떨어지고, DMPA의 함량이 많을 경우 도장 시 도막 물성의 저하가 발생한다. 따라서 최적의 성능 유지하기 위한 DMPA의 함량은 0.3~5중량%가 적당하며 바람직하게는 0.5~2중량%가 적당하다. 또한, 상기 DMPA의 용매로 N-메틸-2-피롤리돈(NMP)를 0.5~2중량%를 사용한다. 폴리우레탄 프리폴리머의 반응 촉매로 주석(Sn)계 촉매인 디부틸틴 디라우레이트(DBTL)를 사용하고, 중화제로는 트리에틸아민(TEA)을 사용하며, 0.5~2중량%가 바람직하다. 또한, 사용되는 물은 모든 실험단계에서 초순수(deioninzed water)를 사용하였다. 이때 초순수는 35~55중량% 사용하였다.In addition, the polyol for the synthesis of the polyurethane uses a benzoic acid-modified polyester, and the content thereof is suitably 20 to 40% by weight, preferably 25 to 35% by weight. As the isocyanate, it is recommended to use isophorone diisocyanate (IPDI, isophorone diisocyanate), which is commonly used, and the content may be 5 to 20% by weight, and 5 to 15% by weight is most preferable. Meanwhile, 2,2-bis(hydroxymethyl)propionic acid (DMPA) may be used to introduce a hydrophilic group. As the content of DMPA increases, the initial particle size decreases, and as the concentration of the ionic group in the continuous phase increases, the final particle size increases, and the concentration of the stabilizeable hydrophilic group increases, but the optimum degree of chain extension decreases. When the content of DMPA is low, the storage properties are poor, and when the content of DMPA is high, the properties of the coating film are deteriorated during painting. Therefore, the content of DMPA for maintaining optimal performance is appropriate in a range of 0.3 to 5% by weight, and preferably 0.5 to 2% by weight. In addition, 0.5 to 2% by weight of N-methyl-2-pyrrolidone (NMP) is used as a solvent for the DMPA. Dibutyltin dilaurate (DBTL), a tin (Sn)-based catalyst, is used as the reaction catalyst of the polyurethane prepolymer, and triethylamine (TEA) is used as the neutralizing agent, and 0.5 to 2% by weight is preferable. In addition, deioninzed water was used in all experimental steps. At this time, 35 to 55% by weight of ultrapure water was used.

상기 카본블랙은 DBP 흡수율이 350 ~ 385 ㎖/100g인 것을 이용하는 것이 바람직하다. DBP(Dibutyl phthalate) 흡수율은 카본블랙의 응집체 크기를 확인할 수 있는 지표로써 이용되며 디부틸 프탈레이트(DBP)가 카본블랙에 흡수되는 정도를 나타내는 것이다. 상기 카본블랙의 DBP 흡수율이 350 ㎖/100g 미만인 것은 튜브용 조성물 제조 시 전도성을 나타내지 않거나 오손 제거효과가 미비할 수 있으며, DBP 흡수율이 385 ㎖/100g 초과인 것은 튜브용 조성물 제조 시 표면이 거칠거나 갈라짐이 형성될 수 있어 바람직하지 못하다.It is preferable to use the carbon black having a DBP absorption rate of 350 to 385 ml/100g. DBP (Dibutyl phthalate) absorption rate is used as an index to confirm the aggregate size of carbon black, and indicates the degree to which dibutyl phthalate (DBP) is absorbed into carbon black. If the carbon black has a DBP absorption rate of less than 350 ml/100g, it may not exhibit conductivity or have inadequate decontamination effect when the composition for tubes is prepared, and when the DBP absorption rate is more than 385 ml/100g, the surface may be rough or Cracks can form, which is undesirable.

또한, 상기 튜브용 조성물은 폴리우레탄 100 중량부 기준 카본블랙이 25 중량부 미만이면 전도성을 나타내지 않거나 오손 제거효과가 미비할 수 있으며, 30 중량부 초과이면 튜브용 조성물 제조 시 표면이 거칠거나 갈라짐이 형성될 수 있어 바람직하지 못하다.In addition, if the composition for tubes is less than 25 parts by weight of carbon black based on 100 parts by weight of polyurethane, it may not exhibit conductivity or may have insufficient stain removal effect, and if it exceeds 30 parts by weight, the surface may be rough or cracked when preparing the composition for tubes. It may be formed, which is not desirable.

추가로, 상기 튜브용 조성물은 폴리우레탄 100 중량부 기준 폴리피롤 15 내지 35 중량부를 포함되는 것이 바람직하다. 폴리우레탄 100 중량부 기준 폴리피롤이 15 중량부 미만이면 전도성이 낮아 오손 제거효과가 미비할 수 있으며, 35 중량부 초과이면 튜브용 조성물 제조시 표면이 거칠거나 구멍이 형성될 수 있어 바람직하지 못하다. 더욱 바람직하게는 폴리우레탄 100 중량부 기준 폴리피롤이 25 내지 35 중량부을 포함하는 튜브용 조성물이 생물오손 제거 효과가 우수하여 가장 바람직하다.In addition, the composition for the tube preferably contains 15 to 35 parts by weight of polypyrrole based on 100 parts by weight of polyurethane. If the amount of polypyrrole based on 100 parts by weight of polyurethane is less than 15 parts by weight, the conductivity may be low, and the stain removal effect may be insufficient, and if it exceeds 35 parts by weight, the surface may be rough or holes may be formed when preparing the tube composition, which is not preferable. More preferably, a composition for tubes containing 25 to 35 parts by weight of polypyrrole based on 100 parts by weight of polyurethane is most preferred because it has excellent biofouling effect.

본 발명의 튜브용 조성물은 폴리우레탄(Polyurethane), 카본블랙 및 폴리피롤(Polypyrrole)을 메틸피롤리돈(1-methyl-2-pyrrolidone)에 60~80℃에서 녹인 후, 12~24시간 동안 건조하여 제조한 것일 수 있다.The composition for tubes of the present invention is prepared by dissolving polyurethane, carbon black, and polypyrrole in methylpyrrolidone at 60 to 80°C and drying for 12 to 24 hours. It may be manufactured.

상기 메틸 피롤리돈에 폴리우레탄, 카본블랙 및 폴리피롤을 첨가한 후 60℃ 미만에서 녹이면 폴리우레탄, 카본블랙 및 폴리피롤이 충분히 분산되지 않아 튜브용 조성물 제조시 전도성을 나타내지 않거나 오손 제거 효과가 미비할 수 있다. 또한, 80℃를 초과하여 녹이면 폴리우레탄, 카본블랙 및 폴리피롤이 변형될 수 있어 바람직하지 못하다.If polyurethane, carbon black and polypyrrole are added to the methyl pyrrolidone and then melted at less than 60° C., polyurethane, carbon black and polypyrrole are not sufficiently dispersed, so that when preparing a composition for a tube, it may not exhibit conductivity or have insufficient stain removal effect. have. In addition, melting exceeding 80° C. is undesirable because polyurethane, carbon black and polypyrrole may be deformed.

한편, 본 발명의 튜브용 조성물은 전압을 인가하여 생물오손 제거 효과를 나타낼 수 있다. 바람직하게는 2V 이하의 전압에서 0.02 내지 0.04A가 흐르는 것이 좋으며 이를 통해 생물오손 제거 효과를 나타낼 수 있다.On the other hand, the composition for tubes of the present invention may exhibit a biofouling effect by applying a voltage. Preferably, 0.02 to 0.04A flows at a voltage of 2V or less, and through this, it is possible to exhibit an effect of removing biofouling.

본 발명은 생물오손 제거 기능성을 갖는 기관절개 튜브용 조성물에 관한 것이다. 저전압 전기 신호에 의하여 점액질의 응집을 방지하는 기능성을 탑재하여 튜브가 가래 등에 의해 막히는 폐색을 방지하고, 또한 튜브의 교체 주기를 장기화할 수 있는 효과가 있다.The present invention relates to a composition for a tracheostomy tube having a biological contamination removal function. It is equipped with a function to prevent agglomeration of mucus by a low-voltage electrical signal to prevent clogging of the tube by phlegm and the like, and to prolong the replacement cycle of the tube.

도 1은 본 발명에 따른 실험예 1에서 제조한 DBP 흡수율이 다른 카본블랙을 첨가하여 각각 제조한 튜브용 조성물의 표면을 비교한 사진이다.
도 2는 본 발명에 따른 실험예 2에서 제조한 카본블랙의 함량에 따라 형성된 튜브용 조성물의 표면을 비교한 사진이다.
도 3은 본 발명에 따른 실험예 3에서 제조한 폴리피롤의 함량에 따라 형성된 튜브용 조성물의 표면을 비교한 사진이다.
도 4는 본 발명에 따른 실험예 3에서 실시한 폴리우레탄과 카본블랙의 함량이 일정할 때 폴리피롤 함량에 대한 튜브용 조성물의 전류 변화를 나타낸 그래프이다.
도 5는 본 발명에 따른 실험예 4에서 실시한 폴리피롤의 함량에 대한 생물오손 제거율을 나타낸 그래프이다.
1 is a photograph comparing the surfaces of a tube composition prepared by adding carbon black having different DBP absorption rates prepared in Experimental Example 1 according to the present invention.
2 is a photograph comparing the surface of a composition for tubes formed according to the content of carbon black prepared in Experimental Example 2 according to the present invention.
3 is a photograph comparing the surface of a composition for tubes formed according to the content of polypyrrole prepared in Experimental Example 3 according to the present invention.
Figure 4 is a graph showing the current change of the composition for a tube with respect to the polypyrrole content when the content of polyurethane and carbon black carried out in Experimental Example 3 according to the present invention is constant.
5 is a graph showing the biofouling removal rate with respect to the content of polypyrrole carried out in Experimental Example 4 according to the present invention.

이하 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 그러나, 본 발명은 여기서 설명되는 실시예에 한정되지 않고 다른 형태로 구체화될 수도 있다. 오히려, 여기서 소개되는 내용이 철저하고 완전해지도록, 당업자에게 본 발명의 사상을 충분히 전달하기 위해 제공하는 것이다.Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, it is provided to sufficiently convey the spirit of the present invention to those skilled in the art so that the contents introduced herein are thorough and complete.

실험예 1. 적절한 카본블랙 선택Experimental Example 1. Selection of appropriate carbon black

먼저 튜브용 조성물을 제조하기 위해 메틸피롤리돈(1-methyl-2-pyrrolidone), 폴리우레탄(polyurethane) 및 카본블랙을 준비하였다.First, methylpyrrolidone (1-methyl-2-pyrrolidone), polyurethane (polyurethane) and carbon black were prepared to prepare a composition for a tube.

1g의 폴리우레탄과 0.4g, 0.05g의 카본블랙을 각각 10㎖ 메틸피롤리돈에 첨가하고, 유리 petri-dish(지름 7.6cm)에 넣어 70℃ hot plate에서 12시간 동안 건조시켜 튜브용 조성물을 제조하였다. 이때 카본블랙은 DBP(Dibutyl phthalate) 흡수율이 370 ㎖/100g 및 500 ㎖/100g인 것을 각각 사용하여 제조하였으며 이를 하기 표 1에 나타내었다. 또한, 제조한 튜브용 조성물의 표면 사진을 도 1에 나타내었다.1 g of polyurethane, 0.4 g, and 0.05 g of carbon black were added to each 10 ml methylpyrrolidone, put in a glass petri-dish (diameter 7.6 cm), and dried on a hot plate at 70° C. for 12 hours to prepare a tube composition. Was prepared. At this time, carbon black was prepared by using those having dibutyl phthalate (DBP) absorption rates of 370 ml/100g and 500 ml/100g, respectively, and are shown in Table 1 below. In addition, a photograph of the surface of the prepared tube composition is shown in FIG. 1.

구분division 폴리우레탄Polyurethane 카본블랙Carbon black 카본블랙의 DBP 흡수율DBP absorption rate of carbon black 실험예 1-1Experimental Example 1-1 1g1g 0.40g0.40g 370㎖/100g370ml/100g 실험예 1-2Experimental Example 1-2 1g1g 0.40g0.40g 500㎖/100g500ml/100g 실험예 1-3Experimental Example 1-3 1g1g 0.05g0.05g 370㎖/100g370ml/100g 실험예 1-4Experimental Example 1-4 1g1g 0.05g0.05g 500㎖/100g500ml/100g

도 1을 참고하면, 0.40g의 카본블랙을 첨가하여 제조한 각 튜브용 조성물(실험예 1-1, 1-2)은 튜브용 조성물이 잘 형성되지 않고 갈라진 것을 볼 수 있다. 그중 DBP 흡수율이 500㎖/100g인 카본블랙을 첨가한 튜브용 조성물(실험예 1-2)이 더욱 심하게 갈라진 것을 확인할 수 있다. 또한, 각 튜브용 조성물에 대해 전도성을 측정한 결과 전류가 흐르는 것을 확인하였다.Referring to FIG. 1, it can be seen that each tube composition (Experimental Examples 1-1 and 1-2) prepared by adding 0.40 g of carbon black was not well formed and cracked. Among them, it can be seen that the composition for tubes (Experimental Example 1-2) to which carbon black having a DBP absorption rate of 500 ml/100 g was added was more severely cracked. In addition, as a result of measuring the conductivity of the composition for each tube, it was confirmed that a current flows.

0.05g의 카본블랙을 첨가하여 제조한 각 튜브용 조성물(실험예 1-3, 1-4)은 튜브용 조성물이 잘 형성된 것을 볼 수 있다. 그중 DBP 흡수율이 500㎖/100g인 카본블랙을 첨가한 튜브용 조성물이 보다 거친 표면을 형성하고 있으므로 DBP 흡수율이 370㎖/100g인 카본블랙이 메틸피롤리돈에 더 잘 분산된다고 생각된다. 그러나 실험예 1-3과 1-4의 튜브용 조성물은 전도성을 측정한 결과 전류가 흐르지 않는 것을 확인함으로써 DBP 흡수율이 370㎖/100g인 카본블랙과 500㎖/100g인 카본블랙의 전도성에 대한 차이가 없어 하기 실험예에서는 DBP 흡수율이 370㎖/100g인 카본블랙을 포함하는 튜브용 조성물을 제조하여 실험하였다.Each tube composition prepared by adding 0.05 g of carbon black (Experimental Examples 1-3 and 1-4) can be seen that the tube composition was well formed. Among them, the composition for tubes to which carbon black with a DBP absorption rate of 500 ml/100 g is added forms a rougher surface, so it is thought that carbon black with a DBP absorption rate of 370 ml/100 g is better dispersed in methylpyrrolidone. However, the difference in conductivity between the carbon black having a DBP absorption rate of 370 ml/100g and carbon black having a DBP absorption rate of 370 ml/100 g and 500 ml/100 g by confirming that no current flows as a result of measuring the conductivity of the tube compositions of Experimental Examples 1-3 and 1-4 In the following experimental example, a composition for a tube containing carbon black having a DBP absorption rate of 370 ml/100 g was prepared and tested.

실험예 2. 카본블랙의 적정 비율 확인Experimental Example 2. Confirmation of the proper ratio of carbon black

상기 실험예 1 이후 카본블랙의 적정 비율을 확인하기 위해 실험예 1과 같은 방법으로 370㎖/100g인 카본블랙을 포함하는 튜브용 조성물을 제조하되, 카본블랙의 함량을 달리하여 제조하였다. 1g의 폴리우레탄과 폴리우레탄 기준 0.08g, 0.10g, 0.15g, 0.20g, 0.25g 및 0.30g의 카본블랙을 각각 10㎖의 메틸피롤리돈에 첨가하고, 유리 petri-dish(지름 7.6cm)에 넣어 70℃ hot plate에서 12시간 동안 건조시켜 튜브용 조성물을 제조하였다. 이를 하기 표 2에 나타내었으며, 제조한 튜브용 조성물의 표면 사진을 도 2에 나타내었다.After Experimental Example 1, a composition for tubes containing 370ml/100g of carbon black was prepared in the same manner as in Experimental Example 1 in order to check the appropriate ratio of carbon black, but the content of carbon black was varied. 1 g of polyurethane and 0.08 g, 0.10 g, 0.15 g, 0.20 g, 0.25 g and 0.30 g of carbon black based on polyurethane were added to 10 ml of methylpyrrolidone, respectively, and free petri-dish (diameter 7.6 cm) Put in and dried for 12 hours on a 70 ℃ hot plate to prepare a composition for tubes. This is shown in Table 2 below, and a photograph of the surface of the prepared tube composition is shown in FIG. 2.

구분division 폴리우레탄Polyurethane 카본블랙Carbon black 카본블랙의 DBP 흡수율DBP absorption rate of carbon black 실험예 2-1Experimental Example 2-1 1g1g 0.08g0.08g 370㎖/100g370ml/100g 실험예 2-2Experimental Example 2-2 1g1g 0.10g0.10g 370㎖/100g370ml/100g 실험예 2-3Experimental Example 2-3 1g1g 0.15g0.15g 370㎖/100g370ml/100g 실험예 2-4Experimental Example 2-4 1g1g 0.20g0.20g 370㎖/100g370ml/100g 실험예 2-5Experimental Example 2-5 1g1g 0.25g0.25g 370㎖/100g370ml/100g 실험예 2-6Experimental Example 2-6 1g1g 0.30g0.30g 370㎖/100g370ml/100g 실험예 2-7Experimental Example 2-7 1g1g 0.35g0.35g 370㎖/100g370ml/100g

도 2를 참고하면, 카본블랙의 함량이 높아질수록 튜브용 조성물이 형성되지 못하고 갈라짐이 심해지지만 DBP 흡수율이 370㎖/100g인 카본블랙을 첨가하여 제조한 튜브용 조성물은 카본블랙의 함량이 높아도 갈라짐이 없이 부드러운 표면인 것을 확인할 수 있다. 도 2에는 나타내지 않았지만 카본블랙의 함량이 0.30g인 실험예 2-6은 갈리지지는 않았지만 거친 표면인 것으로 확인되었고, 카본블랙의 함량이 0.35g인 실험예 2-7의 튜브용 조성물은 갈라짐을 형성했기에 1g 폴리우레탄 기준 카본블랙의 함량은 0.30g 이하인 것이 좋다고 판단되었다.Referring to FIG. 2, as the content of carbon black increases, the composition for tubes cannot be formed and the cracking becomes severe, but the composition for tubes prepared by adding carbon black having a DBP absorption rate of 370 ml/100g cracks even when the content of carbon black is high. It can be seen that it is a smooth surface without this. Although not shown in FIG. 2, Experimental Example 2-6 with a carbon black content of 0.30g was not ground but was confirmed to have a rough surface, and the tube composition of Experimental Example 2-7 with a carbon black content of 0.35g was cracked. Since it was formed, it was judged that the content of carbon black based on 1 g of polyurethane should be 0.30 g or less.

또한, 상기 실험예 2-1 내지 2-7의 튜브용 조성물에 대해 전도성을 측정한 결과 카본블랙의 함량이 0.15g 이상부터 전압을 10V 인가하였을 때 0.01~0.03A였으며, 카본블랙의 함량이 0.25g 이상일 때 전압을 5V 인가하였을 시 0.01A가 흐르는 것을 확인하였다. 따라서 저전압 모듈을 위해서는 카본블랙의 함량이 0.25g 이상이 되어야 하나 전도율을 높이기 위해서는 전도성 도메인을 연결해줄 수 있는 바인더가 필요하다고 판단된다.In addition, as a result of measuring the conductivity of the composition for tubes of Experimental Examples 2-1 to 2-7, the content of carbon black was 0.01 to 0.03 A when voltage was applied from 0.15 g or more to 10 V, and the content of carbon black was 0.25 When the voltage was greater than g, it was confirmed that 0.01A flows when a voltage of 5V is applied. Therefore, for a low-voltage module, the content of carbon black must be 0.25g or more, but it is determined that a binder capable of connecting conductive domains is needed to increase the conductivity.

실험예 3. 바인더(폴리피롤)의 적정 함량 확인Experimental Example 3. Checking the proper content of the binder (polypyrrole)

상기 실험예 2에서 확인한 바와 같이, 카본블랙의 함량은 0.25g 이상이 되어야 하며, 튜브용 조성물의 갈라짐을 방지하기 위해 바인더가 필요하다는 것을 확인하였다. 따라서 본 실험에서는 바인더로써 폴리피롤(Polypyrrole)을 추가로 첨가하여 튜브용 조성물을 제조하였다.As confirmed in Experimental Example 2, the content of carbon black should be 0.25g or more, and it was confirmed that a binder is required to prevent cracking of the tube composition. Therefore, in this experiment, a composition for a tube was prepared by additionally adding polypyrrole as a binder.

먼저 1g의 폴리우레탄, 0.25g의 DBP 흡수율이 370㎖/100g인 카본블랙을 10㎖의 메틸피롤리돈에 첨가하고, 폴리피롤 0.02g, 0.03g, 0.04g, 0.05g, 0.07g, 0.09g, 0.15g, 0.25g, 0.35g, 0.40g, 0.45을 각각 추가로 첨가하였다. 이때 폴리피롤은 전도성이 10~50s/㎝인 펠렛 형태의 고체시료인 것을 사용하였다. 이를 유리 petri-dish(지름 7.6cm)에 넣고 70℃ hot plate에서 12시간 동안 건조시켜 튜브용 조성물을 제조하였으며 이를 하기 표 3에 나타내었다. 또한, 제조한 튜브용 조성물의 표면 사진을 도 3에 나타내었고 전도성을 특정한 그래프를 도 4에 나타내었다.First, 1 g of polyurethane and 0.25 g of carbon black having a DBP absorption rate of 370 ml/100 g were added to 10 ml of methylpyrrolidone, and polypyrrole 0.02g, 0.03g, 0.04g, 0.05g, 0.07g, 0.09g, 0.15g, 0.25g, 0.35g, 0.40g and 0.45 were each additionally added. At this time, polypyrrole was used as a solid sample in the form of pellets having a conductivity of 10 to 50 s/cm. This was put in a glass petri-dish (diameter 7.6cm) and dried on a hot plate at 70° C. for 12 hours to prepare a tube composition, which is shown in Table 3 below. In addition, a photograph of the surface of the prepared tube composition is shown in FIG. 3, and a specific graph of conductivity is shown in FIG. 4.

구분division 폴리우레탄Polyurethane 카본블랙Carbon black 카본블랙의 DBP 흡수율DBP absorption rate of carbon black 폴리피롤Polypyrrole 실험예 3-1Experimental Example 3-1 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.02g0.02g 실험예 3-2Experimental Example 3-2 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.03g0.03g 실험예 3-3Experimental Example 3-3 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.04g0.04g 실험예 3-4Experimental Example 3-4 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.05g0.05g 실험예 3-5Experimental Example 3-5 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.07g0.07g 실험예 3-6Experimental Example 3-6 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.09g0.09g 실험예 3-7Experimental Example 3-7 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.15g0.15g 실험예 3-8Experimental Example 3-8 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.25g0.25g 실험예 3-9Experimental Example 3-9 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.35g0.35g 실험예 3-10Experimental Example 3-10 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.40g0.40g 실험예 3-11Experimental Example 3-11 1g1g 0.25g0.25g 370㎖/100g370ml/100g 0.45g0.45g

도 3을 참고하면, 폴리우레탄 1g 기준 0.25g의 카본블랙에 폴리피롤을 0.02g부터 0.45g까지 늘렸을 때 폴리피롤이 0.35g 첨가된 튜브용 조성물까지는 표면이 점점 부드러워지지만 0.40g이 포함된 튜브용 조성물 이후부터는 점점 표면이 거칠게 형성되고 0.45g 폴리피롤을 함유하는 튜브용 조성물에는 구멍이 생기기 시작하는 것을 확인할 수 있는데 이는 폴리피롤의 함량이 높아질수록 메틸피롤리돈에 대한 용해도는 떨어지고 폴리피롤의 뭉침(aggregation)이 심해져서 표면이 거칠게 형성되거나 구멍이 생긴다고 판단된다. 따라서 폴리우레탄 1g 기준 폴리피롤이 0.40g 이상이 첨가된 튜브용 조성물은 이용하기에 바람지하지 못할 것으로 생각된다.Referring to FIG. 3, when the polypyrrole is increased from 0.02 g to 0.45 g in 0.25 g of carbon black based on 1 g of polyurethane, the surface becomes smoother until the composition for tubes containing 0.35 g of polypyrrole, but the composition for tubes containing 0.40 g From then on, it can be seen that the surface gradually becomes rough and pores begin to form in the tube composition containing 0.45g polypyrrole. This is because the solubility in methylpyrrolidone decreases as the content of polypyrrole increases, and the aggregation of polypyrrole decreases. It is judged that the surface is roughened or holes are formed due to the severe condition. Therefore, it is considered that the composition for tubes in which 0.40 g or more of polypyrrole based on 1 g of polyurethane is added is not desirable to use.

한편, 도 4를 참고하면, 상기 실험예 3-1 내지 3-11의 튜브용 조성물에 대해 전도성을 측정한 결과 전도성 고분자인 폴리피롤의 함유량이 증가할수록 전도성이 높아지는 것을 확인할 수 있었다. 특히, 폴리피롤이 0.15g 이상 첨가된 튜브용 조성물은 2.0V에서 0.04A가 흐르는 것을 볼 수 있다. 따라서 폴리피롤의 도입으로 튜브용 조성물이 갈라지는 것을 방지할 수 있는 바인더로써 작용하여 저전압에서 구동하는 기능을 탑재한 튜브용 조성물을 효과적으로 형성하였음을 알 수 있다.Meanwhile, referring to FIG. 4, as a result of measuring the conductivity of the tube compositions of Experimental Examples 3-1 to 3-11, it was confirmed that the conductivity increased as the content of the conductive polymer polypyrrole increased. In particular, it can be seen that 0.04A flows at 2.0V for the tube composition to which 0.15g or more of polypyrrole is added. Therefore, it can be seen that the introduction of polypyrrole acts as a binder that can prevent the tube composition from cracking, thereby effectively forming a tube composition having a function of driving at a low voltage.

실시예 1. 튜브용 조성물의 제조Example 1. Preparation of composition for tubes

상기 실험예 1 내지 3을 통해 저전압에도 전도성을 가지는 튜브용 조성물을 제조하기 위한 최적의 원료 비율을 알 수 있었다. Through the Experimental Examples 1 to 3, it was possible to know the optimum ratio of raw materials for preparing a composition for a tube having conductivity even at a low voltage.

먼저 튜브용 조성물을 제조하기 위해 메틸피롤리돈(1-methyl-2-pyrrolidone), 폴리우레탄(polyurethane), 폴리피롤(polypyrrole) 및 카본블랙을 준비하였다.First, methylpyrrolidone (1-methyl-2-pyrrolidone), polyurethane (polyurethane), polypyrrole (polypyrrole) and carbon black were prepared to prepare a tube composition.

메틸피롤리돈 10㎖에 폴리우레탄 1g, 폴리피롤 0.35g 및 카본블랙 0.25g을 첨가하고, 유리 petri-dish(지름 7.6cm)에 넣고 70℃ hot plate에서 12시간 동안 건조시켜 튜브용 조성물을 제조하였다. 이때 카본블랙은 DBP 흡수율이 350 ~ 385 ㎖/100g인 것을 사용하였으며 이를 하기 표 4에 나타내었다.1 g of polyurethane, 0.35 g of polypyrrole and 0.25 g of carbon black were added to 10 ml of methylpyrrolidone, put in a glass petri-dish (diameter 7.6 cm), and dried on a hot plate at 70° C. for 12 hours to prepare a tube composition. . At this time, carbon black was used having a DBP absorption rate of 350 ~ 385 ㎖ / 100g, which is shown in Table 4 below.

구분division 내용Contents 실시예 1-1Example 1-1 DBP 흡수율이 350 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 350 ml/100g 실시예 1-2Example 1-2 DBP 흡수율이 360 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 360 ml/100g 실시예 1-3Example 1-3 DBP 흡수율이 370 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 370 ml/100g 실시예 1-4Example 1-4 DBP 흡수율이 385 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with DBP absorption rate of 385 ml/100g

비교예 1. DBP 흡수율이 다른 카본블랙을 첨가한 튜브용 조성물의 제조Comparative Example 1. Preparation of a composition for tubes containing carbon black with different DBP absorption rates

상기 실시예 1과 같은 방법으로 제조하되, DBP 흡수율이 다른 카본블랙을 첨가한 튜브용 조성물을 제조하였다. DBP 흡수율이 350 ~ 385 ㎖/100g인 카본블랙 대신 DBP 흡수율이 다른 카본블랙을 이용하여 튜브용 조성물을 제조하였으며 이를 하기 표 5에 나타내었다.A composition for tubes was prepared in the same manner as in Example 1, but to which carbon black having a different DBP absorption rate was added. Instead of carbon black having a DBP absorption rate of 350 to 385 ml/100g, a composition for a tube was prepared using carbon black having a different DBP absorption rate, which is shown in Table 5 below.

구분division 내용Contents 비교예 1-1Comparative Example 1-1 DBP 흡수율이 330 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 330 ml/100g 비교예 1-2Comparative Example 1-2 DBP 흡수율이 400 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 400 ml/100g 비교예 1-3Comparative Example 1-3 DBP 흡수율이 450 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 450 ml/100g 비교예 1-4Comparative Example 1-4 DBP 흡수율이 500 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with a DBP absorption rate of 500 ml/100g 비교예 1-5Comparative Example 1-5 DBP 흡수율이 520 ㎖/100g인 카본블랙으로 제조된 튜브용 조성물Composition for tubes made of carbon black with DBP absorption rate of 520 ml/100g

비교실험예 1. 튜브용 조성물 표면 비교 및 전도성 확인Comparative Experimental Example 1. Comparison of the surface of the composition for tubes and confirmation of conductivity

상기 실시예 1 및 비교예 2에서 제조한 튜브용 조성물의 표면 상태 및 전도성을 평가하였다. 튜브용 조성물의 표면 상태를 평가할 때 표면이 부드러우면 "◎", 표면이 거칠거나 갈라짐이 생기면 "×"로 하였으며, 전도성에 대한 평가는 전도성을 나타내면 "◎", 그렇지 않으면 "×"로 하여 평가하였고 이를 하기 표 6에 나타내었다.The surface conditions and conductivity of the compositions for tubes prepared in Example 1 and Comparative Example 2 were evaluated. When evaluating the surface condition of the tube composition, if the surface is soft, "◎", if the surface is rough or cracked, "X" is used. The evaluation of conductivity is evaluated as "◎" if it shows conductivity, otherwise it is evaluated as "×". And it is shown in Table 6 below.

구분division 표면 상태Surface condition 전도성 확인Check conductivity 실시예 1-1Example 1-1 실시예 1-2Example 1-2 실시예 1-3Example 1-3 실시예 1-4Example 1-4 비교예 1-1Comparative Example 1-1 ×× ×× 비교예 1-2Comparative Example 1-2 ×× ×× 비교예 1-3Comparative Example 1-3 ×× ×× 비교예 1-4Comparative Example 1-4 ×× ×× 비교예 1-5Comparative Example 1-5 ×× ××

상기 표 6을 참고하면, DBP 흡수율이 350 ~ 385 ㎖/100g인 카본블랙을 첨가하여 제조한 실시예 1-1 내지 실시예 1-4의 튜브용 조성물은 표면 상태가 거칠거나 갈라짐을 형성하지 않으며 전압을 인가하였을 때 전도성을 나타내는 것을 확인할 수 있다. 반면, DBP 흡수율이 330 ㎖/100g인 카본블랙을 첨가하여 제조한 비교예 1-1의 튜브용 조성물이나 DBP 흡수율이 400 ㎖/100g 이상인 카본블랙을 첨가하여 제조한 비교예 1-2 내지 1-5의 튜브용 조성물은 표면이 갈라짐을 형성하며, 전도성 또한 없는 것을 알 수 있다.Referring to Table 6, the tube compositions of Examples 1-1 to 1-4 prepared by adding carbon black having a DBP absorption rate of 350 to 385 ml/100g did not have a rough surface or formed cracks. It can be seen that it shows conductivity when voltage is applied. On the other hand, the composition for tubes of Comparative Example 1-1 prepared by adding carbon black having a DBP absorption rate of 330 ml/100g or Comparative Examples 1-2 to 1- prepared by adding carbon black having a DBP absorption rate of 400 ml/100g or more. It can be seen that the composition for tubes of 5 forms cracks on the surface and has no conductivity.

따라서, 카본블랙의 DBP 흡수율에 따라 튜브용 조성물의 표면 상태 및 전도성의 유무가 달라지는 것을 확인할 수 있었다.Therefore, it was confirmed that the surface condition and the presence or absence of conductivity of the tube composition were changed according to the DBP absorption rate of carbon black.

실험예 4. 튜브용 조성물에 대해 생물오손 제거능 확인Experimental Example 4. Confirmation of biofouling ability of the composition for tubes

상기 실험예 3에서 제조한 튜브용 조성물에 대해 생물오손 제거능을 확인하였다.The biofouling ability of the tube composition prepared in Experimental Example 3 was confirmed.

생체 점액질에 의한 생물오손 제거 방법은 공인 시험으로 알려진 바가 없으므로 'Self-cleaning and antibiofouling enamel surface by slippery liquidinfused technique" Scientific Reports 6 (2016) 25924와 "Biofilm formation of Candida albicans on implant overdenture materials and its removal" journal of dentistry 40 (2012) 686 - 692에 나와 있는 방법을 수정하여 튜브용 조성물의 표면으로부터 세척되어 나온 생물오손 물질의 양을 분석하는 방법으로 실험을 진행하였다.Since there is no known method for removing biofouling by biological mucus,'Self-cleaning and antibiofouling enamel surface by slippery liquidinfused technique' Scientific Reports 6 (2016) 25924 and "Biofilm formation of Candida albicans on implant overdenture materials and its removal" The experiment was conducted by modifying the method described in the journal of dentistry 40 (2012) 686-692 to analyze the amount of biofouling substances washed out from the surface of the tube composition.

먼저, 각각의 튜브용 조성물을 1㎝ × 1㎝ 크기로 잘라 준비하고 1g의 뮤신(musin)을 증류수 10㎖에 넣고 녹인 용액 20㎕을 각 튜브용 조성물 위에 떨어뜨리고 3시간 정도 공기 중에서 말려주었다. 이때 뮤신은 생물오손 물질을 대체하여 사용한 것이다.First, the composition for each tube was cut into 1cm×1cm size and prepared, and 1g of mucin was added to 10ml of distilled water, and 20µl of the dissolved solution was dropped onto the composition for each tube and dried in the air for about 3 hours. At this time, mucin was used as a replacement for biofouling substances.

이후, 암실에서 튜브용 조성물에 전극을 걸어 2V에서 3시간 동안 기판을 구동시켜주었다. 구동 후, 뮤신 위에 알시안블루(Alcian blue) 20㎕을 떨어뜨린 후 2시간 공기 중에서 건조시켜 뮤신을 염색시켜주었다.Thereafter, the electrode was applied to the tube composition in a dark room and the substrate was driven at 2V for 3 hours. After driving, 20 µl of Alcian blue was dropped on the mucin and dried in air for 2 hours to stain the mucin.

각 튜브용 조성물을 20㎖ 크기의 amber vial에 넣은 후 3.5㎖의 과산화수소(Samchun 30~36%)를 넣고 10분 동안 초음파 분쇄한 후 UV로 알시안블루의 양을 정량하였으며 이에 대한 결과를 도 5에 나타내었다.After putting the composition for each tube into an amber vial having a size of 20 ml, 3.5 ml of hydrogen peroxide (Samchun 30-36%) was added and ultrasonically pulverized for 10 minutes. Shown in.

도 5를 참고하면, 20㎕의 알시안블루를 3.5㎖의 과산화수소에 녹인 용액의 λmax = 613㎚에서의 UV-vis 흡수의 세기(intensity)는 1임을 알 수 있다. 각 튜브용 조성물로부터 얻은 과산화수소 내의 알시안블루 양은 Beer-Lambert 법칙에 의해서 구할 수 있으며 오손율은 각 과산화수소의 알시안블루의 λmax = 613㎚에서의 흡수 세기로부터 알 수 있었다.Referring to FIG. 5, it can be seen that the intensity of UV-vis absorption at λ max = 613 nm of a solution in which 20 µl of Alcian Blue is dissolved in 3.5 ml of hydrogen peroxide is 1. The amount of Alcian Blue in hydrogen peroxide obtained from each tube composition can be determined by Beer-Lambert's law, and the contamination rate was determined from the absorption intensity at λ max = 613 nm of Alcian Blue of each hydrogen peroxide.

튜브용 조성물 내 폴리피롤(polypyrrole)의 함량이 높아질수록 알시안블루의 흡수 세기가 높아지는 것을 통해 알시안블루가 보다 더 많이 과산화수소수에 의해 씻겨 나오는 것을 알 수 있다. 폴리우레탄 1g 기준 35%의 폴리피롤이 첨가된 실험예 3-9의 튜브용 조성물의 알시안블루의 흡수 세기가 가장 높게 나타낸 것을 확인할 수 있으며 이는 튜브용 조성물에 부착된 뮤신이 탈락하여 잔존하는 양이 가장 적어 가장 효과가 뛰어나다는 것을 알 수 있다. 한편, 알시안블루의 흡수 세기가 낮은 것은 튜브용 조성물에 잔존하는 뮤신의 양이 많아 오손 제거율이 낮다는 것이다.It can be seen that as the content of polypyrrole in the tube composition increases, the absorption intensity of Alcian Blue increases, so that Alcian Blue is more washed out by the hydrogen peroxide solution. It can be seen that the absorption intensity of Alcian Blue in the tube composition of Experimental Example 3-9 to which 35% of polypyrrole was added based on 1 g of polyurethane was the highest, and this was the amount remaining after the mucin attached to the tube composition was removed You can see that it is the least effective and the most effective. On the other hand, the low absorption intensity of Alcian Blue means that the amount of mucin remaining in the tube composition is large, and thus the contamination removal rate is low.

특히 전도성 물질이 포함되지 않은 순수 폴리우레탄 튜브용 조성물에 대해서 약 7배의 오손 제거율을 보이는 것을 통해 본 발명에 따른 튜브용 조성물의 오손 제거 효과가 매우 우수하다는 것을 알 수 있다.In particular, it can be seen that the stain removal effect of the composition for a tube according to the present invention is very excellent through showing a stain removal rate of about 7 times that of the composition for a pure polyurethane tube that does not contain a conductive material.

Claims (8)

폴리우레탄(Polyurethane), 카본블랙 및 폴리피롤(Polypyrrole)을 포함하는 것을 특징으로 하는 기관절개 튜브용 조성물.Polyurethane (Polyurethane), carbon black and polypyrrole (Polypyrrole), characterized in that the composition for tracheostomy tube comprising a. 제1항에 있어서,
상기 카본블랙은 DBP 흡수율이 350 ~ 385 ㎖/100g인 것을 특징으로 하는 기관절개 튜브용 조성물.
The method of claim 1,
The carbon black is a composition for tracheostomy tubes, characterized in that the DBP absorption rate is 350 ~ 385 ㎖ / 100g.
제1항에 있어서,
상기 폴리피롤은 전도성이 10 ~ 50s/㎝인 펠렛 형태의 고체시료인 것을 특징으로 하는 기관절개 튜브용 조성물.
The method of claim 1,
The polypyrrole is a composition for tracheostomy tube, characterized in that the solid sample in the form of a pellet having a conductivity of 10 ~ 50s / cm.
제1항에 있어서,
상기 폴리우레탄(Polyurethane), 카본블랙 및 폴리피롤(Polypyrrole)은 폴리우레탄 100 중량부 기준 카본블랙 25 내지 30 중량부 및 폴리피롤 15 내지 35 중량부를 포함하는 것을 특징으로 하는 기관절개 튜브용 조성물.
The method of claim 1,
The polyurethane (Polyurethane), carbon black and polypyrrole (Polypyrrole) is a composition for tracheostomy tube, characterized in that it comprises 25 to 30 parts by weight of carbon black and 15 to 35 parts by weight of polypyrrole based on 100 parts by weight of polyurethane.
제1항에 있어서,
상기 폴리우레탄(Polyurethane), 카본블랙 및 폴리피롤(Polypyrrole)을 메틸피롤리돈(1-methyl-2-pyrrolidone)에 60~80℃에서 녹인 후 12~24시간 동안 건조하여 제조한 것을 특징으로 하는 기관절개 튜브용 조성물.
The method of claim 1,
An engine characterized in that the polyurethane (Polyurethane), carbon black and polypyrrole (Polypyrrole) is dissolved in methylpyrrolidone (1-methyl-2-pyrrolidone) at 60 to 80 ℃ and dried for 12 to 24 hours Composition for incision tubes.
상기 제1항 내지 제5항 중 어느 한 항에 있어서,
상기 기관절개 튜브용 조성물은 생물오손 제거 기능성을 갖는 것을 특징으로 하는 기관절개 튜브용 조성물.
The method according to any one of claims 1 to 5,
The composition for tracheostomy tubes is a composition for tracheostomy tubes, characterized in that it has a biological contamination removal function.
제6항에 있어서,
상기 기관절개 튜브용 조성물은 전압을 인가하여 생물오손 제거 기능성을 갖는 것을 특징으로 하는 기관절개 튜브용 조성물.
The method of claim 6,
The composition for tracheostomy tubes is a composition for tracheostomy tubes, characterized in that it has the functionality of removing biofouling by applying a voltage.
상기 제1항 내지 제7항 중 어느 한 항으로 제조된 것을 특징으로 하는 생물오손 제거용 기관절개 튜브.The tracheostomy tube for removing biofouling, characterized in that manufactured according to any one of claims 1 to 7.
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