KR102164484B1 - Polyurethane Foam Surface-coated With Chitosan And Method For Manufacturing The Same - Google Patents
Polyurethane Foam Surface-coated With Chitosan And Method For Manufacturing The Same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/425—Porous materials, e.g. foams or sponges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0278—Polyurethane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
본 발명은 (1) 칼슘이온이 포함된 연속식 시트의 폴리우레탄 폼 제조단계; 및 (2) 상기 폴리우레탄 폼 일면에 키토산 코팅액을 두께조절이 가능한 롤투롤(roll to roll) 방식으로 키토산 코팅층이 형성되는 단계를 포함하는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. The present invention (1) a polyurethane foam manufacturing step of a continuous sheet containing calcium ions; And (2) forming a chitosan coating layer on one surface of the polyurethane foam in a roll-to-roll method capable of adjusting the thickness of the chitosan coating solution. It provides a method for producing a polyurethane foam coated with chitosan.
Description
본 발명은 키토산으로 표면 코팅된 폴리우레탄 폼 및 이의 제조방법에 관한 것으로, 폼의 상층부에 롤투롤(roll to roll)방식으로 압착 도포하여 다공질의 폼 상층부 내부골격표면의 일정두께까지 키토산으로 표면 코팅된 폴리우레탄 폼 및 이의 제조방법에 관한 것이다. The present invention relates to a polyurethane foam surface-coated with chitosan and a method for manufacturing the same, and is coated with chitosan up to a certain thickness of the inner skeleton surface of the upper layer of a porous foam by pressing and applying a roll to roll method on the upper layer of the foam. It relates to a polyurethane foam and a method of manufacturing the same.
인체의 여러 조직 중에 하나인 피부조직은 인체를 외부 환경으로부터 보호하는 역할을 담당하고 있다. 이러한 피부가 교통사고 및 화재와 같은 예기치않은 사고 또는 일상생활에서 발생할 수 있는 작은 상처를 포함하여 손상된 경우, 환자는 상당한 고통을 수반하게 되며, 외부 박테리아에 의한 감염으로 여러 가지 합병증이 유발될 가능성을 배제할 수 없다. The skin tissue, one of the many tissues of the human body, plays a role in protecting the human body from the external environment. If such skin is damaged, including unexpected accidents such as traffic accidents and fires, or small wounds that may occur in daily life, the patient is subject to considerable pain, and infection by external bacteria may lead to various complications. Cannot be excluded.
심한 경우는 생명을 유지할 수 없을 정도로 악화되는 경우도 있으며, 결국 목숨을 잃는 경우도 발생한다. 따라서, 피부에 발생한 상처나 손상의 경우 관리 및 치료는 집중적인 연구 및 관심의 영역일 수 밖에 없다. In severe cases, it may deteriorate to the extent that it cannot sustain life, and eventually, there may be cases of death. Therefore, in the case of wounds or damage to the skin, management and treatment are bound to be areas of intensive research and interest.
여러 가지 원인에 의해 일단 상처가 발생하게 되면 초기에 상처를 빠르게 회복시킬 수 있고, 2차적인 상처를 입히지 않는 드레싱을 하는 것이 매우 중요하다.Once a wound occurs due to various causes, it is very important to quickly recover the wound at the initial stage and to wear a dressing that does not cause secondary wounds.
상처를 치료하기 위한 통상의 방법은 이물질을 제거한 후 거즈, 하이드로 콜로이드, 하이드로겔 등과 같은 전형적인 드레싱으로 상처를 감싸는 것이다.A common method for treating a wound is to remove foreign substances and wrap the wound with a typical dressing such as gauze, hydrocolloid, hydrogel, or the like.
한편, 자연계에 존재하는 다당류로 키토산은 2-아세트아미도-2-디옥시-D-글루코피라노오즈(2-acetamido-2-deoxy-D-glucopyranose)와 2-아미노-2-디옥시-D-글루코피라노오즈(2-amino-2-deoxy-D-glucopyranose)가 β-1→4 결합된 공중합체로 갑각류로부터 쉽게 얻을 수 있는 키틴을 탈 아세틸화하여 얻어지며 독성이 없고 생분해성과 생체적합성이 우수한 재료이다. 특히, 항균성, 지혈 작용, 항암 작용, 중금속 해독 작용 등의 생리 활성이 우수한 재료로 알려져 있다.On the other hand, chitosan as a polysaccharide present in nature is 2-acetamido-2-deoxy-D-glucopyranose (2-acetamido-2-deoxy-D-glucopyranose) and 2-amino-2-dioxy- D-glucopyranose (2-amino-2-deoxy-D-glucopyranose) is a β-1→4 conjugated copolymer. It is obtained by deacetylating chitin, which can be easily obtained from crustaceans. It is a material with excellent compatibility. In particular, it is known as a material having excellent physiological activity such as antibacterial, hemostatic, anticancer, and heavy metal detoxification.
다이네쉬(RevMacromolChemPhys,C40(1),69-83(2000))는 키틴과 키토산 및 이들을 이용한 화합물을 이용한 상처 치유재, 인공피부, 약전성 재료, 혈액응집제, 인공신장막, 생분해성 수술용 봉합사, 항균성 재료로의 적용 가능성과 기능성을 보고하였다. 또한, 마리에판 등(IEEE Engineering in Medicine and Biology Magazine, Vol 18, No 6, 22, 1999)은 상처치유의 목적으로 키토산 박막이 도포된 침대보를 적용 시 흉터를 예방하고 상처치유를 촉진한다는 연구결과를 보여주었다.Dinesh (RevMacromolChemPhys, C40(1),69-83(2000)) is a wound healing material using chitin and chitosan and compounds using them, artificial skin, pharmacological material, blood coagulant, artificial kidney membrane, biodegradable surgery The feasibility and functionality of suture and antimicrobial material were reported. In addition, Mariefan et al. (IEEE Engineering in Medicine and Biology Magazine, Vol 18, No 6, 22, 1999) researched to prevent scars and promote wound healing when applying bedspreads coated with chitosan thin film for the purpose of wound healing. Showed the results.
샤(Shah) 등의 미국 등록특허 제5,527,271호에는 창상 드레싱용 열가소성 하이드로겔이 함침된 복합재가 기재되어 있다. 하이드로겔이 면 거즈 창상 드레싱에 도포되어 있어, 치유 과정 동안 창상 드레싱이 창상에 달라붙는 것을 방지한다. US Patent No. 5,527,271 to Shah et al. discloses a composite material impregnated with a thermoplastic hydrogel for wound dressing. The hydrogel is applied to the cotton gauze wound dressing, preventing the wound dressing from sticking to the wound during the healing process.
또한, 브레싱턴(Brassington)등의 미국 등록특허 제4,838,253호에는 천공된 물질로 이루어진 시트를 가교 결합되지 않은 실리콘 물질로 피복하고 이를 가교 결합시킴으로써 실리콘으로 피복된 창상 드레싱이 기재되어 있으나, 위의 두 경우는 삼출물의 양이 많은 환자에 적용하기 어려운 단점이 있다.In addition, U.S. Patent No. 4,838,253 to Brassington et al. describes a wound dressing coated with silicone by covering a sheet made of a perforated material with a non-crosslinked silicone material and crosslinking it. The case has a disadvantage that it is difficult to apply to patients with a large amount of exudate.
일본국 특개평 5-84290호 공보에는 온도 감응성을 가지는 폴리머를 사용한 창상용 하이드로겔이 제안되었으나, 창상면에 도포한 후, 박리할 때 냉각해야 하는 단점이 있다. 또한, 일본국 특개평 7-250886호 공보에는 폴리비닐피롤리돈과 키토산의 상호작용으로 형성되는 겔이 제안되어 있으나, 환부에 유지하기에는 점착력이 불충분한 문제가 있다.Japanese Unexamined Patent Application Publication No. Hei 5-84290 proposes a hydrogel for wounds using a polymer having temperature sensitivity, but there is a drawback of cooling when peeling after being applied to the wound surface. In addition, Japanese Unexamined Patent Application Publication No. Hei 7-250886 proposes a gel formed by the interaction of polyvinylpyrrolidone and chitosan, but there is a problem that adhesive strength is insufficient to maintain the affected area.
미국 등록특허 제5,902,798호에는 키토산과 헤파린 설페이트를 함유한 상처 치료용 연고가 기재되어 있으나, 연고 제조를 위해서는 점증도 증가를 위해 카르복시 메틸 셀룰로오스(carboxymethyl cellulose)와 같은 점증제를 사용해야 한다. 그러한 점증제는 치료의 효과를 저하시키는 단점을 가지고 있다.U.S. Patent No. 5,902,798 discloses an ointment for treating wounds containing chitosan and heparin sulfate, but for the manufacture of the ointment, a thickener such as carboxymethyl cellulose should be used to increase the viscosity. Such thickeners have the disadvantage of reducing the effectiveness of treatment.
또한 미국 공개특허 제2017/0239095호에서는 표면 기능성 층과 폴리우레탄 폼을 부착시키기 위해 중간층에 접착제(아크릴계통)를 사용하는 방법으로 접착제 추가로 제조방법의 시간 및 비용이 증가된다.In addition, U.S. Patent Publication No. 2017/0239095 uses an adhesive (acrylic-based) on the intermediate layer to attach the surface functional layer and the polyurethane foam, thereby increasing the time and cost of the manufacturing method by adding an adhesive.
대한민국 등록특허 제88522호에는 패드에 혈액응고를 돕는 폴리에틸렌옥사이드를 도포하여 지혈효과를 향상시킨 반창고가 기재되어 있으나, 상기 용품의 경우는 지혈 효과에만 치중한 결과 치료 및 삼출물 흡수력이 떨어지는 단점이 있다.Korean Patent No. 88522 describes a band-aid that improves the hemostatic effect by applying polyethylene oxide to help blood coagulation on the pad, but the above article has a disadvantage in that treatment and exudate absorption are inferior as a result of focusing only on the hemostatic effect.
대한민국 공개특허 제2004-52526호에는 키토산을 물에 분산시키고 여기에 이산화탄소를 통기시켜 키토산 수용액을 제조하는 방법이 기술되어 있으나, 상기 키토산이 물에 대한 용해력이 작아 동결건조 후 드레싱재로 적합하지 않다.Korean Patent Laid-Open Publication No. 2004-52526 describes a method of preparing an aqueous solution of chitosan by dispersing chitosan in water and passing carbon dioxide therein, but the chitosan is not suitable as a dressing material after lyophilization due to its low solubility in water. .
상기와 같은 문제점을 해결하기 위해 본 발명은 혈액 접촉시 직접적 지혈성능이 있는 키토산을 폼 상층부에 넓은 비표면적을 갖도록 폼 골격 외부에 농축코팅하여 일차적인 지혈성능을 발휘토록 하고 부가적으로 폼이 삼출물에 의해 팽윤될 시 칼슘이온이 용해 방출되어 혈액응고 기전에 참여할 수 있도록 칼슘 카르복시메틸 셀룰로오스를 함유한 고흡수성의 생체친화적인 폴리우레탄폼을 제공하여 지혈 및 상처치유성능을 동시에 구현할 수 있는 국소지혈용 드레싱재인 폴리우레탄 폼을 제공하는 데 있다. In order to solve the above problems, the present invention provides a concentrated coating of chitosan, which has direct hemostatic performance when in contact with blood, on the outside of the foam skeleton so as to have a large specific surface area on the upper layer of the foam, to exert primary hemostatic performance, and additionally, the foam is exudate. For local hemostasis that can realize hemostasis and wound healing performance at the same time by providing a highly absorbable bio-friendly polyurethane foam containing calcium carboxymethyl cellulose so that calcium ions can be dissolved and released when swelled by the blood coagulation mechanism. It is to provide a polyurethane foam as a dressing material.
또한 본 발명은 상기 폴리우레탄 폼에 키토산 코팅액을 코팅시 수용성 키토산과 글리세린으로 구성된 점조성 수성 코팅액을 습윤한 특징을 갖는 폴리우레탄 폼에 코팅방식으로 압착 도포한 결과 코팅액에 함유된 수분에 의한 변형이 발생되지 않았고 미처리 폼과 비교하여 거의 동일한 표면특성을 유지하여 상처부위의 혈액이나 삼출물의 흡수속도가 코팅 처리전과 처리 후가 차이가 없이 5초 이내에 모두 흡수되는 폴리우레탄 폼 제조방법을 제공하는 데 있다. In addition, the present invention is a result of compressing and applying a coating method to a polyurethane foam having a feature of moistening a viscous aqueous coating solution composed of water-soluble chitosan and glycerin when coating the chitosan coating solution on the polyurethane foam. The purpose is to provide a polyurethane foam manufacturing method that does not occur and maintains almost the same surface characteristics compared to untreated foam, so that the absorption rate of blood or exudate from the wound area is absorbed within 5 seconds without any difference between before and after coating treatment. .
또한 본 발명은 압착코팅에 의해 지혈성분인 키토산 코팅액이 혈액이 1차적으로 통과하는 폼 스킨층 바로 아래부분에 농축 도포되어 별도로 기능성 물질이 함유된 상처접촉층과 흡수층을 만든 후 접착제를 이용한 합지 등의 추가 공정없이 한 번의 코팅작업으로 지혈층과 흡수층을 동시에 갖는 새로운 형태의 국소지혈용 폼형 드레싱재인 폴리우레탄 폼 제조방법를 제공하는 데 있다. In addition, in the present invention, the chitosan coating solution, which is a hemostatic component, is concentrated and applied to the lower part of the foam skin layer through which blood primarily passes by compression coating to create a wound contact layer and an absorbent layer containing functional substances separately, and then laminate using an adhesive. It is to provide a method of manufacturing polyurethane foam, a foam-type dressing material for local hemostatic, having a hemostatic layer and an absorbing layer at the same time in one coating operation without the additional process of.
본 발명은 (1) 칼슘이온이 포함된 연속식 시트의 폴리우레탄 폼 제조단계; 및 (2) 상기 폴리우레탄 폼 일면에 키토산 코팅액을 두께조절이 가능한 롤투롤(roll to roll) 방식으로 키토산 코팅층이 형성되는 단계를 포함하는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. The present invention (1) a polyurethane foam manufacturing step of a continuous sheet containing calcium ions; And (2) forming a chitosan coating layer on one surface of the polyurethane foam in a roll-to-roll method capable of adjusting the thickness of the chitosan coating solution. It provides a method for producing a polyurethane foam coated with chitosan.
또한 본 발명은 상기 폴리우레탄 폼 제조단계는 칼슘 카르복시메틸셀룰로오스를 폴리우레탄 프리폴리머에 함유시켜 발포하는 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. In addition, the present invention provides a method for producing a polyurethane foam surface-coated with chitosan, characterized in that the polyurethane foam manufacturing step includes calcium carboxymethylcellulose in a polyurethane prepolymer and foams.
또한 본 발명은 상기 폴리우레탄 폼의 칼슘 카르복시메틸셀룰로오스의 함량은 프리폴리머 대비 0.5중량부~1.5중량부인 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. In addition, the present invention provides a method for producing a polyurethane foam surface-coated with chitosan, characterized in that the content of calcium carboxymethyl cellulose in the polyurethane foam is 0.5 parts by weight to 1.5 parts by weight compared to the prepolymer.
또한 본 발명은 상기 폴리우레탄 폼은 밀도 150kg/m3~300kg/m3, 흡수도 4g/g이상, 두께는 2mm~10mm인 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. In addition, the present invention provides a method for producing a polyurethane foam surface-coated with chitosan, characterized in that the polyurethane foam has a density of 150kg/m 3 ~300kg/m 3 , an absorption of 4g/g or more, and a thickness of 2mm to 10mm. .
또한 본 발명은 상기 키토산 코팅액은 증류수에 수용성 키토산 파우더 및 글리세린이 포함된 것으로, 상기 키토산 코팅액 100중량부 대비 키토산 파우더는 5중량부~15중량부이고, 글리세린은 2중량부~8중량부인 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. In addition, the present invention is characterized in that the chitosan coating solution contains water-soluble chitosan powder and glycerin in distilled water, and the chitosan powder is 5 parts by weight to 15 parts by weight relative to 100 parts by weight of the chitosan coating solution, and glycerin is 2 parts by weight to 8 parts by weight. It provides a method for producing a polyurethane foam surface coated with chitosan.
또한 본 발명은 상기 키토산 코팅액은 탈아세틸화도가 80%이상인 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. In addition, the present invention provides a method for producing a polyurethane foam surface-coated with chitosan characterized in that the chitosan coating solution has a degree of deacetylation of 80% or more.
또한 본 발명은 상기 키토산 코팅액에 수용성 물질인 항균제, 지혈물질, 성장인자(growth factor), 비타민(vitamin) 중 적어도 어느 하나 이상이 포함된 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법을 제공한다. In addition, the present invention relates to a method for producing a polyurethane foam surface coated with chitosan characterized in that the chitosan coating solution contains at least one of a water-soluble substance such as an antimicrobial agent, a hemostatic substance, a growth factor, and a vitamin. to provide.
또한 본 발명은 상기 제조방법에 의해 제조된 키토산으로 표면 코팅된 폴리우레탄 폼을 제공한다. In addition, the present invention provides a polyurethane foam surface coated with chitosan prepared by the above manufacturing method.
또한 본 발명은 상기 키토산으로 표면 코팅된 폴리우레탄 폼은 키토산 코팅층 및 폴리우레탄 폼층으로 구분되며, 상기 폴리우레탄 폼은 표면 및 내부에 빈 공간 기공이 균일하게 분포된 스펀지구조이고, 상기 키토산 코팅층은 폴리우레탄 폼의 일면에 일정한 깊이로 코팅되되, 상기 폴리우레탄 폼의 표면 및 내부에 형성된 기공구조가 유지되는 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼을 제공한다. In addition, in the present invention, the polyurethane foam surface-coated with chitosan is divided into a chitosan coating layer and a polyurethane foam layer, and the polyurethane foam has a sponge structure in which voids and pores are uniformly distributed on the surface and inside, and the chitosan coating layer is poly Provided is a polyurethane foam coated with chitosan that is coated on one side of the urethane foam to a certain depth, and maintains a pore structure formed on the surface and inside of the polyurethane foam.
또한 본 발명은 상기 키토산으로 표면 코팅된 폴리우레탄 폼은 키토산 코팅된 표면 이외의 다른 표면에 필름층이 합지된 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼을 제공한다. In addition, the present invention provides a polyurethane foam surface-coated with chitosan characterized in that a film layer is laminated on a surface other than the chitosan-coated polyurethane foam.
본 발명은 압착코팅에 의해 지혈성분인 키토산 코팅액이 혈액이 1차적으로 통과하는 폼 스킨층 바로 아래부분에 농축 도포되어 별도로 기능성 물질이 함유된 상처접촉층과 흡수층을 만든 후 접착제를 이용한 합지 등의 추가 공정없이 한번의 코팅작업으로 지혈층과 흡수층을 동시에 갖는 효과가 있다.In the present invention, the chitosan coating solution, which is a hemostatic component, is concentrated and applied to the lower part of the foam skin layer through which blood primarily passes by compression coating to create a wound contact layer and an absorbent layer containing a functional substance separately, and then use an adhesive. There is an effect of having a hemostatic layer and an absorbing layer at the same time with one coating operation without any additional process.
또한 본 발명은 수용성 키토산 코팅액을 폴리우레탄 폼에 압착도포의 코팅방식으로 제조하여 미처리 폴리우레탄 폼과 유사한 표면특성을 갖는 흡수속도 및 흡수력이 우수한 특징이 있다.In addition, the present invention is characterized by excellent absorption rate and absorption power having a surface characteristic similar to that of untreated polyurethane foam by manufacturing a water-soluble chitosan coating solution by compression coating on a polyurethane foam.
또한 본 발명은 혈액접촉시 직접적 지혈성능이 있는 키토산을 폼 상층부에 넓은 비표면적을 갖도록 폼골격외부에 농축코팅하여 일차적인 지혈성능을 발휘토록 하고 부가적으로 폼이 삼출물에 의해 팽윤될 시 칼슘이온이 용해 방출되어 혈액응고 기전에 참여할 수 있도록 칼슘카르복시메틸 셀룰로오스를 함유한 고흡수성의 생체친화적인 폴리우레탄폼을 제공하여 지혈 및 상처치유성능을 동시에 구현할 수 있는 특징이 있다. In addition, in the present invention, chitosan, which has direct hemostatic performance when in contact with blood, is concentrated and coated on the outside of the foam skeleton so that it has a large specific surface area on the upper layer of the foam, so that the primary hemostatic performance is exhibited, and additionally, calcium ion when the foam is swollen by exudate It provides a highly absorbent, bio-friendly polyurethane foam containing calcium carboxymethyl cellulose so that it can be dissolved and released to participate in the blood coagulation mechanism, thereby achieving hemostasis and wound healing performance at the same time.
도 1은 본 발명 키토산으로 표면 코팅된 폴리우레탄 폼의 단면 모식도이다.
도 2는 키토산 미처리 단면폼 및 키토산 코칭처리 단면폼에 대한 사진이다.
도 3은 폴리우레탄폼에 함유된 칼슘 카르복시메틸셀룰로오스로부터 Ca2 +이온의 방출을 확인하는 사진이다.
도 4는 본 발명 실시예 및 비교예의 혈액응고성능 비교 사진이다.
도 5는 실시예에 대한 세포 생존율을 보여주는 그래프이다. 1 is a schematic cross-sectional view of a polyurethane foam surface-coated with chitosan of the present invention.
2 is a photograph of a cross-sectional form of chitosan untreated and a cross-sectional form of chitosan coaching treatment.
3 is a photograph confirming the release of Ca 2 + ions from calcium carboxymethyl cellulose contained in polyurethane foam.
4 is a picture of a comparison of blood coagulation performance of Examples and Comparative Examples of the present invention.
5 is a graph showing the cell viability for Example.
이하 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 우선, 본 발명을 설명함에 있어, 관련된 공지기능 혹은 구성에 대한 구체적인 설명은 본 발명의 요지를 모호하지 않게 하기 위하여 생략한다.Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.
본 명세서에서 사용되는 정도의 용어 '약', '실질적으로' 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다. The terms'about','substantially', etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and are used in the sense of the present invention. To assist, accurate or absolute figures are used to prevent unfair use of the stated disclosure by unscrupulous infringers.
본 발명은 (1) 칼슘이온이 포함된 연속식 시트의 폴리우레탄 폼 제조단계; 및 (2) 상기 폴리우레탄 폼 일면에 키토산 코팅액을 두께조절이 가능한 롤투롤(roll to roll) 방식으로 키토산 코팅층이 형성되는 단계를 포함하는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법에 관한 것이다. The present invention (1) a polyurethane foam manufacturing step of a continuous sheet containing calcium ions; And (2) forming a chitosan coating layer on one surface of the polyurethane foam in a roll-to-roll method capable of controlling the thickness of the chitosan coating solution. It relates to a method for producing a polyurethane foam coated with chitosan.
상기 폴리우레탄 폼 제조단계는 칼슘 카르복시메틸셀룰로오스를 폴리우레탄 프리폴리머에 함유시켜 발포하는 것에 특징이 있는 키토산으로 표면 코팅된 것에 특징이 있다. The polyurethane foam manufacturing step is characterized in that the surface is coated with chitosan, which is characterized by foaming by containing calcium carboxymethyl cellulose in a polyurethane prepolymer.
상기 폴리우레탄 폼의 칼슘 카르복시메틸셀룰로오스의 함량은 프리폴리머 대비 0.5중량부~1.5중량부가 적당하다. The content of calcium carboxymethylcellulose in the polyurethane foam is preferably 0.5 parts by weight to 1.5 parts by weight compared to the prepolymer.
또한 상기 폴리우레탄 폼은 밀도 150kg/m3~300kg/m3, 흡수도 4g/g이상, 두께는 2mm~10mm가 바람직하다.In addition, the polyurethane foam has a density of 150 kg/m 3 to 300 kg/m 3 , an absorption of 4 g/g or more, and a thickness of 2 mm to 10 mm.
상기 키토산은 강한 양이온성 고분자로 정전기적 인력에 의해 표면이 음으로 하전된 적혈구, 혈소판 등을 포집하여 농축시키고, 칼슘 카르복시메틸셀룰로오스의 칼슘이온은 혈액응고기전에 있어 활성인자로 작용할 수 있으며 이미 칼슘치환된 알지네이트 등에 있어 지혈 성능이 입증된 바 있다. The chitosan is a strong cationic polymer that collects and concentrates red blood cells and platelets whose surface is negatively charged by electrostatic attraction, and calcium ions in calcium carboxymethylcellulose can act as an activating factor in blood clotting. Hemostatic performance has been proven in substituted alginates.
도 3은 폴리우레탄폼에 함유된 칼슘 카르복시메틸셀룰로오스로부터 Ca2 +이온의 방출을 확인하는 것으로,3 is to confirm the release of Ca 2 + ions from calcium carboxymethyl cellulose contained in the polyurethane foam,
본 발명은 폴리우레탄폼에 함유된 칼슘 카르복시메틸셀룰로오스로부터 Ca2 +이온의 방출이 용이하다. 칼슘 카르복시메틸셀룰로오스파우더를 체액과 유사한 생리식염수에서 일정시간 방치 후 상등액을 취하여 여기에 탄산소듐 (Na2CO3)수용액을 가하여 Ca2 +이온과 (CO3)2- 이온과의 이온결합에 의한 불용성 침전물인 탄산칼슘(CaCO3)이 형성되는 것으로 확인가능하다.The present invention facilitates the release of Ca 2 + ions from calcium carboxymethyl cellulose contained in polyurethane foam. Calcium carboxymethyl takes a certain amount of time allowed to stand and then the supernatant the cellulose powder in saline is similar to the body fluid was added to sodium carbonate (Na 2 CO 3) solution here due to the ionic bonding of the Ca 2 + ions (CO 3) 2- ions It can be confirmed that calcium carbonate (CaCO 3 ), which is an insoluble precipitate, is formed.
Ca(OH)2 + Na2CO3 -> CaCO3 ↓ + 2OH- + 2Na+ Ca (OH) 2 + Na 2 CO 3 -> CaCO 3 ↓ + 2OH - + 2Na +
바이알의 하층부에 앙금이 형성되어 침전된 결과에서 볼 수 있듯이 칼슘 카르복시메틸셀룰로오스를 첨가하여 발포한 습윤폼의 경우 자체수분을 함유하고 있고 폼의 특성상 상처부위와 접촉하여 다량의 삼출물을 흡수할 경우 빠른 시간내 흡수 팽윤되면서 수분을 흡수하기 때문에 CaCMC와 접촉하여혈액응고 메카니즘 내에서 혈전형성의 촉매역할을 한다고 알려진 Ca2 + 이온이 방출될 수 있다. As can be seen from the result of sedimentation due to the formation of sediment in the lower layer of the vial, the wet foam foamed by adding calcium carboxymethyl cellulose contains its own moisture, and due to the nature of the foam, it is quickly Because it absorbs moisture while swelling and swelling within time, Ca 2 + ions, known to act as a catalyst for thrombus formation within the blood coagulation mechanism, may be released in contact with CaCMC.
상기 키토산 코팅액은 증류수에 수용성 키토산 파우더 및 글리세린이 포함된 것으로, 상기 키토산 코팅액 100중량부 대비 키토산 파우더는 5중량부~15중량부이고, 글리세린은 2중량부~8중량부인 것에 특징이 있다. The chitosan coating solution contains water-soluble chitosan powder and glycerin in distilled water, and the chitosan powder is 5 parts by weight to 15 parts by weight relative to 100 parts by weight of the chitosan coating solution, and glycerin is 2 parts by weight to 8 parts by weight.
또한 상기 키토산 코팅액은 탈아세틸화도가 80%이상인 것이 바람직하며 더욱 바람직하게는 90%~95%가 타당하다. In addition, the chitosan coating solution preferably has a degree of deacetylation of 80% or more, more preferably 90% to 95%.
또한 상기 키토산 코팅액에 수용성 물질인 항균제, 지혈물질, 성장인자(growth factor), 비타민(vitamin) 중 적어도 어느 하나 이상이 포함될 수 있다.In addition, at least one or more of water-soluble substances such as antibacterial agents, hemostatic substances, growth factors, and vitamins may be included in the chitosan coating solution.
도 1은 본 발명 키토산으로 표면 코팅된 폴리우레탄 폼의 단면 모식도이다. 상기 제조방법에 의해 제조된 키토산으로 표면 코팅된 폴리우레탄 폼은 상기 키토산으로 표면 코팅된 폴리우레탄 폼은 키토산 코팅층 및 폴리우레탄 폼층으로 구분된다.1 is a schematic cross-sectional view of a polyurethane foam surface-coated with chitosan of the present invention. The polyurethane foam surface-coated with chitosan prepared by the above manufacturing method is divided into a chitosan coating layer and a polyurethane foam layer.
상기 폴리우레탄 폼은 표면 및 내부에 빈 공간 기공이 균일하게 분포된 스펀지구조이고, 상기 키토산 코팅층은 폴리우레탄 폼의 일면에 일정한 깊이로 코팅되되, 상기 폴리우레탄 폼의 표면 및 내부에 형성된 기공구조가 유지되는 것에 특징이 있다. The polyurethane foam has a sponge structure in which empty spaces and pores are uniformly distributed on the surface and inside, and the chitosan coating layer is coated to a certain depth on one surface of the polyurethane foam, and the pore structure formed on the surface and inside of the polyurethane foam is It is characterized by being maintained.
도 2는 키토산 미처리 단면폼 및 키토산 코칭처리 단면폼에 대한 사진이다.2 is a photograph of a cross-sectional form of chitosan untreated and a cross-sectional form of chitosan coaching treatment.
상기 도 2의 사진을 보면 발포 전과 발포 후 폼의 표면 양상이 크게 다르지 않았고 대부분의 코팅층이 상부 폼 스킨층 아래표면에 도포됨을 알 수 있다. 또한 하기 표 2,3의 흡수도 및 흡수속도(실시예 및 비교예 3)의 물성확인결과 미처리 폼과 거의 동일한 결과로부터 표면 폼층의 기공등이 막히지 않고 혈액 및 삼출물등이 안정적으로 폼 내부로 흡수될 수 있음을 확인할 수 있었다. 2, it can be seen that the surface aspect of the foam before and after foaming was not significantly different, and most of the coating layer was applied to the lower surface of the upper foam skin layer. In addition, as a result of confirming the physical properties of the absorption rate and absorption rate (Example and Comparative Example 3) in Tables 2 and 3 below, the pores of the surface foam layer are not clogged, and blood and exudates are stably absorbed into the foam from the results of almost the same as the untreated foam. It could be confirmed.
이상에서 설명한 바와 같은 본 설명의 특징 및 기타의 장점은 후술되는 실시예로부터 보다 명백하게 될 것이며, 하기 실시예는 예시적인 목적으로 기재될 뿐 본 발명의 보호범위를 한정하거나 제한하는 것으로 해석될 수 없다.Features and other advantages of the present description as described above will become more apparent from the examples to be described later, and the following examples are described for illustrative purposes only and cannot be construed as limiting or limiting the protection scope of the present invention. .
*실시예 및 비교예 *Examples and Comparative Examples
<실시예><Example>
칼슘 카르복시메틸셀룰로오스 파우더 1 중량부를 폴리우레탄 폼제조에 사용되는 프리폴리머 제조공정에 투입하여 칼슘이온이 함유된 연속식 폴리우레탄 폼 시트를 제조한다. 이어서 증류수에 코팅액 100중량부 대비 탈아세틸화도 80%이상인 수용성 키토산 파우더 10중량부를 균일하게 용해시키고 여기에 2중량부의 글리세린을 첨가하여 코팅액을 제조한다. 준비된 칼슘 카르복시메틸셀룰로오스를 함유한 폴리우레탄 폼 시트를 코팅라인 앞단에 거치한 후 연속으로 공급하며 코팅두께 조절가능한 롤투롤(roll to roll)방식의 코팅부를 통과하도록 준비한 후 코팅액을 공급한다. 코팅롤의 간극을 폼 두께의 90%정도로 압착하여 도포된 코팅액이 폼 상층부로 침투할 수 있도록 하며 연속으로 80도로 설정된 터널형 오븐존을 통과시켜상층부 폼 내부골격 표면에 고착시킨다.1 part by weight of calcium carboxymethylcellulose powder is added to the prepolymer manufacturing process used in the polyurethane foam manufacturing to prepare a continuous polyurethane foam sheet containing calcium ions. Subsequently, 10 parts by weight of water-soluble chitosan powder having a degree of deacetylation of 80% or more relative to 100 parts by weight of the coating solution is uniformly dissolved in distilled water, and 2 parts by weight of glycerin are added thereto to prepare a coating solution. The prepared polyurethane foam sheet containing calcium carboxymethylcellulose is mounted on the front end of the coating line and supplied continuously, and the coating solution is supplied after preparing to pass through a roll-to-roll coating portion with adjustable coating thickness. The gap of the coating roll is compressed to about 90% of the foam thickness so that the applied coating liquid can penetrate into the upper part of the foam, and it is fixed to the surface of the inner frame of the upper foam by passing through a tunnel-type oven zone set at 80 degrees continuously.
<비교예 1><Comparative Example 1>
상기 실시예 1에서 준비한 키토산 수용액에 도막형성시 균일성을 확보할 수 있도록 비이온계 계면활성제를 첨가하여 준비된 박리용 이형지에 20㎛의 두께로 나이프 코팅한 후 80도로 설정된 터널형 오븐을 통과 건조시켜 키토산 필름을 미리 제조한다. 완성된 필름원단을 하부에 공급하며 이 위에 폴리우레탄 폼 원액을 공급하며 일체형으로 발포시킨 후 연속적으로 뒷단에서 박리시켜 키토산 필름과 폴리우레탄 폼이 일체형으로 합지된 폴리우레탄 폼 시트를 제조한다.The chitosan aqueous solution prepared in Example 1 was knife-coated with a thickness of 20 μm on a release paper prepared by adding a nonionic surfactant to ensure uniformity during film formation, and then dried through a tunnel-type oven set at 80 degrees. To prepare a chitosan film in advance. The finished film fabric is supplied to the lower part, and the polyurethane foam undiluted solution is supplied thereon, and after being integrally foamed, it is continuously peeled from the rear end to produce a polyurethane foam sheet in which the chitosan film and the polyurethane foam are integrally laminated.
<비교예 2><Comparative Example 2>
상기 비교예 2에서 흡수속도를 향상시키기 위해 키토산 필름을 전면으로 형성시키지 않고 다트(DOT) 형태로 미리 제조한 후 일제형으로 합지된 폴리우레탄 폼 시트를 제조한다.In Comparative Example 2, in order to improve the absorption rate, a chitosan film was prepared in advance in the form of a dart (DOT) without forming the entire surface, and then a polyurethane foam sheet laminated in a Japanese-made type was prepared.
<비교예 3><Comparative Example 3>
상기 실시예 1에서 사용된 키토산 파우더를 폴리우레탄 폼 원액의 주제와 경화제에 각각 투입한 후 발포하여 키토산이 함유된 폴리우레탄 폼 시트를 일체형으로 제조한다.The chitosan powder used in Example 1 was added to the main material and the curing agent of the polyurethane foam stock solution, respectively, and then expanded to produce a polyurethane foam sheet containing chitosan.
*물성평가 * Property evaluation
1. 흡수도 및 보유도 평가 1. Absorption and retention evaluation
표1은 실시예 1의 키토산 코팅폼과 비교예 3의 미처리폼의 흡수도 및 보유도 평가에 대한 것으로 키토산 코팅폼과 미처리폼의 흡수특성 비교결과로 처리 전후 흡수도 및 보유도에 있어 큰 차이를 보이지 않고 있어 기본적인 고흡수성 폼의 기능성이 코팅 후에도 발휘되고 있음을 확인되며, 다만 키토산 코팅필름의 비교예1 및 다트형식 필름의 비교예 2는 PU폼 흡수력에 방해가 되여 실시예보다 흡수도, 보유도에서 낮은 값을 갖는다. Table 1 is for evaluating the absorption and retention of the chitosan-coated foam of Example 1 and the untreated foam of Comparative Example 3. As a result of comparing the absorption characteristics of the chitosan-coated foam and the untreated foam, there is a large difference in absorption and retention before and after treatment. It is confirmed that the functionality of the basic superabsorbent foam is exerted even after coating.However, Comparative Example 1 of the chitosan coating film and Comparative Example 2 of the dart-type film interfere with the absorption of PU foam, so that the absorbency, It has a low value in retention.
2. 흡수속도 평가 2. Evaluation of absorption rate
표2는 본 발명의 실시예 및 비교예의 흡수속도에 관한 것으로, 비교예 3의 일체 발포형 폼의 경우 반응속도가 빨라져 셀(Cell)의 공개(open)성이 떨어짐에 의해 흡수속도가 떨어지며, 실시예 1의 키토산 코팅폼의 경우 폼 스킨층의 표면특성의 변화가 거의 없어 미처리 외산제품과 비교하여도 매우 빠른 흡수속도를 보이고 있음을 확인할 수 있고, 비교예 1 및 2는 키토산이 필름층 및 다트층으로 PU폼 일면 접착으로 인해 PU폼의 흡수력을 방해되여 흡수속도가 더 떨어진다. Table 2 relates to the absorption rate of Examples and Comparative Examples of the present invention, in the case of the integral foamed foam of Comparative Example 3, the reaction rate was accelerated, and the absorption rate was lowered due to the decrease in the openness of the cell, In the case of the chitosan-coated foam of Example 1, it can be confirmed that the surface characteristics of the foam skin layer are almost unchanged, so that it shows a very fast absorption rate even compared to the untreated foreign product. In Comparative Examples 1 and 2, chitosan Due to the adhesion of one side of the PU foam to the dart layer, the absorption power of the PU foam is hindered, resulting in a lower absorption rate.
3. 혈액응고성능 평가3. Blood coagulation performance evaluation
도 4는 본 발명 실시예 및 비교예의 혈액응고성능 비교 사진이다. 비교예 3의 키토산 코팅층이 없는 미처리폼의 경우 출혈부위 경계가 없고 혈액응고가 현저히 떨어짐을 볼 수 있고, 비교예 2의 키토산 닷필름(dot film)의 경우 닷필름을 중심으로 혈액응고가 상대적으로 많이 진행되었음을 확인할 수 있었으나 드레싱 제거시 상처부위에 필름이 폼에서 탈락하여 잔류하는 문제가 있으며, 실시예의 키토산 전면코팅의 경우출혈부위의 경계면이 확실하며 혈액응고가4 is a picture of a comparison of blood coagulation performance of Examples and Comparative Examples of the present invention. In the case of the untreated foam without the chitosan coating layer of Comparative Example 3, it can be seen that there is no boundary of the bleeding area and blood coagulation significantly decreases, and in the case of the chitosan dot film of Comparative Example 2, blood coagulation was relatively reduced around the dot film. It was confirmed that a lot of progress was made, but there is a problem that the film is removed from the foam and remains on the wound area when the dressing is removed. In the case of the chitosan front coating of the embodiment, the boundary of the bleeding area is certain and blood coagulation is
빠르게 진행되었고 농축된 혈액응고 성분이외의 삼출물이 폼에 흡수되어 제거되었음을 확인할 수 있다. It was confirmed that the exudate proceeded rapidly and was removed by absorption of the exudate other than the concentrated blood clotting component.
4. 세포 생존율 평가4. Cell viability evaluation
도 5는 실시예에 대한 세포 생존율을 보여주는 그래프이다. ISO-10993-5의 시험방법으로 진행하였으며, 실시예인 키토산 코팅된 폴리우레탄 폼 드레싱재를 2회 실험한 것으로 배향 후 세포생존율에 두 번 모두 96.5%, 99.1%로써 대조군과 비교시 양호한 결과를 나타냄으로 인체에 무해한 국소지혈드레싱으로 적용가능함을 확인할 수 있다. 5 is a graph showing the cell viability for Example. The test method of ISO-10993-5 was conducted, and the chitosan-coated polyurethane foam dressing material was tested twice. After orientation, the cell viability was 96.5% and 99.1% both times, showing good results compared to the control group. As a result, it can be confirmed that it can be applied as a local hemostatic dressing that is harmless to the human body.
또한 드레싱재를 제거시 수용성 키토산이 녹아 윤활작용을 함으로써 상처가 드레싱에 유착되지 않고 통증없이 쉽게 제거될 수 있다. In addition, when the dressing material is removed, the water-soluble chitosan melts and acts as a lubrication, so that the wound does not adhere to the dressing and can be easily removed without pain.
본 발명은 폴리우레탄 폼에 키토산 코팅액을 코팅시 수용성 키토산과 글리세린으로 구성된 점조성 수성 코팅액을 습윤한 특징을 갖는 폴리우레탄 폼에 코팅방식으로 압착 도포한 결과 코팅액에 함유된 수분에 의한 변형이 발생되지 않으며 미처리 폼(비교예 3)과 비교하여 거의 동일한 표면특성을 유지하여 상처부위의 혈액이나 삼출물의 흡수속도가 코팅 처리전과 처리 후가 차이가 없는 것이 확인된다.In the present invention, when the chitosan coating solution is coated on the polyurethane foam, a viscous aqueous coating solution composed of water-soluble chitosan and glycerin is moistened by pressing and applying a coating method to a polyurethane foam that does not cause deformation due to moisture contained in the coating solution. It was confirmed that there was no difference in the rate of absorption of blood or exudate from the wound site before coating treatment and after treatment by maintaining almost the same surface characteristics compared to the untreated foam (Comparative Example 3).
더욱이 압착코팅에 의해 지혈성분인 키토산 코팅액이 혈액이 1차적으로 통과하는 폼 스킨층 바로 아래부분에 농축 도포되어 별도로 기능성 물질이 함유된 상처접촉층과 흡수층을 만든 후 접착제를 이용한 합지 등의 추가공정 없이 한 번의 코팅작업으로 지혈층과 흡수층을 동시에 갖는 새로운 형태의 국소지혈용 폼형 드레싱재의 특징을 갖는다. Furthermore, the chitosan coating solution, which is a hemostatic component, is concentrated and applied to the lower part of the foam skin layer through which blood primarily passes through compression coating to create a wound contact layer and an absorbent layer containing functional substances separately, and then an additional process such as lamination using an adhesive. It has the feature of a new type of foam-type dressing material for local hemostatic that has a hemostatic layer and an absorbent layer at the same time in one coating operation without.
이상에서 설명한 본 발명은 전술한 실시예 및 첨부된 도면에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능함은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어서 명백할 것이다. The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the technical spirit of the present invention. It will be obvious to those who have the knowledge of.
10 : 코팅층 20 : 폼층10: coating layer 20: foam layer
Claims (10)
(2) 상기 폴리우레탄 폼 일면의 표면에 키토산 코팅액을 균일하게 공급하고, 롤투롤(roll to roll) 방식으로 상기 폴리우레탄 폼을 압착하여 키토산 코팅층이 형성되는 단계를 포함하되,
상기 코팅액은 증류수에 수용성 키토산 파우더 및 글리세린이 포함되고,
상기 키토산 코팅액 100중량부 대비 키토산 파우더는 5중량부~15중량부이고, 글리세린은 2중량부~8중량부이며,
상기 키토산 코팅층은 폴리우레탄 폼의 일면에 일정한 깊이로 코팅되고,
상기 폴리우레탄 폼의 표면 및 내부에 형성된 기공구조가 유지되는 것에 특징이 있는 폴리우레탄 폼 제조방법.
(1) Polyurethane foam of a continuous sheet with a density of 150kg/m 3 ~300kg/m 3 containing calcium ions, an absorption of 4g/g or more, a thickness of 2mm to 10mm, and uniformly distributed empty spaces on the surface and inside Manufacturing step; And
(2) uniformly supplying the chitosan coating solution to the surface of one surface of the polyurethane foam, and forming a chitosan coating layer by compressing the polyurethane foam in a roll to roll method,
The coating solution contains water-soluble chitosan powder and glycerin in distilled water,
Chitosan powder compared to 100 parts by weight of the chitosan coating solution is 5 parts by weight to 15 parts by weight, glycerin is 2 parts by weight to 8 parts by weight,
The chitosan coating layer is coated to a certain depth on one surface of the polyurethane foam,
Polyurethane foam manufacturing method characterized in that the pore structure formed on the surface and inside of the polyurethane foam is maintained.
상기 폴리우레탄 폼 제조단계는 칼슘 카르복시메틸셀룰로오스를 폴리우레탄 프리폴리머에 함유시켜 발포하는 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법.
The method of claim 1,
The polyurethane foam manufacturing step is a method for producing a polyurethane foam surface coated with chitosan, characterized in that calcium carboxymethyl cellulose is contained in a polyurethane prepolymer to foam.
상기 폴리우레탄 폼의 칼슘 카르복시메틸셀룰로오스의 함량은 프리폴리머 대비 0.5중량부~1.5중량부인 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법.
The method of claim 2,
The method for producing a polyurethane foam surface coated with chitosan, characterized in that the content of calcium carboxymethyl cellulose in the polyurethane foam is 0.5 parts by weight to 1.5 parts by weight compared to the prepolymer.
상기 (2)단계는 롤투롤(roll to roll)의 간격을 폴리우레탄 폼 두께의 90%로 유지하여 압착하는 것에 특징이 있는 폴리우레탄 폼 제조방법.
The method of claim 1,
The step (2) is a method for producing a polyurethane foam characterized in that the roll to roll interval is maintained at 90% of the thickness of the polyurethane foam and is compressed.
상기 키토산 코팅액은 탈아세틸화도가 80%이상인 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법.
The method of claim 1,
The chitosan coating solution is a method for producing a polyurethane foam surface coated with chitosan, characterized in that the degree of deacetylation is 80% or more.
상기 키토산 코팅액에 수용성 물질인 항균제, 지혈물질, 성장인자(growth factor), 비타민(vitamin) 중 적어도 어느 하나 이상이 포함된 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼 제조방법.
The method of claim 1,
The method for producing a polyurethane foam coated with chitosan, characterized in that the chitosan coating solution contains at least one of a water-soluble substance such as an antimicrobial agent, a hemostatic substance, a growth factor, and a vitamin.
The polyurethane foam surface-coated with chitosan prepared by any one of claims 1 to 4, 6, or 7.
키토산으로 표면 코팅된 폴리우레탄 폼에 있어서,
키토산 코팅층 및 폴리우레탄 폼층으로 구분되며,
상기 폴리우레탄 폼은 칼슘이온이 포함된 밀도 150kg/m3~300kg/m3, 흡수도 4g/g이상, 두께 2mm~10mm이고,
상기 폴리우레탄 폼은 표면 및 내부에 빈 공간 기공이 균일하게 분포된 스펀지구조이고,
상기 키토산 코팅층은 폴리우레탄 폼의 일면에 일정한 깊이로 키토산 코팅액으로 코팅되되,
상기 코팅액은 증류수에 수용성 키토산 파우더 및 글리세린이 포함된 것으로, 상기 키토산 코팅액 100중량부 대비 키토산 파우더는 5중량부~15중량부이고, 글리세린은 2중량부~8중량부이며,
상기 폴리우레탄 폼의 표면 및 내부에 형성된 기공구조가 유지되는 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼.
The method of claim 8,
In the polyurethane foam surface coated with chitosan,
It is divided into chitosan coating layer and polyurethane foam layer,
The polyurethane foam is a calcium ion-containing density 150kg / m 3 ~ 300kg / m 3, absorbency 4g / g or more, thickness 2mm ~ 10mm,
The polyurethane foam has a sponge structure in which voids and pores are uniformly distributed on the surface and inside,
The chitosan coating layer is coated with a chitosan coating solution to a certain depth on one surface of the polyurethane foam,
The coating liquid contains water-soluble chitosan powder and glycerin in distilled water, and the chitosan powder is 5 parts by weight to 15 parts by weight relative to 100 parts by weight of the chitosan coating solution, and glycerin is 2 parts by weight to 8 parts by weight,
Polyurethane foam surface-coated with chitosan characterized in that the pore structure formed on the surface and inside of the polyurethane foam is maintained.
상기 키토산으로 표면 코팅된 폴리우레탄 폼은 키토산 코팅된 표면 이외의 다른 표면에 필름층이 합지된 것에 특징이 있는 키토산으로 표면 코팅된 폴리우레탄 폼.
The method of claim 8,
The chitosan-coated polyurethane foam is a chitosan-coated polyurethane foam characterized in that a film layer is laminated on a surface other than the chitosan-coated surface.
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