KR20210000009A - Manufacturing method water-soluble hydrofiber having antibiotic and crosslinkability and wound dressing using the water-soluble hydrofiber - Google Patents

Manufacturing method water-soluble hydrofiber having antibiotic and crosslinkability and wound dressing using the water-soluble hydrofiber Download PDF

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KR20210000009A
KR20210000009A KR1020190074711A KR20190074711A KR20210000009A KR 20210000009 A KR20210000009 A KR 20210000009A KR 1020190074711 A KR1020190074711 A KR 1020190074711A KR 20190074711 A KR20190074711 A KR 20190074711A KR 20210000009 A KR20210000009 A KR 20210000009A
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nonwoven fabric
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조석형
송진
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조석형
주식회사 진바이오메드
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • A61F13/00012
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/00051Accessories for dressings
    • A61F13/00063Accessories for dressings comprising medicaments or additives, e.g. odor control, PH control, debriding, antimicrobic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/01Non-adhesive bandages or dressings
    • A61F13/01008Non-adhesive bandages or dressings characterised by the material
    • A61F13/01012Non-adhesive bandages or dressings characterised by the material being made of natural material, e.g. cellulose-, protein-, collagen-based
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F2013/00089Wound bandages
    • A61F2013/00238Wound bandages characterised by way of knitting or weaving
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/13Physical properties anti-allergenic or anti-bacterial
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00Medical; Hygiene
    • D10B2509/02Bandages, dressings or absorbent pads
    • D10B2509/022Wound dressings

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  • Health & Medical Sciences (AREA)
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  • Animal Behavior & Ethology (AREA)
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  • General Health & Medical Sciences (AREA)
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Abstract

본 발명은 키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 및 코발트화합물을 첨가하여 혼합용액을 제조하고, 상기 혼합용액에 카르복실화 부직포를 상온에서 침적, 반응시킴으로써, 키토산의 아민기-금속-카르복실기의 킬레이트 반응에 의한 항균성과 가교특성을 동시에 부여하여, 높은 항균성을 가지며 카르복실화 부직포를 가교화시켜 겔강도를 증가시킨 수용성 하이드로화이버 부직포의 제조방법과, 이로부터 제조된 수용성 하이드로화이버 부직포를 이용한 운드드레싱에 관한 것이다.The present invention prepares a mixed solution by adding an aluminum compound, a zinc compound, a silver compound, and a cobalt compound to the chitosan solution, and by dipping and reacting a carboxylated nonwoven fabric in the mixed solution at room temperature, the amine group-metal-carboxyl group of chitosan A method for producing a water-soluble hydrofiber nonwoven fabric having high antibacterial properties and increasing gel strength by crosslinking a carboxylated nonwoven fabric by providing antibacterial properties and crosslinking properties simultaneously by chelate reaction of, and a water-soluble hydrofiber nonwoven fabric prepared therefrom. It is about round dressing.

Description

항균성과 가교특성을 동시에 부여하는 수용성 하이드로화이버 부직포 제조방법, 이로부터 제조된 수용성 하이드로화이버 부직포를 이용한 운드드레싱{MANUFACTURING METHOD WATER-SOLUBLE HYDROFIBER HAVING ANTIBIOTIC AND CROSSLINKABILITY AND WOUND DRESSING USING THE WATER-SOLUBLE HYDROFIBER}Manufacturing method of water-soluble hydrofiber nonwoven fabric that gives antibacterial and crosslinking properties at the same time, and Wound dressing using water-soluble hydrofiber nonwoven fabric manufactured therefrom {MANUFACTURING METHOD WATER-SOLUBLE HYDROFIBER HAVING ANTIBIOTIC AND CROSSLINKABILITY AND WOUND DRESSING USING THE WATER-SOLUBLE HYDROFIBER}

본 발명은 키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 및 코발트화합물을 첨가하여 혼합용액을 제조하고, 상기 혼합용액에 카르복실화 부직포를 상온에서 침적, 반응시킴으로써, 키토산의 아민기-금속-카르복실기의 킬레이트 반응에 의한 항균성과 가교특성을 동시에 부여하여, 높은 항균성을 가지며 카르복실화 부직포를 가교화시켜 겔강도를 증가시킨 수용성 하이드로화이버 부직포의 제조방법과, 이로부터 제조된 수용성 하이드로화이버 부직포를 이용한 운드드레싱에 관한 것이다.The present invention prepares a mixed solution by adding an aluminum compound, a zinc compound, a silver compound, and a cobalt compound to the chitosan solution, and by dipping and reacting a carboxylated nonwoven fabric in the mixed solution at room temperature, the amine group-metal-carboxyl group of chitosan A method for producing a water-soluble hydrofiber nonwoven fabric having high antibacterial properties and increasing gel strength by crosslinking a carboxylated nonwoven fabric by providing antibacterial properties and crosslinking properties simultaneously by chelate reaction of, and a water-soluble hydrofiber nonwoven fabric prepared therefrom. It is about round dressing.

전 세계적으로 전통적인 거즈 형태의 상처관리 제품에 상처 재생 효과가 높은 창상피복재의 사용이 확대되면서 창상피복재 시장은 기존의 상처관리 제품의 성장 2.2% 보다 높은 3.1%의 성장이 예상되고 있다.With the increasing use of wound healing products with high wound regeneration effects in traditional gauze-type wound care products around the world, the wound dressing market is expected to grow 3.1%, which is higher than 2.2% of existing wound care products.

국내 시장 또한 상처치료에 대한 인식 변화로 창상피복재의 사용이 확대되고 있다. 최근 국산 제품의 생산(30.8%) 및 사용률(38.2%)이 급격히 증가하면서, 국내 시장에서 국내 기업과 외산 기업 간의 치열한 시장 경쟁이 진행되고 있는 중이다.In the domestic market, the use of wound coverings is also expanding due to the changing perception of wound healing. With the recent rapid increase in production (30.8%) and usage rate (38.2%) of domestic products, fierce market competition between domestic and foreign companies is in progress in the domestic market.

일반적으로 상처치료는 건조한 상태보다 수분환경이 유지되는 경우가 훨씬 치료 속도가 빠르다. 현재 사용되고 있는 드레싱제 중 수화겔은 습윤 상태가 지속적으로 요구되는 화상치료 또는 피부 재생 목적에 사용되는 재료로서, 대개 60% 이상의 수분을 함유하여야만 목적을 달성할 수 있다.In general, wound healing is much faster when the moisture environment is maintained than in a dry state. Among the currently used dressings, hydrogel is a material used for burn treatment or skin regeneration that requires a constant moist state, and can achieve its purpose only when it contains more than 60% moisture.

심한 화상 치료의 경우에는 자가이식이나 환자의 섬유아세포의 생체 내(in vitro)에서 배양한 조직을 이식하게 된다. 그러나 상기의 시술을 시행하기까지는 상당한 시간이 요구되기 때문에 시술 전에 환부의 감염을 막는 것이 필수적이다.In the case of severe burn treatment, autograft or in vivo culture of fibroblasts from patients is transplanted. However, it is essential to prevent infection of the affected area before the procedure because it takes a considerable amount of time to perform the above procedure.

창상의 형태에 따라 다양한 형태로 창상피복제가 개발되고 있으며 국내에서는 주로 폼(Foam), 필름(Film), 하이드로겔(Hydrogel)의 드레싱제를 개발하여 생산하고 있다. 국외 다국적 기업에서는 이보다 진보된 형태로서, 하이드로겔(Hydrogel), 알기네이트(Alginate), 하이드로화이버(Hydrofiber), 폴리우레탄 폼(Polyurethane foam)등을 활용한 다양한 제품이 개발되어 판매되고 있다.Various types of wound covering agents are being developed depending on the shape of the wound, and in Korea, dressing agents such as foam, film, and hydrogel are mainly developed and produced. Overseas multinational companies have developed and sold a variety of products using hydrogel, alginate, hydrofiber, and polyurethane foam as more advanced forms.

일반적으로 습윤성 폼드레싱제나 수화겔을 제조하기 위해서는 수화겔을 형성할 수 있는 고분자가 선택되어야 하고, 외부 환경의 변화(온도, pH, 용매조성, 전기장, 광도, 화학물질 등)에 대하여 민감하게 반응하지 않아 함수율 등의 물성변화를 나타내지 않아야 한다.In general, in order to manufacture a wettable foam dressing agent or hydrogel, a polymer capable of forming a hydrogel must be selected, and it does not react sensitively to changes in the external environment (temperature, pH, solvent composition, electric field, light intensity, chemicals, etc.). It should not show changes in physical properties such as moisture content.

현재 사용되고 있는 드레싱제인 폼드레싱제 및 수화겔은 대부분 습윤상태만을 유지하거나 삼출물 등에 의해 용해되어 상처부위에 잔여물이 달라붙어 있어 2차적으로 상처부위를 세척해야 하는 문제점이 있다. 그리고 상기 폼드레싱제는 우레탄 등으로 제조되기 때문에 상처의 치유를 촉진할 수 있는 물질이나 항균성을 부여하기 어렵고, 수화겔의 경우에도 공정상 항균성을 부여하기 어렵다.Foam dressing agents and hydrogels, which are currently used dressing agents, mostly remain wet or dissolved by exudates, so that residues adhere to the wound area, so there is a problem that the wound area must be cleaned secondarily. In addition, since the foam dressing agent is made of urethane, it is difficult to impart antibacterial properties or substances capable of promoting wound healing, and even in the case of a hydrogel, it is difficult to impart antibacterial properties in the process.

이와 같은 문제를 해결하기 위하여, 고분자 구조의 특성상 모세관 및 삼투압 현상에 의해 물을 흡수하여 수분을 함유하고, 정전기적, 친유성 상호작용 및 고분자쇄 사이의 적당한 가교를 통해 삼출물이나 물에 용해되지 않는 특징을 가지면서 항균성 및 상처치유에 도움이 되는 물질이 함유된 드레싱제의 개발이 필요한 실정이다.In order to solve such a problem, due to the nature of the polymer structure, it absorbs water by capillary and osmotic pressure to contain moisture, and does not dissolve in exudate or water through electrostatic, lipophilic interaction and proper crosslinking between polymer chains. There is a need to develop a dressing agent that has characteristics and contains substances that are useful for antibacterial properties and wound healing.

본 발명과 종래 개시된 특허기술들을 살펴보면, 미국 등록특허 제5,389,376호의 경우, 방사선 가교법을 이용한 상처치료용 드레싱의 제조방법을 개시하고 있으며, 폴리비닐피롤리돈에 아가, 폴리에틸렌옥사이드를 혼합하고 이것을 방사선으로 조사 및 가교하여 이루어지는 기술을 개시하고 있다. Looking at the present invention and the conventionally disclosed patent technologies, US Patent No. 5,389,376 discloses a method of manufacturing a dressing for wound treatment using a radiation crosslinking method. Agar and polyethylene oxide are mixed with polyvinylpyrrolidone, and this A technique obtained by irradiation and crosslinking is disclosed.

본 발명과 비교하여 볼 때, 방사선의 가교법의 특징, 즉 가교와 멸균을 동시에 추진할 수 있는 장점이 있으나, 폴리비닐피롤리돈과 아가의 혼합시 수화겔의 강도가 낮고, 혼용성이 좋지 않아서 강도가 약해 찢어지는 문제가 있다.Compared with the present invention, there is a characteristic of the radiation crosslinking method, that is, crosslinking and sterilization can be simultaneously promoted, but the strength of the hydrogel is low when mixing polyvinylpyrrolidone and agar, and the strength of the hydrogel is poor. Is weak and has a problem of tearing.

미국 등록특허 제5,480,717호의 경우, 점착제가 부착된 고분자 필름에 폴리비닐피롤리돈 수용액을 캐스팅하고 방사선으로 조사하여 제조된 수화겔을 개시하고 있다. In the case of US Patent No. 5,480,717, a hydrogel prepared by casting an aqueous solution of polyvinylpyrrolidone on a polymer film with an adhesive and irradiating with radiation is disclosed.

본 발명과 비교하여 볼 때, 상기 수화겔은 강도가 약한 반면, 점착성이 너무 강하여 상처부위에, 수화겔을 제조할 때 사용된 폴리비닐피롤리돈이 잔류하는 문제가 있다.Compared to the present invention, the hydrogel has a weak strength, but has a problem in that polyvinylpyrrolidone used when preparing the hydrogel remains in the wound area due to too strong adhesiveness.

일본 공개특허 제9-267453호의 경우, 폴리비닐알콜을 기본 소재로 하고 여기에 다른 적층제를 첨가하여 물성을 개선하는 기술에 대해 개시하고 있다.Japanese Patent Application Laid-Open No. 9-267453 discloses a technique for improving physical properties by using polyvinyl alcohol as a basic material and adding another laminating agent thereto.

본 발명과 비교하여 볼 때, 단순히 방사선 조사로 제품을 제조하기 때문에 물성 개선에 한계가 있어, 방사선 조사를 하지 않고는 포장재에 형태를 유지시키면서 넣을 수 없기 때문에 2회에 걸쳐 방사선을 조사해야 하며, 환부에 장기 사용시에는 항균제를 별도로 사용해야 하는 문제가 있다.Compared with the present invention, since the product is manufactured simply by irradiation, there is a limit to improvement in physical properties, and since it cannot be put in a packaging material while maintaining its shape without irradiation, radiation must be irradiated twice, When used for a long time on the affected area, there is a problem that an antibacterial agent must be used separately.

이외에, 대한민국 공개특허 제2001-0086864호는 폴리비닐피롤리돈 합성 고분자를 키토산, 키토산과 폴리에틸렌 옥사이드 또는 알긴산나트륨과 폴리에틸렌옥사이드와 혼합하여 수용액을 제조하고, 시트 형태로 성형한 후에 포장하는 단계 및 포장된 시트에 방사선을 조사하는 단계로 이루어지는 기술에 대해 개시하고 있으며,In addition, Korean Patent Laid-Open Publication No. 2001-0086864 describes the steps of preparing an aqueous solution by mixing a polyvinylpyrrolidone synthetic polymer with chitosan, chitosan and polyethylene oxide or sodium alginate and polyethylene oxide, forming a sheet, and then packaging Discloses a technology consisting of the step of irradiating radiation on the sheet,

대한민국 공개특허 제2004-0085646호는 폴리비닐피롤리돈, 다가알코올 및 카라기난으로 이루어진 조성물을 포함하는 수화겔 드레싱, 트레이 및 방사선 조사에 의한 그의 제조방법 및 이를 이용한 상처치료용 드레싱 또는 피부미용 팩제를 개시하고 있다.Korean Patent Laid-Open No. 2004-0085646 discloses a hydrogel dressing comprising a composition consisting of polyvinylpyrrolidone, polyhydric alcohol and carrageenan, a tray, and a method of manufacturing the same by irradiation with radiation, and a wound treatment dressing or skin beauty pack using the same Are doing.

또한 대한민국 등록특허 제10-1318421호는 지혈 및 상처치유용 카복시메틸셀룰로오스 폼 및 그의 제조방법으로 카복시메틸셀룰로오스폼을 동결건조방식으로 제조한 후, 적절한 산처리 및 압착단계를 거침으로써 폼의 흡액도를 현저히 증가시켰으며, 흡액시에도 겔화되지 않고 형상을 그대로 유지하는 기술을 개시하고 있다.In addition, Republic of Korea Patent Registration No. 10-1318421 is a carboxymethyl cellulose foam for hemostasis and wound healing and its manufacturing method. After manufacturing a carboxymethyl cellulose foam by a freeze-drying method, the liquid absorption of the foam is carried out by performing an appropriate acid treatment and compression step. Was significantly increased, and a technique for maintaining the shape as it is without gelation even when absorbed is disclosed.

종합적으로 검토하여 볼 때, 종래 개시된 기술들은 사용가능 시간이 짧은 문제가 있어, 12시간 이상 공기 중에 노출되면 수분이 증발되어 상처치료의 기능을 할 수 없고, 제조공정이 복잡하고 제조 코스트가 많이 드는 문제가 있다.Comprehensive review, the conventionally disclosed technologies have a short usable time problem, and when exposed to air for more than 12 hours, moisture is evaporated and thus cannot function as wound healing, and the manufacturing process is complex and manufacturing cost is high. there is a problem.

그리고 항균제 등의 처리를 따로 해야하는 기술적 문제와 삼출물의 흡수가 충분하지 않다는 문제가 있다.In addition, there are technical problems that require treatment with antibacterial agents, etc., and the absorption of exudate is insufficient.

이와 같은 문제를 해결하기 위하여, 본 출원인은 공개특허 10-2018-0041980호(공개일자 2018년04월25일)를 통해 '수용성 하이드로화이버 제조방법, 이로부터 제조된 수용성 하이드로화이버를 이용한 운드드레싱'에 대한 기술을 개시한 바 있다.In order to solve such a problem, the applicant of the present invention reads ``A water-soluble hydrofiber manufacturing method, a round dressing using a water-soluble hydrofiber prepared therefrom'' through Korean Patent Publication No. 10-2018-0041980 (published on April 25, 2018). Has disclosed a description of.

상기 공개특허에는 이미 가교된 하이드로화이버 부직포 또는 직포를 제3혼합용액(키토산 용액에 알루미늄화합물 또는 칼슘화합물을 첨가하여 용해시킨 용액)에 침적, 반응시켜 항균성을 부여하는 기술이 개시되어 있다.The above disclosed patent discloses a technology for imparting antimicrobial properties by dipping and reacting an already crosslinked hydrofiber nonwoven fabric or woven fabric in a third mixed solution (a solution obtained by adding an aluminum compound or a calcium compound to a chitosan solution and dissolving it).

본 출원인은 상기 하이드로화이버 부직포의 항균성을 향상시킬 수 있는 방법에 대해 많은 연구 및 실험을 진행하였으며, 그 결과 본 발명에서 제시하는 혼합용액에 카르복실화 부직포를 침적, 반응시킴으로써 가교반응이 일어남과 동시에 항균성이 동시에 부여되어 높은 항균특성의 수용성 하이드로화이버 부직포를 개발하게 되었다.The applicant of the present invention has conducted a number of studies and experiments on a method to improve the antibacterial properties of the hydrofiber nonwoven fabric. As a result, the crosslinking reaction occurs and at the same time by dipping and reacting the carboxylated nonwoven fabric in the mixed solution presented in the present invention. The antimicrobial properties were simultaneously imparted, and the water-soluble hydrofiber nonwoven fabric with high antibacterial properties was developed.

본 발명을 통해 상기 가교반응이 일어남과 동시에 항균성이 동시에 부여되어 높은 항균특성을 갖는 수용성 하이드로화이버 부직포와, 상기 수용성 하이드로화이버 부직포를 이용한 운드드레싱을 제공하고자 한다.An object of the present invention is to provide a water-soluble hydrofiber nonwoven fabric having high antimicrobial properties by providing antibacterial properties at the same time as the crosslinking reaction occurs, and a round dressing using the water-soluble hydrofiber nonwoven fabric.

미국 등록특허 제5,389,376호(등록일자 1995.02.14)US Patent No. 5,389,376 (Registration Date 1995.02.14) 미국 등록특허 제5,480,717호(등록일자 1996.01.02)US Patent No. 5,480,717 (Registration Date 1996.01.02) 일본 공개특허 제9-267453호(공개일자 1997.10.14)Japanese Laid-Open Patent No. 9-267453 (published date 1997.10.14) 대한민국 공개특허 제2001-0086864호(공개일자 2001.09.15)Republic of Korea Patent Publication No. 2001-0086864 (published date 2001.09.15) 대한민국 공개특허 제2004-0085646호(공개일자 2004.10.08)Republic of Korea Patent Publication No. 2004-0085646 (published date 2004.10.08) 대한민국 등록특허 제10-1318421호(등록일자 2013.10.08)Korean Patent Registration No. 10-1318421 (Registration Date 2013.10.08) 대한민국 공개특허 10-2018-0041980호(공개일자 2018.04.25)Republic of Korea Patent Publication No. 10-2018-0041980 (Publication date 2018.04.25)

본 발명은 키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 및 코발트화합물을 첨가하여 혼합용액을 제조하고, 상기 혼합용액에 카르복실화 부직포를 상온에서 침적, 반응시킴으로써, 키토산의 아민기-금속-카르복실기의 킬레이트 반응에 의한 항균성과 가교특성을 동시에 부여하여, 높은 항균성을 가지며 카르복실화 부직포를 가교화시켜 겔강도를 증가시킨 수용성 하이드로화이버 부직포의 제조방법과, 이로부터 제조된 수용성 하이드로화이버 부직포를 이용한 운드드레싱을 제공하고자 하는 것을 발명의 목적으로 한다.The present invention prepares a mixed solution by adding an aluminum compound, a zinc compound, a silver compound, and a cobalt compound to the chitosan solution, and by dipping and reacting a carboxylated nonwoven fabric in the mixed solution at room temperature, the amine group-metal-carboxyl group of chitosan A method for producing a water-soluble hydrofiber nonwoven fabric having high antibacterial properties and increasing gel strength by crosslinking a carboxylated nonwoven fabric by providing antibacterial properties and crosslinking properties simultaneously by chelate reaction of, and a water-soluble hydrofiber nonwoven fabric prepared therefrom. It is an object of the invention to provide a round dressing.

상기 목적을 이루기 위하여, To achieve the above purpose,

본 발명은 면 또는 레이온으로 이루어진 섬유로 직조된 부직포를 그대로 카르복실화하여 수득한 순수한 수용성 카르복실화 하이드로화이버 부직포를 이용하는 항균성 하이드로화이버 부직포 제조방법에 있어서,The present invention in the antibacterial hydrofiber nonwoven fabric manufacturing method using a pure water-soluble carboxylated hydrofiber nonwoven fabric obtained by carboxylating the nonwoven fabric made of cotton or rayon as it is,

키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 또는 코발트화합물 중 선택되는 어느 1종 이상의 금속을 첨가하고 용해시켜 키토산-금속 혼합용액을 제조하는 단계(S10)와,A step (S10) of preparing a chitosan-metal mixed solution by adding and dissolving at least one metal selected from an aluminum compound, a zinc compound, a silver compound, or a cobalt compound to the chitosan solution; and

상기 키토산-금속 혼합용액 내에 상기 카르복실화 하이드로화이버 부직포를 35 ~ 45 ℃에서 2 분 ~ 10 분 동안 침적, 반응시켜 가교와 동시에 항균성을 부여하는 단계(S20)와,The step of immersing and reacting the carboxylated hydrofiber nonwoven fabric in the chitosan-metal mixed solution at 35 to 45° C. for 2 to 10 minutes to give crosslinking and antibacterial properties at the same time (S20),

항균성을 부여한 부직포를 탈수한 후, 물과 에탄올의 혼합용액에 상기 탈수과정을 거친 부직포를 침적한 후 탈수하는 과정을 2 ~ 4회 반복하는 단계(S30)를 포함하는, 수용성 하이드로화이버 부직포 제조방법을 제공한다.After dehydrating the nonwoven fabric with antimicrobial properties, the process of dipping the nonwoven fabric subjected to the dehydration process in a mixed solution of water and ethanol, and repeating the dehydration process 2 to 4 times (S30), a method for producing a water-soluble hydrofiber nonwoven fabric Provides.

그리고 상기 수용성 하이드로화이버 부직포 제조방법을 통해 제조된 수용성 하이드로화이버를 원하는 규격에 맞게 재단한 것을 특징으로 하는 운드드레싱을 제공한다.And it provides a round dressing, characterized in that the water-soluble hydrofiber manufactured through the method of manufacturing the water-soluble hydrofiber nonwoven fabric is cut according to a desired standard.

본 발명은 키토산 용액에 금속인 알루미늄화합물, 아연화합물, 은화합물 및 코발트화합물을 첨가하여 제조한 혼합용액에 카르복실화 부직포를 침적, 반응시킴으로써 가교와 동시에 항균성을 부여할 수 있어 높은 항균특성을 가지며 또한 카르복실화 부직포를 가교화시켜 겔강도를 증가시키는 효과를 갖는다.The present invention has high antibacterial properties as it can provide antibacterial properties at the same time as crosslinking by dipping and reacting a carboxylated nonwoven fabric in a mixed solution prepared by adding a metal aluminum compound, a zinc compound, a silver compound, and a cobalt compound to a chitosan solution. In addition, it has the effect of increasing the gel strength by crosslinking the carboxylated nonwoven fabric.

도 1은 본 발명의 수용성 하이드로화이버 부직포 제조방법에 따른 공정순서도.1 is a process flow chart according to the method of manufacturing a water-soluble hydrofiber nonwoven fabric of the present invention.

본 발명에 따른 기술 구성을 도면과 함께 구체적으로 살펴보도록 한다.The technical configuration according to the present invention will be described in detail together with the drawings.

도 1에 도시된 바와 같이,As shown in Figure 1,

본 발명에 따른 수용성 하이드로화이버 부직포 제조방법은,The method for producing a water-soluble hydrofiber nonwoven fabric according to the present invention,

면 또는 레이온으로 이루어진 섬유로 직조된 부직포를 그대로 카르복실화하여 수득한 순수한 수용성 카르복실화 하이드로화이버 부직포를 이용하는 것으로서,A pure water-soluble carboxylated hydrofiber nonwoven fabric obtained by carboxylating a nonwoven fabric made of cotton or rayon as it is,

키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 또는 코발트화합물 중 선택되는 어느 1종 이상의 금속을 첨가하고 용해시켜 키토산-금속 혼합용액을 제조하는 단계(S10)와,A step (S10) of preparing a chitosan-metal mixed solution by adding and dissolving at least one metal selected from an aluminum compound, a zinc compound, a silver compound, or a cobalt compound to the chitosan solution; and

상기 키토산-금속 혼합용액 내에 상기 카르복실화 하이드로화이버 부직포를 35 ~ 45 ℃에서 2 분 ~ 10 분 동안 침적, 반응시켜 가교와 동시에 항균성을 부여하는 단계(S20)와,The step of immersing and reacting the carboxylated hydrofiber nonwoven fabric in the chitosan-metal mixed solution at 35 to 45° C. for 2 to 10 minutes to give crosslinking and antibacterial properties at the same time (S20),

항균성을 부여한 부직포를 탈수한 후, 물과 에탄올의 혼합용액에 상기 탈수과정을 거친 부직포를 침적한 후 탈수하는 과정을 2 ~ 4회 반복하는 단계(S30)를 포함한다.After dehydrating the nonwoven fabric with antimicrobial properties, the process of dipping the nonwoven fabric subjected to the dehydration process in a mixed solution of water and ethanol is repeated 2 to 4 times (S30).

이하, 상기 수용성 하이드로화이버 부직포 제조방법의 각 단계별 기술 구성에 대해 더욱 구체적으로 살펴보도록 한다.Hereinafter, the technical configuration of each step of the method for manufacturing the water-soluble hydrofiber nonwoven fabric will be described in more detail.

1. 키토산-금속 혼합용액 제조단계(S10)1. Chitosan-metal mixed solution manufacturing step (S10)

상기 키토산-금속 혼합용액은 키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 또는 코발트화합물 중 선택되는 어느 1종 또는 2종 이상의 금속을 첨가하여 제조한다.The chitosan-metal mixed solution is prepared by adding one or two or more metals selected from an aluminum compound, a zinc compound, a silver compound, or a cobalt compound to the chitosan solution.

상기 키토산 용액은 분자량이 5 만 내지 20 만인 키토산을 물과 에탄올의 혼합 용액에 용해시키되, 상기 키토산의 농도가 0.5 wt% ~ 3.0 wt%가 되도록 용해시키는 것을 사용한다.As the chitosan solution, chitosan having a molecular weight of 50,000 to 200,000 is dissolved in a mixed solution of water and ethanol, and the chitosan is dissolved in a concentration of 0.5 wt% to 3.0 wt%.

상기 키토산의 농도가 0.5 wt% 미만인 경우에는 키토산의 양이 너무 적어 항균성이나 가교특성을 내기 어렵고, 3.0 wt%를 초과하게 되는 경우에는 점도가 너무 높아 카르복실화 부직포의 내부로 들어가기가 어렵고 반응 후 세척해야 하는 단점이 있으므로, 상기 키토산의 농도는 0.5 wt% ~ 3.0 wt%의 범위 내에서 유지되는 것이 바람직하다.When the concentration of chitosan is less than 0.5 wt%, the amount of chitosan is too small to produce antimicrobial or crosslinking properties, and when it exceeds 3.0 wt%, the viscosity is too high to enter the carboxylated nonwoven fabric after reaction. Since there is a disadvantage to be washed, the concentration of chitosan is preferably maintained within the range of 0.5 wt% to 3.0 wt%.

상기 금속의 사용량은 부직포의 카르복실기 및 키토산의 아민기에 대하여 동몰 내지 1/32몰의 범위 내로 한정한다.The amount of the metal used is limited to within the range of equal to 1/32 mole of the carboxyl group of the nonwoven fabric and the amine group of chitosan.

바람직하게는 1/4 내지 1/16몰의 범위 내로 한정한다.It is preferably limited to within the range of 1/4 to 1/16 mol.

상기 사용량이 동몰보다 큰 경우에는 가교특성이 나타나지 않는 문제가 있고, 1/32몰보다 작은 경우에는 항균성 및 겔 강도가 너무 작아 부직포가 물이나 혈액을 흡수했을 때 부직포의 형태가 무너지는 단점이 있으므로, 상기 금속의 사용량은 부직포의 카르복실기 및 키토산의 아민기에 대하여 동몰 내지 1/32몰의 범위 내로 한정하는 것이 바람직하다.When the amount is greater than the same mole, there is a problem that the crosslinking property does not appear, and when the amount is less than 1/32 mole, the antibacterial property and gel strength are too small, so the shape of the nonwoven fabric collapses when the nonwoven fabric absorbs water or blood. , It is preferable that the amount of the metal is limited within the range of the same mole to 1/32 mole with respect to the carboxyl group of the nonwoven fabric and the amine group of chitosan.

상기 금속 중 알루미늄화합물은 질산알루미늄, 초산알루미늄, 젓산알루미늄 또는 염화알루미늄 중 선택되는 어느 1종 또는 2종 이상의 1가의 산으로 이루어진 화합물을 사용하고,Among the metals, the aluminum compound is a compound consisting of one or two or more monovalent acids selected from aluminum nitrate, aluminum acetate, aluminum nitrate, or aluminum chloride,

상기 아연화합물은 질산아연, 초산아연, 젓산아연 또는 염화아연을 사용하고,The zinc compound is zinc nitrate, zinc acetate, zinc nitrate or zinc chloride,

상기 은화합물은 산화은 또는 질산은을 사용하며,The silver compound uses silver oxide or silver nitrate,

상기 코발트화합물은 질산코발트, 염화코발트 또는 초산코발트 중 선택되는 어느 1종 또는 2종 이상인 것을 사용한다.The cobalt compound is one or two or more selected from cobalt nitrate, cobalt chloride, or cobalt acetate.

이때 질산알루미늄, 초안아연, 산화은 또는 염화코발트 중에서 선택하여 사용하는 것이 바람직하고, 2개 이상의 화합물을 같이 사용해도 상관없다.At this time, it is preferable to use aluminum nitrate, zinc oxide, silver oxide, or cobalt chloride, and two or more compounds may be used together.

각 성분들의 배합비를 한정하는 이유는 카르복실기와 아민기의 반응할 수 있는 리간드가 한정되어 있으며 키토산과 카르복실화 부직포 사이에 킬레이트 반응에 의한 적당한 가교도를 유지시켜 부직포의 흡수성, 지혈특성 및 항균성을 갖기 위함이다.The reason for limiting the mixing ratio of each component is that the ligand that can react with the carboxyl group and the amine group is limited, and by maintaining an appropriate degree of crosslinking between chitosan and the carboxylated nonwoven fabric by chelate reaction, the nonwoven fabric has absorbency, hemostatic properties and antibacterial properties It is for sake.

2. 키토산-금속 혼합용액에 카르복실화 하이드로화이버 부직포를 침적, 반응시키는 단계(S20)2. Step of dipping and reacting a carboxylated hydrofiber nonwoven fabric in a chitosan-metal mixed solution (S20)

상기 카르복실화 하이드로화이버 부직포는 면 또는 레이온으로 이루어진 섬유로 직조된 부직포를 그대로 카르복실화하여 제조된 순수한 수용성 카르복실화 하이드로화이버 부직포이다.The carboxylated hydrofiber nonwoven fabric is a pure water-soluble carboxylated hydrofiber nonwoven fabric manufactured by carboxylating a nonwoven fabric made of cotton or rayon as it is.

상기 면(Cotton)은 목화씨에 붙어있는 단섬유(staple fiber)를 말한다.The cotton (Cotton) refers to the staple fiber (staple fiber) attached to the cotton seed.

상기 레이온은 목재 또는 무명의 부스러기 등을 화학적 방법으로 처리하여 순수한 섬유소로 이루어진 펄프를 만들고 이를 화학적으로 용해하여 다시 섬유상으로 응고시킨 것을 말한다. 상기 펄프는 기계적, 화학적 처리에 의하여 식물체의 섬유를 추출한 것으로 주로 섬유나 종이 따위의 원료로 사용된다.The rayon refers to a pulp made of pure fiber by chemically treating wood or cotton debris, and chemically dissolving it to solidify it into fibrous form. The pulp is obtained by extracting the fiber of a plant by mechanical or chemical treatment, and is mainly used as a raw material for fiber or paper.

상기 순수한 수용성 카르복실화 하이드로화이버 부직포의 구체적인 제조예는 다음과 같다.A specific example of preparation of the pure water-soluble carboxylated hydrofiber nonwoven fabric is as follows.

물과 에탄올이 3:7의 부피비율로 혼합된 에탄올 수용액 12 L에 NaOH 1 kg을 용해시키고 면으로 제조된 부직포 500 g을 침적시켜 25℃의 상온에서 24 시간 동안 반응시킨다. 반응시켜 생성된 반응물에 모노클로로아세트산 1 kg을 넣어 5 시간 동안 반응시켜 카르복실화 면부직포를 제조한다. 이 카르복실화 부직포를 3회 세척하여 순수한 카르복실화 면부직포를 제조한다. 이때 상기 면부직포의 카르복실화율은 80 %이다.1 kg of NaOH was dissolved in 12 L of an aqueous ethanol solution in which water and ethanol were mixed in a volume ratio of 3:7, and 500 g of a nonwoven fabric made of cotton was immersed and reacted at room temperature at 25°C for 24 hours. 1 kg of monochloroacetic acid was added to the reaction product and reacted for 5 hours to prepare a carboxylated nonwoven fabric. The carboxylated nonwoven fabric was washed three times to prepare a pure carboxylated cotton nonwoven fabric. At this time, the carboxylation rate of the cotton nonwoven fabric is 80%.

상기 부직포는 섬유를 기계적, 화학적 또는 열로 처리하여 섬유집합체로 결속시켜 직접 포의 형태를 이루게 한 것으로서 접착포(bonded fabric)이라고도 한다.The nonwoven fabric is a fiber that is mechanically, chemically or thermally treated to bind it into a fiber aggregate to form a fabric directly, and is also referred to as a bonded fabric.

본 단계(S20)는 상기 순수한 수용성 카르복실화 하이드로화이버 부직포를 전 단계(S10)에서 수득한 키토산-금속 혼합용액에 침적, 반응시키되, 상기 키토산-금속 혼합용액의 온도를 35 ~ 45 ℃로 유지한 상태에서 2 분 ~ 10 분 동안 침적, 반응시킴으로써, 키토산의 아민기-금속-카르복실기의 킬레이트 반응에 의한 항균성과 가교특성을 동시에 부여하는 단계이다.In this step (S20), the pure water-soluble carboxylated hydrofiber nonwoven fabric is immersed and reacted in the chitosan-metal mixed solution obtained in the previous step (S10), but the temperature of the chitosan-metal mixed solution is maintained at 35 to 45°C. This is a step to simultaneously impart antimicrobial properties and crosslinking properties by chelating reaction of an amine group-metal-carboxyl group of chitosan by immersion and reaction for 2 to 10 minutes in one state.

3. 물과 에탄올의 혼합용액에 침적, 탈수하는 단계(S30)3. Step of immersion and dehydration in a mixed solution of water and ethanol (S30)

본 단계(S30)는 전 단계(S20)의 항균성을 부여한 부직포를 탈수한 후, 물과 에탄올의 혼합용액에 상기 탈수과정을 거친 부직포를 침적, 탈수하여 본 발명에 따른 수용성 하이드로화이버 부직포를 완성하는 단계이다.This step (S30) is to complete the water-soluble hydrofiber nonwoven fabric according to the present invention by dehydrating the nonwoven fabric provided with antibacterial properties in the previous step (S20), and then immersing and dehydrating the nonwoven fabric subjected to the dehydration process in a mixed solution of water and ethanol. Step.

이때, 상기 침적과 탈수과정은 2 ~ 4회 반복한다. 더욱 구체적으로는 3회 반복한다.At this time, the deposition and dehydration processes are repeated 2 to 4 times. More specifically, it repeats 3 times.

상기 물과 에탄올의 혼합용액은 구체적인 예로서, 순수한 물과 에탄올을 3:7 의 부피비율로 혼합한 혼합용액을 사용한다.The mixed solution of water and ethanol is a specific example, and a mixed solution of pure water and ethanol in a volume ratio of 3:7 is used.

상기 수용성 하이드로화이버 부직포 제조에 대한 구체적인 예를 실시예를 통해 살펴보도록 한다.A specific example of manufacturing the water-soluble hydrofiber nonwoven fabric will be described through Examples.

물과 에탄올을 3:7의 부피비로 혼합한 혼합용액 20 L에 키토산 200 g(0.25몰)를 용해시키고, 여기에 질산알루미늄 58.59 g(0.16몰)을 용해시킨다.200 g (0.25 mol) of chitosan was dissolved in 20 L of a mixed solution of water and ethanol in a volume ratio of 3:7, and 58.59 g (0.16 mol) of aluminum nitrate was dissolved therein.

다음으로 온도를 40 ℃로 유지하면서 상기 제조예를 보인 카르복실화 면부직포 1 kg을 5 분간 침적시킨다. Next, 1 kg of the carboxylated nonwoven fabric shown in Preparation Example was immersed for 5 minutes while maintaining the temperature at 40°C.

그리고 상기 카르복실화 면부직포를 꺼내어 탈수기로 탈수한 후 순수한 물과 에탄올을 3:7 부피비로 혼합한 혼합용액 20 L에 침적-탈수를 3회함으로써, 본 발명에 따른 키토산의 아민기-금속-카르복실기의 킬레이트 반응이 이루어진 수용성 하이드로화이버가 완성된다.Then, the carboxylated cotton nonwoven fabric is taken out, dehydrated with a dehydrator, and then immersed in 20 L of a mixed solution in which pure water and ethanol are mixed in a volume ratio of 3:7-and dehydration is performed three times, so that the amine group of chitosan according to the present invention-metal- A water-soluble hydrofiber having a chelating reaction of a carboxyl group is completed.

실시예 1의 질산알루미늄을 대신하여, 질산은 3.3 g(0.02몰)을 사용하는 것을 제외하고 실시예 1과 동일하게 실시하여 수용성 하이드로화이버를 제조하였다.In place of the aluminum nitrate of Example 1, a water-soluble hydrofiber was prepared in the same manner as in Example 1, except that 3.3 g (0.02 mol) of silver nitrate was used.

실시예 1의 질산알루미늄을 대신하여, 초산아연 4.3 g(0.02몰)을 사용하는 것을 제외하고 실시예 1과 동일하게 실시하여 수용성 하이드로화이버를 제조하였다.A water-soluble hydrofiber was prepared in the same manner as in Example 1, except that 4.3 g (0.02 mole) of zinc acetate was used in place of the aluminum nitrate of Example 1.

실시예 1의 질산알루미늄을 대신하여, 질산은 1.3 g(0.01몰)과 초산아연 2.2 g(0.01몰)을 사용하는 것을 제외하고 실시예 1과 동일하게 실시하여 수용성 하이드로화이버를 제조하였다.In place of the aluminum nitrate of Example 1, a water-soluble hydrofiber was prepared in the same manner as in Example 1, except that 1.3 g (0.01 mol) of silver nitrate and 2.2 g (0.01 mol) of zinc acetate were used.

[시험예 1][Test Example 1]

[ 항균성 측정 ][Measurement of antibacterial activity]

키토산과 금속을 킬레이트화한 수용성 하이드로화이버 부직포의 항균성을 ASTM E2149-10에 의해 측정하였다. 측정 방법은 다음과 같다.The antibacterial properties of the water-soluble hydrofiber nonwoven fabric obtained by chelation of chitosan and metal were measured by ASTM E2149-10. The measurement method is as follows.

① 완제품을 페트리디쉬에 무균적으로 놓는다.① Put the finished product in a petri dish aseptically.

② 최소 106 cfu/mL의 균액 1 mL을 시료에 접종한 다음 지정된 온도에서 배양한다.② Inoculate the sample with 1 mL of at least 10 6 cfu/mL of bacterial solution and incubate at the designated temperature.

③ 접촉시간을 설정하여 정해진 시간에 맞춰 시료와 중화용액 섞은 다음 Stomacher을 사용하여 시료에서 균을 분리한다.③ Set the contact time, mix the sample with the neutralization solution according to the specified time, and separate the bacteria from the sample using a Stomacher.

④ 균액 1 mL을 적절히 희석하여 Pour plating 방법이나 Spread plating방법을 사용하여 도말한다.④ Dilute 1 mL of the bacteria solution appropriately and paint using the Pour plating method or the Spread plating method.

⑤ 지정된 온도에서 24 시간 혹은 48 시간 배양하여 생균수를 측정한다.⑤ Incubate for 24   hours or 48   hours at the designated temperature and measure the number of viable cells.

⑥ 아래의 공식을 사용하여 감소율을 구한다.⑥ Calculate the reduction rate using the formula below.

Log10 reduction (LR) = mean log10(초기균수) - mean log10(생존균수)Log 10 reduction (LR) = mean log 10 (number of initial bacteria)-mean log 10 (number of surviving bacteria)

Percent reduction(%) = 100 × (1-10-LR)Percent reduction(%) = 100 × (1-10 -LR )

상기 항균성 측정에 따른 결과는 다음의 표 1 내지 표 4와 같다.Results according to the antimicrobial measurement are shown in Tables 1 to 4 below.

하기 표 1은 실시예 1에 따른 결과이다.Table 1 below shows the results according to Example 1.

하기 표 2는 실시예 2에 따른 결과이다.Table 2 below shows the results according to Example 2.

하기 표 3은 실시예 3에 따른 결과이다.Table 3 below shows the results according to Example 3.

하기 표 4는 실시예 4에 따른 결과이다.Table 4 below shows the results according to Example 4.

시험항목Test Items 초기농도
(CFC/mL)
Initial concentration
(CFC/mL)
24시간 후 농도
(CFC/mL)
Concentration after 24 hours
(CFC/mL)
세균감소율(%)Bacterial reduction rate (%)
대장균Coli BLANKBLANK 1.7×104 1.7×10 4 5.9×104 5.9×10 4 99.999.9 항균제 처리Antibacterial treatment 1.4×104 1.4×10 4 <10<10 황색포도상구균Staphylococcus aureus BLANKBLANK 1.3×104 1.3×10 4 2.2×104 2.2×10 4 99.999.9 항균제 처리Antibacterial treatment 1.1×104 1.1×10 4 <10<10 살모넬라Salmonella BLANKBLANK 4.2×105 4.2×10 5 6.0×105 6.0×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10 녹농균Pseudomonas aeruginosa BLANKBLANK 5.2×105 5.2×10 5 9.2×105 9.2×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10

시험항목Test Items 초기농도
(CFC/mL)
Initial concentration
(CFC/mL)
24시간 후 농도
(CFC/mL)
Concentration after 24 hours
(CFC/mL)
세균감소율(%)Bacterial reduction rate (%)
대장균Coli BLANKBLANK 1.7×104 1.7×10 4 6.9×104 6.9×10 4 99.999.9 항균제 처리Antibacterial treatment 1.7×104 1.7×10 4 <10<10 황색포도상구균Staphylococcus aureus BLANKBLANK 1.3×104 1.3×10 4 4.2×104 4.2×10 4 99.999.9 항균제 처리Antibacterial treatment 1.3×104 1.3×10 4 <10<10 살모넬라Salmonella BLANKBLANK 4.2×105 4.2×10 5 7.0×105 7.0×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10 녹농균Pseudomonas aeruginosa BLANKBLANK 5.2×105 5.2×10 5 9.2×105 9.2×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10

시험항목Test Items 초기농도
(CFC/mL)
Initial concentration
(CFC/mL)
24시간 후 농도
(CFC/mL)
Concentration after 24 hours
(CFC/mL)
세균감소율(%)Bacterial reduction rate (%)
대장균Coli BLANKBLANK 2.7×104 2.7×10 4 8.9×104 8.9×10 4 99.999.9 항균제 처리Antibacterial treatment 1.7×104 1.7×10 4 <10<10 황색포도상구균Staphylococcus aureus BLANKBLANK 1.3×104 1.3×10 4 6.2×104 6.2×10 4 99.999.9 항균제 처리Antibacterial treatment 1.3×104 1.3×10 4 <10<10 살모넬라Salmonella BLANKBLANK 2.2×105 2.2×10 5 6.0×105 6.0×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10 녹농균Pseudomonas aeruginosa BLANKBLANK 5.2×105 5.2×10 5 8.2×105 8.2×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10

시험항목Test Items 초기농도
(CFC/mL)
Initial concentration
(CFC/mL)
24시간 후 농도
(CFC/mL)
Concentration after 24 hours
(CFC/mL)
세균감소율(%)Bacterial reduction rate (%)
대장균Coli BLANKBLANK 2.7×104 2.7×10 4 8.9×104 8.9×10 4 99.999.9 항균제 처리Antibacterial treatment 1.7×104 1.7×10 4 <10<10 황색포도상구균Staphylococcus aureus BLANKBLANK 1.3×104 1.3×10 4 7.2×104 7.2×10 4 99.999.9 항균제 처리Antibacterial treatment 1.3×104 1.3×10 4 <10<10 살모넬라Salmonella BLANKBLANK 1.2×105 1.2×10 5 9.0×105 9.0×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10 녹농균Pseudomonas aeruginosa BLANKBLANK 2.2×105 2.2×10 5 8.2×105 8.2×10 5 99.999.9 항균제 처리Antibacterial treatment -- <10<10

측정 결과, 상기 표 1 내지 표 4를 통해 확인되는 바와 같이, 모든 실시예에서 99.99%의 항균력을 나타내었다.As a result of the measurement, as confirmed through Tables 1 to 4, the antimicrobial activity of 99.99% was exhibited in all examples.

[시험예 2][Test Example 2]

[ 흡수성 시험 ][Absorption test]

수용성 하이드로 화이버로 운드드레싱 샘플을 제작하여(5cm×5cm) 페트리디쉬에 놓고 무게(W1)을 잰다. 37(±1) ℃로 데워진 증류수를 ±0.5 g 까지 정확하게 측정한 후, 상기 시료의 흡수력을 고려하여 시료 무게의 40 배를 첨가한다.A round dressing sample was prepared with water-soluble hydrofiber (5cm×5cm), placed in a petri dish, and weighed (W 1 ). After accurately measuring distilled water warmed to 37 (±1) °C to ±0.5 g, 40 times the weight of the sample is added in consideration of the absorption power of the sample.

그리고 37(±1) ℃ 항온기에서 30 분 동안 방치한 후 핀셋을 이용해 운드드레싱 샘플을 30초간 매단 후 무게(W2)를 측정하여 아래의 계산식을 이용하여 흡수량을 측정한다. 결과는 다음 표 5와 같다.Then, after leaving it in a thermostat at 37 (±1) °C for 30 minutes, hang the round dressing sample for 30 seconds using tweezers, measure the weight (W 2 ), and measure the amount of absorption using the following calculation formula. The results are shown in Table 5 below.

흡수량 = (W2 - W1/W1) × 100Absorption amount = (W 2 -W 1 /W 1 ) × 100

여기서, W1 : 초기무게(g)Here, W 1 : Initial weight (g)

W2 : 30분 후 운드드레싱 샘플 무게(g)W 2 : Wound dressing sample weight after 30 minutes (g)

흡수량 단위: % Absorption amount unit:%

구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 W1(g)W 1 (g) 0.640.64 0.640.64 0.630.63 0.640.64 W2(g)W 2 (g) 12.9412.94 10.9010.90 12.412.4 11.5211.52 흡수량(%)Absorption (%) 19221922 16031603 18681868 17001700

[시험예 3][Test Example 3]

[ 지혈 특성 시험 ][Hemostasis Characteristics Test]

체중 250 ~ 300 g 사이의 흰쥐 9 마리를 실험하였다. A 군은 본 발명의 수용성 하이드로화이버(실시예 4)로 만들어진 운드드레싱을 실험군으로, B 군은 양성대조군으로 기존 폼형태의 드레싱제(메디폼)으로 C군은 음성대조군으로 기존에 시판중인 살균된 거즈를 사용하여 드레싱을 하였다.Nine rats weighing between 250 and 300 g were tested. Group A is an experimental group using the round dressing made of the water-soluble hydrofiber of the present invention (Example 4), Group B is a positive control group, a dressing agent in the form of an existing foam (Mediform), and Group C is a negative control group. Dressing was done using gauze.

시험부위에 수술용 칼로 창상을 1.0×1.0(cm)크기로 내어 출혈을 시키고 각각 드레싱 1.5×1.5(cm)로 잘라 출혈부위에 대고 덮은 뒤 200 g의 추를 올려 지혈되는 시간을 30 초, 60 초, 90 초, 90 초이상(실패)로 4가지 항목을 보았다. 각각 5 마리씩 실험을 하였다.(표 6)Cut the wound into a size of 1.0×1.0(cm) with a surgical knife on the test site, cut it into 1.5×1.5(cm) dressings, cover it on the bleeding area, and then put a 200 g weight to stop the bleeding time for 30 seconds and 60 I saw 4 items in seconds, 90 seconds, and over 90 seconds (failure). Each of 5 animals was tested (Table 6).

구분division 30 초30 seconds 60 초60 seconds 90 초90 seconds 90 초 이상More than 90 seconds A군(실험군)Group A (experimental group) 1One 33 1One 00 B군(양성대조군)Group B (positive control group) 1One 33 1One 00 C군(음성대조군)Group C (negative control group) 00 1One 1One 33

상기 표 5에서 확인되는 바와 같이, 90 초 이상은 실패로 보고 실험군은 지혈율 100 %, 양성대조군은 100 %, 음성대조군은 40 %의 결과가 나왔다.As can be seen in Table 5, more than 90 seconds were reported as failure and the experimental group had a hemostatic rate of 100%, the positive control group 100%, and the negative control group 40%.

본 발명의 수용성 하이드로화이버 창상피복제는 혈액이 방출되면 신속히 겔을 형성하면서 혈액을 흡수하고 도포된 하이드로화이버의 겔화에 의한 신속한 막을 형성하여 키토산의 양이온이 적혈구 표면의 음이온과 결합되면서 신속하게 지혈되는 것으로 판단하였다.The water-soluble hydrofiber wound coating agent of the present invention quickly forms a gel when blood is released, absorbs blood, and forms a rapid membrane by gelation of the applied hydrofiber, so that cations of chitosan are combined with anions on the surface of red blood cells, thereby bleeding rapidly. Was judged.

본 발명에 따른 수용성 하이드로화이버와, 이를 이용하여 제조된 운드드레싱은 급성, 만성 상처, 심각하게 훼손된 상처와 감염된 상처의 삼출물을 신속하게 흡수하고 습윤 환경을 유지하며 항균력, 신속한 지혈과 창상치유 상승효과를 갖는 고흡수성 외과용 드레싱제로서 산업상 이용가능성이 크다.The water-soluble hydrofiber according to the present invention, and the wound dressing manufactured using the same, rapidly absorb exudate from acute and chronic wounds, severely damaged wounds and infected wounds, maintain a moist environment, and have antimicrobial properties, rapid hemostasis and wound healing synergistic effect As a superabsorbent surgical dressing agent having a high industrial applicability.

Claims (5)

면 또는 레이온으로 이루어진 섬유로 직조된 부직포를 그대로 카르복실화하여 수득한 순수한 수용성 카르복실화 하이드로화이버 부직포를 이용하는 항균성 하이드로화이버 부직포 제조방법에 있어서,
키토산 용액에 알루미늄화합물, 아연화합물, 은화합물 또는 코발트화합물 중 선택되는 어느 1종 이상의 금속을 첨가하고 용해시켜 키토산-금속 혼합용액을 제조하는 단계(S10)와,
상기 키토산-금속 혼합용액 내에 상기 카르복실화 하이드로화이버 부직포를 35 ~ 45 ℃에서 2 분 ~ 10 분 동안 침적, 반응시켜 가교와 동시에 항균성을 부여하는 단계(S20)와,
항균성을 부여한 부직포를 탈수한 후, 물과 에탄올의 혼합용액에 상기 탈수과정을 거친 부직포를 침적한 후 탈수하는 과정을 2 ~ 4회 반복하는 단계(S30)를 포함하는 것을 특징으로 하는 수용성 하이드로화이버 부직포 제조방법.
In the antibacterial hydrofiber nonwoven fabric manufacturing method using a pure water-soluble carboxylated hydrofiber nonwoven fabric obtained by carboxylating the nonwoven fabric woven with fibers made of cotton or rayon as it is,
A step (S10) of preparing a chitosan-metal mixed solution by adding and dissolving at least one metal selected from an aluminum compound, a zinc compound, a silver compound, or a cobalt compound to the chitosan solution; and
The step of immersing and reacting the carboxylated hydrofiber nonwoven fabric in the chitosan-metal mixed solution at 35 to 45° C. for 2 to 10 minutes to give crosslinking and antibacterial properties at the same time (S20),
A water-soluble hydrofiber comprising the step (S30) of dehydrating the nonwoven fabric with antimicrobial properties, immersing the nonwoven fabric subjected to the dehydration process in a mixed solution of water and ethanol, and repeating the dehydration process 2 to 4 times (S30). Non-woven manufacturing method.
청구항 1에 있어서,
키토산 용액은 분자량이 5 만 내지 20 만인 키토산을 물과 에탄올의 혼합 용액에 용해시키되, 상기 키토산의 농도가 0.5 wt% ~ 3.0 wt%가 되도록 용해시키는 것을 특징으로 하는 수용성 하이드로화이버 부직포 제조방법.
The method according to claim 1,
Chitosan solution is a method for producing a water-soluble hydrofiber nonwoven fabric, characterized in that dissolving chitosan having a molecular weight of 50,000 to 200,000 in a mixed solution of water and ethanol, and dissolving the chitosan concentration to be 0.5 wt% to 3.0 wt%.
청구항 1에 있어서,
금속의 사용량은 부직포의 카르복실기에 대하여 동몰 내지 1/32몰의 범위 내인 것을 특징으로 하는 수용성 하이드로화이버 부직포 제조방법.
The method according to claim 1,
A method for producing a water-soluble hydrofiber nonwoven fabric, characterized in that the amount of metal is in the range of equal to 1/32 mole with respect to the carboxyl group of the nonwoven fabric.
청구항 1에 있어서,
금속의 사용량은 키토산의 아민기에 대하여 동몰 내지 1/32몰의 범위 내인 것을 특징으로 하는 수용성 하이드로화이버 부직포 제조방법.
The method according to claim 1,
A method for producing a water-soluble hydrofiber nonwoven fabric, characterized in that the amount of metal is in the range of equimolar to 1/32 mol with respect to the amine group of chitosan.
청구항 1 내지 청구항 4 중 선택되는 어느 한 항의 제조방법을 통해 제조된 수용성 하이드로화이버를 원하는 규격에 맞게 재단한 것을 특징으로 하는 운드드레싱.



Wound dressing, characterized in that the water-soluble hydrofiber manufactured through the manufacturing method of any one of claims 1 to 4 is cut to a desired standard.



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