201219067 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種皮膚傷口癒合材料及其製造方法，特別是關 於一種雙親性（amphiphilic)含氟高分子之皮膚傷口癒合材料及其製造 方法。 【先前技術】 皮膚的總表面積約1.5〜2.0平方公尺’它可以保持人體的溫度及 水分，避免受到細菌及外界環境的傷害。皮膚依構造可區分為表皮、 真皮及皮下組織。當皮膚受到傷害時便產生傷口，傷口發生至癒合的 過程可分為三階段：發炎期（phase )、纖維增生期 (fibroplasia phase)、成熟期（maturation or remodeling phase)。這三個 階段的過程順利與否則決定了傷口能完好癒合、抑或是復原不良、狀 況更加惡化。 傷口敷料需要具有（1)加速傷口癒合、（2)材料必須讓患者感到 猶如皮膚般的舒適、（3)癒合後的疤痕越少越好之功能。 最常見的傷口敷料為紗布（cotton gauze)等傳統紡織敷料，但是 這種敷料只是暫時性覆蓋材料，需常更換。目前市售的敷料，可分為 不具封閉性以及具有封閉性（〇cclusive)或半封閉性之敷料。不具封閉 性敷料，例如由含有如明谬（gelatin)、多膽類（p〇lysaccharides)等親 水性聚合物構成之树（hydrQgd)，其具有雜分崎（α處e)的 功能’市售商品例如Vigil〇n (CRBard，USA)。另一方面，封閉性敷料 通常由薄的可撓性薄膜（thin flexible membrane )構成，例如聚胺醋 (polyurethane) ’再加上黏著披覆層，可限制水從傷口表面揮發，傷口 保持濕潤’市售商品例如TegadermTM (3M，USA)商品。半封閉性敷 料’比賴性敷料具有較高的揮發速率，所以傷口表面為半乾狀態， 201219067 市售商品例如 Omiderm (latroMedical Systems,UK)。 再者’具有吸收功能的封閉性敷料，例如市售TegasorbTM( 3M，USA， US patentNo. 4,952,618)、DuodermTM (Convatec，UK)，其為水狀膠體 " 敷料（hydrocdloid办㈣啤），由水狀膠體粒子嵌入疏水性基質所構成， - 通常這些敷料是層合於封閉性薄膜或發泡塑膠層上。這些商品通常用 來處理慢性傷口潰瘍，但是研究顯示這些水狀膠體敷料，雖然可在短 時間加速傷口癒合，附帶地有慢性發炎或生成的皮膚粗糙等現象。 關於水狀膠體敷料，例如美國專利第4,952,618號（us patent N〇. • 4,952,618by3M，USA)揭露水狀麵#著«物，纟水& 膠體粒子之橡膠似的彈性體’其中至少—部分為聚正離子水狀膠體粒 子使用成丁質蘋果g文鹽或楚胺酸鹽（chit〇san ma〗ate或giutamate )作 為正離子水狀膠體粒子，橡膠似的彈性體為聚異丁烯 (polyisobutylene) ’水狀膠體的背襯為多孔性聚乙婦或聚胺醋，背觀的 濕蒸氣透過率（moisture vaportransmission rate) MVTR 為 500g/m2/day (於40C、8G%濕度差），但是使用如此的聚乙埽或聚胺醋之缺點是 薪、不抗菌，且透氣性不佳。 • ^目此，評估這些敷料對傷口的功效，主要在於生物相容性、以及 疋否能促進皮膚上皮化（epithelizati〇n),減少傷口排斥與發炎反應。目 別並沒有完美無瑕的商品，在使用這錄料時，考慮傷口狀況、醫療 花費及產品價格’以最經财效的方法制最㈣效果，對於傷口魔 合之研發方向’期望使傷口的癒合變成再生而非修補，提供無症痕組 織的皮膚再生。 【發明内容】 繁於上述之發明背景中，為了符合產業上之要求，本發明 提供-種皮膚傷口癒合材料及其製造方法，特別是提供一種雙親性皮 膚傷口癒合材料。 201219067 本發明之目的之-，是在提供—種皮膚傷口癒合材料使 卜，j面，可具有透氣、保水氣、防水、抗g、抗凝血的特性。因 具有抗菌性質，使傷口癒合過程中不會感染發炎，亦具有可同時 傷口潤濕及透紐質。本發縣由特定材料紐於财㈣料表面及 調整皮膚傷讀合㈣之貼近傷σ的表面之脉_肖在特定的範 圍’不僅可使傷Π加速癒合，料留缝，達職化細的目標。調201219067 VI. Description of the Invention: [Technical Field] The present invention relates to a skin wound healing material and a method of manufacturing the same, and more particularly to an amphiphilic fluoropolymer skin wound healing material and a method of manufacturing the same . [Prior Art] The total surface area of the skin is about 1.5 to 2.0 square meters. It maintains the temperature and moisture of the human body and is protected from bacteria and the external environment. The skin can be distinguished by the structure as the epidermis, the dermis and the subcutaneous tissue. Wounds are created when the skin is damaged, and the process from wound to healing can be divided into three phases: the phase, the fibroplasia phase, and the maturation or remodeling phase. The three stages of the process went smoothly and otherwise determined that the wound could heal properly, or that the recovery was worse and the condition worsened. Wound dressings need to have (1) accelerated wound healing, (2) materials that must be perceived as comfortable by the patient, and (3) less scars after healing. The most common wound dressings are traditional textile dressings such as cotton gauze, but such dressings are only temporary covering materials and need to be replaced frequently. Currently available dressings can be divided into dressings that are not closed and have a closed or semi-closed nature. A non-sealing dressing, for example, a tree (hydrQgd) composed of a hydrophilic polymer such as gelatin or p〇lysaccharides, which has a function of a heterogeneous (α at e) 'commercially available Commodities such as Vigil〇n (CRBard, USA). Closed dressings, on the other hand, are usually composed of a thin flexible membrane, such as polyurethane' plus a sticky coating that limits the evaporation of water from the wound surface and keeps the wound moist. Commercial goods such as TegadermTM (3M, USA) are commercially available. The semi-hermetic dressing has a higher rate of volatilization than the dressing, so the wound surface is semi-dry, 201219067 commercial item such as Omiderm (latroMedical Systems, UK). Further, 'a sealing dressing having an absorbent function, such as commercially available TegasorbTM (3M, USA, US patent No. 4, 952, 618), DuodermTM (Convatec, UK), which is a hydrocolloid " dressing (hydrocdloid (four) beer), by water The colloidal particles are embedded in a hydrophobic matrix, and typically these dressings are laminated to a closed film or a foamed plastic layer. These products are commonly used to treat chronic wound ulcers, but studies have shown that these hydrocolloid dressings can accelerate wound healing in a short period of time, incidentally with chronic inflammation or rough skin formation. With regard to hydrocolloid dressings, for example, U.S. Patent No. 4,952,618 (us patent N., 4,952,618 by 3M, USA) discloses a water-like surface of a rubber-like elastomer of colloidal particles. For the polypositron hydrocolloid particles, a chitin apple g-salt or a sulphate (chit〇san ma ate or giutamate) is used as the positive ion hydrocolloid particles, and the rubber-like elastomer is polyisobutylene. The backing of the hydrocolloid is a porous polymethylene or polyamine vinegar, and the moisture vapor transmission rate MVTR is 500g/m2/day (at 40C, 8G% humidity difference), but the use is so The disadvantages of polyacetamidine or polyamine vinegar are salary, non-antibacterial, and poor gas permeability. • To assess the efficacy of these dressings on wounds, mainly in terms of biocompatibility and whether it promotes skin epithelialization and reduces wound rejection and inflammatory response. There is no perfect product in the eyes. When using this material, consider the wound condition, medical expenses and product price. The most economical method is to make the most (four) effect, and the development direction of the wound magic is 'expected to make the wound. Healing becomes regeneration rather than repair, providing skin regeneration without diseased tissue. SUMMARY OF THE INVENTION In the context of the above-described invention, in order to meet the industrial requirements, the present invention provides a skin wound healing material and a method of manufacturing the same, and more particularly to providing an amphipathic skin wound healing material. 201219067 The object of the present invention is to provide a skin wound healing material, which has the characteristics of venting, water retention, water resistance, anti-g, and anti-coagulation. Due to its antibacterial properties, it will not cause inflammation during wound healing, and it can also moisturize and penetrate the wound at the same time. This county is made up of specific materials, such as Niu Caicai (4) material surface and adjustment of skin injury and reading (4). The surface of the surface of the wound σ is _ _ in a specific range 'can not only accelerate the healing of the scar, the material remains seam, the job is fine The goal. Tune
整皮膚傷Π癒合材料之貼近傷π絲面之對水的觸肖在較的範圍 之方法’可於該貼近傷D的表面上，接枝共聚合生物相容性高分子， 以_調㈣水的接觸角’其中該生物相容性高分子可包含2種型態 的高分子，即不具有帶電基團與含有雙離子性或擬雙離子性 (zwitteric)nieOTpseud㈣itteriQni〇基團之高分子，較理想為含有雙離 子性或擬雙離子性基團之高分子。 本發明之目的之-’是在提供一種皮膚傷口癒合材料之製造方 法，藉由f壓電漿處理’使生物姆性高分子紐共聚合於含敦薄膜 的表面，可以製造具有魏、保械、防水、誠、抗凝血的特性之 皮膚傷口瘡合材料。 3氟薄膜在本質上為疏水性，對微生物、細菌、微粒狀物質等為 有=的阻絕材料’且具有透氣性但液體不通透性，氧氣透過率為500 g/m/day aji (MVTR {i(m〇isture vap〇r transmission rate) ； ASTM E96 80) ’因此使用表面接枝高分子之含氟薄膜，除可利用上述含氟薄 膜的，性’再加上接枝高分子的特性，作為皮膚傷口癒合材料，可具 有透氣、保水氣、防水、抗菌、抗凝血的特性。 人一本發明之一特徵在於提供一種皮膚傷口癒合材料，其包含：一 3亂疏水性薄膜，具有相對的一第一表面及-第二表面，該疏水性薄 膜具有透氣性但雜顿·;至少—生物相雜高奸，共價鍵結⑴ 201219067 =於該疏水性_的該第—表面之—部分；其中該職有生物相容 子的f表面之對水的接觸_ 4Q度町。該鈔—生物相容 子為選自不具有帶電基團之高分子、含有雙離子性基團之高分 子及含有擬雙軒絲社高分顿_中的至少一種。 . 本發明之另—特徵在於提供-種皮贿π癒合材料之製造方The skin lesion healing material is close to the injury π silk surface of the water in the range of the method of 'can be applied to the surface of the near wound D, graft copolymerization of biocompatible polymer, to _ t (4) The contact angle of water, wherein the biocompatible polymer may comprise two types of polymers, that is, a polymer having no charged group and a diionic or pseudo-ionic (nie) nieOTpseud (tetra)itteriQni〇 group. It is preferably a polymer containing a diionic or pseudoionic group. The object of the present invention is to provide a method for manufacturing a skin wound healing material, which can be manufactured by f-piezoelectric slurry treatment to co-polymerize a biomolecular polymer on a surface of a film containing a film. A skin wound sore material that is waterproof, honest, and anticoagulated. The 3 fluorine film is hydrophobic in nature, and is a resisting material for microorganisms, bacteria, particulate matter, etc., and has gas permeability but liquid impermeability, and oxygen permeability is 500 g/m/day aji (MVTR) {i(m〇isture vap〇r transmission rate) ; ASTM E96 80) 'Therefore, a fluorine-containing film of a surface-grafted polymer is used, in addition to the properties of the above-mentioned fluorine-containing film, plus the characteristics of the graft polymer As a skin wound healing material, it can have the characteristics of venting, water retention, water repellency, antibacterial and anticoagulation. One of the features of the present invention is to provide a skin wound healing material comprising: a 3 hydrophobic film having a first surface and a second surface, the hydrophobic film having gas permeability but being mixed; At least - biologically mixed, covalently bonded (1) 201219067 = part of the first surface of the hydrophobic _; wherein the surface of the f-synthesis of the biocompatible sub-water contact _ 4Q degrees. The banknote-biocompatible is at least one selected from the group consisting of a polymer having no charged group, a high molecular group containing a diionic group, and a high-density group containing a pseudo-xanthene group. Another feature of the present invention is to provide a manufacturer of a skin bribe π healing material.
法，其包含··提供—疏水性薄膜，具有相對的-第-表面及-第二I =，該疏水性賴具概但㈣不通透性；塗佈—生物相容性高 i子先驅體溶液於該疏水性薄膜之第-表面；進行-乾燥程序，乾燥 • 該第—表面上之該塗有生物相容性高分子先驅體溶液’·以及對該乾燥 觸塗有生物相容性高分子先驅體溶液之疏水性薄媒，進行常壓電聚 處理，接枝魅物相高好難财第—表面，使該疏 水性溥膜的第一表面成為親水性表面，第一表面對水的接觸角小於仙 度，更理想為20〜30度。 於上述皮膚傷口癒合獅讀造方財，麵佈高好先驅體溶 液則，該疏水性薄膜之第一表面可先進行表面活化處理。 、，综上所述，本發明揭露了 一種皮膚傷口癒合材料及其製造方 參 法1、優點在於藉由使用表面接枝高分子之含氟薄膜，除可利用上 述含氟薄膜的特性，再加上接枝高分子的特性，作為皮膚傷口癒合材 料，可具有透氣、保水氣、防水、抗菌、抗凝血的特性，此外皮膚傷 口癒合材料之觀方法，藉由傾„纽進行接枝聚合，可達成低 價量產之效果。據此，本發明能符合經濟上的效益與產業上的利 用性〇 【實施方式】 本發明在此揭示-種皮膚傷口癒合材料及其製造方法。為了 能徹底地瞭解本發明，將在下列的描述巾提出詳盡的轉及其⑸ 201219067 習的特殊A Μ ” 細節中， 組成。顯然地’本發明的施行並未限定於該領域之技a method comprising: providing a hydrophobic film having a relative -first surface and - a second I =, the hydrophobic property being substantially (4) impervious; coating - biocompatible high i precursor The body solution is on the first surface of the hydrophobic film; performing a drying process, drying the biocompatible polymer precursor solution on the first surface, and biocompatibility to the dry touch The hydrophobic thin medium of the polymer precursor solution is subjected to the constant piezoelectric polymerization treatment, and the grafted charm phase is high and difficult, and the first surface of the hydrophobic ruthenium membrane becomes a hydrophilic surface, and the first surface is The contact angle of water is less than the centimeter, more preferably 20 to 30 degrees. In the above skin wound healing lion reading and making money, the surface of the first film of the hydrophobic film can be surface-activated first. In summary, the present invention discloses a skin wound healing material and a method for producing the same, which is advantageous in that, by using a fluorine-containing film of a surface-grafted polymer, in addition to utilizing the characteristics of the above-mentioned fluorine-containing film, In addition to the characteristics of the grafted polymer, as a skin wound healing material, it can have the characteristics of venting, water retention, water repellency, antibacterial, anticoagulant, and the method of skin wound healing material, by grafting polymerization According to the present invention, it is possible to achieve economical benefits and industrial applicability. [Embodiment] The present invention discloses a skin wound healing material and a method for producing the same. A thorough understanding of the present invention will be made in the detailed description of the following description of the towel and its special details of (5) 201219067. Obviously, the implementation of the present invention is not limited to the technology in the field.
智的娃破，…Μ ^ ^ Ρίτ I -个質明的較佳實施 詳細描述之外，本發明還可 且本發明的範圍不受限定， 例會詳細描述如下’然而除了這些 以廣泛地施行在其他的實施例中， 其以之後的專利範圍為準。 本發明之皮雜π癒合漏為-機紐材料，贼皮膚 為親水性’暴露於錢的表面（無近皮膚的表面械的表面 • 水性。第一圖⑷表示皮膚傷口癒合材料的結構之上視圖，第—圖(b)i .示其剖面圖。第-圖(b)的上方為疏水側或遠離傷口側，⑼的下方 水側或貼近傷口側。藉由調整皮膚傷σ癒合材料之貼近傷口的表面 對水的接觸角在特定的顧，不僅可使傷口加速癒合，且不留范痕， .該方法係於該貼近傷口的表面上，接枝共聚合生物相容性高分子，以 達到調整對水的接觸角，其中該生物相容性高分子可包含2種型態的 问分子’即不具有帶電基團與含有雙離子性或擬雙離子性基團之高八 子。 w # 本發明之第一實施例揭露-種皮膚傷口療合材料，其包含：-含 I疏水性細’具有相對的__第__表@及—第二表面，該疏水性薄膜 具有透氣性但賴不通透性；至少—生物相容性高分子，共價鍵結形 f於該疏水性薄膜的該第—表面之—部分；其中該形成有生物相容性 向分子的第-表面之對水的接觸角為4G度以τ，更理想為1G〜40度， 更加理想為20〜30度。對水的接觸角為2〇〜30度時，不留症痕的效 果更佳。而第二表面為疏水性，其對水的接觸角為1〇〇度以上。 上述實施例中’該至少一生物相容性高分子為選自不具有帶電 基團之高分子、含有雙離子性基團之高分子及含有擬雙離子性基圈之 尚刀子所成群中的至少—種，例如甲基丙稀酸聚乙二醇酿邮咖⑸ 201219067 glycol methacrylate; PEGMA )及曱基丙稀酸聚續酸甜菜驗 (polysulfobetaine methacrylate; PSBMA)。其中，甲基丙稀酸聚乙二醇 酯為不具有帶電基團的例，甲基丙烯酸聚磺酸甜菜鹼為含有雙離子性 基團之例。該擬雙離子性基團之高分子為帶正電基團與帶負電基團以 莫耳比1 : 1的比例聚合所成。 上述帶正電基團，例如為The wisdom of the baby is broken, ... Μ ^ ^ Ρίτ I - a detailed description of the preferred embodiment of the invention, and the scope of the invention is not limited, and the examples will be described in detail below. In other embodiments, it is subject to the scope of the patents that follow. The skin π-healing leakage of the present invention is a mechanical material, and the skin of the thief is hydrophilic. The surface exposed to money (the surface of the surface mechanical surface without near skin). The first figure (4) indicates the structure of the skin wound healing material. View, Fig. (b) i. shows its sectional view. The top of Fig. (b) is the hydrophobic side or away from the wound side, the lower side of the water side of (9) or close to the wound side. By adjusting the skin injury σ healing material The contact angle of the surface close to the wound to the water is not only to accelerate the healing of the wound, but also to leave no traces. The method is based on the surface of the wound adjacent to the graft copolymerized biocompatible polymer. In order to achieve an adjustment of the contact angle to water, wherein the biocompatible polymer may comprise two types of molecules, ie, no charged groups and high eight-ionic or pseudo-diionic groups. The first embodiment of the present invention discloses a skin wound healing material comprising: - containing I hydrophobic fine 'having a relative ____ table @ and - a second surface, the hydrophobic film having gas permeability But it is not permeable; at least - biocompatible polymer a covalent bond f is a portion of the first surface of the hydrophobic film; wherein the contact angle of the water forming the first surface of the molecule to the surface of the molecule is 4 G degrees to τ, more preferably 1 G 〜 40 degrees, more desirably 20 to 30 degrees. When the contact angle to water is 2 〇 to 30 degrees, the effect of leaving no symptoms is better. The second surface is hydrophobic, and its contact angle with water is 1〇. In the above embodiment, the at least one biocompatible polymer is selected from the group consisting of a polymer having no charged group, a polymer containing a diionic group, and a knife containing a pseudo-ionic base. At least one species in the group, such as methacrylic acid PEG PEG (5) 201219067 glycol methacrylate; PEGMA) and polysulfobetaine methacrylate (PSBMA). Among them, the polyethylene glycol methacrylate is an example having no charged group, and the polysulfonic acid betaine methacrylate is an example containing a diionic group. The polymer of the pseudo-ionic group is formed by polymerization of a positively charged group and a negatively charged group at a molar ratio of 1:1. The above positively charged group, for example
CH, H2C^ (λ 0 Η2 NHcCH, H2C^ (λ 0 Η2 NHc
8 201219067 h2c- H2 上述帶負電基團，例如為 〇 OH C I o 以 ch3 I h2 H2C#C>Xrr^〇\c/C、 08 201219067 h2c- H2 The above negatively charged group, for example 〇 OH C I o to ch3 I h2 H2C#C> Xrr^〇\c/C, 0
-S — OK H2 h2 6 及 o o-S — OK H2 h2 6 and o o
於一實施例中，該至少一生物相容性高分子在該第一表面接枝共 聚合。在第一表面之該形成有生物相容性高分子的部分，於生物相容 f兩力子為甲基丙稀酸聚乙一醇g旨（polyethylene glycol methacrylate; PEGMA)的情況，發現其接枝密度為0.03 mg/cm2以上0.2 mg/cm2以 下時’成為皮膚傷口癒合材料之效果佳。於生物相容性高分子為甲基 丙稀酸聚續酸甜菜驗（p〇lysulf〇betainemethacrylate;pSBMA)的情況， 其接枝密度為_ mgW以上〇.2 mg/em2以下，皮絲口瘡合材 料之效果佳。 上述皮膚傷口癒合材料進行細菌（例如大腸桿菌、上皮葡萄球菌） 吸附試驗時’吸附於第-表面的細目為1%以下。上述皮膚傷口癒 合材料進行蛋白質吸附試驗時，吸附於第—表面的蛋白f數目為⑼二 下。 上述含氟疏水性薄膜為聚四氟乙稀（PTFE)或聚偏二氣乙稀 (P卿），其氧氣透過率(〇xygenpermeab卿)至少為 ^m2/day/atm 以上。上述含氟疏水性薄膜的厚度，例如為ι〇〜卿，較理想為扣 〜300叫^更理想為50〜15〇 μπι。 關於生物姆性高分子職於該疏水性薄商第—表面之方法， 由於親水性物質與疏雜歸以鱗結合，所Μ舰計特殊的方In one embodiment, the at least one biocompatible polymer is graft copolymerized on the first surface. The portion of the first surface on which the biocompatible polymer is formed is found to be grafted when the biocompatible f is a polyethylene glycol methacrylate (PEGMA). When the density is 0.03 mg/cm2 or more and 0.2 mg/cm2 or less, it is effective as a skin wound healing material. When the biocompatible polymer is p〇lysulf〇betainemethacrylate (pSBMA), the grafting density is _mgW or more 〇.2 mg/em2 or less, and the skin is sore. The effect of the material is good. When the skin wound healing material is subjected to an adsorption test of bacteria (e.g., Escherichia coli or S. epidermidis), the amount of adsorption to the first surface is 1% or less. When the above skin wound healing material was subjected to a protein adsorption test, the number of proteins f adsorbed on the first surface was (9) two. The fluorine-containing hydrophobic film is polytetrafluoroethylene (PTFE) or polyvinylidene chloride (P), and has an oxygen transmission rate (〇xygenpermeab) of at least ^m2/day/atm. The thickness of the above-mentioned fluorine-containing hydrophobic film is, for example, ι〇~卿, and more desirably, it is preferably from 50 to 15 μm. Regarding the method in which the bio-molecular polymer acts on the hydrophobic thin-mersed surface, since the hydrophilic substance is combined with the impurity and the scale, the special method of the ship is calculated.
I 201219067 式使這兩種物f結合，根據本發明之製造方法，藉由將疏水性薄 表面活性化’湘電漿或躲處轉方法，再輯電輯導聚合反應， 而達成親水性高分子化學鍵結_疏水性_的表面上之效果。^ • 本發歡.實_揭露—歡膚如癒合材料之製造方法，盆 - &含：提供-疏水性細，具有相朗-第-表面及—第二表面，ς 疏水性薄膜具有透氣性但㈣不職性；塗佈—生物姆性高分子先 驅體溶液於該疏水性薄膜之第一表面；進行一乾燥程序，乾燥該第一 表面上之錄有生物相容性高分子先驅齡液；以及對練燥過的塗 • 有生物相容性高分子先驅體溶液之疏水性薄媒，進行常壓電漿處理， 触該生物相容性高分子於該疏水性薄朗第—表面，使該疏水性薄 膜的第-表面成為親水性表面，第一表面對水的接觸角小於4〇度，更 理想為10〜40度，更加理想為2〇〜3〇度。 上述實施财，含驗水性_為聚讀乙稀（pTFE)或聚偏二 氟乙烯（PVDF)，其氧氣透過率（〇辦如peme祕以）至少為娜 CC/m2/day/atm以上。上述含氟疏水性薄膜的厚度，例如$ 1〇〜叫， 較理想為30〜300 μιη，更理想為5〇〜15〇 μιη。 • 肖至少一生物相容性高分子為選自不具有帶電基團之高分子、含 有雙離子性基團之高分子及含有擬雙離子性基團之高分子所成群中的 至少一種’該至少一生物相容性高分子包含選自下列族群之一者及 其任意組& ·甲基丙稀酸聚乙二醇g旨(P〇lyethylenegiyc〇lmethacrylate; PEGMA) (polysulfobetaine methacrylate; PSBMA)。 該第-表㈣水的接觸肖隨該常壓電漿處理的時間之增加而減 少。該第-表面對水的接觸角為4〇度以下，較理想為2〇〜3〇度。於 -實施例中’上述常壓電衆處理可使用氬氣電襞進行處理，例如功率 10 201219067 本發明之第三實施例揭露一種皮膚傷口癒合材料之製造方法，於 上述第二實施例的皮膚傷口癒合材料之製造方法中，在塗佈高分子先 驅體溶液前，該疏水性薄膜之第一表面可先進行表面活化處理。對該 第一表面進行表面活化處理可為低壓電梁處理或臭氧處理。於一實施 • 例，上述常壓電漿處理可使用氬氣電漿進行處理，處理時間為60秒以 上。另外，上述低壓電漿處理可使用氬氣電漿進行處理，處理時間為 60秒以上。 Φ 範例一.製備PTFE_g_ PEGMA/SBMA/SA/TM之皮膚傷口癒合材料 第二圖表示根據本發明的皮膚傷口癒合材料之製造方法的流程 圖。使用PTFE薄膜作為疏水性薄膜，分別製備PTFE (聚四氟乙烯） 薄膜表面接枝(a)PEGMA (甲基丙稀酸聚乙二醇酯）；（b)sBMA (甲基 丙烯酸聚磺酸甜菜鹼）；（c) SA(3-確酸丙基甲基丙烯酸卸鹽）；及(d)T]VI (甲基丙烯醯氧乙基三甲基氯化銨），其中(c)及(d)為比較對照組。各 PTFE薄膜的第一表面為惰性疏水表面。分別將各pTFE薄膜放置於真 空中’以氣氣電漿處理（功率l5〇W ’ 60秒）後，於4〇°c下暴露於大 φ 氣10分鐘，塗佈3〇wt%之PEGMA (或SBMA、SA、TM)水溶液於 PTFE薄膜的第-表面上，乾燥後，在常壓下進行氮氣電聚處理（處理 時間為5、I5、3〇、6〇或12〇秒），於第一表面上產生電漿誘導接枝聚 合’分別使PEGMA/SBMA/SA/TM共價鍵結於各PTFE薄膜的第一表 面上。 第三圖表示製備PTFE薄膜表面接枝⑷pEGMA (甲基丙稀酸聚乙 二醇酯）及（b)SBMA (曱基丙烯酸聚磺酸甜菜鹼）（記為 PTFE_g-PEGMA/SBMA)時氬氣電漿處理時間與所得的接枝密度、接 觸角之關係圖。由第三圖得知，氬氣電漿處理時間對接枝密度、接觸 角的影響。所得的皮膚傷口癒合材料之接枝密度，有隨氬氣電焚處理⑸I 201219067 The combination of the two substances f, according to the manufacturing method of the present invention, by the hydrophobic thin surface activation of the 'Xiang electric pulp or hiding method, and then the electricity to guide the polymerization reaction, to achieve high hydrophilicity The effect on the surface of molecular chemical bonding _ hydrophobic _. ^ • 本发欢.实_揭露—Careful skin such as healing material manufacturing method, basin- & contains: provides - hydrophobic, with phase-first surface and - second surface, 疏水 hydrophobic film with breathable But (4) incompetence; coating-biomolecular polymer precursor solution on the first surface of the hydrophobic film; performing a drying process to dry the first surface of the biocompatible polymer precursor precursor And a hydrophobic thin medium having a biocompatible polymer precursor solution, which is subjected to a normal piezoelectric slurry to contact the biocompatible polymer on the hydrophobic thin surface-surface The first surface of the hydrophobic film is made to be a hydrophilic surface, and the contact angle of the first surface with respect to water is less than 4 degrees, more preferably 10 to 40 degrees, and still more preferably 2 to 3 degrees. The above-mentioned implementation, including water test _ is poly-ready (pTFE) or polyvinylidene fluoride (PVDF), and its oxygen transmission rate (such as peme secret) is at least Na / CC / m2 / day / atm. The thickness of the fluorine-containing hydrophobic film, for example, is preferably from 30 to 300 μm, more preferably from 5 to 15 μm. • At least one biocompatible polymer is at least one selected from the group consisting of a polymer having no charged group, a polymer containing a diionic group, and a polymer containing a pseudoionic group. The at least one biocompatible polymer comprises one selected from the group consisting of: & dimethyl methacrylate (PEGMA) (polysulfobetaine methacrylate; PEGMA) (polysulfobetaine methacrylate; PSBMA) . The contact of the water in the first-fourth (four) water is reduced as the time of treatment of the normal piezoelectric slurry increases. The contact angle of the first surface to water is 4 degrees or less, more preferably 2 to 3 degrees. In the embodiment, the above-mentioned constant piezoelectric treatment can be processed using an argon gas, for example, power 10 201219067. A third embodiment of the present invention discloses a method of manufacturing a skin wound healing material, the skin of the second embodiment described above. In the method for producing a wound healing material, the first surface of the hydrophobic film may be subjected to a surface activation treatment before the application of the polymer precursor solution. The surface activation treatment of the first surface may be low voltage electric beam treatment or ozone treatment. In one embodiment, the above-mentioned normal piezoelectric slurry treatment can be treated with argon plasma for a treatment time of 60 seconds or more. Alternatively, the low pressure plasma treatment described above may be treated with argon plasma for a treatment time of 60 seconds or more. Φ Example 1. Preparation of PTFE_g_PEGMA/SBMA/SA/TM Skin Wound Healing Material The second figure shows a flow chart of a method of manufacturing a skin wound healing material according to the present invention. Surface grafting of PTFE (polytetrafluoroethylene) film by using PTFE film as hydrophobic film (a) PEGMA (polyethylene glycol methacrylate); (b) sBMA (polyacrylic acid sulfonic acid beet) (c) SA (3-acid propyl methacrylate demineralized); and (d) T] VI (methacryloyloxyethyltrimethylammonium chloride), wherein (c) and d) is a comparison control group. The first surface of each PTFE film is an inert hydrophobic surface. Each pTFE film was placed in a vacuum atmosphere (treated by gas plasma (power l5 〇 W ' 60 seconds), exposed to large φ gas at 4 ° C for 10 minutes, and coated with 3 〇 wt% of PEGMA ( Or SBMA, SA, TM) aqueous solution on the first surface of the PTFE film, after drying, nitrogen electropolymerization treatment under normal pressure (treatment time is 5, I5, 3 〇, 6 〇 or 12 〇 seconds), Plasma induced graft polymerization on one surface 'covalently bonds PEGMA/SBMA/SA/TM to the first surface of each PTFE film, respectively. The third figure shows the preparation of PTFE film surface grafted with (4) pEGMA (polymethyl glycol methacrylate) and (b) SBMA (mercaptoacrylic acid polysulfonic acid betaine) (denoted as PTFE_g-PEGMA/SBMA) argon A plot of the plasma treatment time versus the resulting graft density and contact angle. From the third figure, the effect of argon plasma treatment time on graft density and contact angle is obtained. The graft density of the obtained skin wound healing material is treated with argon gas (5)
II 201219067 時間的增加而增加之趨勢，而對水接觸角有隨氬氣電漿處理時間的增 加而減少之趨勢。 第四圖表示原始 PTFE (raw)、PTFE-g-PEGMA 及 PTFE-g-SBMA 之傅立葉轉換紅外線（FTIR)光譜圖，其中1730cm·1的波峰表示c=〇 . 基團的吸收峰，1030 cn^的波峰表示_s=0基團的吸收峰。 以下進行PTFE-g- PEGMA/SBMA/SA/TM之皮膚傷口癒合材料的 特性測試。 蛋白質吸附試驗 # 使用纖維素原（flbrinogen)作為蛋白質，測試所製備的 PTFE-g-PEGMA/SBMA/TM/SA皮膚傷口癒合材料之吸附特性^第五圖 表示蛋白質（使用纖維素原(fibrinogen))吸附試驗的結果。其中，於橫 軸中，依序為#1_P 5/10/15/60/120 sec表示PEGMA接枝於PTFE表面， 處理 5/10/15/60/120 秒；#2-SBMA 5/10/15/60 sec 表示 SBMA 接枝於 PTFE 表面’處理 5/10/15/60 秒;SBMA 水膠(hydrogel);#2-SA 5/15/30/60 sec 表示 SA 接枝於PTFE 表面，處理 5/15/30/60 sec ; #2-TM 5/15/30/60 sec表示TM接枝於PTFE表面，處理5/15/30/60 sec ; PS表示聚砜。由 鲁 第五圖得知，表面接枝PEGMA、SBMA及SA之纖維素原吸附率較 TM低。 細菌吸附試驗 分別使用上皮葡萄球菌(S. epidermidis)及大腸桿菌(E. coli)，作為細 菌的例。第六圖表示細菌（使用上皮葡萄球菌(S.epidermidis))吸附試 驗的結果，第七圖表示細菌（使用大腸桿菌(E· coli))吸附試驗的結果， 其中#1 為 PTFE ; #2, #3, #4, #5, #6 為 PTFE-g-PEGMA，分別經過電漿 處理5/10/15/60/120 sec。由第六圖及第七圖的結果得知，表面接枝 PEGMA的PTFE與原始PTFE的表面比較，處理過的PTFE表面對細 菌的吸附率顯著地減少。 f 12 201219067 此外’對PTFE-g-SBMA進行細菌吸附試驗時，第八圖表示.細菌（使 用上皮葡萄球菌(S · epidermidis))吸附試驗的結果，第九圖表示細菌（使 用大腸桿菌(E_ coli))吸附試驗的結果，依序表示未處理之pTFE，扪 〜#4 為 PTFE-g-SBMA 5/15/30/60 sec，#5〜#8 為 PTFE-g-SA 5/15/30/60 sec ’及#9〜#12為PTFE-g-TM 5/15/30/60 sec。由第八圖及第九圖的結 果得知’表面接枝SBMA的PTFE與原始PTFE的表面比較，處理過 的PTFE表面對細菌的吸附率顯著地減少。 範例一雖然使用PTFE薄膜作為含氟疏水性薄膜，亦可使用pvdf 薄膜。 範例二：皮膚傷口瘡合材料之製造方法 以下’利用PVDF作為含氟疏水性薄膜之例，製造 之材料。第十圖表示製備PVDF-g-SBMA之皮膚傷口癒合材料之流程 圖。使用PVDE薄膜作為疏水性薄膜，先將pvDF薄膜進行低壓電漿 處理，活化表面後，以去離子水清洗，塗佈SBMA溶液，乾燥後，進 行常壓電漿處理’於該表面接枝SBMA，接著浸潰於碟酸緩衝（PBS; phosphate buffered solution)溶液中。第十一圖表示原始 pVDF ( Virgin PVDF)、PVDF-OH 及 PVDF-g-PSBMA 之傅立葉轉換紅外線（FTIR) 光譜圖’其中PVDF-g-PSBMA分別進行30/60/90/120秒之電漿處理。 第十二圖表示PVDF薄膜表面接枝SBMA時氬氣電漿處理時間與 所得的接枝密度、接觸角之關係圖9 蛋白質吸附試驗 第十三圖表示原始PVDF ( Virgin PVDF )、PVDF-OH及 PVDF-g-PSBMA之血毁蛋白質（piasma pr〇tein)吸附試驗之結果，顯 示血漿蛋白質吸附率的量與PVDF-g-PSBMA的處理時間的關係。 m 13 201219067 範例三：製作皮膚傷口癒合用貼片II 201219067 The trend of increasing time increases, and the water contact angle decreases with the increase of argon plasma treatment time. The fourth graph shows the Fourier transform infrared (FTIR) spectra of the original PTFE (raw), PTFE-g-PEGMA, and PTFE-g-SBMA, where the peak at 1730 cm·1 indicates c = 〇. The absorption peak of the group, 1030 cn The peak of ^ represents the absorption peak of the _s=0 group. The characterization of the PTFE-g-PEGMA/SBMA/SA/TM skin wound healing material was carried out as follows. Protein Adsorption Test # Using cellulose (flbrinogen) as a protein, the adsorption characteristics of the prepared PTFE-g-PEGMA/SBMA/TM/SA skin wound healing material were tested. The fifth figure shows the protein (using fibrinogen) The results of the adsorption test. Wherein, in the horizontal axis, the order is #1_P 5/10/15/60/120 sec, indicating that PEGMA is grafted on the PTFE surface, and the treatment is 5/10/15/60/120 seconds; #2-SBMA 5/10/ 15/60 sec means SBMA grafted onto PTFE surface 'treatment 5/10/15/60 sec; SBMA hydrogel; #2-SA 5/15/30/60 sec means SA grafted onto PTFE surface, treated 5/15/30/60 sec; #2-TM 5/15/30/60 sec means TM is grafted onto the PTFE surface for 5/15/30/60 sec; PS stands for polysulfone. It is known from the fifth figure of Lu that the cellulose adsorption rate of surface grafted PEGMA, SBMA and SA is lower than that of TM. Bacterial adsorption test S. epidermidis and E. coli were used as examples of the bacteria. Figure 6 shows the results of the adsorption test of bacteria (using S. epidermidis), and the seventh figure shows the results of the adsorption test of bacteria (using E. coli), where #1 is PTFE; #2, #3, #4, #5, #6 is PTFE-g-PEGMA, which is treated by plasma for 5/10/15/60/120 sec. From the results of the sixth and seventh figures, the surface-grafted PEGMA PTFE was significantly reduced in the adsorption rate of the treated PTFE surface to the original PTFE surface. f 12 201219067 In addition, when 'bacterial adsorption test for PTFE-g-SBMA, the eighth figure shows the results of the adsorption test of bacteria (S. epidermidis), and the ninth figure shows the bacteria (using E. coli (E_) Coli)) The results of the adsorption test, sequentially indicating untreated pTFE, 扪~#4 is PTFE-g-SBMA 5/15/30/60 sec, #5~#8 is PTFE-g-SA 5/15/ 30/60 sec ' and #9~#12 are PTFE-g-TM 5/15/30/60 sec. From the results of the eighth and ninth figures, it was found that the surface-grafted SBMA PTFE has a significantly reduced adsorption rate to bacteria on the surface of the treated PTFE as compared with the surface of the original PTFE. Example 1 Although a PTFE film is used as the fluorine-containing hydrophobic film, a pvdf film can also be used. Example 2: Method for producing a skin wound sore material The following materials were produced by using PVDF as an example of a fluorine-containing hydrophobic film. Figure 11 is a flow chart showing the preparation of PVDF-g-SBMA skin wound healing material. The PVDE film is used as the hydrophobic film. The pvDF film is firstly treated by low-pressure plasma. After the surface is activated, it is washed with deionized water, coated with SBMA solution, dried, and then subjected to normal piezoelectric slurry treatment. Then, it was immersed in a solution of phosphate buffered solution (PBS). Figure 11 shows the Fourier Transform Infrared (FTIR) spectrum of the original pVDF (virgin PVDF), PVDF-OH, and PVDF-g-PSBMA, where PVDF-g-PSBMA is plasma for 30/60/90/120 seconds, respectively. deal with. Figure 12 shows the relationship between the treatment time of argon plasma and the graft density and contact angle when grafting SBMA on the surface of PVDF film. Figure 9 shows the original PVDF (virgin PVDF), PVDF-OH and The results of the blood-degrading protein (piasma pr〇tein) adsorption test of PVDF-g-PSBMA showed the relationship between the amount of plasma protein adsorption rate and the treatment time of PVDF-g-PSBMA. m 13 201219067 Example 3: Making a patch for skin wound healing
使用範例一所製備之皮膚傷口癒合材料，使用聚四氟乙烯薄膜， 於其表面接枝曱基丙烯酸聚乙二醇酯（pTFE_g_pEGMA)或甲基丙烯 酸聚磺酸甜菜鹼（FTFE_g_SBMA)，如第一圖所示，PTFE薄膜之令間 部分為PEGMA或SBMA接枝於PTFE表面，周圍部分為一般習知的 感壓黏著劑層，例如聚乙烯醚黏著劑ether a此es〖ve)、共聚 合丙烯酸酯（copolymer acrylate)。第一圖中，雖然中間部分為矩形， 但可為其他任意形狀，例如圓形、方形等。PTFE薄膜的形狀，除了第 一圖所示的矩形外，可為其他任意形狀，例如圓形、方形、多角形等。 皮膚傷口癒合用貼片之動物實驗 使用根據本發明的皮膚傷口癒合用貼片作為測試樣品，覆蓋老鼠 的傷口，（大小1.5X1.5 cm2)，貼上具有防水透氣功能的膠帶，以確保 貼附的膜不會脫落，1G天後進行傷口抓分析。另外，使用紗布、市 售人工皮（3M公製造）、雜PTFE(記為pTFE)、超疏水處理卩顶 (記為CF4)作為對照組，比較結果。 第十四圖表示皮膚傷口癒合用貼片的動物實驗之顯微鏡照月，其 中⑻表示正常皮膚，使_紗布，⑷”人卫皮，_始pTF£ (記 為PTFE)，⑷超疏水處理PTFE (記為CR)，（f)pTFE_g-SBMA (記為 sbma)及(g) PTFE兮PEGMA (記為舰祖處理ι〇秒）覆蓋老鼠 的傷口。 由第十四圖(b)，對照組（control)只覆蓋紗布之傷口，可觀察到 表面出血的情況還是存在’且可明顯的看到組織排列情形較為鬆散， 而微血#較無明騎增生。由⑷，市售商品的切片可看到在真皮组織 的頂部並無触的情況發生，也無_的表皮輯生成，不過卻有明 .4的微血s增生’並且在傷口形成了規律的纖維狀結構。由⑷，p顶 薄臈的切片’可看到在傷口的頂部聚集了許多的免疫細胞，而在最頂⑸ 201219067 部有-層賴的細產生，從4G倍（概）的切4圖來看可明顯的看 到較深層的組織已開始有微血管的增生。由(e)，超疏水處理過後的 PTFE膜切片’邊明顯的看到有一層薄薄的表皮組織開始分化，而且在 傷口組織中可明顯看到許多的微血管分化。 由(f)’使用根據本發明的pTFE_g_SBMA之切片圖可明顯發現已有 明顯的表皮分化itj來’巾在纽下的_也已接近復原。 由(g) ’使用根據本發明的PTFE_g_pEGMA處理1〇秒之切片圖可 看到有細生餅傷Π頂端，*在細下方並無嚴重的纽細胞聚 集並有觀察到表皮層的增生，微血管的增生情況較明顯。 下述表-顯示上述動物實驗的評價結果，評價方式係由皮膚復原 時，、微血管、免疫細胞及表皮層之增娜兄進行判斷，其中符號「X」 越多表不增生纽越_。由於皮膚傷口復科，長出的皮膚越 2近原本的皮f祕，_柯望有献免疫_增生，而期望微血 s與表皮層的增生。 ^二、動物實驗的g僧結果Using the skin wound healing material prepared in Example 1, using a polytetrafluoroethylene film, grafting a surface of methacrylic acid polyethylene glycol ester (pTFE_g_pEGMA) or methacrylic acid polysulfonic acid betaine (FTFE_g_SBMA), such as the first As shown in the figure, the inter-membrane portion of the PTFE film is PEGMA or SBMA grafted onto the surface of the PTFE, and the surrounding portion is a conventional pressure-sensitive adhesive layer such as a polyvinyl ether adhesive, a copolymerized acrylic acid. Copolymer acrylate. In the first figure, although the middle portion is rectangular, it may be of any other shape such as a circle, a square, or the like. The shape of the PTFE film may be any other shape other than the rectangle shown in the first figure, such as a circle, a square, a polygon, or the like. Animal test for patch of skin wound healing The patch for skin wound healing according to the present invention was used as a test sample to cover the wound of a mouse (size 1.5X1.5 cm2), and a tape with waterproof and breathable function was attached to ensure the sticker. The attached membrane will not fall off, and the wound grasping analysis will be performed after 1G. Further, gauze, commercially available artificial skin (manufactured by 3M), miscellaneous PTFE (denoted as pTFE), and superhydrophobic treated dome (denoted as CF4) were used as a control group, and the results were compared. Figure 14 shows the microscopic observation of the animal experiment of the skin wound healing patch, wherein (8) indicates normal skin, _ gauze, (4) "human skin, _ initial pTF £ (denoted as PTFE), (4) superhydrophobic treatment of PTFE (Remarked as CR), (f) pTFE_g-SBMA (denoted as sbma) and (g) PTFE 兮 PEGMA (recorded as ancestor treated 〇 〇 )) covering the wound of the mouse. From Figure 14 (b), the control group (control) only covered the wound of gauze, it can be observed that the surface bleeding is still present 'and can clearly see the arrangement of the tissue is looser, and the micro blood # is less than the growth of the elephant. From (4), the slice of the commercial goods can be seen There is no contact at the top of the dermal tissue, and no epidermis is produced, but there is a slight blood s hyperplasia of the .4 and a regular fibrous structure is formed in the wound. From (4), p top thin The slice of sputum can be seen that a large number of immune cells are gathered at the top of the wound, and at the top (5) 201219067, there is a fine production of the layer, which can be clearly seen from the 4G magnification. Deeper tissue has begun to proliferate microvessels. (e), after superhydrophobic treatment The PTFE membrane section clearly shows a thin layer of epidermal tissue that begins to differentiate, and many microvascular differentiations are clearly visible in the wound tissue. It is evident from (f)' using the pTFE_g_SBMA slice according to the present invention. It has been found that there is already a significant epidermal differentiation of it. The _ is also near recovery. From (g) 'Using the PTFE_g_pEGMA treatment according to the invention for 1 sec slice, the top of the fine cake scar can be seen. * There is no serious cell accumulation under the fine and the epidermal layer is observed to proliferate, and the proliferation of microvessels is more obvious. The following table - shows the evaluation results of the above animal experiments, the evaluation method is from skin recovery, microvascular, The immune cells and the epidermis are judged by the brothers, and the more the symbol "X", the more the hyperplasia. As the skin wounds are rehabilitated, the skin that grows is closer to the original skin, and _ Kewang has an immune _ hyperplasia, and expects micro-blood s and epidermal layer hyperplasia. ^ Second, the results of animal experiments
試樣 痴 微血管 免疫細胞 紗布 X XXX Α又/曰 售商品 XXX X PTFE ---- X XX XXX ----— CF4 ----- XXX X XX __SBMA XXX XXX J2?ma-i〇s XX XXX X X 由表一得知，根據本發明的PTFE_g_s難貼片，既沒有疮的生 E S] 15 201219067 ，生成表皮組織，已接 成，亦沒有免疫細胞，而且與耗人工皮比較 近復原，而且復原速度比較快。 ^上财’根縣發狀皮膚傷轉合磐及雜造方法， 表面接枝高分子之含氟薄膜，除可利用上述含氣薄膜的特性 接枝心子的特性，作為皮膚傷口癒合材料，可具有透氣、保水 防水、域、抗凝血的概，此外皮賴σ癒合㈣之製造方法 藉由«魏處理進行接枝聚合，可奴健量紅縣。 ，Sample microvascular vascular immune cell gauze X XXX Α / / sale of goods XXX X PTFE ---- X XX XXX ----- CF4 ----- XXX X XX __SBMA XXX XXX J2? ma-i〇s XX XXX XX is known from Table 1, according to the PTFE_g_s difficult patch of the present invention, there is no sore ES ES 15 201219067, the epidermal tissue is formed, has been formed, has no immune cells, and is relatively restored with the consumption of artificial skin, and The recovery speed is faster. ^上财 '根县 hairy skin injury and sputum and mixed method, surface grafted polymer fluoride film, in addition to the characteristics of the above gas-containing film grafted heart, as a skin wound healing material, can It has the advantages of venting, water-repellent waterproofing, domain and anti-coagulation. In addition, the manufacturing method of Pirai σ healing (4) is carried out by the treatment of "Wei", and it can be used in the county. ,
顯然地，依照上面實施例中的描述，本發明可能有許多的 修正與差異。因此需要在其附加的權利要求項之㈣内加以避 解’除了上述詳細的描述外，本發明還可以廣泛地在其他 施例中施行。上述僅為本發明之較佳實施例而已，並非用 定本發明之巾請專利範圍；凡其它未脫離本發明所揭示之精神、 下所完成的等效改變或修飾，均應包含在下述中請專利範圍 【圖式簡單說明】 第-圖⑷表示皮膚傷口癒合材料的結構之上視圖，第—剛表示 傷口癒合材料的結構之剖面圖； 價 第二圖表示根據本伽敝膚傷喊合材料之製造方法的流程圖； 第三圖表示製倩PTFE (聚四氟乙稀）薄膜表面接枝(a)pEGMA (甲義 丙稀酸聚乙二鞠）；及(b)SBMA ( f基丙賊聚雜甜絲）（記^ PTFE-g-PEGMA/SBMA)時氬氣電漿處理時_所_紐密度、抵 觸角之關係圖； @ 第四圖表示原始PTFE (raw)及PTFE_g_PEGMA/SBMA之傅立葉轉換 紅外線（FTIR)光譜圖’其中173G em.i的波峰表示c=〇基團的吸吹 峰，1030 cm·1的波峰表示_s=〇基團的吸收峰； 第五圖表*蛋自質（伽纖維錢(fibrinGgen))吸附試驗的結果； 201219067 第六圖表示PTFE-g-PEGMA之細菌（使用上皮葡萄球菌（s. epidermidis))吸附試驗的結果，其中#1 為 pTFE ; #2, #3, #4, #5, #6 為 ?71^-§视〇祖，分別經過電漿處理5/1〇/15/6〇/12〇北(；； 第七圖表示PTFE-g-PEGMA之細菌（使用大腸桿菌(E c〇li))吸附試驗 的結果，其中#1 為 PXFE ; #2, #3, #4, #5, #6 為 PTFE-g-PEGMA，分別 經過電漿處理5/10/15/60/120 sec ; 第八圖表示PTFE-g~SBMA之細菌（使用上皮葡萄球菌(S. epidermidis)) 吸附試驗的結果； 第九圖表示PTFE-g-SBMA之細菌（使用大腸桿菌(E· coli))吸附試驗 的結果； 第十圖表不製備PVDF—gjBMA之皮膚傷口癒合材料之流程圖；Obviously, many modifications and differences may be made to the invention in light of the above description. Therefore, it is to be avoided in the fourth aspect of the appended claims. In addition to the above detailed description, the present invention can be widely practiced in other embodiments. The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the invention. Any other equivalent changes or modifications that are not departing from the spirit of the present invention should be included in the following. Patent Scope [Simple Description of the Drawings] Figure-4 (4) shows the top view of the structure of the skin wound healing material, the first section shows the structure of the wound healing material; the second figure shows the material according to the gamma skin lesions. The flow chart of the manufacturing method; the third figure shows the surface grafting of the PTFE (polytetrafluoroethylene) film (a) pEGMA (polyethyl methacrylate); and (b) SBMA (f-propyl Thief polystyrene) (remember PTFE-g-PEGMA/SBMA) argon plasma treatment when _ _ _ density, the relationship between the angle of contact; @ The fourth figure shows the original PTFE (raw) and PTFE_g_PEGMA / SBMA Fourier-converted infrared (FTIR) spectrogram 'where the peak of 173G em.i indicates the absorption peak of c=〇 group, the peak of 1030 cm·1 indicates the absorption peak of _s=〇 group; the fifth chart* egg Self-quality (fibrinGgen) adsorption test results; 201219067 sixth chart PTFE-g-PEGMA bacteria (using s. epidermidis) adsorption test results, where #1 is pTFE; #2, #3, #4, #5, #6 is ?71^-§ 〇祖, respectively, after plasma treatment 5/1〇/15/6〇/12〇北(;; Figure 7 shows the results of adsorption test of PTFE-g-PEGMA bacteria (using Ec〇li) , #1 is PXFE; #2, #3, #4, #5, #6 is PTFE-g-PEGMA, respectively treated by plasma treatment 5/10/15/60/120 sec; Figure 8 shows PTFE- G~SBMA bacteria (using S. epidermidis) adsorption test results; Figure IX shows PTFE-g-SBMA bacteria (using E. coli) adsorption test results; Flow chart of skin wound healing material without PVDF-gjBMA;
第十一圖表示原始 PVDF( VirginPVDF)、PVDF-OH及PVDF-g-PSBMA 之傅立葉轉換紅外線（FTIR)光譜圖，其中pVDF兮pSBMA分別進行 30/60/90/120秒之電漿處理； 第十一圖表示PVDF薄膜表面接枝SBMA時氬氣電漿處理時間與所得 的接枝密度、接觸角之關係圖； 第十二圖表示原始 PVDF( Virgin PVDF )、PVDF-OH 及 PVDF-g-PSBMA 之血漿蛋白質（Plasma protein )吸附試驗之結果； 丨十圖表示皮膚傷口癒合用貼片的動物實驗之顯微鏡照片。 【主要元件符號說明】 1〇1 :薄臈 200.皮膚傷口癒合材料 έ， 300 ··黏著層 m 17Figure 11 shows the Fourier transform infrared (FTIR) spectrum of the original PVDF (virgin PVDF), PVDF-OH, and PVDF-g-PSBMA, where pVDF兮pSBMA is subjected to plasma treatment of 30/60/90/120 seconds, respectively; Figure 11 shows the relationship between the treatment time of argon plasma and the graft density and contact angle when grafting SBMA on the surface of PVDF film. The twelfth figure shows the original PVDF (virgin PVDF), PVDF-OH and PVDF-g- The results of PSBMA's plasma protein adsorption test; Figure 10 shows a microscopic photograph of an animal experiment of a patch for skin wound healing. [Explanation of main component symbols] 1〇1: Thin 臈 200. Skin wound healing material έ, 300 ··Adhesive layer m 17
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW099138703ATWI425959B (en) | 2010-11-10 | 2010-11-10 | Wound healing material and method for fabricating the same |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW099138703ATWI425959B (en) | 2010-11-10 | 2010-11-10 | Wound healing material and method for fabricating the same |
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| TW201219067Atrue TW201219067A (en) | 2012-05-16 |
| TWI425959B TWI425959B (en) | 2014-02-11 |
| Application Number | Title | Priority Date | Filing Date |
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| TW099138703ATWI425959B (en) | 2010-11-10 | 2010-11-10 | Wound healing material and method for fabricating the same |
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| CN108070325A (en)* | 2016-11-14 | 2018-05-25 | 高雄大学 | Hydrophilic and hydrophobic amphoteric patch structure |
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| GB2396109B (en)* | 2002-12-12 | 2006-04-19 | Johnson & Johnson Medical Ltd | Absorbent multilayer hydrogel wound dressings |
| GB2403146B (en)* | 2003-06-23 | 2007-07-11 | Johnson & Johnson Medical Ltd | Method of making a wound dressing comprising lactate oxidase |
| TW200934449A (en)* | 2007-12-12 | 2009-08-16 | 3M Innovative Properties Co | Hydrophilic gel materials and methods of making |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108070325A (en)* | 2016-11-14 | 2018-05-25 | 高雄大学 | Hydrophilic and hydrophobic amphoteric patch structure |
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| TWI425959B (en) | 2014-02-11 |
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