200938234 九、發明說明 【發明所屬之技術領域】 本發明係有關具有良好之伸縮性、傷口面之滲出液之 吸收性’可長時間維持適於促進傷口面治癒之濕潤環境， 且於更換被覆傷口材料時，不致產生疼痛或再生皮膚受損 之水凝膠被覆傷口材料。 _ 【先前技術】 先前技術中’作爲傷口面之治療劑者，一般使用紗布 、粉末劑、噴霧劑、軟膏、霜劑、海綿劑等。此大部份經 由吸收由傷口面之滲出液’使傷口部位乾燥，進行治療。 惟’近年來被判定’相較於乾燥傷口部位，其於傷口面維 持滲出液’保持適度的濕潤環境，其促進傷口之治療效果 較爲明顯’被認定使傷口部位維持於適度濕潤環境之必要 性，被開發適於其之被覆傷口材料。 ❹ 作爲被覆傷口材料之要件者，被要求吸收性、保持濕 潤、防止細菌侵入、防止細菌增殖、機械性強度、黏著性 、等。機械性強度係指，即使吸收滲出液，該被覆材料仍 不會分散、於更換時不會殘留碎片於傷口部位之意。透明 性係爲觀察患部所必要之條件。 作爲被覆傷口材料者’公知者如：聚胺基甲酸乙酯薄 膜、水膠質、PVA水凝膠、褐藻酸鹽凝膨等。 上述之被覆傷口材料中，於聚胺基甲酸乙酯薄膜中塗 佈丙烯系黏著劑之被覆傷口材料雖具有極良好之伸縮性， -5- 200938234 卻完全無滲出液之吸收性，因此，用於滲出滲出液之傷口 面時’引起液積，務必進行排水。另外，黏著力亦強，更 換時’伴隨疼痛，恐損傷再生皮虜（專利文獻1、2、3) 〇 水膠質其含於疏水性基劑中之親水性膠質粒子經由膨 潤後，進行滲出液之吸收性，因此吸收性良好，惟，更換 時傷口面容易殘留凝膠狀物質。又，半透明及不透明者多 @ ，不易觀察傷口面。甚至黏著力亦強，更換時，伴隨疼痛 ，恐損及再生皮膚。 P V A水凝膠，於製劑中含有約8 0 %之精製水，因此， 藉由濕潤環境之維持、冷卻效果後疼痛緩和，且透明性極 佳，惟黏著力幾乎沒有，務必以崩帶、補助背膠之固定材 料。又’ PVA水凝膠具黏著力，因此，施予輻射線照射等 方法亦被揭示之（專利文獻4)，惟黏著力並不足。 褐藻酸鹽凝膠具良好的止血性、滲出液之吸收性，惟 Q 藉由滲出液出現凝膠化，故於更換時易殘留凝膠狀物質於 傷口面，且爲開放系，因此爲維持濕潤、防止細菌侵入、 防止細菌增殖，務必以薄膜材料進行被覆等（專利文獻5 )° 因此’被期待一種伸縮性良好，滲出液具吸收性，可 長期維持適於促進傷口面之治癒之濕潤環境，於被覆傷口 材料更換時無疼痛，不致損及再生皮膚之水凝膠被覆傷口 材料。 〔專利文獻1〕特開昭58-87153號公報 200938234 〔專利文獻2〕特開平4-272765號公報 〔專利文獻3〕特開2006-61263號公報 〔專利文獻4〕特許第3773983號公報 〔專利文獻5〕特開平8-187280號公報 【發明內容】 本發明係提供一種伸縮性良好，具有傷口面滲出液之 φ 吸收性’可長時間維持適於促進傷口面癒合之濕潤環境， 且更換被覆傷口材料時無疼痛，或再生皮膚受損之虞之水 凝膠被覆傷口材料。 爲取得上述被覆傷口材料，本發明者進行精密硏討後 ’結果發現’將含有水溶性合成或半合成高分子、甘油及 水所成之水凝膠塗佈於由聚胺基甲酸乙酯薄膜與疏水性纖 維所成之雙層層合薄膜上，其透濕度經由JIS Z0208杯式 法測定値爲5 00〜2000 (g/m2/24h)後，可取得伸縮性良好 Q ’傷口面的保護良好，具有滲出液之吸收性，可長時間維 持適於促進傷口癒合之濕潤環境，於更換被覆傷口材料時 無疼痛或再生皮膚受損之虞之水凝膠被覆傷口材料，進而 完成本發明。 本發明水凝膠被覆傷口材料係具有良好的伸縮性、$ 好的保護傷口面、具有滲出液的吸收性，可長時間維持適 於促進傷口面癒合之濕潤環境，於更換被覆傷口材料時無 疼痛，或再生皮膚受損之虞等效果。 亦即，本發明係有關使含有水溶性合成或半合 200938234 子、甘油及水所成之水凝膠塗佈於由聚胺基甲酸乙醒 與疏水性纖維所成之雙層層合薄膜上，其透濕度經s Z0208杯式法所測定爲500〜2000 (g/m2/24h)之水凝 覆傷口材料。 又，藉由使用聚胺基甲酸乙酯薄膜之厚度5〜2 5 其恆載延伸率5%以上之支撐體後，可維持傷口面之 濕潤環境，同時可保持可觀察傷口面之透明性。更使 0 基甲酸乙酯薄膜與疏水性纖維所成之雙層層合薄膜之 度經由JIS L1 099氯化鈣法所測定爲200〜5000 ( g/m )之範圍內’亦可取得可長時間維持適度的濕潤環境 止悶濕之刺激皮膚之效果。 又’使水凝膠中之水份含量作成3 0 ~ 8 0 %後，可 適度之黏著性。亦即，可兼備可維持傷口面適度之濕 境與更換被覆傷口材料時，可防止剝離後皮膺受損之 。甚至具有可確保滲出液之高吸收性。 ❹ 【實施方式】 〔發明實施之最佳形態〕 以下，進行本發明更詳細的說明。 本發明水凝膠被覆傷口材料其透濕度爲經由 2〇2〇8杯式法所測定値爲5〇〇〜2〇〇〇(8/012/2411)，較 爲 7〇〇〜1500 (§/1112/2411)。當透濕度未達 500 (£/111 )時’則恐因悶濕產生皮膚刺激，而不理想。反之， 2000 ( g/m2/24h )則無法長時間維持傷口面之適度的 i薄膜 3 JIS :膠被 μιη， 適度 聚胺 透濕 2/24h 與防 維持 潤環 效果 JIS 佳者 2/24h 超出 濕潤 200938234 環境，亦不理想。 構成本發明聚胺基甲酸乙酯薄膜之聚胺基甲酸乙酯樹 脂可使用醚系、酯系等之一般胺基甲酸乙酯樹脂，並未特 別限定。 本發明所使用之聚胺基甲酸乙酯薄膜其厚度爲5~2 5 μιη者宜、恆載延伸率爲5 %以上者宜。當聚胺基甲酸乙酯 薄膜之厚度未達5 μιη時，將藉由機械性強度不足及穿孔 增大而無法維持傷口面之適度的濕潤環境，而不理想。反 ❹ 之，厚度超出2 5 μιη則恆載延伸率未達5 %，恐損及伸縮 性，不易保護傷口面。且，透明性亦降低、無法觀察傷口 面，亦不理想。 作爲於聚胺基甲酸乙酯薄膜進行層合之疏水性纖維者 ，可使用聚酯、尼龍、丙烯酸、聚丙烯、聚乙烯等。 由此所製作之聚胺基甲酸乙酯薄膜與疏水性纖維所成 之雙層層合薄膜之透濕度爲了長時間維持適於促進傷口面 ❹ 癒合之濕潤環境，經由JIS L1099氯化鈣法所測定爲 200~5000 ( g/m2/24h)之範圍者宜，更佳者爲3 00〜3000 ( g/m2/2 4h)之範圍。當透濕度大於5000 ( g/m2/24h )，則 將無法長時間保持濕潤環境，降低促進傷口面之癒合效果 。反之未達200 ( g/m2/24h )則恐因悶濕而對皮膚產生刺 激，而不理想。 作爲本發明所使用之水溶性合成或半合成高分子例者 ’如：聚丙烯酸、聚丙烯酸鈉、聚丙烯酸部份中和物、聚 丙烯酸澱粉、羥丙基纖維素、羥丙基甲基纖維素、羥乙基 -9- 200938234 纖維素、甲基纖維素、羧甲基纖維素鈉、羧乙烯基聚合物 、N-乙烯基乙醯胺共聚物等例，此等可單獨使用，亦可組 合2種以上使用之。其中又特別以組合羧乙烯基聚合物， 聚丙烯酸、聚丙烯酸部份中和物及羧甲基纖維素鈉爲最佳 〇 水凝膠中之該水溶性合成或半合成高分子配合量爲 3~20重量％者宜，更佳者爲5〜15重量％。當配合量未達3 重量％時’則凝膠黏度太低不易作成貼附劑成形之，反之 Ό ，超出2 0重量％則其水溶性合成或半合成高分子無法均句 溶解於凝膠中，未能形成理想之凝膠，而不理想。 水凝膠中水的配合量，對於凝膠重量而言，爲30〜80 重量％者宜，更佳者爲40〜75重量％。當含水量超出80重 量％時，則滲出液之吸收性降低，而不理想。反之，未達 3 0重量％則黏著力太強，恐於更換被覆傷口材料時，出現 疼痛或損及再生皮膚，對皮膚之保濕性減少，而無法維持 ^ 適於促進傷口面癒合之濕潤環境，而不理想。 又，水凝膠中之甘油配合量爲10〜40重量％者宜，更 佳者爲15~30重量％。當水凝膠中之甘油配合量未達1〇重 量％時’則對於皮膚之保濕性降低，而無法維持適於促進 傷口面癒合之濕潤環境。反之，水凝膠中之甘油配合量大 於4 0重量％時’則產生浮出無法維持於凝膠表面之甘油， 貼附時出現黏腻現象，降低黏著力之問題。 有關構成水凝膠之上述以外之組成，只要不阻礙本發 明效果，未特別限定，一般可配合如：賦形劑、保濕劑、 -10- 200938234 穩定化劑、交聯劑等。 作爲賦形劑者，可單獨或組合2種以上之如：陶土、 氧化鈦、矽酸酐、氧化鋅、膨潤土等使用之。惟，於傷口 面貼附水凝膠時，務必具有可觀察傷口面之透明性的水凝 膠’故特別以矽酸酐爲最佳，其配合量爲0.1〜5重量％者 宜。 作爲甘油以外之保濕劑例者如：以單獨或組合2種以 φ 上之D -山梨糖醇液、1，3-丁二醇、二丙二醇、聚乙二醇、 聚丙二醇、DL-吡咯烷酮羧酸鈉液等使用之，其配合量爲 1 0〜30重量％者宜。200938234 IX. INSTRUCTIONS OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a moisturizing environment having a good stretchability and an exudate of a wound surface, which can maintain a moist environment suitable for promoting healing of a wound surface for a long time, and replace the covered wound In the case of materials, the hydrogel does not cause pain or damage to the regenerated skin to coat the wound material. [Prior Art] In the prior art, as a therapeutic agent for a wound surface, gauze, a powder, a spray, an ointment, a cream, a sponge, or the like is generally used. Most of this is treated by absorbing the exudate from the wound surface to dry the wound site. However, 'resolved in recent years' compared with the dry wound site, it maintains the exudate on the wound surface to maintain a moderately moist environment, and the therapeutic effect of promoting the wound is more obvious' is necessary to maintain the wound site in a moderately humid environment. Sex, developed to cover wound materials. ❹ As a requirement for covering wound materials, it is required to absorb, keep moist, prevent bacterial invasion, prevent bacterial proliferation, mechanical strength, adhesion, and the like. Mechanical strength means that even if the exudate is absorbed, the covering material does not disperse, and no residue remains on the wound site at the time of replacement. Transparency is a condition necessary to observe the affected part. As a person who covers the wound material, a known one is, for example, a polyurethane film, a hydrocolloid, a PVA hydrogel, a brown alginate, or the like. In the above-mentioned coated wound material, the coated wound material coated with the propylene-based adhesive in the polyurethane film has excellent stretchability, and -5-200938234 has no absorption of exudate at all, therefore, When oozing out the wound surface of the exudate, 'cause liquid accumulation, be sure to drain. In addition, the adhesive force is also strong, and the skin is damaged when it is replaced, and the skin is damaged. (Patent Documents 1, 2, and 3) The hydrophobic gel particles contained in the hydrophobic base are swollen and exudate. The absorbency is good, so the absorbability is good, but the gel-like substance is likely to remain on the wound surface at the time of replacement. Also, more translucent and opaque @, it is not easy to observe the wound surface. Even the adhesion is strong, and when it is replaced, it is accompanied by pain, fear and regeneration of the skin. PVA hydrogel contains about 80% purified water in the preparation. Therefore, it is relieved by the maintenance of the moist environment and the cooling effect, and the transparency is excellent. However, the adhesion is almost no, and it must be collapsed and subsidized. Adhesive fixing material. Further, the PVA hydrogel has an adhesive force, and therefore, a method of applying radiation irradiation or the like is also disclosed (Patent Document 4), but the adhesion is insufficient. Alginate gel has good hemostatic property and absorption of exudate. However, Q is gelated by exudate, so it is easy to leave gelatinous substance on the wound surface during replacement, and it is open, so it is maintained. Moisture, prevention of bacterial invasion, prevention of bacterial growth, and coating with a film material (Patent Document 5). Therefore, it is expected that the stretchability is good, and the exudate absorbs, and the moisturization suitable for promoting the healing of the wound surface can be maintained for a long period of time. The environment, no pain when the covered wound material is replaced, does not damage the hydrogel coated wound material of the regenerated skin. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei 8-187280. SUMMARY OF THE INVENTION The present invention provides a good stretchability and a φ absorbency of a wound surface exudate, which can maintain a moist environment suitable for promoting healing of a wound surface for a long period of time, and replaces the cover. The wound material is free of pain, or the hydrogel that regenerates the damaged skin coats the wound material. In order to obtain the above-mentioned coated wound material, the inventors of the present invention conducted a precise beating and found that a hydrogel composed of a water-soluble synthetic or semi-synthetic polymer, glycerin and water was applied to a film of polyurethane. On the two-layer laminated film formed with the hydrophobic fiber, the moisture permeability is determined by the JIS Z0208 cup method and the enthalpy is 5 00 to 2000 (g/m 2 /24 h), and the stretchable Q 'wound surface protection can be obtained. It is good, has the absorption property of the exudate, can maintain the moist environment suitable for promoting wound healing for a long time, and coats the wound material with the hydrogel coated with no pain or damaged skin damaged when the wound material is replaced, and the present invention is completed. The hydrogel coated wound material of the invention has good stretchability, good protection of the wound surface, and absorption of exudate, and can maintain a moist environment suitable for promoting healing of the wound surface for a long time, and is not replaced when the wound material is replaced. Pain, or the effects of regenerating skin damage. That is, the present invention relates to the application of a hydrogel comprising water-soluble synthetic or semi-synthetic 200938234, glycerin and water to a two-layer laminated film formed by awakening of polyurethane and hydrophobic fibers. The water permeability of the wound material is 500~2000 (g/m2/24h) measured by the s Z0208 cup method. Further, by using a support having a thickness of 5 to 2 5 of a polyurethane film having a constant elongation of 5% or more, the wet environment of the wound surface can be maintained while maintaining the transparency of the wound surface. Further, the degree of the two-layer laminated film formed by the ethyl methacrylate film and the hydrophobic fiber is determined to be in the range of 200 to 5000 (g/m) by the JIS L1 099 calcium chloride method. Time to maintain a moderately moist environment to stop the effects of irritating skin. Further, after the water content in the hydrogel is made to be 30 to 80%, the adhesion is moderate. That is, it is possible to prevent the skin from being damaged after peeling, while maintaining the humidity of the wound surface and replacing the wound material. It even has the ability to ensure high absorbency of the exudate. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail. The hydrogel coated wound material of the present invention has a moisture permeability of 5 〇〇 2 〇〇〇 (8/012/2411), which is determined by the method of 2 〇 2 〇 8 cups, and is more than 7 〇〇 1500 (§ /1112/2411). When the moisture permeability is less than 500 (£/111), it may cause skin irritation due to dampness, which is not ideal. On the other hand, 2000 (g/m2/24h) can not maintain the proper degree of i-film 3 JIS for the wound surface for a long time: the glue is μιη, the moderate polyamine is permeable for 2/24h and the anti-maintenance effect is JIS 2/24h. Wet 200938234 environment is also not ideal. The polyurethane urethane resin constituting the polyurethane film of the present invention may be a general urethane resin such as an ether system or an ester system, and is not particularly limited. The polyurethane film used in the present invention has a thickness of 5 to 25 μm, and a constant elongation of 5% or more. When the thickness of the polyurethane film is less than 5 μm, it is not preferable because the mechanical strength is insufficient and the perforation is increased to maintain a moderate moist environment of the wound surface. In contrast, when the thickness exceeds 25 μm, the dead load elongation is less than 5%, which is fearful and stretchable, and it is difficult to protect the wound surface. Moreover, the transparency is also lowered, and the wound surface cannot be observed, which is not desirable. As the hydrophobic fiber laminated on the polyurethane film, polyester, nylon, acrylic, polypropylene, polyethylene, or the like can be used. The moisture permeability of the double-layered laminated film formed by the thus formed polyurethane film and the hydrophobic fiber is maintained in a moist environment suitable for promoting wound healing of the wound surface for a long period of time, and is passed through JIS L1099 calcium chloride method. It is preferably in the range of 200 to 5000 (g/m2/24h), and more preferably in the range of 3 to 00 to 3000 (g/m2/2 4h). When the moisture permeability is greater than 5000 (g/m2/24h), it will not be able to maintain a moist environment for a long time, and reduce the healing effect of the wound surface. On the other hand, if it is less than 200 (g/m2/24h), it may cause irritation to the skin due to dampness, which is not ideal. As a water-soluble synthetic or semi-synthetic polymer used in the present invention, such as polyacrylic acid, sodium polyacrylate, polyacrylic acid partial neutralizer, polyacrylic acid starch, hydroxypropyl cellulose, hydroxypropyl methyl fiber , hydroxyethyl-9- 200938234 cellulose, methyl cellulose, sodium carboxymethyl cellulose, carboxyvinyl polymer, N-vinyl acetamide copolymer, etc., these can be used alone or Two or more types are used in combination. In particular, the combination of the carboxyvinyl polymer, the polyacrylic acid, the polyacrylic acid partial neutralizer and the sodium carboxymethylcellulose is the best water-soluble synthetic or semi-synthetic polymer in the hydrogel. It is preferably about 20% by weight, more preferably 5 to 15% by weight. When the compounding amount is less than 3% by weight, the gel viscosity is too low to be formed into a patching agent. Conversely, when it exceeds 20% by weight, the water-soluble synthetic or semi-synthetic polymer cannot be dissolved in the gel. The failure to form the ideal gel is not ideal. The amount of water in the hydrogel is preferably from 30 to 80% by weight, more preferably from 40 to 75% by weight, based on the weight of the gel. When the water content exceeds 80% by weight, the absorbency of the exudate is lowered, which is not preferable. On the other hand, if the weight is less than 30% by weight, the adhesion is too strong. It may cause pain or damage to the regenerated skin when the wound material is replaced. The moisturizing property of the skin is reduced, and it is impossible to maintain a moist environment suitable for promoting healing of the wound surface. Not ideal. Further, the amount of the glycerin in the hydrogel is preferably 10 to 40% by weight, more preferably 15 to 30% by weight. When the amount of glycerin in the hydrogel is less than 1% by weight, the moisturizing property of the skin is lowered, and the moist environment suitable for promoting healing of the wound surface cannot be maintained. On the other hand, when the amount of glycerin in the hydrogel is more than 40% by weight, glycerin which cannot be maintained on the surface of the gel is generated, and stickiness occurs at the time of attachment, and the problem of adhesion is lowered. The composition other than the above-mentioned constituents of the hydrogel is not particularly limited as long as it does not inhibit the effects of the present invention, and generally, an excipient, a moisturizer, a stabilizer such as -10-200938234, a crosslinking agent, and the like can be blended. As the excipient, two or more kinds thereof such as clay, titanium oxide, phthalic anhydride, zinc oxide, bentonite or the like can be used alone or in combination. However, when the hydrogel is attached to the wound surface, it is necessary to have a hydrogel which can observe the transparency of the wound surface. Therefore, in particular, phthalic anhydride is preferable, and the compounding amount is preferably 0.1 to 5% by weight. As a moisturizing agent other than glycerin, for example, D-sorbitol liquid, 1,3-butanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, DL-pyrrolidone carboxylic acid, which are φ on φ alone or in combination It is preferably used in the form of a sodium acid solution or the like in an amount of 10 to 30% by weight.
又’水凝膠之pH，由其皮膚刺激性之面視之，爲 PH3.5〜6.5之範圍者宜，更佳者爲ΡΗ4·0〜5.5之範圍。pH 調節劑可使用酒石酸、亞硫酸氫鈉、乙烯二胺四乙酸鹽等 〇 作爲交聯劑例者如：可單獨或組合2種以上之乾燥氫 φ 氧化鋁凝膠、鋁甘氨酸鹽、二羥基鋁胺基乙酸酯、合成水 滑石、矽酸鋁酸金屬鹽等之多價金屬化合物等使用之。其 配合量依其種類而異，一般爲〇〇〇 id重量％者宜。 另外’必要時可配合防腐劑、抗氧化劑、可塑劑、乳 化劑、界面活性劑等。 本發明水凝膠被覆傷口材料，適用於傷口部位時，務 必具有可隨著皮膚活動之黏著力，且於更換時被要求不可 損及再生皮膚之黏著力。因此，適用本發明水凝膠被覆傷 口材料時（吸水前）之黏著力其球號設定於8~12，更換時 -11 - 200938234 (8小時吸水後）之球號被設定於 號爲8~12者則適用於傷口部位時 動之適當黏著力。當球號未達8時 適用於可動的傷口部位時，將無法 上剝離之問題，而不理想。反之， 口部位時，其黏著力太強引起皮膚 外，更換時之球號爲3以下時，貝IJ ^ 傷再生皮膚之黏著力，若超出球號 時將出現疼痛，或損及再生皮膚， 另外，上述球號之値係依JIS 法爲基準，由所進行傾斜角30°角 試驗時之値。 作爲被覆水凝膠表面之塑膠薄 聚丙烯、聚酯、聚氯化乙烯或此等 電暈放電處理、凹凸處理、電漿處 φ 本發明水凝膠被覆傷口材料之 方法進行製造之。如：將該各種組 於支撐體上，以塑膠薄膜被覆水凝 膠被覆傷口材料。 必要時，可進行一般滅菌方法 滅菌、環氧乙烷滅菌處理。 〔實施例〕 以下，顯示實施例及比較例， 3以下。只要適用時球 ，可具有可隨著皮膚活 :，則降低初期黏著力， 隨著皮膚活動，導致馬 超出球號12則用於傷 的刺激，而不理想。另 丨更換時將呈無疼痛或損 3則黏著力太高，更換 而不理想。 Z023 7之球黏著度試驗 之球黏著度試驗法進行 膜者，可使用聚乙烯、 表面進行聚矽氧處理、 理等。 製造方法，可依公知之 成所構造之水凝膠展延 膠表面後，可製造水凝 之輻射線滅菌、電子線 進行本發明更具體之說 -12- 200938234 明，惟本發明並未受限於此等實施例。 〔實施例1〕 於適量精製水中，溶解羧乙烯聚合物（1.6g)後，加 入D -山梨糖醇液（20g)進行混合至均勻爲止。更將聚丙 稀酸（0.3g)、酒石酸（1.2g) '濃甘油（20.7g)、殘甲 基纖維素鈉（3.5g)、聚丙烯酸部份中和物（4g)、矽酸 酐（0.1 g )、蓖麻子油（1 · 5 g )、二羥基鋁胺基乙酸酯（ 〇 . 〇 7 g )、乙烯二胺四乙酸二鈉（〇.〇8g)及精製水（適量 )均勻混合後，調製水凝膠。將此水凝膠展延於胺基甲酸 乙酯（20 μιη ) /尼龍彈性體（25g/m2 )上，以聚酯薄膜被 覆凝膠表面後’製作水凝膠被覆傷口薄膜。 〔實施例2〕 使用表1所示之實施例2成份’與實施例1同法，調 ❹ 製水凝膠’將此展延於胺基甲酸乙酯（20 μιη) /尼龍羊毛 針織品（支撐體）中’以聚酯薄膜被覆凝膠表面後，製作 水凝膠被覆傷口材料。 〔實施例3〕 於適量精製水中溶解矽酸酐（〇.5g )後，加入尿素（ 1 ,6g )、乙烯二胺四乙酸二鈉（〇.〇8g)、箆麻子油（〇.5g )，進行混合至均勻爲止。更將20%聚丙烯酸水溶液（ 15.0g)、酒石酸（〇-3g)、濃甘油（16.〇g)、竣甲基纖 -13- 200938234 維素鈉（4.Og )、聚丙烯酸部份中和物（5.〇g )、矽酸鋁 酸鎂（〇.〇6g)、乾燥氫氧化鋁凝膠（〇.〇2g)、及適量精 製水，均勻混合後，調製水凝膠。將此水凝膠展延於胺基 甲酸酯（20 μιη ) /尼龍彈性體（25g/m2 )上’以聚酯薄膜 被覆凝膠表面後，製作水凝膠被覆傷口材料。 〔比較例1〕 使用表1所示之比較例1之成份，與實施例1同法， 進行調製水凝膠’將此展延於PET不織布（100g/m2 )中 ，製作被覆材料。 〔比較例2〕 使用表1所示之比較例2之成份，與實施例1同法， 調製水凝膠’將此展延於PET ( 20 μηι ) /PET不織布（ 35g/m2)中，製作被覆材料。 -14- 200938234 〔表1〕 ❹ 成份(重量％) 實施例1 實施例2 實施例3 比較例1 比較例2 矽酸酐酸 0.1 0.1 0.5 0.1 0.1 聚丙烯酸 0.3 0.3 0.3 0.3 羧乙烯聚合物 1.6 1.6 參 1.6 1.6 D-山梨糖醇 20 20 20 20 濃甘油 20.7 20.7 16 20.7 20.7 羧甲基纖維素鈉 3.5 3.5 4 3.5 3.5 聚丙烯酸部份中和物 4 4 5 4 4 蔑麻子油 1.5 1.5 0.5 1.5 1.5 20%聚丙烯酸水職 _ _ 15 _ . 酒石酸 1 1 0.3 1 1 尿素 . _ 1.0 . 二羥基銘胺基乙酸酯 0.07 0.07 0.07 0.07 矽釀麵 . • 0.06 . 乾燥氫氧化鋁凝膠 _ • 0.02 乙烯二胺四乙酸二鈉 0.08 0.08 0.08 0.08 0.08 精製水 適量 適量 適量 適量 適景 支撑體 銨基甲酸酯 2(W尼龍彈性 體 25g/m2 銨基甲酸酯 20μη/尼龍 羊毛針織品 銨基甲酸酯 2〇μπι/尼龍彈 性體25g/m2 PET不織布 100g/in2 PET2 μπι/ PET不織布 35g/m2 〔比較例3〕duo active a錄商》(外層：聚胺基甲酸乙酯薄 膜’黏著層：親水性膠體與粒子疏水性聚合物，剝離紙： 聚矽氧剝離紙） 〔比較例4〕輔助設施胃樣（於聚胺基甲酸乙酯薄膜上塗佈 丙烯酸系黏著劑） 〔比較例 bugel *錄商《 (支撐體：聚乙烯，水凝膠吸收 -15- 200938234 體：聚維酮，PVA，苯氧基乙醇，水（8〇)) 〔試驗例1〕 實施例1〜3之被覆傷口材料及比較例之被覆傷口 材料之使用後’依以下試驗方法測定伸縮性、透濕性、吸 水性及黏著力。測定値係分別進行3次之測定，求取其平 均値。其結果示於表2。 ❹ (伸縮性試驗） 伸縮性試驗係依：Π S L 1 0 9 6之一般織物試驗方法之伸 縮織物爲基準’進行實施。將該試驗材料切取2x6cm，以 4cm間隔附上矢印（lq )。於線外側上夾，加入1 〇〇g定 荷重，測定矢印間的距離（L i )，藉由下式算出。 延伸率（％ ) = ( Lo-L! ) /L〇xl00 L〇 :原矢印間之長度（4cm ) Q L!:加入l〇〇g定荷重時之矢印間之長度（cm ) (透濕性試驗） 透濕性試驗係依ns Z0208之杯式法爲基準進行。於 玻璃容器（內徑：56 mm、深度11 mm)置入約l〇mL之精 製水，使試驗材料切成直徑80mm之圓形（試驗片），使 膏體面作成內側，被覆玻璃容器開口部位’以石蠟系之伸 縮薄膜將玻璃容器端部位進行密封，測定此重量（WG )。 接著，於40。(： -7 5 %之恆溫恆濕器中靜置24小時後’精密 -16- 200938234 測定放冷後之重量（W!)，藉由下式算出透濕度。 透濕度（g/m2· 24h) ^(WG-Wi) xlOOOO + A W〇 :試驗前重量（g ) W!:試驗後重量（g ) A:玻璃容器開口部面積（26.4cm2) (吸水性試驗） 於不錄鋼容器（內徑：88mm、深度15mm)中置入約 10mL之生理食鹽水，將試驗材料切成4x4cm (試驗片） ，使膏體面作成內側，密封於容器內之狀態下保存8小時 。進行比較置入容器前之試驗片重量（WQ)與8小時後取 出之試驗片重量（)。 吸收量：WkWo (黏著力試驗） 使用醫藥品製造販賣指針2005 (第IV部醫藥品之製 造販賣確認申請，第1章 黏著力試驗）所載之試驗器 ，對於水平呈30度之斜面上使試驗製劑之黏著面往上放 置之。以適當的紙被覆上部l〇cm，下部15cm之部份，於 中央殘留 5cm之黏著面。由斜面的上端旋轉直徑 3.2mm~34.9mm之一連串的鋼球，測定中央黏著面上停止 5秒之球號數。將此於吸水前與8小時吸水後之製劑進行 評定。 -17- 200938234 〔表2〕 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 比較例4 比較例5 延伸率(％) 縱 14.2 5.0 50 12.5 0 5.7 12.5 2.5 橫 15.0 39.2 55 23.3 0 5.8 10.8 2.5 透濕度 (g/m2/24h) 884 1385 1367 1935 661 343 377 28 吸水量 (g/8h/16cm2) 2.52 2.79 2.71 2.02 2.37 0.64 0 1.14 黏著力 吸水前 10 10 11 8 7 21 17 3 (球號數） 吸水後 2 2 3 3 1 2 8 1 Ο (試驗例2) 依JIS LI 099纖維製品之透濕度試驗方法，以氯化鈣 法（A-1法、40°C -90%RH )測定實施例1〜3之被覆傷口材 料及比較例1〜2之被覆傷口材料所使用之各支撐體的透濕 度。其結果示於表3。 〔表3〕 實施例1 實施例2 實施例3 比較例1 比較例2 透濕度 (g/m2/24h) 1282 3699 3799 8541 942Further, the pH of the hydrogel is preferably in the range of pH 3.5 to 6.5, and more preferably in the range of ΡΗ4·0 to 5.5, depending on the skin irritation. As the pH adjuster, ruthenium acid such as tartaric acid, sodium hydrogen sulfite or ethylene diamine tetraacetate may be used as a crosslinking agent. For example, two or more kinds of dry hydrogen φ alumina gel, aluminum glycinate, and dihydroxy group may be used alone or in combination. A polyvalent metal compound such as an aluminoacetate, a synthetic hydrotalcite or a metal citrate is used. The amount of the compound varies depending on the type, and is generally 〇〇〇 id% by weight. In addition, preservatives, antioxidants, plasticizers, emulsifiers, surfactants, etc. may be added as necessary. The hydrogel of the present invention is coated with a wound material, and is suitable for use in a wound site, and must have an adhesive force with skin activity, and is required to be incapable of not damaging the adhesion of the regenerated skin upon replacement. Therefore, when the hydrogel coated wound material of the present invention is applied (before water absorption), the ball number is set to 8 to 12, and when the replacement is -11 - 200938234 (8 hours after water absorption), the ball number is set to 8~ The 12 applies to the proper adhesion of the wound site. When the ball number is less than 8, it will not be peeled off when applied to a movable wound site, which is not ideal. On the other hand, when the mouth part is too strong, the adhesion is too strong to cause the skin to be outside. When the ball number is 3 or less when replacing, the adhesion of the skin to the skin is increased, and if the ball exceeds the ball number, pain will occur, or the skin will be damaged. In addition, the above-mentioned ball number is based on the JIS method, and is subjected to a tilt angle of 30°. The method for producing a hydrogel coated wound material of the present invention is as a plastic thin polypropylene, polyester, polyvinyl chloride or the like, which is coated with a hydrogel surface, or a corona discharge treatment, a concavo-convex treatment, or a plasma. For example, the various types are grouped on the support, and the wound material is coated with a plastic film coated with a hydrogel. If necessary, it can be sterilized by general sterilization method or sterilized by ethylene oxide. [Examples] Hereinafter, examples and comparative examples are shown, and 3 or less. As long as the ball is applied, it can have an activity that can be used with the skin: it reduces the initial adhesion, and as the skin moves, the horse exceeds the ball number 12 and is used for the stimulation of the injury, which is not desirable. In addition, there will be no pain or damage when changing. 3 The adhesion is too high and the replacement is not ideal. Z023 7 Ball Adhesion Test The ball adhesion test method can be carried out by using polyethylene or a surface for polyfluorination treatment. The manufacturing method can be carried out by hydrolyzing the surface of the hydrogel which is known to be constructed, and then sterilizing the radiation of the hydrogel, and the electron beam can be carried out. More specifically, the present invention is not limited to the present invention. Limited to these embodiments. [Example 1] After carboxyvinyl polymer (1.6 g) was dissolved in an appropriate amount of purified water, D-sorbitol liquid (20 g) was added and mixed until uniform. More polyacrylic acid (0.3g), tartaric acid (1.2g) 'concentrated glycerin (20.7g), residual methylcellulose sodium (3.5g), polyacrylic acid partial neutralizer (4g), phthalic anhydride (0.1 g ), castor bean oil (1 · 5 g ), dihydroxy aluminum amino acetate (〇. 〇7 g), ethylene diamine tetraacetic acid disodium (〇.〇8g) and refined water (appropriate amount) are uniformly mixed , modulating the hydrogel. The hydrogel was spread on a urethane (20 μm) / nylon elastomer (25 g/m2), and the surface of the gel was coated with a polyester film to prepare a hydrogel-coated wound film. [Example 2] The composition of Example 2 shown in Table 1 was used in the same manner as in Example 1, and the hydrogel was adjusted to be extended to urethane (20 μm) / nylon wool knitwear ( In the support body, after the surface of the gel is covered with a polyester film, a hydrogel-coated wound material is prepared. [Example 3] After dissolving phthalic anhydride (〇5 g) in an appropriate amount of purified water, urea (1,6 g), disodium ethylenediaminetetraacetate (〇.〇8 g), and castor oil (〇5 g) were added. Mix until uniform. 20% polyacrylic acid aqueous solution (15.0g), tartaric acid (〇-3g), concentrated glycerin (16.〇g), 竣methylcellulose-13-200938234 素素素(4.Og), polyacrylic acid part A hydrogel was prepared by uniformly mixing the mixture (5. 〇g), magnesium phthalate (6 g), dry aluminum hydroxide gel (〇. 〇 2 g), and an appropriate amount of purified water. The hydrogel was spread on a urethane (20 μmη) / nylon elastomer (25 g/m2). After coating the surface of the gel with a polyester film, a hydrogel-coated wound material was prepared. [Comparative Example 1] Using the components of Comparative Example 1 shown in Table 1, a modified hydrogel was prepared in the same manner as in Example 1 and this was spread in a PET nonwoven fabric (100 g/m2) to prepare a coating material. [Comparative Example 2] Using the components of Comparative Example 2 shown in Table 1, in the same manner as in Example 1, the preparation of the hydrogel was extended to PET (20 μηι) / PET non-woven fabric (35 g/m2) to prepare Covered material. -14- 200938234 [Table 1] ❹ Ingredient (% by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Phthalic Anhydride 0.1 0.1 0.5 0.1 0.1 Polyacrylic acid 0.3 0.3 0.3 0.3 Carboxyrene polymer 1.6 1.6 Reference 1.6 1.6 D-sorbitol 20 20 20 20 Concentrated glycerol 20.7 20.7 16 20.7 20.7 Sodium carboxymethylcellulose 3.5 3.5 4 3.5 3.5 Polyacrylic acid partial neutralizer 4 4 5 4 4 Castor oil 1.5 1.5 0.5 1.5 1.5 20 % polyacrylic acid water _ _ 15 _ . tartaric acid 1 1 0.3 1 1 urea. _ 1.0 . Dihydroxy- amidoacetate 0.07 0.07 0.07 0.07 矽 面. • 0.06 . Dry aluminum hydroxide gel _ • 0.02 ethylene Disodium diaminetetraacetate 0.08 0.08 0.08 0.08 0.08 Refined water, moderate amount, moderate amount, suitable support, ammonium urethane 2 (W nylon elastomer 25g/m2 ammonium urethane 20μη/nylon wool knit ammonium urethane Ester 2〇μπι/nylon elastomer 25g/m2 PET non-woven fabric 100g/in2 PET2 μπι/PET non-woven fabric 35g/m2 [Comparative Example 3] duo active a recorder" (outer layer: polyurethane film 'adhesive layer: hydrophilic Hydrocolloid and particle hydrophobic Polymer, release paper: Polyoxynide release paper) [Comparative Example 4] Auxiliary facility stomach sample (applying an acrylic adhesive on a polyurethane film) [Comparative example bugel * Recorder" (support) : Polyethylene, hydrogel absorption -15- 200938234 体: Povidone, PVA, phenoxyethanol, water (8 〇)) [Test Example 1] Covered wound materials of Examples 1 to 3 and coatings of Comparative Examples After the use of the wound material, the stretchability, moisture permeability, water absorbency, and adhesion were measured according to the following test methods. The tannins were measured three times, and the average enthalpy was measured. The results are shown in Table 2. Sexuality test) The test of the stretchability is carried out according to the standard of the woven fabric of the SL 1 0 9 6 standard fabric test method. The test material is cut into 2x6 cm, and the sagittal print (lq) is attached at intervals of 4 cm. Clip, add 1 〇〇g fixed load, measure the distance between the marks (L i ), and calculate by the following formula: Elongation (%) = ( Lo-L! ) /L〇xl00 L〇: Length of the original mark (4cm) QL!: Length of the sagittal (cm) when adding l〇〇g to the load Moisture test) The moisture permeability test was carried out in accordance with the cup method of ns Z0208. About 1 〇mL of purified water was placed in a glass container (inner diameter: 56 mm, depth 11 mm), and the test material was cut into a circular shape (test piece) having a diameter of 80 mm so that the surface of the paste was formed inside, and the opening portion of the glass container was covered. The glass container end portion was sealed with a paraffin-based stretch film, and the weight (WG) was measured. Next, at 40. (: -7 5 % of the constant temperature and humidity device is allowed to stand for 24 hours. 'Precision-16- 200938234 Measure the weight after cooling (W!), and calculate the moisture permeability by the following formula. Permeability (g/m2· 24h) ^(WG-Wi) xlOOOO + AW〇: pre-test weight (g) W!: weight after test (g) A: glass container opening area (26.4cm2) (water absorption test) in non-recorded steel container (within A physiological saline solution of about 10 mL was placed in a diameter of 88 mm and a depth of 15 mm. The test material was cut into 4 x 4 cm (test piece), and the surface of the paste was placed inside, and sealed in a container for 8 hours. The weight of the test piece (WQ) and the weight of the test piece taken out after 8 hours. Absorbed amount: WkWo (adhesion test) The use of pharmaceutical products for sale and sales of the hand-in-hand 2005 (Part IV, the manufacture and sale confirmation of pharmaceutical products, the first The tester contained in the chapter Adhesive Test) placed the adhesive surface of the test preparation upward on a slope of 30 degrees horizontally. The upper part of the test piece was covered with appropriate paper, the lower part of 15 cm, and the center remained 5 cm. Adhesive surface. Rotated by the upper end of the inclined surface with a diameter of 3.2mm~34.9mm The ball was measured for the number of balls stopped on the central adhesive surface for 5 seconds, and the preparation was absorbed before water absorption and after 8 hours of water absorption. -17- 200938234 [Table 2] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Elongation (%) Vertical 14.2 5.0 50 12.5 0 5.7 12.5 2.5 Cross 15.0 39.2 55 23.3 0 5.8 10.8 2.5 Moisture permeability (g/m2/24h) 884 1385 1367 1935 661 343 377 28 Water absorption (g/8h/16cm2) 2.52 2.79 2.71 2.02 2.37 0.64 0 1.14 Adhesive force 10 10 11 8 7 21 17 3 (number of balls) 2 2 3 3 1 2 8 1 1 after water absorption (test case 2) According to the moisture permeability test method of JIS LI 099 fiber product, the coated wound materials of Examples 1 to 3 and Comparative Examples 1 to 2 were measured by the calcium chloride method (A-1 method, 40 ° C - 90% RH). The moisture permeability of each support used for covering the wound material. The results are shown in Table 3. [Table 3] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Moisture permeability (g/m2/24h) 1282 3699 3799 8541 942
(試驗例3) 將實施例1~3之被覆傷口材料及比較例丨、3、4之被 覆傷口材料貼附於濕潤的海綿上。將此海綿置於循環3 7 t 溫水之不銹鋼容器中。更於被覆傷口材料與海綿間挾夾溫 濕度感應器經時的測定貼附部位之溫濕度變化至2 4小時 -18- 200938234 者。其結果示於圖1。 (討論） 由圖1，市售品之比較例3及4之被覆傷口材料（製 劑之透濕度：3 4 3及3 7 7 )其由貼附後約第2小時開始適 用部位之濕度幾乎爲100%，此狀態持續24小時。因此， 比較例3及4之被覆傷口材料適用於傷口面時，其製劑的 0 透濕度太低，導致由傷口面之滲出液容易滯留於傷□面， 使傷口面維持於過度的濕潤狀態，長時間貼附時，於貼附 部位出現斑點，恐有不快感，務必頻繁更換被覆傷口材料 等問題存在。又，比較例1之被覆傷口材料由貼附後適用 部位之濕度下降開始，貼附後第2小時呈60%，此狀態持 續24小時。因此，使用高透濕度之支撐體（支撐體之透 濕度：8 54 1 )之比較例1之被覆傷口材料適用於傷口部位 時，貼附後傷口面之水份消失無法維持適度的濕潤環境， φ 長時間適用後，水凝膠乾燥後，導致再生皮膚與水凝膠之 黏合，於更換時，恐損及再生皮膚。 對於此，本發明之實施例1及3之被覆傷口材料（製 劑之透濕度：8 8 4及1 3 6 7 )於貼附後濕度慢慢下降開始， 維持約80%之濕度24小時，顯示可長時間維持利於傷口 癒合之理想的濕潤狀態。 亦即，支撐體透濕度爲200〜5000 ( g/m2/24hr )之支 撐體與由水凝膠所成之本發明被覆傷口材料適用於傷口部 位時，水凝膠將傷口面之滲出液吸收後，使滲出液中多餘 -19- 200938234 的水份藉由由支撐體透過後’防止滲出液之滯留，因此， 不會使傷口面呈過度濕潤狀態’由本試驗結果，顯示可長 時間維持適於促進傷口面癒合之濕潤環境，證明可保持適 於促進傷口面癒合之濕潤環境。 (試驗例4) 將實施例1〜3之被覆傷口材料及市售品之比較例3〜5 之被覆傷口材料貼附於5名受驗者之前腕’ 4個小時後’ 藉由下述基準，進行評定皮膚黏著性及剝離時之疼痛狀況 (皮膚黏著性） 針對皮膚黏著性，作成「未剝離」、「剝離一半」、 「剝離」之3階段評定。 其結果示於表4。 ❹ 〔表4〕 實施例1 實施例2 實施例3 比較例3 比較例4 比較例5 評定點 1 1 2 1 1 3 評定基準點 1 =無剝離 2 :剝離一半 3 :剝離 -20- 200938234 (剝離時之疼痛） 針對由皮膚剝離時之疼痛狀態，作成「完全不痛」、 「不太有疼痛感覺」、「疼痛感」之三階段評定。其結果 示於表5 ^ 〔表5〕 實施例1 實施例2 實施例3 比較例3 比較例4 比較例5 評定點 1 1 1 3 3 1 評價基準點 1 :完全不痛 2:不太有疼痛感覺 3 :疼痛感 【圖式簡單說明】 〔圖1〕代表各被覆傷口材料之經時性局部濕度變化 ❹ 之圖。 '21-(Test Example 3) The coated wound materials of Examples 1 to 3 and the coated wound materials of Comparative Examples 3 and 4 were attached to a wet sponge. The sponge was placed in a stainless steel container with a circulating water of 3 7 t. Moreover, the temperature and humidity of the attached parts were changed to 24 hours -18- 200938234 by the temperature of the covered wound material and the temperature of the sponge. The result is shown in Fig. 1. (Discussion) From Fig. 1, the coated wound materials of Comparative Examples 3 and 4 of the commercial products (the moisture permeability of the preparations: 3 4 3 and 37 7 ) are almost the humidity of the applicable portion from the second hour after the attachment. 100%, this state lasts for 24 hours. Therefore, when the coated wound materials of Comparative Examples 3 and 4 are applied to the wound surface, the moisture permeability of the preparation 0 is too low, so that the exudate from the wound surface is easily retained on the wound surface, and the wound surface is maintained in an excessively moist state. When attaching for a long time, spots appear on the attached parts, which may cause unpleasant feelings, and it is necessary to frequently replace the wound material. Further, the coated wound material of Comparative Example 1 was started from the humidity drop of the applied portion after the attachment, and was 60% at the second hour after the attachment, and this state was continued for 24 hours. Therefore, when the coated wound material of Comparative Example 1 using the high moisture permeability support (the moisture permeability of the support: 8 54 1 ) is applied to the wound site, the moisture of the wound surface after the attachment disappears, and the moderate moist environment cannot be maintained. φ After long-term application, after the hydrogel is dried, the regenerated skin and the hydrogel will adhere to each other, and when replaced, the skin will be damaged and regenerated. In this regard, the coated wound materials of the first and third embodiments of the present invention (the moisture permeability of the preparation: 8 8 4 and 1 3 6 7) began to slowly decrease in humidity after attachment, and maintained a humidity of about 80% for 24 hours, showing It maintains the ideal moist state for wound healing for a long time. That is, when the support having a moisture permeability of 200 to 5000 (g/m 2 /24 hr) and the coated wound material of the present invention made of a hydrogel are applied to a wound site, the hydrogel absorbs the exudate of the wound surface. After that, the excess -19-200938234 of the water in the exudate is passed through the support to prevent the retention of the exudate, so that the wound surface is not over-wet. As a result of the test, it can be maintained for a long time. In a moist environment that promotes wound healing, it has been proven to maintain a moist environment suitable for promoting wound healing. (Test Example 4) The coated wound materials of Examples 1 to 3 and the coated wound materials of Comparative Examples 3 to 5 of the commercial products were attached to the wrists of the subjects 5 hours after the '4 hours' by the following criteria For assessing skin adhesion and pain during peeling (skin adhesion) For skin adhesion, a three-stage evaluation of "not peeled off", "half peeled off", and "peeled off" was made. The results are shown in Table 4. 〔 [Table 4] Example 1 Example 2 Example 3 Comparative Example 3 Comparative Example 4 Comparative Example 5 Evaluation point 1 1 2 1 1 3 Evaluation reference point 1 = no peeling 2: peeling half 3: peeling -20- 200938234 ( Pain at the time of peeling) A three-stage evaluation of "no pain at all", "no pain feeling", and "painful feeling" is made for the pain state when the skin is peeled off. The results are shown in Table 5 ^ [Table 5] Example 1 Example 2 Example 3 Comparative Example 3 Comparative Example 4 Comparative Example 5 Evaluation Point 1 1 1 3 3 1 Evaluation Reference Point 1: No pain at all 2: Not quite Pain sensation 3: Pain sensation [Simplified illustration] [Fig. 1] A graph showing temporal changes in local humidity of each coated wound material. 'twenty one-