CN1116085A - 表面层由至少一种透明质酸酯组成的多层无纺织物 - Google Patents
表面层由至少一种透明质酸酯组成的多层无纺织物 Download PDFInfo
- Publication number
- CN1116085A CN1116085A CN94116145A CN94116145A CN1116085A CN 1116085 A CN1116085 A CN 1116085A CN 94116145 A CN94116145 A CN 94116145A CN 94116145 A CN94116145 A CN 94116145A CN 1116085 A CN1116085 A CN 1116085A
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- woven material
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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Abstract
本发明提供的是多层无纺材料,包括一个和皮肤接触的表面层,一个或多个不和皮肤接触的层;其中所述的和皮肤接触的表面层选自下述的表面层:含至少一种透明质酸衍生物的表面层;含有所述至少一种透明质酸衍生物和至少一种天然聚合物、半合成聚合物或合成聚合物的混合物的表面层;以及含有和生长在其表面上的细胞相容的天然、合成或半合成生物可相容多孔膜的表面层。透明质酸衍生物可以是透明质酸酯。这种材料可以广泛应用于医疗和卫生领域。
Description
本发明涉及一种新的材料,即多层无纺织物,其中多层之一含有透明质酸的衍生物。
本领域的研究目的在于获得具有良好皮肤覆盖性的生物材料,其由透明质酸酯或与其它聚合物混合组成,这些研究已产生出各种产品。例如涉及的纱和薄膜等织物分别记载在US.4,851,521和US.4,965,353中。作为覆盖皮肤,使用这些制品的缺陷是由于其硬度,这可能随它们的制造方法而变化,及由于不良的流体吸收性,例如在织物修补过程中流体从伤口处流出。通过利用无纺织物制造技术,可得到既有柔韧性又有充分吸收流体之性能的制品。这些特征在不少专利中都有描述,如US.5,041,104。
利用现有已知技术得到由透明质酸衍生物和/或它们的混合物组成的制品,其缺陷大致归纳如下:
(1)该物质在湿的时候不良的机械特性,这是因为当和水性流体如生理流体接触时,它趋于形成凝胶;
(2)过多使用昂贵物质如透明质酸衍生物或与其它生物可相容和生物可吸收聚合物的混合物,这导致成品高费用,尽管聚合物仅需存在于与施用部位直接接触的层中;
(3)过高的蒸汽传递值。
在有不良流出物产生时,上述缺陷表现得尤其明显。
因此,本发明的一个目的是提供多层无纺材料,包含与皮肤接触的一个表面层和一个或多个不与皮肤接触其它层,其中所述的与皮肤接触的表面层是选自下列的表面层:至少包括一种透明质酸的衍生物的表面层,包括至少一种上述透明质酸衍生物和至少一种天然聚合物、半合成聚合物或合成聚合物的表面层,包括和生长在表面上的细胞相容的天然、合成或半合成的生物可容性多孔膜的表面层。在优选的实施方案中,与皮肤接触的层含有透明质酸衍生物,即含透明质酸部分的化合物,尤其是透明质酸酯或其混合物。
这样的制品具有良好的机械和流体吸收特性,柔韧、松软、价格合理,而且根据它们渗透水蒸汽的能力可以变化。
本发明的另一个目的是提供多层无纺材料,其中所述的一个或多个不接触皮肤的层包含作为所述多层无纺材料加强部分和/或流体吸收体系的天然的、合成的或半合成的材料,因此把生物可容和生物可吸收聚合物的用量减少到最小,在需要部位集中其作用。
本发明进一步的目的是提供如上所述的多层无纺材料,其中把所述的皮肤接触的表面层和一个或多个不接触皮肤的层固定在一起的方法利用了下列至少一种技术:化学凝固剂法、粘合剂法和机械缝合。
这些多层无纺织物可用作非粘性卫生或外科制品在例如外科、皮肤科如治疗皮肤病症、口腔科(odontostomatology)、整形外科、神经外科和治疗耳朵或鼻子中使用。
本发明进一步应用的范围将从下面的详细描述中得以证明,但是,应该理解到在本发明阐述优选实施方案时,细节的描述和特定的实施例仅为提供说明,因为在本发明精神和范围内的各种变化和改动,对于本领域的技术人员来说,从这些详细的描述中会很清楚。
本发明下列的详细说明为本领域技术人员在实施本发明时提供了帮助,但是,以下的详细描述不应理解为过分地限制本发明,在不脱离本发明精神和范围的前提下,本发明所讨论实施方案中的改动和变化,对于本领域技术人员来说是可以做到的。
本文提到的每篇参考文献的内容在此被全文引作参考。
通过利用本发明的多层无纺织物完成上述的和别的目的,该织物的织物单位重量为20g/mq~500g/mq,厚0.5mm~20mm,最少2~4层,和其重量相比水吸收百分比为60%~150%,24小时的水蒸汽渗透值为100~4500g/mq。
多层无纺织物可描述为含有多层的材料,它们通过化学凝固剂和/或粘结剂或机械缝合的方法固定在一起。每层含有直径为8-60微米、长度为5mm~100mm的纤维,用化学凝固剂或粘结剂或机械缝合法把它们结合在一起。
和皮肤接触层包含透明质酸酯如EPA0216453和US.4,851,521、US.4,965,353、US.5,202,431中所述,在各种百分值下既可单独使用也可混合使用。另外,该层也可包含透明质酸酯纤维与下列纤维的混合物,来自天然聚合物的纤维,这些天然聚合物如胶原蛋白和胶原蛋白葡糖胺聚糖(glycosaminoglycan)共沉淀物、纤维素、形式为凝胶的多糖如几丁质、脱乙酰几丁质、果胶、或果胶酸、琼脂、琼脂糖、黄原胶、gellan、藻酸、各种藻酸盐、藻酸酯、聚甘露聚糖或多聚糖、淀粉、天然树胶;或从天然聚合物的半合成衍生物得到的纤维,这些衍生物例如:与交联剂交联的胶原蛋白、交联剂如醛类或其前体、二羧酸或其卤化物、二胺、所述衍生物又如纤维素、藻酸、淀粉、透明质酸、几丁质、脱乙酰几丁质、gellan、黄原胶、果胶、果胶酸、多聚糖、聚甘露聚糖、琼脂、琼脂糖、天然树胶、葡糖胺聚糖的衍生物;或从合成聚合物得到的纤维,所述聚合物例如聚乳酸、聚乙二醇酸或其共聚物或它们的衍生物、聚二噁烷、聚膦嗪、聚砜和聚氨基甲酸乙酯。
作为这里利用的,术语“衍生物”指含有所述部分的化合物,例如术语“纤维素衍生物”定义为含有纤维素部分的化合物。
上层可以为无纺织物或机织结构的形式,它们具有强化制品和/或吸收流体和调节水蒸汽渗透的功能。它们可以由天然纤维如棉,或再生纤维如粘胶人造丝,或合成聚合物如聚酯、聚酰胺、聚亚烷基或它们的混合物的纤维构成。另外,这些层可由柔韧的泡沫组成,如聚氨基甲酸乙酯,或合成的弹性类型的膜如弹性聚硅氧烷或弹性聚氨基甲酸乙酯。
通过无纺材料技术普通的方法把各种层固定在一起。这些方法包括例如机械缝合方法或用凝固剂或粘结剂的化学法,它们适合于纤维的固结或各种层的连接,这些方法记载在《卫生吸收制品的无纺技术》(Nonwoven Technologies for Sanitary Absorbent Products)第185-190页。一个粘合剂的例子是丙烯酸酯粘合剂,AcronalDS 2331 X。
因此本发明涉及一个新制品:多层无纺织物,用于医疗/药物领域以覆盖皮肤以及用于外科手术中。和皮肤接触的表面层由至少一种透明质酸酯或其与其它天然的或合成的聚合物的混合物组成;其它合成或半合成材料的层作为材料的强化和/或流体吸收体系。
和皮肤接触的表面层也可由天然的、合成的或半合成的、与生长在其表面上的细胞相容的生物可相容的多孔膜组成。这些天然的和半合成生物可容的多孔膜的例子记载在EP 0462426中。用于这些膜的天然物质包括胶原蛋白或胶原蛋白和葡糖胺聚糖的共沉淀物,纤维素、胶凝的多糖如几丁质、脱乙酰几丁质、果胶、果胶酸、琼脂、琼脂糖、黄原胶、gellan、藻酸、藻酸盐、聚甘露聚糖、多聚糖、淀粉、或天然橡胶,它们既可以单独使用也可在合适的沉淀剂或胶凝剂如金属盐、聚阳离子或聚阴离子存在下,互相混合或与合成的或半合成的聚合物混合。用于本发明多层无纺织物的合成的生物可容多孔膜的例子包括聚乳酸、聚乙二醇酸、它们的共聚物或衍生物、聚二噁烷、聚膦嗪、聚砜、聚氨基甲酸乙酸、天然聚合物的半合成衍生物如交联的胶原蛋白,交联剂如二醛或其前体、二羧酸或其卤化物、二胺、或纤维素、藻酸、淀粉、几丁质、脱乙酰几丁质、gellan、黄原胶、果胶、果胶酸、多聚糖、聚甘露聚糖、琼脂、琼脂糖、天然橡胶或葡糖胺聚糖的衍生物。这些合成膜也可包括非生物降解的合成聚合物如聚硅氧烷、硅烷、或硅氧烷橡胶、含氟聚合物如聚氟代乙烯、聚氟代丙烯、聚氟代醚、聚苯乙烯、聚乙烯氯化物、聚丙烯酸酯或其衍生物、多羟基丙烯酸酯、多羟基异丁烯酸酯、羧乙烯基聚合物和它们的衍生物、马来酐聚合物和它们的衍生物、聚氯乙烯、聚乙烯醇和它们的衍生物、聚乙烯和聚丙烯。
本发明的无纺织物也可用下列物质的溶液浸渍:抗菌素、防腐剂、抗有丝分裂物、多肽、蛋白质、或任何其它类型的药物活性化合物。
本发明新材料的特性使其在外科手术领域特别有用,例如耳科和耳神经的显微外科官能的、外伤和内窥鼻窦显微外科、整形和修复外科以及其它的外科适应症,它们利用了具有本发明所要求特性包括其抗粘的特性的材料。
仅为达到说明的目的,下面记叙了本发明多层无纺织物的一些实施例。
实施例1
通过下列方法得到一种多层无纺织物,其组成为:透明质酸苄基酯层HYAFF 11和无纺粘胶纤维(ORSA的Jettex 2005),织物单位重量80g/mq,厚2mm,水吸收百分值560%wt。
和皮肤接触的层包括用湿纺技术以30g/mq薄层的形式制造的HYAFF11纤维。纤维形成薄层的方法参见WO93/11803。
通过缝合法把上述层与织物单位重量30g/mq的第二层无纺粘胶纤维织物结合起来。
因此,最后该无纺产品包含两个牢固粘合的薄层,总织物单位重量为80g/mq,厚2mm,水吸收百分值为560%wt。
实施例2
按照下列方法得到一种多层无纺织物,包括一个透明质酸乙酯HYAFF 7层,和一个无纺聚酯层(FNT的BEST BOND 20PS),织物单位量量为50g/mq,厚1mm,水吸收值为400%wt。
和皮肤接触的层为用湿纺技术以30g/mq薄层的形式制造的HYAFF 7纤维,其通过缝合法与织物单位重量20g/mq的第二层无纺聚酯相连。
因此,最后的无纺制品由两个牢固粘合的薄层组成,总的织物单位重量为50g/mq,厚1mm,水吸收百分值为400%wt。
实施例3
通过下列方法得到一种多层无纺织物,为透明质酸苄基酯,HYAFF11和藻酸钙以比例1∶1混合的层及聚丙烯无纺织物强化层(来自NEUBERGER的纺丝粘合的无纺基,50g/mq),织物单位重量70g/mq,厚1.5mm,水吸收百分值450%wt。
由传统的湿纺技术得到长40mm的HYAFF11和藻酸钙纤维,将它们混合,制成20g/mq薄层,通过缝合法将其和织物单位重量为50g/mq纺丝粘合(nonwoven spurbonded)的无纺织物结合。
所得物质包括两层无纺织物,总织物单位重量70g/mq,厚1.5mm,水吸收百分值为450%wt。
实施例4
通过下列方法得到一种多层无纺织物,其包括透明质酸75%部分苄酯HYAFF11 P75层,和聚氨基甲酸乙酯泡沫层如LYOBENO(来自DELCON),织物单位重量100g/mq,厚5mm,水吸收百分值为950%wt。
和皮肤接触层包括由湿纺技术制造的HY AFF 11 P75纤维,制成45g/mq薄层,通过缝合法将其和聚氨基甲酸乙酯泡沫层结合。
所得的无纺制品包括两个牢固结合在一起的层,总织物单位重量100g/mq,厚4mm,水吸收百分值为950%wt。
实施例5
通过下列方法得到一种多层无纺织物,其包括透明质酸苄酯HYAFF11层和聚氨基甲酸乙酯泡沫层如LYOBEND(来自DELCON),织物单位重量100g/mq,厚6mm,水吸收百分值860%wt。
和皮肤接触的层包括由湿纺技术制造的HYAFF11纤维,并制成45g/mq薄层,通过缝合法和聚氨基甲酸乙酯泡沫层结合。
所得的无纺制品包含两个牢固粘合层,总织物单位重量100g/mq,厚6mm,水吸收百分值为860%wt。
实施例6
按照下列方法得到一种多层无纺织物,其包括三层,织物单位重量200g/mq,厚3mm,其中和皮肤接触的层为按等比例混合的透明质酸部分苄酯HYAFF11P75和藻酸苄酯ALAFF11;第二层为聚氨基甲酸乙酯缓冲层如DS50 FOAN(来自ORSA),密度为55/69kg/cc(UNI规则6349);第三层为聚氨基甲酸乙酯膜,24小时水蒸汽渗透值为426g/mq。ALAFF11和其它完全和部分藻酸酯的制备记载在EPA.0251905和US.5,264,422中。
通过湿纺法得到长40mm的HYAFF11和ALAFF11纤维,与聚氨基甲酸乙酯泡沫缓冲层表面缝合,另一表面用DURO-TAK 380-1054胶(来自NATIONAL)和聚氨基甲酸乙酯膜粘合。最后的材料包括三层,最终织物单位重量200g/mq,厚度8mm,水吸收百分值为1100%wt。24小时蒸汽渗透值为450g/mq。
实施例7
按照下列方法得到一种多层无纺织物,其包括透明质酸苄酯层HYAFF11;和无纺粘胶纤维层(Jettex 2005来自ORSA),织物单位重量80g/mq,厚2mm,其和有0.5mm孔的多孔HYAFF 11膜结合,该膜制法见EPA 0462426。
在按实施例1所述方法得到的无纺织物的HYAFF11表面上喷以浓度为60mg/ml的HYAFF11/DMSO溶液,然后把有0.5mm孔的多孔膜贴在它上面。接着,把膜和无纺织物压在一起,浸于乙醇浴中,洗涤并干燥。
所得的无纺织物织物单位重量80g/mq,厚2mm,包括三层,其中有一层由具有0.5mm孔的多孔膜构成。
很显然,本文所描述的发明可以以多种方法进行改进。这样的修改不能认为是脱离本发明的精神和目的,对于本领域技术人员来说显而易见的任何改动均属于下面权利要求的范围。
Claims (36)
1.一种多层无纺材料,包括一个和皮肤接触的表面层,一个或多个不和皮肤接触的层,其中所述的和皮肤接触的表面层选自以下的表面层,含至少一个透明质酸衍生物的表面层、含有所述至少一个透明质酸衍生物和至少一个天然聚合物、半合成聚合物或合成聚合物的混合物的表面层,以及含有和生长在其表面上的细胞相容的生物可容的天然、合成或半合成的多孔膜的表面层。
2.根据权利要求1的多层无纺材料,其中所述的至少一种透明质酸的衍生物是透明质酸酯。
3.根据权利要求1的多层无纺材料,其中所述的至少一种天然聚合物选自胶原蛋白、胶原蛋白-葡糖胺聚糖(glycosaminoglycan)共沉淀物、纤维素、几丁质、脱乙酰几丁质、果胶、果胶酸、琼脂、琼脂糖、黄原胶、gellan、藻酸、藻酸盐、聚甘露聚糖、多聚糖、淀粉、天然树胶;所述的至少一种半合成聚合物选自藻酸酯、交联的胶原蛋白、纤维素衍生物、藻酸衍生物、淀粉衍生物、透明质酸衍生物、几丁质衍生物、脱乙酰几丁质衍生物、gellan衍生物、黄原胶衍生物、果胶衍生物、果胶酸衍生物、多聚糖衍生物、聚甘露聚糖衍生物、琼脂衍生物、琼脂糖衍生物、天然树胶衍生物、葡糖胺聚糖衍生物;所述的至少一种合成聚合物选自聚乳酸、聚乙二醇酸、聚乳酸和聚乙二醇酸的共聚物、聚乳酸衍生物和聚乙二醇酸衍生物的共聚物、聚二噁烷、聚膦嗪、聚砜和聚氨基甲酸乙酯。
4.根据权利要求1的多层无纺织物,其中所述的一个或多个不和皮肤接触的层为一天然的、合成的或半合成的材料,其作为所述多层无纺材料的加强物和/或流体吸收体系。
5.根据权利要求4的多层无纺织物,其中所述的天然材料是棉;所述的合成材料选自粘胶人造丝、聚酯、聚酰胺、聚亚烷基、以上几种的混合物、聚氨基甲酸乙酯、弹性聚硅氧烷、弹性聚氨基甲酸乙酯;所述的半合成材料为至少一种透明质酸酯。
6.根据权利要求1的多层无纺材料,其中所述的和皮肤接触的表面层包括至少一种透明质酸酯。
7.根据权利要求6的多层无纺材料,其中所述的至少一种透明质酸酯选自透明质酸苄基酯和透明质酸乙酯。
8.根据权利要求7的多层无纺材料,其中所述的透明质酸苄酯是透明质酸75%部分苄酯。
9.根据权利要求1的多层无纺材料,其中所述的和皮肤接触的表面层为透明质酸苄酯和藻酸苄酯的混合物。
10.根据权利要求1的多层无纺材料,其中所述的和皮肤接触的表面层为透明质酸苄酯和藻酸钙的混合物。
11.根据权利要求1的多层无纺材料,其中所述的和皮肤接触的表面层包括与生长在其表面的上的细胞相容的天然的、合成的或半合成的生物可相容多孔膜。
12.根据权利要求11的多层无纺材料,其中所述的天然的、合成的或半合成的生物可相容多孔膜厚度为10~500μ,具有一系列孔,固定孔径为10~1000μ,其中每个孔和相邻的孔分开距离为50~1000μ。
13.根据权利要求11的多层无纺材料,其中所述的半合成生物可相容多孔膜包括至少一种透明质酸酯。
14.根据权利要求13的多层无纺材料,其中所述的至少一种透明质酸酯为透明质酸苄酯。
15.根据权利要求11的多层无纺材料,其中所述的天然的生物可相容多孔膜包括的材料选自胶原蛋白、胶原蛋白和葡糖胺聚糖的共沉淀物、纤维素、几丁质、脱乙酰几丁质、果胶、果胶酸、琼脂、琼脂糖、黄原胶、gellan、藻酸、藻酸盐、聚甘露聚糖、多聚糖、淀粉、天然橡胶、上述任何物质的混合物、上述任意物质和合成聚合物的混合物、上述任意物质和半合成聚合物的混合物。
16.根据权利要求11的多层无纺材料,其中所述的合成生物可相容的多孔膜包括的物质选自聚乳酸、聚乙二醇酸、聚乳酸和聚乙二醇酸的共聚物、聚乳酸的衍生物和聚乙二醇酸衍生物的共聚物、聚二噁烷、聚膦嗪、聚砜、聚氨基甲酸乙酯、天然聚合物的半合成衍生物、纤维素衍生物、藻酸、淀粉、几丁质、脱乙酰几丁质、gellan、黄原胶、果胶、果胶酸、多聚糖、聚甘露聚糖、琼脂、琼脂糖、天然橡胶、葡糖胺聚糖、聚硅氧烷、硅烷、硅氧烷橡胶、含氟聚合物、聚苯乙烯、聚乙烯氯化物、聚丙烯酸酯、聚丙烯酸酯的衍生物、聚羟基丙烯酸酯、聚羟基异丁烯酸酯、羧乙烯基聚合物、羧乙烯基聚合物的衍生物、马来酐聚合物、马来酐聚合物的衍生物、聚氯乙烯、聚乙烯醇、聚乙烯醇衍生物、聚乙烯和聚丙烯。
17.根据权利要求16的多层无纺材料,其中所述的天然聚合物的半合成衍生物是和交联剂交联的胶原蛋白,交联剂选自二醛、二醛前体、二羧酸、二羧酸的卤化物和二元胺。
18.根据权利要求16的多层无纺材料,其中所述的含氟聚合物选自聚氟代乙烯、聚氟代丙烯、聚氟代醚。
19.根据权利要求1的多层无纺材料,其中所述的一个或几个不和皮肤接触的层含有粘胶人造丝。
20.根据权利要求1的多层无纺材料,其中所述的一个或多个不和皮肤接触的层含有无纺纺丝粘合(nonwoven spunbonded)的聚丙烯。
21.根据权利要求1的1多层无纺材料,其中所述的一个或多个不和皮肤接触的层含有聚氨基甲酸乙酯泡沫。
22.根据权利要求1的多层无纺材料,织物单位重量40g/mq~500g/mq厚0.5mm~20mm,纤维直径8μm~60μm,长5mm~100mm,2~4层,水吸收百分值为60%~500%,水蒸汽渗透值100~4500g/mq·24小时。
23.根据权利要求1的多层无纺材料,其中所述的和皮肤接触的表面层和所述一个或多个不和皮肤接触的层固定在一起的方法至少选自化学凝固剂法、粘结剂法和机械缝合法。
24.根据权利要求1的多层无纺材料,包括缝合在一起的两层或多层。
25.根据权利要求1的多层无纺材料,包括缝合在一起的两层,其中所述的不和皮肤接触的层为聚氨基甲酸乙酯泡沫。
26.根据权利要求1的多层无纺材料,包括三层,其中所述的和皮肤接触的层是含透明质酸完全苄基酯的生物可相容多孔膜。
27.根据权利要求1的多层无纺材料,含有药物活性化合物。
28.根据权利要求27的多层无纺材料,其中所述的药物活性化合物选自抗菌素、防腐剂、抗有丝分裂物、多肽和蛋白质。
29.根据权利要求1-28任何之一的多层无纺材料在外科中的应用。
30.根据权利要求1-28任何之一的多层无纺材料在治疗皮肤疾病中的应用。
31.根据权利要求1-28任何之一的多层无纺材料用在皮肤科的应用。
32.根据权利要求1-28任何之一的多层无纺材料用于口腔科(odontostomatology)的应用。
33.根据权利要求1-28任何之一的多层无纺材料用于整形外科的应用。
34.根据权利要求1-28任何之一的多层无纺材料用于神经外科的应用。
35.根据权利要求1-28任何之一的多层无纺材料用于治疗耳或鼻的应用。
36.根据权利要求1-28任何之一的多层无纺材料用作抗粘材料的应用。
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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ITPD930024A IT1263316B (it) | 1993-02-12 | 1993-02-12 | Tessuto non tessuto multistrato in cui uno degli strati e' costituito essenzialmente da esteri dell'acido ialuronico |
EP94907550A EP0683679B1 (en) | 1993-02-12 | 1994-02-11 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
US08/505,325 US5658582A (en) | 1993-02-12 | 1994-02-11 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
PCT/EP1994/000397 WO1994017837A1 (en) | 1993-02-12 | 1994-02-11 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
ES94907550T ES2184759T3 (es) | 1993-02-12 | 1994-02-11 | Elemento laminar no tejido, de capas multiples, que contiene una capa superficial que comprende como minimo un ester de acido hialuronico. |
JP6517674A JPH08506255A (ja) | 1993-02-12 | 1994-02-11 | 少なくとも1つのヒアルロン酸エステルを含んでなる表面層を含む多層不織組織 |
CA002155319A CA2155319C (en) | 1993-02-12 | 1994-02-11 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
AT94907550T ATE226452T1 (de) | 1993-02-12 | 1994-02-11 | Mehrschichtige, nichtgewebte gewebe mit einer oberflächenschicht mit mindestens einem hyaluronsäure-esterderivat |
DE69431591T DE69431591T2 (de) | 1993-02-12 | 1994-02-11 | Mehrschichtige, nichtgewebte gewebe mit einer oberflächenschicht mit mindestens einem hyaluronsäure-esterderivat |
AU61088/94A AU681873B2 (en) | 1993-02-12 | 1994-02-11 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
CNB941161455A CN1136823C (zh) | 1993-02-12 | 1994-07-30 | 表面层由至少一种透明质酸酯组成的多层无纺织物 |
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ITPD930024A IT1263316B (it) | 1993-02-12 | 1993-02-12 | Tessuto non tessuto multistrato in cui uno degli strati e' costituito essenzialmente da esteri dell'acido ialuronico |
CNB941161455A CN1136823C (zh) | 1993-02-12 | 1994-07-30 | 表面层由至少一种透明质酸酯组成的多层无纺织物 |
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CN1136823C CN1136823C (zh) | 2004-02-04 |
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CNB941161455A Expired - Fee Related CN1136823C (zh) | 1993-02-12 | 1994-07-30 | 表面层由至少一种透明质酸酯组成的多层无纺织物 |
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US (1) | US5658582A (zh) |
EP (1) | EP0683679B1 (zh) |
JP (1) | JPH08506255A (zh) |
CN (1) | CN1136823C (zh) |
AT (1) | ATE226452T1 (zh) |
AU (1) | AU681873B2 (zh) |
CA (1) | CA2155319C (zh) |
DE (1) | DE69431591T2 (zh) |
ES (1) | ES2184759T3 (zh) |
IT (1) | IT1263316B (zh) |
WO (1) | WO1994017837A1 (zh) |
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US5264422A (en) * | 1986-06-30 | 1993-11-23 | Fidia S.P.A. | Esters of alginic acid with steroidal alcohols |
FR2617502B1 (fr) * | 1987-06-30 | 1990-03-09 | Elf Aquitaine | Preparation enzymatique d'anhydro-1,5 d fructose |
IT1219587B (it) * | 1988-05-13 | 1990-05-18 | Fidia Farmaceutici | Polisaccaridi carbossiilici autoreticolati |
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GB9109367D0 (en) * | 1991-05-01 | 1991-06-26 | Merck Sharp & Dohme | Surgical dressing |
IT1254704B (it) * | 1991-12-18 | 1995-10-09 | Mini Ricerca Scient Tecnolog | Tessuto non tessuto essenzialmente costituito da derivati dell'acido ialuronico |
IT1260154B (it) * | 1992-07-03 | 1996-03-28 | Lanfranco Callegaro | Acido ialuronico e suoi derivati in polimeri interpenetranti (ipn) |
SE507207C2 (sv) * | 1992-10-21 | 1998-04-20 | T & M Biopolymer Ab | alpha-1,4-glukanlyas från alg, sätt att bryta ned terminala alpha-1,4-D-glukosidbindningar med sagda enzym samt nedbrytningsprodukten 1,5-anhydrofruktos och dess användning som läkemedel och som antioxidant |
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1993
- 1993-02-12 IT ITPD930024A patent/IT1263316B/it active IP Right Grant
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1994
- 1994-02-11 JP JP6517674A patent/JPH08506255A/ja active Pending
- 1994-02-11 ES ES94907550T patent/ES2184759T3/es not_active Expired - Lifetime
- 1994-02-11 DE DE69431591T patent/DE69431591T2/de not_active Expired - Lifetime
- 1994-02-11 EP EP94907550A patent/EP0683679B1/en not_active Expired - Lifetime
- 1994-02-11 WO PCT/EP1994/000397 patent/WO1994017837A1/en active IP Right Grant
- 1994-02-11 CA CA002155319A patent/CA2155319C/en not_active Expired - Lifetime
- 1994-02-11 AT AT94907550T patent/ATE226452T1/de active
- 1994-02-11 AU AU61088/94A patent/AU681873B2/en not_active Ceased
- 1994-02-11 US US08/505,325 patent/US5658582A/en not_active Expired - Lifetime
- 1994-07-30 CN CNB941161455A patent/CN1136823C/zh not_active Expired - Fee Related
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CN106456829A (zh) * | 2014-03-21 | 2017-02-22 | 吴帆 | 卫生吸收性结构 |
CN107249651A (zh) * | 2015-02-27 | 2017-10-13 | 大日精化工业株式会社 | 医疗用材料和防粘连材料 |
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CN105220459A (zh) * | 2015-11-12 | 2016-01-06 | 长兴县高强纺织有限公司 | 一种涤纶面料的抗菌柔软整理助剂 |
CN105256537A (zh) * | 2015-11-13 | 2016-01-20 | 浙江森悦纺织科技有限公司 | 一种涤纶面料的防晒整理剂 |
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CN110483832A (zh) * | 2019-09-06 | 2019-11-22 | 云南师范大学 | 多特性的天然橡胶和琼脂复合介孔膜及制备方法 |
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CN110483832B (zh) * | 2019-09-06 | 2022-03-04 | 云南师范大学 | 多特性的天然橡胶和琼脂复合介孔膜及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH08506255A (ja) | 1996-07-09 |
ITPD930024A1 (it) | 1994-08-12 |
ITPD930024A0 (it) | 1993-02-12 |
EP0683679A1 (en) | 1995-11-29 |
CA2155319C (en) | 2004-11-02 |
AU681873B2 (en) | 1997-09-11 |
IT1263316B (it) | 1996-08-05 |
DE69431591T2 (de) | 2003-07-03 |
ES2184759T3 (es) | 2003-04-16 |
US5658582A (en) | 1997-08-19 |
ATE226452T1 (de) | 2002-11-15 |
CA2155319A1 (en) | 1994-08-18 |
CN1136823C (zh) | 2004-02-04 |
AU6108894A (en) | 1994-08-29 |
DE69431591D1 (de) | 2002-11-28 |
WO1994017837A1 (en) | 1994-08-18 |
EP0683679B1 (en) | 2002-10-23 |
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