CN1865341A - 聚合水凝胶组合物 - Google Patents
聚合水凝胶组合物 Download PDFInfo
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Abstract
本公开内容提供了一种聚合组合物。该聚合组合物可单独用作水凝胶,或用于制造包括如传输电极和监测电极的各种医用设备。
Description
技术领域
本发明公开内容涉及聚合组合物及其与生物医用电极的一道应用。
背景技术
生物粘合性水凝胶被广泛用作将生物医用设备和个人护理产品附着至皮肤的手段。水凝胶在将电极粘附于皮肤中特别有用,这是由于其具有如下性能:非永久性粘附、相对高的水含量以及其掺杂离子传导性物质以改进电导性的能力。具体地,水凝胶可与传输电极(例如经皮电神经刺激(TENS)设备);除纤颤器电极和监测电极[例如心电图(ECG)电极,脑电图(EEG)电极和肌电图(EMG)电极]一道使用。
水凝胶要有效用作生物胶粘剂,需要具备几个性能。通常的生物胶粘剂,特别是与生物医用电极一道使用的生物胶粘剂,必须能在整个临床操作中紧密粘附于皮肤,并且经常须粘附至长毛发的、油性的或潮湿的皮肤,并且期望其经历长时间使用后仍具粘附性。对于住院操作的情况,特别是对于重症护理和新生儿护理的情况,常常需应用、移除和再应用电极。电极的剥离强度(即将水凝胶从皮肤分离所需的力)合适地须低于人体皮肤的剥离强度(即破坏皮肤完整性所需的力),从而可除去粘附的物品而不会导致明显的疼痛或皮肤损伤。水凝胶组合物必须充分粘稠,从而使其在正常使用条件下,例如依赖于应用的室温或体温,高湿度或过湿,以及在施加电流的过程中,能基本抵抗流动性。
生物粘合性水凝胶通常是不可重复使用的,因为许多水凝胶在第一次使用后明显丧失粘合性。替换性地,长时间应用或多次应用之后仍保持粘合性的生物粘合性水凝胶常具有过高的剥离强度,因而在移除时引起严重的不适和/或组织损伤。
本发明的目的是提供长时间使用后仍保持对皮肤的粘附性的聚合组合物,其可被移除和重复使用而不会导致性能的明显损失。
发明内容
本发明一方面提供了一种聚合组合物,其包含:(i)含至少一种烯不饱和水溶性单体的约5-30wt%交联聚合物;(ii)平均分子量低于约50,000的约5-20wt%直链、支链或星型非交联聚合物;(iii)约40-60wt%的多元醇;和(iv)低于约5-20wt%的水。在该方面的优选实施方案中,非交联聚合物具有低于约20,000、低于约10,000或低于约7,500的平均分子量。
本发明第二方面仍提供了一种聚合组合物,其包含:(i)含至少一种烯不饱和水溶性单体的约5-30wt%交联聚合物,其中非交联聚合物不是羧酸基聚合物;(ii)平均分子量低于约25,000,000的约5-20wt%直链、支链或星型非交联聚合物;(iii)约40-60wt%的多元醇;和(iv)低于约5-20wt%的水。在该方面的优选实施方案中,非交联聚合物具有低于约10,000,000、低于约6,000,000或低于约1,000,000的平均分子量。
在前述诸方面的优选实施方案中,交联聚合物与非交联聚合物形成互聚物。优选地,非交联聚合物被缠结入交联聚合物内。
该交联聚合物可以是均聚物或共聚物。特别有用的烯不饱和水溶性单体包括,例如2-丙烯酰胺-2-甲基丙磺酸(AMPS)、丙烯酸、丙烯酸-3-磺丙酯(SPA)及其盐。特别有用的盐包括,例如水溶性单体的钠盐、钾盐、镁盐、钙盐、锂盐和铵盐。特别有用的共聚物是AMPS/丙烯酸共聚物。优选地,AMPS∶丙烯酸的比例在约0.4∶1到2.1∶1之间。优选地,AMPS∶丙烯酸的比例在约1∶1到1.75∶1之间,或者甚至在1.50∶1到1.65∶1之间。
尽管在本发明中可使用任意的直链、支链或星型非交联聚合物,但特别有用的非交联聚合物为丙烯酸酯或甲基丙烯酸酯均聚物和共聚物。其他有用的非交联聚合物包括,例如聚丙烯酸酯(例如由Noveon,Inc.,Cleveland,OH售出的GOOD-RITEK-732)、松香酯(由ArizonaChemical,Inc.Jacksonville,FL售出的Aquatac9027)、聚乙烯醇(PVA聚合物;例如由Air Products and Chemicals,Inc.,Allentown,PA售出的各种Flexcryl聚合物)、聚乙烯吡咯烷酮(PVP)、聚氧化乙烯(PEO)、非离子型或离子型聚丙烯酰胺、刺梧桐胶、印度胶、阿拉伯胶、琼脂胶(Gum agar)、黄蓍胶、瓜尔胶、改性瓜尔胶产物(例如羟丙基瓜尔胶)、槐树豆胶、纤维素(cellulosics)、改性纤维素(羟乙基纤维素等)、麦芽糖糊精、多糖、妥尔油、松香酯以及其二元、三元和四元共混物。此外,本发明所用非交联聚合物还可包括尼龙聚合物,例如ε-己内酰胺。特别有用的非羧酸基聚合物包括聚丙烯酰胺。
有用的多元醇包括,例如甘油、丙二醇、聚丙二醇、新戊二醇、三乙醇胺、二乙醇胺、ethanolamione、丁二醇、聚乙二醇、N-甲基二乙醇胺和异丙醇胺。在理想的实施方案中,多元醇与水的摩尔比在约1∶1到约3.5∶1之间。
在理想的实施方案中,聚合组合物具有低于约40,000cps、低于20,000cps或低于约1500cps的布氏粘度(Brookfield viscosity)。优选地,该布氏粘度为约500-1000cps。
本发明的聚合组合物可作为用于各种个人护理产品、医用设备和伤口敷料的生物胶粘剂。本发明的水凝胶特别用作供电极使用的生物胶粘剂,所述电极包括传输电极和监测电极。
具体实施方式
本发明提供了如下组成的聚合组合物:至少一种烯不饱和水溶性单体的约5-30wt%交联聚合物;平均分子量低于20,000的约5-20wt%直链、支链或星型非交联聚合物;约40-60wt%的多元醇;和低于约5-20wt%的水。本发明还提供了如下组成的聚合组合物:含至少一种烯不饱和水溶性单体的约5-30wt%交联聚合物,其中非交联聚合物不是羧酸基聚合物;平均分子量低于约25,000,000的约5-20wt%直链、支链或星型非交联聚合物;约40-60wt%的多元醇;以及低于约5-20wt%的水。优选地,交联聚合物和非交联聚合物形成互聚物。本发明的聚合组合物含有至少两种聚合物、交联剂、一种或多种聚合引发剂、一种或多种湿润剂、以及中和剂(碱),所述聚合物为非交联聚合物和至少一种烯不饱和水溶性单体的交联聚合物。
交联聚合物包含烯不饱和水溶性单体的均聚物或共聚物。合适的单体包括,例如烯不饱和羧酸、羧酸酐和磺酸,如丙烯酸、甲基丙烯酸、马来酸、肉桂酸、衣康酸、巴豆酸、乙基丙烯酸、柠康酸(citoconicacid)、中康酸、富马酸、β-sterylacrylic acid、丙烯酸酯、丙烯酰胺、烯烃、乙烯基酯、乙烯基醚、乙烯酰胺、2-丙烯酰胺-2-甲基丙磺酸(AMPS)和丙烯酸-3-磺丙酯(SPA)、二甲基丙烯酰胺、二丙酮丙烯酰胺、甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸二甲氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸乙氧基乙氧基乙酯、乙氧基、甲基丙烯酸乙氧基乙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸。特别有用的共聚物包括丙烯酸/AMPS、丙烯酸/SPA、AMPS/SPA、二丙酮丙烯酰胺/丙烯酸、以及丙烯酸/丙烯酰胺共聚物;但可采用任意合适单体的共聚物。
上述均聚物和共聚物可以以任意的多烯(例如癸二烯和三乙烯基环己烷)、丙烯酰胺(n-n’-亚甲基双丙烯酰胺(nnMBA)、多官能丙烯酸酯(例如三羟甲基丙烷三丙烯酸酯)或者含有至少两个末端CH2基团的多官能亚乙烯基单体(例如丁二烯、异戊二烯、二乙烯基苯、二乙烯基萘以及丙烯酸烯丙酯)进行交联。特别有用的交联剂是nnMBA。可与共聚物使用的其他交联单体包括,例如每分子内具有多个烯基醚基团的多烯基多醚。这种类型的有用交联剂包括,例如二烯丙基酯、二甲代烯丙基醚、丙烯酸烯丙酯或丙烯酸甲代烯丙酯、聚乙基乙二醇甲基丙烯酸酯(即PEG 400、PEG 800等)以及丙烯酰胺、四烯丙基锡、四乙烯基硅烷、聚烯基甲烷、二丙烯酸酯和二甲基丙烯酸酯、以及二乙烯基化合物如二乙烯基苯、聚磷酸烯丙酯、及二烯丙氧基化合物和季铵化合物。除二官能交联剂外,也可采用三和四官能单体(例如三羟甲基丙烷三丙烯酸酯)。交联剂的用量通常是低的,低于约1wt%,优选低于约0.7wt%,更优选低于约0.4wt%。
将不饱和水溶性单体进行聚合和交联,从而形成交联聚合物,在非交联聚合物存在下即产生出具有可重复使用和延长耐久性的生物粘合性水凝胶。在聚合/交联过程中,非交联聚合物通过物理缠结于交联聚合物网络中而形成半互穿聚合物网络(semi-IPN;互聚物)。合适的非交联聚合物包括直链、支链和星型聚合物。支链和星型聚合物与交联聚合物具有更强的立体相互作用,因而赋予了更高的粘度。通常,支链和星型聚合物用于具有较少量交联聚合物或者期望更高粘度的水凝胶中。合适的聚合物通常具有低于20,000的平均分子量,优选低于15,000,更优选低于10,000,或者甚至约5,000。此类聚合物包括,例如丙烯酸、SPA和AMPS的均聚物和共聚物,如聚丙烯酸酯(如Noveon,Inc.生产的GOOD-RITEK732)、polyAMPS、聚(丙烯酸-(3-磺丙基)酯),以及FlexcrylPVA聚合物(Air Products and Chemicals,Inc.生产)。其他有用的聚合物包括松香酯、熔融石英、离子型(例如阳离子型)和非离子型聚丙烯酰胺(商标为Magnifloc和/或Cyanamer,由CytecIndustries,Five Garrett Mountain Road,West Patterson,New Jersey,USA生产;例如CyanamerN-300 LMW,CyanamerN-100)。这些聚合物具有的平均分子量范围为250,000-25,000,000,其可以是非离子型、阴离子型或阳离子型的。
可基于最终组合物的期望性能,对多元醇及其在最终聚合组合物中与水的相对比例进行选择。高比例的多元醇∶水(即约3.5∶1)。例如,相对低的水含量是有利的,因为其使得聚合组合物具有更高的电阻抗,这特别适用作电极生物胶粘剂。此外,低水含量的组合物具有优良的“重粘着”性,对变干具有抵抗性。这些组合物还倾向于低过敏性(hypoallergenic)。
所得聚合组合物的粘度可测量并表示为例如布氏粘度。可采用本领域内已知的任意操作法测量布氏粘度。例如,将以整体板(integralplate)机制的校准转轴以指定速度穿过流体旋转而确定溶液粘度。当板穿过流体旋转时,其所经受的迟滞或拖曳与流体粘度相关。粘度计上面的刻度盘显示0-100刻度。将刻度结果乘以用于补偿速度和板几何形状的因子,即得到单位为厘泊的粘度。在该特定情况下,于BrookfieldRVF粘度计上以20rpm的速度使用#4转轴。
本发明的聚合组合物可用作与各种个人护理产品、医用设备和伤口敷料一道使用的水凝胶。当与一次性废物处理设备(即尿、月经液、粪便废物)一道使用时,通常将聚合组合物施用至供胶粘剂附着用的孔或法兰处。本发明的聚合组合物可与本领域内已知的任意一次性尿、月经液或粪便废物处理设备一道使用。
本发明的聚合组合物特别用作需具有长时间皮肤粘附性或在频繁移除和重使用条件下需保持其粘合性的生物胶粘剂,供与各种医用设备和伤口敷料一道使用。此类医用设备包括,例如生物医用电极(例如ECG、EMG、EEG、TENS和除纤颤电极)、绷带、带子和导管。
生物医用电极是本领域内公知的,通常主要基于其预期用途而进行设计。例如,监测电极(如ECG和EEG电极)倾向于比传输电极(TENS和除纤颤电极)更小。任一传输生物医用电极的原理特征是其在患者皮肤与连接至医用设备(即刺激器)的电缆之间有效传输电信号的能力。监测电极须具有检测皮肤的离子电位或电位并将电信号传输至医用设备(即监测器)的能力。典型的电极包含常通过按扣与医用设备的电缆保持电接触的电导元件、延伸出接触表面的传导性包覆(如炭黑包覆、金属包覆)翼片(tab)或金属翼片(即翼片电极)。电导元件还与患者的皮肤保持电接触。该电接触常通过将传导性凝胶材料置于电导元件和患者的皮肤之间而实现。该凝胶可局部施用,其可存在于与生物医用电极组件一体化的吸收芯内,或可涂覆于生物医用电极组件的朝向皮肤的表面上。由于水凝胶的电性能是公知的,可容易地为各种目的而对其进行操作,因此经常使用聚合水凝胶以使生物医用电极的电导元件与患者的皮肤之间保持电接触。另外,许多聚合水凝胶具有理想的生物粘合性能,用以辅助将生物医用电极安置并附着至患者。
实施例1
由如下凝胶前(pre-ge1)溶液形成聚合组合物。
NaAMPS 1.77720pph nn-MBA 0.34828pph
AMPS酸 12.10408pph Irgacure184 0.05672pph
丙烯酸 8.75665pph Darocur1173 0.22688pph
甘油 51.38166pph NaCl 0.49754pph
Good-RiteK-732 11.94089pph 50%NaOH 4.7684pph
ddH2O 3.3733pph
按如下方式形成凝胶前溶液:测量丙烯酰胺甲基丙磺酸钠酯(NaAMPS)溶液并将其加入至清洁、干燥的容器中。然后于搅拌的同时顺序加入如下试剂:处于去离子水中的n,n’-亚甲基双丙烯酰胺(nn-MBA)(1%w/v),丙烯酸,另外的去离子水(ddH2O),甘油(1,2,3-丙三醇),GoodriteK-732(来自Noveon,Inc.的未交联聚丙烯酸),Irgacure184(1-羟基-环己基-苯酮),AMPS酸以及氯化钠。将该溶液混合直至全部试剂均溶解。将50%w/v溶液形式的氢氧化钠缓慢加入用于控制批料温度。然后加入Darocur1173(2-羟基-2-甲基-1-苯基-1-丙酮),并将所得溶液混合直至均匀。
上述溶液一旦均匀,即将其涂覆至基质(通常为硅化的塑料膜,但任意合适的材料均可)上。使凝胶前溶液流延(cast),随后通过自由基聚合作用进行聚合,所述自由基聚合作用是通过促进自由基引发的光敏引发剂的均匀分解及随后的增长和断链而产生。可通过改变剂量的持续时间和/或紫外光的强度,而调节固化的程度及由此而致的最终互聚水凝胶的物理性能。优选的水凝胶由采用1.2J/cm2(UVA)的剂量进行固化而得到。
经HPLC测定,所得聚合组合物含有约100ppm残留的丙烯酸单体和约80ppm残留的AMPS单体,并具有约5.1的最终pH。该聚合组合物具有内聚和粘合性能的理想平衡,能良好粘附至皮肤,并能清晰地传输电信号和脉冲。
生成这些组合物后,将其聚合成片型并改制成可供试验的贴片。优化过程中所采用的具体试验属性包括对志愿者(人体)皮肤的粘附性,经HPLC测得的残留单体值,最终pH,对志愿者的连续重粘贴粘附试验,经湿气平衡而得的水含量,以及按AAMI/ANSI EC12:(2000)准则测得的电导率。
实施例2
在另一系列的试验中,采用交替交联共聚物作为改良组合物的基础,制备数种组合物。具体地,采用替代碱(氢氧化钾)、交替交联剂(二甲基丙烯酸三甘醇酯;“TEGDMA”)将二丙酮丙烯酰胺、丙烯酸和丙烯酸钾的一种共聚物共混物进行混配,并加入未共价连接至聚合物主链的直链聚合物用以促进对皮肤粘附性的改良。聚合组合物基本按实施例1所述进行制备。该凝胶前溶液的组分如下:
二丙酮丙烯酰胺 6.33pph Darocur1173 0.49pph
丙烯酸 17.63pph N-甲基二乙醇胺 3.62pph
甘油 37.52pph 三乙醇胺 3.62pph
Good-RiteK-732 10.71pph 4-甲氧基酚 0.05pph
PVP K-90* 0.90pph NaCl 1.36pph
TEGDMA 0.15pph 45%KOH 14.92pph
ddH2O 2.71pph
*平均分子量=90,000
生成这些组合物后,将其聚合成片型并改制成可供试验的贴片。优化过程中所采用的具体试验属性包括对志愿者(人体)皮肤的粘附性,经HPLC测得的残留单体值,最终pH,对志愿者的连续重粘贴粘附试验,经湿气平衡而得的水含量,以及按AAMI/ANSI EC12:(2000)准则测得的电导率。
实施例3
为进一步研究结构/性能关系而生成了一系列聚合组合物。单体浓度、单体比例和水含量按如下改变(所有给出浓度均为pph):
A | B | C | D | E | F | G | H | I | |
18.81614.99947.0290.0000.0202.77510.0000.0750.3002.4903.0000.500 | 19.1368.32947.8570.0000.0204.62516.6660.0750.3002.4900.0000.500 | 18.9968.32947.4930.0000.0204.62516.6660.0750.3000.0003.0000.500 | 16.89010.73050.6780.0000.0203.70014.3600.0750.3001.2501.5000.500 | 15.4468.32954.0420.0000.0204.62516.6660.0750.3000.0000.0000.500 | 14.7905.80051.7649.1990.0204.55010.0000.0750.3000.0003.0000.500 | 14.0674.64049.2053.6900.0205.33716.6660.0750.3002.5003.0000.500 | 14.9015.80052.1509.2000.0204.55110.0000.0750.3002.5000.0000.500 | 20.37614.99950.9500.0000.0202.77510.0000.0750.3000.0000.0000.500 | |
335 | 252 | 357 | 394 | 293 | 419 | 375 | 396 | 239 | |
13 | 6 | 1 | 12 | 6 | 6 | 4 | 5 | 257 | |
405 | 336 | 400 | 505 | 650 | 742 | 812 | 677 | 302 |
上述聚合组合物的制造方法与实施例1中所述相同。
生成这些组合物后,将其聚合成片型并改制成可供试验的贴片。优化过程中所采用的具体试验属性包括对志愿者(人体)皮肤的粘附性,经HPLC测得的残留单体值,最终pH,对志愿者的连续重粘贴粘附试验,经湿气平衡而得的水含量,以及按AAMI/ANSI EC12:(2000)准则测得的电导率。
作为对该组合物评测的一部分,根据ISO 10993准则对优选试样测试生物相容性和低敏性,确定优选组合物是无细胞毒性(USP琼脂扩散(USP AGAR Diffusion))、非刺激性(原发皮肤刺激(Primary SkinIrritation))、非敏化性(局部封闭接触试验(Buehler Patch Test))和低过敏性(重复皮肤损伤接触试验(Repeated skin Insult Patch Test))的。所有上述试验均在GLP条件下完成。
该情况下,更理想的聚合物是可施用至设备、然后移除并重复施用而不会明显损失其粘合性的聚合物。优选的组合物是从基质(皮肤)上移除后留有极少(如有的话)残留物的组合物。
尽管为清楚理解的目的以说明和实施例方式详细描述了上述公开内容,但对参照本公开内容的本领域普通技术人员而言很明显的是,可对本公开内容作某些改变和修正而不会背离所附权利要求的主旨或范围。
Claims (24)
1.一种聚合组合物,其包括:
(i)含至少一种烯不饱和水溶性单体的约5-30wt%交联聚合物;
(ii)平均分子量低于约50,000的约5-20wt%直链、支链或星型非交联聚合物;
(iii)约40-60wt%的多元醇;和
(iv)低于约5-20wt%的水。
2.如权利要求1的聚合组合物,其中所述交联聚合物和所述非交联聚合物形成互聚物。
3.如权利要求1的聚合组合物,其中所述水溶性单体的至少一种选自包括2-丙烯酰胺-2-甲基丙磺酸(AMPS)、丙烯酸、丙烯酸-3-磺丙酯(SPA)及其盐的组。
4.如权利要求1的聚合组合物,其中所述交联聚合物是AMPS/丙烯酸共聚物。
5.如权利要求4的聚合组合物,其中所述交联聚合物中AMPS∶丙烯酸的摩尔比例在约0.4∶1到约2.1∶1之间。
6.如权利要求5的聚合组合物,其中所述交联聚合物中AMPS∶丙烯酸的比例在约1.50∶1到1.65∶1之间。
7.如权利要求1的聚合组合物,其中所述聚合组合物中多元醇∶水的摩尔比例在约1∶1到约3.5∶1之间。
8.如权利要求1的聚合组合物,其中所述非交联聚合物是丙烯酸酯均聚物或共聚物。
9.如权利要求8的聚合组合物,其中所述非交联聚合物是平均分子量低于10,000的聚丙烯酸酯。
10.如权利要求1的聚合组合物,其中所述多元醇是甘油。
11.如权利要求1的聚合组合物,其中所述聚合组合物具有低于约40,000cps的布氏粘度。
12.如权利要求11的聚合组合物,其中所述聚合组合物具有低于约1500cps的布氏粘度。
13.如权利要求12的聚合组合物,其中所述聚合组合物具有约500-1000cps的布氏粘度。
14.一种聚合组合物,其包括:
(i)含至少一种烯不饱和水溶性单体的约5-30wt%交联聚合物;
(ii)平均分子量低于约25,000,000的约5-20wt%直链、支链或星型非交联聚合物,其中所述非交联聚合物不是羧酸基聚合物;
(iii)约40-60wt%的多元醇;和
(iv)低于约5-20wt%的水。
15.如权利要求14的聚合组合物,其中所述交联聚合物和所述非交联聚合物形成互聚物。
16.如权利要求14的聚合组合物,其中所述水溶性单体的至少一种选自包括2-丙烯酰胺-2-甲基丙磺酸(AMPS)、丙烯酸、丙烯酸-3-磺丙酯(SPA)及其盐的组。
17.如权利要求14的聚合组合物,其中所述交联聚合物是AMPS/丙烯酸共聚物。
18.如权利要求17的聚合组合物,其中所述交联聚合物中AMPS∶丙烯酸的摩尔比例在约0.4∶1到约2.1∶1之间。
19.如权利要求14的聚合组合物,其中所述非交联聚合物是聚丙烯酰胺。
20.如权利要求14的聚合组合物,其中所述非交联聚合物具有低于6,000,000的平均分子量。
21.如权利要求1的聚合组合物,其中所述多元醇是甘油。
22.一种聚合组合物,其包括:
(i)含2-丙烯酰胺-2-甲基丙磺酸(AMPS)或其盐以及丙烯酸或其盐的约5-30wt%交联共聚物,其中所述AMPS对所述丙烯酸的比例在约0.5∶1到约2.1∶1之间;
(ii)平均分子量低于20,000的约5-15wt%非交联聚丙烯酸酯;和
(iii)约40-60wt%的甘油;
(iv)约5-20wt%的水;
其中所述交联共聚物和所述聚丙烯酸酯形成互聚物,且其中所述聚合组合物具有低于约1500cps的布氏粘度。
23.与权利要求1的聚合组合物一道使用的生物医用电极。
24.与权利要求22的聚合组合物一道使用的生物医用电极。
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- 2005-05-13 US US11/128,940 patent/US20060258788A1/en not_active Abandoned
-
2006
- 2006-05-04 CA CA002545757A patent/CA2545757A1/en not_active Abandoned
- 2006-05-08 SG SG200603058A patent/SG127802A1/en unknown
- 2006-05-08 EP EP06252428A patent/EP1721917A1/en not_active Withdrawn
- 2006-05-10 AU AU2006201948A patent/AU2006201948A1/en not_active Abandoned
- 2006-05-11 JP JP2006132426A patent/JP2006316273A/ja active Pending
- 2006-05-12 TW TW095116818A patent/TW200700487A/zh unknown
- 2006-05-12 KR KR1020060043036A patent/KR20060117269A/ko not_active Application Discontinuation
- 2006-05-12 AR ARP060101930A patent/AR055946A1/es not_active Application Discontinuation
- 2006-05-12 CN CNA2006100803960A patent/CN1865341A/zh active Pending
- 2006-05-15 BR BRPI0601778-9A patent/BRPI0601778A/pt not_active Application Discontinuation
- 2006-05-15 RU RU2006116526/04A patent/RU2006116526A/ru not_active Application Discontinuation
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102481112A (zh) * | 2009-07-10 | 2012-05-30 | 斯特拉斯克莱德大学 | 带有阻抗传感器的伤口敷料 |
CN102481112B (zh) * | 2009-07-10 | 2016-01-27 | 斯特拉斯克莱德大学 | 带有阻抗传感器的伤口敷料 |
US10716490B2 (en) | 2009-07-10 | 2020-07-21 | University Of Strathclyde | Wound dressing with impedance sensor |
CN106038063A (zh) * | 2015-04-14 | 2016-10-26 | 财团法人纺织产业综合研究所 | 伤口护理用敷材 |
CN109661198A (zh) * | 2016-09-30 | 2019-04-19 | 积水化成品工业株式会社 | 凝胶片 |
CN109661198B (zh) * | 2016-09-30 | 2021-11-23 | 积水化成品工业株式会社 | 凝胶片 |
CN112533997A (zh) * | 2018-08-31 | 2021-03-19 | 积水化成品工业株式会社 | 水凝胶和其用途 |
CN112533997B (zh) * | 2018-08-31 | 2023-09-26 | 积水化成品工业株式会社 | 水凝胶和其用途 |
Also Published As
Publication number | Publication date |
---|---|
CA2545757A1 (en) | 2006-11-13 |
BRPI0601778A (pt) | 2007-05-02 |
AR055946A1 (es) | 2007-09-12 |
KR20060117269A (ko) | 2006-11-16 |
JP2006316273A (ja) | 2006-11-24 |
SG127802A1 (en) | 2006-12-29 |
US20060258788A1 (en) | 2006-11-16 |
TW200700487A (en) | 2007-01-01 |
EP1721917A1 (en) | 2006-11-15 |
AU2006201948A1 (en) | 2006-11-30 |
RU2006116526A (ru) | 2007-11-20 |
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