CN1131966A - 处理染色织物的组合物和方法 - Google Patents
处理染色织物的组合物和方法 Download PDFInfo
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- CN1131966A CN1131966A CN94193532.9A CN94193532A CN1131966A CN 1131966 A CN1131966 A CN 1131966A CN 94193532 A CN94193532 A CN 94193532A CN 1131966 A CN1131966 A CN 1131966A
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- cellulase
- fabric
- acid
- nacrite
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Abstract
一种处理染色织物的方法,该方法包括在含水介质中让织物与纤维素分解酶和热膨胀珍珠石相接触,后两者的用量能有效地在染色织物表面的色密度方面体现局部变化;以及一种组合物,它包括纤维素酶,热膨胀珍珠石和缓冲剂以及任意性的分解剂和/或螯合剂。
Description
本发明涉及用来处理染色织物,例如粗斜棉布或粗斜纹棉布的组合物,以及在染色织物,尤其纤维素织物如粗斜棉布的表面色密度方面获得改进的局部变化的方法。
更具体地说,本发明涉及一种组合物,它包括纤维素分解酶,珍珠石,缓冲剂和任意性的分散剂和/或螯合剂。
在粗斜棉布织物或粗斜纹棉布上获得“石洗(stone-washed)”状外观(局部颜色磨耗)的最常见方法是在浮石存在下洗涤从此类织物制造的粗斜棉布或粗斜纹棉布,以获得织物颜色的所需局部发亮。为此目的使用浮石的缺点是:处理后不得不从织物或布料上洗去浮石颗粒,及浮石和浮石颗粒使用于该方法的机器高度磨损。同时,处理大量的石头也是问题。
因而曾提出了其它使粗斜棉布织物或粗斜纹棉布具有“石洗”外观的措施。例如,酶,尤其纤维素酶,已建议用于此目的,或者单独使用(US4,832,864)或者与用量比传统工艺方法所需量低的浮石一起使用。
有人指出,在石洗工艺中用珍珠石、尤其热膨胀珍珠石代替浮石是有利的。由于珍珠石比浮石具有更低的密度,这一代替可以减少上述使用浮石的缺点。
然而,已经发现,在常规的石洗工艺方法中,即在珍珠石存在下处理织物(“石洗”),代替浮石使用珍珠石不能得到所需要的染色织物的“石洗”外观。
珍珠石是一种粉尘物质,尤其当进行“石洗”工艺时它的处理可产生粉尘,因而是令人不愉快和讨厌的,甚至危害人们的健康,而且需要经常清洗工艺环境。
所以,仍然需要在染色织物上获得石洗外观的改进方法,它消除了已知方法的处理问题,同时成本上合算;以及需要用来处理染色织物的改进组合物。
现已惊奇地发现,纤维素酶与珍珠石,尤其与热膨胀珍珠石相结合使用对于在染色织物的色密度方面获得改进的局部变化而言,如对于获得“石洗外观”而言,可以得到优异的结果。
此外,已惊奇地发现,通过制备一种可用于本发明的工艺方法的组合物,有可能消除来自上述酶催“石洗”工艺的珍珠石粉尘,该组合物包括珍珠石,纤维素酶和缓冲剂和选择性的分散剂和/或螯合剂。
使用本发明的方法和/或组合物处理染色织物的另一优点是:为了人工获得例如粗斜棉布(尤其粗斜纹棉布)的老化外观和柔软度而使用该方法和/或组合物,有可能减少珍珠石的需要量至10wt%以下,大概至约5~2wt%,与浮石(它方便地与纤维素酶一起使用)的量相比较而言。
同时,珍珠石和缓冲剂的存在似乎提高了纤维素酶的性能。已经发现,使用本发明的组合物可以获得所需要的石洗外观,该组合物的酶催活性比使用包括酶和浮石的已知方法时所需要的酶催活性低,因而本发明的组合物与单独使用酶或酶与浮石一起使用的已知方法相比而言成本更低。
所以,本发明组合物的高效率,低成本及无毒和无刺激性使该组合物十分有用。
本发明的组合物用于含纤维素织物,如棉,粘胶丝,人造纤维,宁麻,亚麻,Iyocell(Tencel)或它们的混合物,或任何这些纤维的混合物,是最有益的。尤其,该织物是粗斜棉布。该织物可用瓮染料如靛蓝,直接染料如直接红185,硫染料如硫绿6,或固定在织物表面上的粘结剂上的活性染料来染色。
在本发明方法的最优选实施方案中,织物是靛蓝染色的粗斜棉布,包括从它制造的服装。
本发明组合物所包含的纤维素分解酶可以是前面为此目的所推荐的任何酶,例如,在US4,832,864中所描述的那些,该文献引入本文供参考。所以,纤维素分解酶可以是微生物来源,优选真菌或细菌纤维素酶。
根据本发明,已发现可以使用酸性以及中性和碱性纤维素酶。
术语“酸性纤维素酶”,“中性纤维素酶”和“碱性纤维素酶”分别是指分别在酸性pH(优选低于约pH6),中性PH或碱性PH(优选高于约PH8,更优选高于约PH9)下具有其最佳活性或性能的纤维素酶。
合适的酸性纤维素酶的例子是从木霉属、耙菌属、梭菌属或热杆菌属的菌株得到的那些纤维素酶。合适的中性或碱性纤维素酶的例子是从腐质霉属、镰刀菌属、芽孢杆菌属、纤维杆菌属,假单胞菌属,毁丝霉属或Phanerochaete的菌株得到的那些纤维素酶。优选的纤维素酶可从真菌类Humicola insolens,更优选从真菌类Humicola insolens,DSM 1800(根据布达佩斯条约(1981年10月1日)保藏在Deutsche Sammlung von Mikroorganismen)获得。目前优选的纤维素酶是从Humicola insolens,DSM 1800得到的~43KD内-β-葡聚糖酶,如WO 91/17243所述,该专利文献引入本文供参考。最优选的,~43KD内-β-葡聚。酶是单组分纤维素酶,即由普通的重组技术如在同源或异源宿主细胞中克隆和表达所得到的内-β-葡聚糖酶。
优选地,纤维素酶在本发明组合物中的存在量能有效地在染色织物表面的色密度方面获得改进的局部变化。酶的需求量取决于酶的活性。
在本发明的优选实施方案中,酶是内-β-葡聚糖酶。内-β-葡聚糖酶的纤维素分解活性相对于分析标准来测定并以单位EGU(内-β-葡聚糖酶单位)或以单位ECU表达。优选地,本发明的组合物所包含的内-β-葡聚糖酶的量对应于20~300EGU或ECU,更优选20~200EGU或ECU,尤其40~150EGU或ECU/每克组合物。
纤维素分解酶水解CMC,从而提高了培养混合物的粘度。粘度的下降可由振动粘度计(例如MIVI 3000,购自Sofraser,France)测出。
纤维素分解活性的测定,按ECU测试,可根据下述分析方法(试验方法)来进行。
ECU试验为存在于样品中的催化活性定量,方式是测量样品减少羧甲基纤维素(CMC)溶液的粘度的能力。试验在如下条件下进行:40℃;PH7.5;0.1M磷酸盐缓冲液;时间30分钟;使用降低CMC(羧甲基纤维素Hercules 7 LFD)底物的粘度的相对酶标准;酶浓度大约0.15 ECU/ml。拱(arch)标准定义为8200ECU/g。
单位EGU(内-β-葡聚糖酶单位)是在以下反应条件下相对于酶标准测定的:PH6.0;0.1M磷酸盐缓冲液;34.0g/l底物(羧甲基纤维素Hercules 7 LFD);温度40℃;时间30分钟;酶浓度大约0.020 EGU/ml。拱标准被定义为880 EGU/g。
缓冲剂可适宜地为磷酸盐,硼酸盐,柠檬酸盐.乙酸盐,己二酸盐,三乙醇胺,单乙醇胺,二乙醇胺,碳酸盐(尤其碱金属或碱土金属,特别是钠或钾的碳酸盐,或铵和HCl盐),二胺(尤其乙二胺),咪唑,或氨基酸缓冲剂。优选地,缓冲剂是单,二或三乙醇胺缓冲剂。
缓冲剂优选在本发明组合物中以1-50w/w%,更优选以5-40w/w%,尤其15-35w/w%的量存在,以组合物的总重为基础。
珍珠石是天然火山岩。优选使用热膨胀珍珠石,优选密度(砂)为2200~2400kg/m3和堆积密度为40~100kg/m3。在本发明的优选实施方案中,热膨胀珍珠石的粒度优选在0.2mm和20mm之间,更优选在0.3mm和10mm之间,尤其在1mm和5mm之间。
热膨胀珍珠石在本发明组合物中优选以20~95w/w%,更优选以25~80w/w%,尤其以30~65w/w%的量存在,以组合物的总重为基础。
本发明的组合物优选是固体组合物,包括:热膨胀珍珠石,一起混合的纤维素分解酶和缓冲剂和任意性的分散剂和/或螯合剂。本发明的固体组合物是备用产品,它可直接用于石洗方法通常使用的机器中。该固体组合物一般包括纤维素分解酶组合物在固体基料中的悬浮体,基料可以是无机的或有机的。本发明的组合物的形式可以是微粒,细粒或颗粒。
实验发现,当本发明组合物另外包含分散剂时,使用该组合物能获得非常好的结果。
分散剂可适当地选自非离子,阴离子,阳离子,两性或两性离子表面活性剂。更具体地说,分散剂选自羧甲基纤维素,羟丙基纤维素,烷基芳基磺酸盐类,长链醇硫酸酯(伯和仲烷基硫酸酯),磺化烯烃,硫酸化单甘油酯,硫酸化醚,磺基琥珀酸盐,磺化甲醚,链烷基磺酸盐,磷酸酯,异硫代硫酸烷基酯,酰基肌氨酰胺,烷基牛磺酰胺,氟表面活性剂,脂肪醇和烷基酚缩合物,脂肪酸缩合物,环氧乙烷与胺的缩合物,环氧乙烷与酰胺的缩合物,嵌段共聚物(聚乙二醇,聚丙二醇,乙二胺与环氧乙烷或环氧丙烷的缩合物),蔗糖酯,山梨糖酯,烷基酰胺,脂肪胺氧化物,乙氧基化单胺,乙氧基化二胺,乙氧基化多胺。乙氧基化胺聚合物及其混合物。
分散剂优选是乙氧基化脂肪酸酯或壬基苯基聚乙二醇醚。
分散剂在本发明组合物中优选以0.1~10w/w%,更优选0.5~8w/w%,尤其0.5~5w/w%的量存在,以组合物总重为基础。
在本发明的另一方面,通过向组合物中添加螯合剂有可能改进纤维素酶的能力,在染色织物中获得局部颜色变化。
螯合剂可以是一种在酸性、中性或碱性PH值可溶的和能够与二或三价阳离子(如钙离子)形成配合物的物质。螯合剂的选择取决于用于本工艺方法的纤维素酶。因此,如果包含了酸性纤维素酶,螯合剂应该是一种在酸性PH值下是可溶的且能够与二价或三价阳离子形成配合物的物质。另一方面,如果纤维素酶是中性或碱性的,螯合剂应该是一种在中性或碱性PH下可溶的且能够与二价或三价阳离子形成配合物的物质。
螯合剂可适当地选自氨基羧酸;羟基氨基羧酸;羟基羧酸;磷酸盐,二磷酸盐,三聚磷酸盐,多聚磷酸盐,焦磷酸盐;沸石;多羧酸;糖类,包括多糖类;羟基吡啶酮;包含儿茶酚基的有机化合物;包含hydroxymate基团的有机化合物;硅酸盐;或多羟基磺酸盐。
当螯合剂是羟基羧酸时,它适当地选自葡糖酸,柠檬酸,酒石酸,草酸,二甘醇酸,或葡庚糖酸盐。
当螯合剂是多氨基或多羟基磷酸或多磷酸时,它适当地选自PBTC(磷酰丁烷三乙酸盐),ATMP(氨基三(亚甲基膦酸)),DTPMP(二亚乙基三胺五(亚甲基膦酸)),EDTMP(乙二胺四(亚甲基膦酸)),HDTMP(羟乙基-乙二胺三(亚甲基膦酸)),HEDP(羟基乙烷二膦酸),或HMDTMP(六亚甲基二胺四(亚甲基膦酸))。
可以想到的是,当组合物另外包含聚合物试剂时,使用本发明的组合物可获得非常理想的效果。
聚合物试剂可以是能吸附到所述织物上或能溶解所述染料的那些。合适聚合物的例子包括蛋白质(例如牛血清清蛋白,乳清,酪蛋白或豆蛋白),蛋白质水解产物(例如乳清、酪蛋白或大豆蛋白质的水解产物〕,多肽,木质素磺酸盐,多糖类和其衍生物,聚乙二醇,聚丙二醇,聚乙烯基吡咯烷酮,乙二胺与环氧乙烷或环氧丙烷的缩合物,乙氧基化多胺,或乙氧基化胺聚合物。
一方面,本发明涉及一种在染色织物表面的色密度上获得局部变化的方法,该方法包括在含水介质中让染色织物与包含纤维素分解酶,热膨胀珍珠石和缓冲剂及任意性的分散剂和/或螯合剂的组合物相接触。
所以,本发明的方法包括让染色织物或服装与含有本发明组合物的水溶液或悬浮液接触,并将织物或服装搅拌足够长的时间,在织物或服装表面的色密度上产生局部变化。一件件的织物可由溶液或悬浮液润湿,然后在本发明组合物的水溶液或悬浮液中搅拌。
用来处理染色织物的组合物的量一般取决于组合物中纤维素分解酶、缓冲剂和珍珠石的比例及将要洗涤的染色织物的干重。一般情况,用于本发明方法中的组合物含有至少(最低量)20EGU或20ECU的内-β-葡聚糖酶和至少(最低量)20w/w%的珍珠石,以获得石洗外观。在优选的方法中,染色织物在大约55℃下与大约40-150EGU或40-150ECU内-β-葡聚糖酶/每升洗液接触75分钟。优选的PH值取决于纤维素分解酶的最佳PH值,即不管使用酸性、中性或碱性纤维素酶。
本发明的优选组合物包括20-95(w/w)%的珍珠石,一定量的纤维素分解酶,该含量能够有效地在染色织物表面的色密度上获得局部变化,1-50(w/w)%的缓冲剂和任意性地,0.1~10(w/w)%的分散剂和/或0.1~10(w/w)%的螯合剂,以组合物的总重为基础。
本发明的组合物可以在常用的工业混合器中配制。一般,混合液体酶组合物和缓冲剂,并以足够慢的速度加入到热膨胀珍珠石中,产生均匀的酶分散体。
本发明组合物一般在家用、种研用或工业用机器内在水中使用,该机器具有以水平或垂直方式固定的圆形鼓,为的是产生石洗外观。最常见的是,根据制造商的建议,按照机器的容量将织物加入到机器中。织物在向鼓中引入水之前加进去或加入到机器内的水中或加入到包含本发明组合物的水中。织物与组合物接触,并在机器中搅拌足够长的时间,以确保织物被完全润湿和确保纤维素分解酶和织物上珍珠石的作用。
在下面的实施例中进一步描述本发明,它们决不是为了限定本发明的范围。
实施例1
本发明的组合物
制造下面的组合物:
组合物A:
*珍珠石(牌号0515,购自Nordisk Perlite Aps,丹麦)
*纤维素酶(来自Humicola in solens,DSM 1800的~43KD内-β-葡聚糖酶,由Novo Nordisk A/S,Bagsvaerd,丹麦):84ECU/g珍珠石
*三乙醇胺(85%):0.83g/g珍珠石
*分散剂(购自Nobel Kemi AB的Berol 08*):0.083g/g珍珠石
Berol*08是非离子表面活性剂(乙氧基化C18-脂肪酸酯)。在Berol*08中氧化乙烯基单元的平均数是80。
组合物B:
*珍珠石(牌号0515)
*纤维素酶(从Humicola insolens,DSM 1800获得的纤维素酶制剂,由Novo Nordisk A/S,Bagsvaerd,丹麦生产和销售):51EGU/g珍珠石
*磷酸盐缓冲剂(70%KH2PO4+30%Na2HPO4·2H2O):0.83g/g珍珠石
*分散剂(来自Nobel Kemi AB的Berol*08):0.083g/g珍珠石
组合物C:
*珍珠石(牌号0515)
*纤维素酶(从Trichoderma reesi获得的酸性纤维素酶制剂;由Novo Nordisk A/S,Bagsvaerd,丹麦生产和销售):98EGU/g珍珠石
*三乙醇胺(85%):0.75g/g珍珠石
*分散剂(来自Nober kemi AB的Berol 08):0.083g/g珍珠石
实施例2
用本发明的组合物处理染色织物(石洗)和与已知方法比较
进行以下实验:
材料和方法:
使用了40升水的12kg Wascator FL 120 wash extractor用来石洗2.6kg织物。
机器负载:2.6kg-40升水。
用三种方法/酶组合物进行试验:
A:用80g商品纤维素酶制剂处理,142EGU/g,从Humicolainsolens,DSM 1800获得;从Novo Nordisk A/S,Bagsvaerd,丹麦购得。
B:与A一样,但是用150g在A中所述纤维素酶制剂处理。
C:用60g在A中所述纤维素酶制剂处理并添加0.5kg浮石/每kg粗斜棉布织物。
D:用333g的本发明的下述组合物处理:
56w/w%的热膨胀珍珠石,
22.5w/w%三乙醇胺,
8w/w%柠檬酸/柠檬酸钠,
5.5w/w%分散剂(Nobel Kemi AB的Berol 08,和
0.25w/w%的~43KD内-β-葡聚糖酶,约70ECU/g,从Humicola insolens DSM1800获得;由Novo NordiskA/S,Bagsvaerd,丹麦生产。
将粗斜棉布放入机器内,加入组合物,开始机器洗涤周期。
“石洗”在55-60℃和PH约7下进行60分钟。
通过使用反射计(Texflash 2000)在波长420nm下测量反射率来测定磨耗水平,在光箱中由肉眼观察评估来证实结果。
结果示于下表。
表
方法/组合物 | 纤维素酶的量浮石 | 磨耗水平%R,在420nm | |
ABCD | 11360EGU21300EGU8520EGU22975ECU | --0.5kg/kg- | 11.4612.7113.3614.51 |
结果表明,使用本发明的组合物可显著改善磨耗水平,与根据已知方法的处理相比较,即与单独用酶处理或酶处理与用浮石洗涤相结合相比较。
实施例3
淘洗粉尘
为了测定本发明组合物的起尘效果,与常规的热膨胀珍珠石相比较,特意进行如下实验。
方法:样品在玻璃柱中淘洗。松落的粉尘收集在过滤器上,测定其重量。
将60.0g样品置于穿孔钢板上,钢板大致放置在玻璃柱底部上方7cm处,该玻璃柱的内径为0.0345m和总长度为1.83m。玻璃柱通过塑料管与过滤接受器连通。为了避免粉尘在过滤接受器外部发生任何沉积作用,塑料管被导入过滤接受器内。过滤接受器是在紧密密封的不锈钢接受器内的穿孔不锈钢板组成的。过滤器(Whatman 15.0cm CF/C玻璃纤维过滤器)被称重并放入过滤接受器内。排气通风机和空气流动被启动,空气流速被调节至2.69m3/h~0.8m/s。在流化过程中空气被调节相对湿度为40~50%。总流化时间是40分钟。停止空气流入和排气通风机,在过滤接受器盖上的粉尘被转移至过滤器上。将过滤器称重,测定所收集粉尘的量。
样品:
试验两个样品:
样品1:珍珠石(牌号0515,粒度1.5-1.5mm)。
样品2:根据实施例1的组合物A
结果: 收集的粉尘,mg
样品1:(珍珠石) 216.0
样品2:(本发明的组合物) 1.4
可以得出结论,使用热膨胀珍珠石时的粉尘问题在使用本发明组合物之后几乎被消除了。
Claims (22)
1.一种处理染色织物的方法,该方法包括在含水介质中让织物与纤维素分解酶和热膨胀珍珠石相接触,后两者的用量能有效地在染色织物表面的色密度上获得局部变化。
2.根据权利要求1的方法,其中组合物进一步包括缓冲剂和任意性的分散剂和/或螯合剂。
3.根据权利要求1的方法,其中织物是用瓮染料、直接染料、硫染料或活性染料染色的。
4.根据权利要求3的方法,其中织物是纤维素织物。
5.根据权利要求4的方法,其中织物是粗斜棉布,优选用靛蓝染色的粗斜棉布。
6.根据权利要求1的方法,其中纤维素分解酶和热膨胀珍珠石是固体组合物的成分,它们能够在染色织物表面的色密度上获得局部变化。
7.根据权利要求2的方法,其中缓冲剂选自磷酸盐,硼酸盐,柠檬酸盐,马来酸盐,乙酸盐,己二酸盐,三乙醇胺,单乙醇胺,二乙醇胺,碳酸盐,二胺,咪唑,和氨基酸缓冲剂,更好的是选自单、二和三乙醇胺缓冲剂。
8.根据权利要求2的方法,其中分散剂是非离子、阴离子、阳离子、两性或两性离子表面活性剂。
9.根据权利要求8的方法,其中分散剂选自羧甲基纤维素,羟丙基纤维素,烷基芳基磺酸盐,长链醇硫酸酯,伯和仲烷基硫酸酯,磺化烯烃,硫酸化单甘油酯,硫酸化醚,磺基琥珀酸盐,磺化甲醚,链烷磺酸盐,磷酸酯,异硫代硫酸烷基酯,酰基肌氨酰胺,烷基牛磺酰胺,氟表面活性剂,脂肪醇和烷基酚缩合物,脂肪酸缩合物,环氧乙烷与胺的缩合物,环氧乙烷与酰胺的缩合物,嵌段聚合物如聚乙二醇、聚丙二醇和乙二胺与环氧乙烷或环氧丙烷的缩合物,蔗糖酯,山梨糖酯,烷基酰胺,脂肪胺氧化物,乙氧基化单胺,乙氧基化二胺,乙氧基化多胺,乙氧基化胺聚合物,乙氧基化脂肪酸酯,和壬基苯基聚乙二醇醚,以及它们的混合物,优选的情况是选自乙氧基化脂肪酸酯和壬基苯基聚乙二醇醚。
10.根据权利要求1的方法,其中纤维素分解酶或纤维素酶属于微生物来源,优选真菌或细菌纤维素酶。
11.根据权利要求10的方法,其中纤维素酶是酸性纤维素酶,即纤维素酶的PH值至少低于约7,优选低于约6。
12.根据权利要求11的方法,其中酸性纤维素酶是从木霉属、耙菌属、梭菌属或热杆菌属的菌株得到的。
13.根据权利要求10的方法,其中纤维素酶是中性或碱性纤维素酶。
14.根据权利要求13的方法,其中纤维素酶是从腐质霉属、镰刀菌属、芽孢杆菌属、纤维杆菌属、假单胞菌属、毁丝霉属或显毛菌属(Phanerochaete)得到的。
15.根据权利要求10-14的方法,其中纤维素酶是单组分纤维素酶,优选单组分的内-β-葡聚糖酶。
16.根据权利要求1-15中的任何一项的方法,其中组合物进一步包括螯合剂。
17.根据权利要求16的方法,其中螯合剂是在酸性、中性或碱性PH值下可溶的并能与二价或三价阳离子形成配合物,优选选自葡糖酸、柠檬酸、酒石酸、草酸、二甘醇酸或葡庚糖酸盐;或磷酸盐,二磷酸盐,三或多聚磷酸盐,或焦磷酸盐。
18.根据权利要求1的方法,其中热膨胀珍珠石的粒度在约0.2mm和约20mm之间,优选在约0.3mm和约10mm之间,尤其在约1mm和约5mm之间。
19.根据权利要求1-18中任一项的方法,其中织物与组合物接触,该组合物包括20-95(w/w)%的珍珠石,一定量的纤维素分解酶,其含量能有效地在染色织物表面的色密度上获得局部变化,1-50(w/w)%的缓冲剂,和任意性的0.1-10(w/w)%的分散剂和/或0.1~10(w/w)%的螯合剂,以组合物的总重为基础。
20.根据权利要求19的方法,其中组合物包含约20~约300EGU,优选约20~约200EGU,尤其约40~约150EGU的内-β-葡聚糖酶/每克组合物的一种能从真菌类Humicolainsolens,DSM1800获得的纤维素解酶或纤维素酶。
21.根据权利要求19的方法,其中组合物包含约20~约300ECU,优选约20~约200 ECU,尤其约40~约150ECU/每克组合物的一种能从真菌类Humicola insolens,DSM 1800获得的~43KD内-β-葡聚糖酶。
22.用来处理染色织物的组合物,它包括纤维素分解酶,热膨胀珍珠石和缓冲剂。
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-
1994
- 1994-09-27 EP EP94928304A patent/EP0721494A1/en not_active Withdrawn
- 1994-09-27 JP JP7510067A patent/JPH09503032A/ja not_active Expired - Lifetime
- 1994-09-27 WO PCT/DK1994/000360 patent/WO1995009225A1/en not_active Application Discontinuation
- 1994-09-27 BR BR9407657A patent/BR9407657A/pt not_active Application Discontinuation
- 1994-09-27 TW TW083108949A patent/TW282503B/zh active
- 1994-09-27 AU AU77393/94A patent/AU7739394A/en not_active Abandoned
- 1994-09-27 CN CN94193532.9A patent/CN1131966A/zh active Pending
-
1995
- 1995-05-18 US US08/444,115 patent/US5674427A/en not_active Expired - Fee Related
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101239840B (zh) * | 2007-02-05 | 2010-07-28 | 山东理工大学 | 膨胀珍珠岩陶瓷水洗球的制备方法 |
CN103201367A (zh) * | 2010-11-15 | 2013-07-10 | 荷兰联合利华有限公司 | 用纤维状聚合物和水溶性聚合物结构化的液体表面活性剂组合物 |
CN103201367B (zh) * | 2010-11-15 | 2015-07-29 | 荷兰联合利华有限公司 | 用纤维状聚合物和水溶性聚合物结构化的液体表面活性剂组合物 |
CN103403249A (zh) * | 2010-12-30 | 2013-11-20 | 诺维信公司 | 用具有纤维素分解增强活性的多肽处理纺织品的工艺 |
CN103403249B (zh) * | 2010-12-30 | 2016-11-23 | 诺维信公司 | 用具有纤维素分解增强活性的多肽处理纺织品的工艺 |
CN104583394A (zh) * | 2012-08-16 | 2015-04-29 | 诺维信公司 | 用内切葡聚糖酶处理纺织品的方法 |
CN104583394B (zh) * | 2012-08-16 | 2019-06-07 | 诺维信公司 | 用内切葡聚糖酶处理纺织品的方法 |
CN103866584A (zh) * | 2014-02-21 | 2014-06-18 | 朱文潮 | 一种有机碱染色方法 |
CN111945443A (zh) * | 2020-08-28 | 2020-11-17 | 湖南蓝印文化发展有限公司 | 一种蓝印花布染料配方 |
Also Published As
Publication number | Publication date |
---|---|
EP0721494A1 (en) | 1996-07-17 |
AU7739394A (en) | 1995-04-18 |
WO1995009225A1 (en) | 1995-04-06 |
US5674427A (en) | 1997-10-07 |
JPH09503032A (ja) | 1997-03-25 |
BR9407657A (pt) | 1997-01-28 |
TW282503B (zh) | 1996-08-01 |
US5565006A (en) | 1996-10-15 |
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