CN1360625A - 无毒的杀菌洗涤剂 - Google Patents
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- C03C4/00—Compositions for glass with special properties
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
本发明涉及一种无毒洗涤剂,它具有杀生物和去斑迹的特性,并与溶剂一起使用,它含有至少一种表面活性介质。该洗涤剂的特征在于,它含有生物活性玻璃,每克该玻璃可释放优选大于250μg的碱金属离子和/或碱土金属离子。这类洗涤剂特别适用于洗涤表面和纺织物,并适合作为洗碗洗涤剂,特别是在医疗界和给养工业。
Description
本发明涉及一种有杀菌作用的无毒的对织物有保护作用的洗涤剂，特别是用于纺织物，并还涉及其制备方法和应用。
洗涤剂通常是含有能将污物溶于溶剂，特别是溶于含水溶剂中的表面活性介质的组合物。因为大部分污物含有脂肪或有类似脂肪的特性，所以用表面活性介质，特别是表面活性剂来去除。但采用这种方法仅能去除含脂肪的污物。其它类的污物例如蛋白质或含蛋白质的污物如血迹、有色物质如咖啡或茶和看不见的污物，特别是微生物等不易采用这种方法去除。为此，洗涤剂通常还含有至少一种漂白剂和/或至少一种消毒剂，以便去除残留的污物，至少是从视觉上不再能看到。在去除脂肪污物和有色污物后，再用氧化方法去除斑迹。
最后，还经常使用释放氯的化学试剂，因其有高的氧化能力，所以同时也作为消毒剂。但是这种氧化常常仅去掉斑迹的有色部分，其它不溶性物质仍然污染基底物质。但是，因氯漂白剂的高反应性，它有侵蚀有色纺织物的缺点，并在许多情况下，改变了其颜色或引起退色。此外，有腐蚀性的氯漂白剂含侵蚀待洗涤的材料，特别是纺织物，以致在经多次洗涤后，其基本结构受到破坏，这就使其强度下降。
为此，过去曾试图用过乙酸来完成氧化漂白。虽然该酸本身有足够的消毒作用，但其穿透多孔材料差，特别是在纺织物的情况下会造成不足的消毒作用。此外，像氯漂白剂一样，过乙酸在洗涤剂中是由过硼酸盐和分解的酰基形成，所以起到了氧化作用，虽然其程度较低。
这种氧化作用虽然足够起到去除有色斑迹的漂白作用以及对许多材料比其它漂白剂更温和，但在所有情况下不能达到合适的消毒作用。例如，不能去除需氧的孢子形成物。此外，每种酸的使用会对毛织物有明显的损害。
最后，过氧化合物与蛋白质污物反应，引起蛋白质老化，特别是在血迹的情况下。但是，老化的蛋白质在洗涤剂以通常用的时间洗涤时，或多或少不能由洗涤剂完全去除。
因此，本发明的目的是提供一种洗涤剂，它除有良好的洗涤特性外，还有消毒作用，并且其本身又是无毒的。
很早就已知生物活性玻璃，例如Larry L.Hench和John K.West在“生物活性玻璃的生物学应用”，生命化学报告1996，13卷，P.187-241或在“生物陶瓷概念”，由L.Hench和J.Wilson编辑的世界科学，New Jersey(1993)中综述了此内容。与通常的玻璃相比，生物活性玻璃的特征在于，在水介质中可溶的，并在表面形成羟基磷灰石层。常用的生物活性玻璃或以熔融玻璃制备或它是所谓的溶胶-凝胶玻璃，熔融玻璃比通常的窗玻璃或瓶玻璃有低得多的SiO2含量和高得多的钠含量，与熔融玻璃不同，溶胶-凝胶玻璃有高的二氧化硅含量以及含少量钠或完全不含钠。
生物活性玻璃的基本特性是专业人员所知的，如在US-A-5074916中所描述的。由此，生物活性玻璃与通常的钙-钠-硅玻璃的区别在于它能与生物组织结合。
这种生物活性玻璃例如可用于治疗受损伤的骨骼，特别是作为合成骨植入物。此外，它们正成功地用于治疗慢性创伤，特别是糖尿病患者的溃疡以及老年病人的压疼和褥疮。例如，John E.Rectenwald，Sean Lee和Lyle L.Moldawer等人(感染和免疫，送交出版)曾表明，在鼠中，生物活性玻璃起到了抗炎症的作用，这是由于促进了白细胞介素-6(IL-6)的活性，并同时抑制了增加炎症的细胞因子TNF-α、IL-1-α和IL-10以及MPO(髓过氧物酶)(参看外科感染学会第19次年会，1999，4月28日-5月1日，1999)。
再则，由E.Allen等人(Eastman牙周牙科学院微生物学系)报导，由美国生物材料公司，FL32615得到的商标为Bioglas的生物活性玻璃45-S-5具有抗细菌的作用，这是用通常的玻璃小球粒(窗玻璃)所没有的。
但是，这种生物活性玻璃释放出大量的Ca2+离子。因此，预计会明显增加水的硬度，这又会导致增加钙沉积和降低洗涤作用，这样就不适合用于洗涤剂中。
此外，还预计该玻璃颗粒的摩擦作用会引起对材料的机械损伤，特别是会引起纺织物的破坏。
意外的是，我们发现上述的目的可以借助于含生物活性玻璃颗粒的洗涤剂来达到。这种颗粒的溶解度最好大于250μg碱金属离子/g玻璃，术语“碱金属离子”包括碱土金属离子。
意外的是，我们发现含有这种玻璃颗粒的洗涤剂不仅可作为病毒和细菌的生物杀伤剂，而且对皮肤和织物是温和的，不引起过敏反应，此外，能消除难以去除的污物如老化的蛋白质。意外的是，碱金属离子和特别是碱土金属离子如Ca2+和Mg2+的释放不会降低洗涤作用，也不会增加钙的沉积。此外，所加的玻璃颗粒对拟清洗的材料，特别是纺织物不会造成可怕的破坏或损害。
因此，本发明涉及一种与溶剂一起使用的有杀生物和去污物特性的无毒洗涤剂，该洗涤剂包含至少一种表面活性剂。本发明的特征在于，该洗涤剂含有玻璃颗粒，该每克玻璃颗粒能释放出大于250μg的碱金属离子或碱土金属离子和/或在水溶液，特别是生理水溶液中在其表面上会形成羟基磷灰石层。优选地，包括在洗涤剂中的每克玻璃颗粒能释放出大于300μg，特别是大于500μg的碱金属离子。特别优选的是每克玻璃能释放出大于1mg碱金属离子/碱土金属离子的玻璃颗粒。
这种洗涤剂不仅适于清洗和消毒表面和外科器械，而且适于纺织材料，特别是在医院和诊所以及食品服务中心。
本发明的洗涤剂也特别适合用作洗碗剂，特别是用于洗碗机。
本发明包含的生物活性玻璃优选是专业人员所熟知的通常的生物活性玻璃。这类玻璃含有最大60重量％的SiO2、高含量的Na2O和CaO以及磷，后者有高摩尔比的钙∶磷，其值大多数为但不必定是约5。如果该生物活性玻璃与水或体液接触，它表征出特殊的反应，即玻璃的钠离子和钙离子以阳离子交换反应置换溶液中的H+离子，由此形成含硅烷醇基的表面，其上缔合有氢氧化钠和氢氧化钙。羟基离子浓度的增加导致在玻璃表面上与硅网络进一步反应，由此形成另外的可处于玻璃更深处的硅烷醇基。
因为在玻璃空间的高的碱性pH值，由CaO和P2O5形成混合的羟基磷灰石相，它在SiO2表面上结晶，并在生物材料中与糖胺聚糖、骨胶原和糖蛋白结合。
钙∶磷的摩尔比优选＞2，特别是＞3，并且优选＜30，特别是＜20，并且比例小于10是特别优选。
含有生物活性玻璃颗粒的洗涤剂特别优选是含有SiO2、CaO、Na2O、P2O5、CaF2、B2O3、K2O和/或MgO。如果洗涤剂含有由熔融玻璃组成的生物活性玻璃颗粒，则按玻璃的总重量计优选含40-60重量％的SiO2、10-30重量％的CaO、10-35％重量％的Na2O、2-8重量％的P2O5、0-25重量％的CaF2、0-10重量％的B2O3、0-8重量％的K2O和/或0-5重量的MgO。如果生物玻璃是熔融玻璃，则所含SiO2的上限约为60重量％，优选约为55重量％，而且50重量％的上限是优选的。氧化钠的含量优选大于15重量％，特别是大于18重量％。氧化钠含量大于20重量％是特别优选的。
如果在本发明的洗涤剂中所含的生物活性玻璃是通过溶胶-凝胶-方法生产的生物活性玻璃，则其氧化硅的含量比熔融玻璃中的明显较高，并且其氧化钠含量可以是0。用溶胶-凝胶-方法生产的生物活性玻璃优选含40-90重量％SiO2、4-45重量％的CaO、0-10重量％的Na2O、2-6重量％的P2O5、0-25重量％的CaF2、0-4重量％的B2O3、0-8重量％的K2O和/或0-5重量％的MgO。
在上述两类生物活性玻璃中，氧化磷的含量优选至少2重量％，特别是至少4重量％。
本发明的洗涤剂中的杀微生物的玻璃颗粒的平均颗粒大小d50≤400μm，特别是≤250μm，粒度≤100μm是特别优选的。基本上是较高的表面∶重量比或表面∶体积比要比较大颗粒有较高的杀生物消毒活性。例如粒度＜50μm，特别是＜20μm或＜10μm的颗粒可获得异常高的杀生物活性，颗粒＜5μm是特别优选的。
但是已发现，在实用的范围内，粒度为2-60μm，特别是2-50μm和优选2-20μm的玻璃颗粒会由于其摩擦作用增加污物颗粒的机械去除，因此明显提高了清洗作用。
此外，本发明的洗涤剂显示出降解蛋白质，即溶解蛋白质的作用。这种作用也以老化的蛋白质，即变性蛋白质得到证实。
采用本发明的洗涤剂可实现所需的消毒、杀病菌的作用，而无需加入其它添加剂，特别是无需加入能释放Ag+、Cu+、Cu2+和/或Zn+的添加剂。但这些添加剂对达到协同效应是所需的。本发明的洗涤剂的杀生物活性可由加入其它的有抗菌作用的消毒和杀病菌剂而协同增加。
虽然曾预计，将本发明的玻璃颗粒加到洗涤剂中，特别是对于含钙的水，会要求加入大量的络合剂以防止钙和污物沉积在所清洗的材料上，但已意外地发现，如络合剂的去钙剂，例如多磷酸盐的加入可明显地减少或可不加入，同时不会出现可怕的钙积垢。再则，由于玻璃颗粒的摩擦作用，任何存在的钙积垢都被去除。
在本发明的优选实施方案中，本发明洗涤剂所含玻璃颗粒的量按干基计达20重量％或达10重量％，优选达7重量％和特别是达5重量％。最小量为0.01重量％，特别是0.1重量％，至少0.5重量％或1重量％是特别优选的。通常含量为1-4重量％。
本发明还涉及制备这种洗涤剂的方法，该方法的特征在于，表面活性介质，特别是不同表面活性介质的混合物，特别是表面活性剂是与前述的玻璃颗粒相混合，并且该混合物还可以溶剂稀释。
本发明还涉及该洗涤剂在清洗表面、外科器械和饮料瓶以及作为或在洗碗剂中应用。另外的特殊应用包括清洗纺织物，特别是用于医疗中心、医院工作人员和食品服务中心的纺织物。
Claims (12)
1.一种无毒洗涤剂，它具有杀生物和去污物特性，并与溶剂联合使用，该洗涤剂含有至少一种表面活性介质，其特征在于，它包含生物活性玻璃颗粒。
2.权利要求1的洗涤剂，其特征在于，该生物活性玻璃的每克玻璃颗粒释放至少300μg碱金属离子。
3.权利要求1的洗涤剂，其特征在于，玻璃颗粒的平均粒度＜400μm。
4.上述权利要求之一的洗涤剂，其特征在于，玻璃颗粒的平均粒度＜100μm。
5.上述权利要求之一的洗涤剂，其特征在于，它含有表面活性剂作为表面活性介质。
6.上述权利要求之一的洗涤剂，其特征在于，生物活性玻璃含40-60重量％的SiO2、10-30重量％的CaO、10-35重量％的Na2O、2-8重量％的P2O5、0-25重量％的CaF2、0-10重量％的B2O3、0-8重量％的K2O和0-5重量％的MgO。
7.上述权利要求之一的洗涤剂，其特征在于，它含有按固体总量计的1-7重量％的生物活性玻璃。
8.一种用于制备权利要求1-7中之一的洗涤剂的方法，其特征在于，将至少一种表面活性介质加到生物活性玻璃中，每克生物活性玻璃可释放至少250μg的碱金属离子。
9.权利要求1-8中之一的洗涤剂在清洗物体和/或表面中的应用。
10.权利要求9的应用，其特征在于，该物体是纺织材料。
11.权利要求9作为洗碗剂的应用。
12.权利要求1-11在医疗和食品服务中心用于洗涤的应用。
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| CN108018133A (zh) * | 2017-12-20 | 2018-05-11 | 刘海报 | 不含航空煤油的可快速清洁麻将的无毒环保抗菌清洗剂 |
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| US7597900B2 (en) * | 2001-03-27 | 2009-10-06 | Schott Ag | Tissue abrasives |
| DE10141117A1 (de) * | 2001-08-22 | 2003-03-13 | Schott Glas | Antimikrobielles Silicatglas und dessen Verwendung |
| CN1599702A (zh) * | 2001-12-12 | 2005-03-23 | 舱壁玻璃公司 | 抗菌的碱－硅酸盐玻璃陶瓷及其应用 |
| DE10161075C1 (de) | 2001-12-12 | 2003-08-21 | Schott Glas | UV-Strahlung absorbierende, antimikrobielle, entzündungshemmende Glaskeramik, Verfahren zu ihrer Herstellung und ihre Verwendungen |
| DE10214273A1 (de) * | 2002-03-28 | 2003-10-23 | Schott Glas | Glas- und/oder Glaskeramikpulver oder-fasern zur kontrollierten Ionenabgabe |
| DE102004026433A1 (de) | 2004-05-29 | 2005-12-22 | Schott Ag | Nanoglaspulver und deren Verwendung |
| US7754194B2 (en) * | 2005-04-06 | 2010-07-13 | L'oréal | Hair relaxer compositions utilizing bioactive glass |
| US10238507B2 (en) | 2015-01-12 | 2019-03-26 | Surgentec, Llc | Bone graft delivery system and method for using same |
| US10687828B2 (en) | 2018-04-13 | 2020-06-23 | Surgentec, Llc | Bone graft delivery system and method for using same |
| US11116647B2 (en) | 2018-04-13 | 2021-09-14 | Surgentec, Llc | Bone graft delivery system and method for using same |
| KR102456463B1 (ko) * | 2020-12-15 | 2022-10-18 | 엘지전자 주식회사 | 친환경 세제용 유리 조성물 및 이를 이용한 친환경 세제용 유리 분말 제조 방법 |
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| DE752622C (de) | 1940-03-09 | 1951-08-23 | Otto Hoehn K G | Streufaehiges Metallputz- und -poliermittel, insbesondere fuer Herdplatten |
| US4155870A (en) * | 1976-04-19 | 1979-05-22 | Minnesota Mining And Manufacturing Company | Skin cleaning compositions containing water-insoluble glass bubbles |
| HU195976B (en) * | 1986-07-24 | 1989-01-30 | Ilona Susko | Environment-compatible scrubbing agent for cleaninenvironment-protekting scouring composition first of all for cleaning surfaces with rust, scale, fatg mainly rusty, scaly, greasy, sooty surface and for washing mould , soot, and for washing mould |
| US4828723A (en) | 1987-07-15 | 1989-05-09 | Colgate-Palmolive Company | Stable non-aqueous suspension containing organophilic clay and low density filler |
| US5074916A (en) | 1990-05-18 | 1991-12-24 | Geltech, Inc. | Alkali-free bioactive sol-gel compositions |
| FI101129B (sv) * | 1995-01-13 | 1998-04-30 | Vivoxid Oy | Nya bioaktiva glas och deras användning |
| DE19509303A1 (de) | 1995-03-15 | 1996-09-19 | Henkel Kgaa | Silicatische Builder durch Temperung von Stückenglas |
| US5834008A (en) * | 1996-09-19 | 1998-11-10 | U.S. Biomaterials Corp. | Composition and method for acceleration of wound and burn healing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108018133A (zh) * | 2017-12-20 | 2018-05-11 | 刘海报 | 不含航空煤油的可快速清洁麻将的无毒环保抗菌清洗剂 |
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| NO20020083D0 (no) | 2002-01-08 |
| HUP0202268A2 (en) | 2002-10-28 |
| DE50007916D1 (de) | 2004-10-28 |
| AU770305B2 (en) | 2004-02-19 |
| CA2378648A1 (en) | 2001-01-18 |
| ZA200200157B (en) | 2003-12-31 |
| BR0012272A (pt) | 2002-03-12 |
| SK18502001A3 (sk) | 2002-05-09 |
| PL352122A1 (en) | 2003-07-28 |
| NO20020083L (no) | 2002-01-08 |
| EP1194518A1 (de) | 2002-04-10 |
| HUP0202268A3 (en) | 2004-03-01 |
| HK1046706A1 (zh) | 2003-01-24 |
| CZ20014626A3 (cs) | 2002-08-14 |
| AU6818300A (en) | 2001-01-30 |
| MXPA01013166A (es) | 2002-11-04 |
| WO2001004252A1 (de) | 2001-01-18 |
| US6589928B1 (en) | 2003-07-08 |
| ATE277162T1 (de) | 2004-10-15 |
| NZ516135A (en) | 2004-01-30 |
| IL147147A0 (en) | 2002-08-14 |
| JP2003504489A (ja) | 2003-02-04 |
| EP1194518B1 (de) | 2004-09-22 |
| KR20020013592A (ko) | 2002-02-20 |
| TR200103637T2 (tr) | 2002-04-22 |
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