CN108473920A - 染料 - Google Patents
染料 Download PDFInfo
- Publication number
- CN108473920A CN108473920A CN201780006823.7A CN201780006823A CN108473920A CN 108473920 A CN108473920 A CN 108473920A CN 201780006823 A CN201780006823 A CN 201780006823A CN 108473920 A CN108473920 A CN 108473920A
- Authority
- CN
- China
- Prior art keywords
- weight
- acid
- dyestuff
- surfactant
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000975 dye Substances 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
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- 239000003599 detergent Substances 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
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- -1 carbon atoms Organic sulfate Chemical class 0.000 description 17
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 108020002496 Lysophospholipase Proteins 0.000 description 3
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 125000002252 acyl group Chemical group 0.000 description 2
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- 229910052791 calcium Inorganic materials 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
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- 230000008021 deposition Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- 150000002832 nitroso derivatives Chemical class 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
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- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
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- KCZIUKYAJJEIQG-UHFFFAOYSA-N 1,3,5-triazin-2-amine Chemical compound NC1=NC=NC=N1 KCZIUKYAJJEIQG-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
-
- C—CHEMISTRY; METALLURGY
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
Abstract
本发明提供了包含吩噁嗪蓝色或紫色染料和表面活性剂的洗衣处理组合物和用所述组合物的水溶液处理纺织品的家用方法。
Description
技术领域
本发明涉及蓝紫色光漂白剂和所述蓝紫色光漂白剂在洗衣组合物中的用途。
背景技术
调色染料(shading dye)是从洗涤物沉积到织物以提供蓝色或紫色色调的蓝色或紫色染料,其增强织物白度。调色染料在WO2012/172038(Unilever)中讨论。
WO2005/003277(Unilever)公开了呫吨染料作为有效的洗衣光漂白剂。该等化合物的颜色是红色,并且为了获得蓝紫色,必须与绿蓝染料混合。呫吨染料含有具有3个稠合6元环的芳族体系,因此比WO2005/014769(Ciba)中讨论的绿色金属化酞菁洗衣光漂白剂简单得多。
US2006/230547公开了吩噁嗪染料和作为染发剂的用途。
发明内容
需要基于本文提供的简单的三稠环结构的用于洗衣洗涤剂的有效蓝紫色光漂白剂。
在一个方面,本发明提供一种洗衣处理组合物,其包含:
(i)2至70重量%的表面活性剂,优选5至30重量%;和,
(ii)作为钠盐测量,0.0001至0.1重量%的下式的蓝色或紫色吩噁嗪染料及其N-氧化物:
其中R1至R6独立地选自H和Cl,并且其中R1至R6中的至少4个是Cl。
另一方面,本发明提供了一种处理纺织品的家用方法,所述方法包括以下步骤:用如本文定义的洗衣洗涤剂组合物的0.5至20g/L,更优选1至10g/L的水溶液处理纺织品。
具体实施方式
用于本发明的染料是蓝色或紫色。在这方面,染料给白布带来蓝色或紫色,其色调角为240至330,更优选260至320,最优选265至300。所用的白布是经漂白的、未作丝光处理的编织棉片。
蓝色或紫色吩噁嗪染料的抗衡离子可以是碱金属、碱土金属或季胺,最优选抗衡离子是钠盐。
吩噁嗪染料可以通过间苯二酚和4-亚硝基间苯二酚之间的酸催化缩合简单地合成。例如:
方案1
在可逆反应中,染料可以容易地氧化成N-氧化物形式。
染料通常显示约6的pKa并在此之上变为带负电荷。优选地,制剂在2g/L(去矿物质水)的洗液中的pH为大于pKa,更优选大于7,最优选大于10。
优选地,作为钠盐测量,组合物包含0.0001至0.1重量%,更优选0.002至0.05重量%的蓝色或紫色吩噁嗪染料。
表面活性剂
洗衣组合物包含2至70重量%的表面活性剂,更优选10至30重量%。通常,表面活性剂体系的非离子和阴离子表面活性剂可以选自“Surface Active Agents”,卷1,Schwartz&Perry,Interscience 1949;卷2,Schwartz,Perry&Berch,Interscience 1958;Manufacturing Confectioners Company出版的“McCutcheon's Emulsifiers andDetergents”的当前版本,或“Tenside Taschenbuch”,H.Stache,第2版,Carl HauserVerlag,1981中描述的表面活性剂。优选地,所用表面活性剂是饱和的。
可以使用的合适的非离子洗涤剂化合物包括,特别地,具有疏水基团和反应性氢原子的化合物(例如脂肪醇、酸、酰胺)与环氧烷(特别是环氧乙烷单独或与环氧丙烷一起)的反应产物。具体的非离子洗涤剂化合物是脂肪族C8至C18直链或支链伯或仲醇与环氧乙烷的缩合产物,通常为5至40EO,优选为7EO至9EO。
可以使用的合适的阴离子洗涤剂化合物通常是具有含约8至约22个碳原子的烷基的有机硫酸盐和磺酸盐的水溶性碱金属盐,术语烷基用于包括高级酰基的烷基部分。合适的合成阴离子洗涤剂化合物的实例是烷基硫酸钠和烷基硫酸钾,特别是通过硫酸化例如从牛油或椰子油产生的高级C8至C18醇而获得的那些;烷基C9至C20苯磺酸钠和钾,特别是直链仲烷基C10至C15苯磺酸钠;和烷基甘油醚硫酸钠,特别是衍生自牛油或椰子油的高级醇和衍生自石油的合成醇的那些醚。优选的阴离子洗涤剂化合物是C11至C15烷基苯磺酸钠和C12至C18烷基硫酸钠。还适用的是例如EP-A-328 177(Unilever)中描述的那些表面活性剂,其显示耐盐析,EP-A-070 074中描述的烷基多糖苷表面活性剂,以及烷基单糖苷。
优选的表面活性剂系统是阴离子与非离子洗涤剂活性物质的混合物,特别是在EP-A-346 995(Unilever)中指出的阴离子和非离子表面活性剂的组和实例。特别优选的是作为C16至C18伯醇硫酸盐的碱金属盐与C12至C15伯醇3至7EO乙氧基化物的混合物的表面活性剂体系。
非离子洗涤剂优选以表面活性剂体系的小于50重量%,最优选小于20重量%的量存在。阴离子表面活性剂可以例如以表面活性剂体系的约50%至100重量%范围的量存在。
在同样优选的另一方面,表面活性剂可以是阳离子的,使得制剂是织物调理剂。
阳离子化合物
当本发明用作织物调理剂时,其需要含有阳离子化合物。
最优选的是季铵化合物。
如果季铵化合物是具有至少一个C12至C22烷基链的季铵化合物,则是有利的。
如果季铵化合物具有下式:
其中R1是C12至C22烷基或烯基链;R2、R3和R4独立地选自C1至C4烷基链,并且X-是相容的阴离子,则是优选的。这种类型的优选的化合物是季铵化合物鲸蜡基三甲基溴化季铵。
与本发明一起使用的第二类物质是具有上述结构的季铵,其中R1和R2独立地选自C12至C22烷基或烯基链;R3和R4独立地选自C1至C4烷基链,并且X-是相容的阴离子。
根据权利要求1所述的洗涤剂组合物,其中(ii)阳离子材料与(iv)阴离子表面活性剂的比率为至少2:1。
其他合适的季铵化合物公开于EP 0 239 910(Procter和Gamble)。
如果阳离子与非离子表面活性剂的比率为1:100至50:50,则是是优选的,更优选1:50至20:50。
阳离子化合物可以以组合物总重量的1.5重量%至50重量%存在。优选地,阳离子化合物可以以2重量%至25重量%存在,更优选的组成范围是5重量%至20重量%。
软化材料优选地以总组合物的2至60重量%,更优选2至40重量%,最优选3至30重量%的量存在。
组合物任选地包含硅酮。
助洗剂或络合剂
助洗剂材料可以选自1)钙螯合剂材料,2)沉淀材料,3)钙离子交换材料,及4)其混合物。
钙螯合剂助洗剂材料的实例包括碱金属聚磷酸盐,如三聚磷酸钠,和有机螯合剂,如乙二胺四乙酸。
沉淀助洗剂材料的实例包括正磷酸钠和碳酸钠。
钙离子交换助洗剂材料的实例包括各种类型的水不溶性晶体或无定形铝硅酸盐,其中沸石是最有名的代表,例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y以及在EP-A-0,384,070中描述的沸石P型。
组合物还可以含有0至65%的助洗剂或络合剂,如乙二胺四乙酸、二亚乙基三胺五乙酸、烷基或烯基琥珀酸、次氮基三乙酸,或下文所述的其他助洗剂。许多助洗剂因其络合金属离子的能力而同样是漂白稳定剂。
沸石和碳酸盐(碳酸盐(包括碳酸氢盐和倍半碳酸盐))是优选的助洗剂。
组合物可以含有晶体铝硅酸盐,优选碱金属铝硅酸盐,更优选铝硅酸钠作为助洗剂。这通常以小于15重量%的水平存在。铝硅酸盐是具有以下通式的材料:
0.8-1.5M2O·Al2O3·0.8-6SiO2
其中M是一价阳离子,优选钠。这些材料含有一些结合水并需要具有至少50mgCaO/g的钙离子交换容量。优选的铝硅酸钠在上式中含有1.5-3.5个SiO2单元。它们可以通过硅酸钠与铝酸钠之间的反应容易地制备,如文献中所充分描述的。表面活性剂与铝硅酸盐(存在时)的比率优选大于5:2,更优选大于3:1。
替代性地,或除铝硅酸盐助洗剂以外地,可以使用磷酸盐助洗剂。在本领域中术语“磷酸盐”包括二磷酸盐、三磷酸盐和膦酸盐种类。助洗剂的其他形式包括硅酸盐,例如可溶性硅酸盐、偏硅酸盐、层状硅酸盐(例如来自Hoechst的SKS-6)。
优选地,洗衣洗涤剂制剂是非磷酸盐助洗的洗衣洗涤剂制剂,即含有少于1重量%的磷酸盐。优选地,洗衣洗涤剂制剂是碳酸盐助洗的。
荧光剂
组合物优选地包含荧光剂(光学增亮剂)。荧光剂是众所周知的,并且许多这样的荧光剂是可商购的。通常,这些荧光剂以其碱金属盐,例如钠盐的形式供应和使用。组合物中使用的一种或多种荧光剂的总量通常为0.005至2重量%,更优选0.01至0.1重量%。优选的荧光剂类别是:二苯乙烯基联苯化合物,如Tinopal(商标)CBS-X;二胺二苯乙烯二磺酸化合物,如Tinopal DMS pure Xtra和Blankophor(商标)HRH;以及吡唑啉化合物,如Blankophor SN。优选的荧光剂是:2(4-苯乙烯基-3-磺苯基)-2H-萘酚[1,2-d]三唑钠、4,4'-双{[(4-苯胺基-6-(N甲基-N-2羟乙基)氨基1,3,5-三嗪-2-基)]氨基}二苯乙烯-2,2'二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠,和4,4'-双(2-磺苯乙烯基)联苯二钠。
优选的是用于该方法的水溶液具有荧光剂存在。当用于该方法的水溶液中存在荧光剂时,其优选在0.0001g/l至0.1g/l,更优选0.001至0.02g/l的范围内。
香料
优选地,组合物包含香料。香料优选地在0.001至3重量%,最优选0.1至1重量%范围内。香料的许多合适的实例在由CFTA出版社出版的CTFA(Cosmetic,Toiletry andFragrance Association)1992International Buyers Guide和由Schnell PublishingCo.出版的OPD 1993Chemicals Buyers Directory 80th Annual Edition中提供。
在制剂中存在多种香料组分是常见的。在本发明的组合物中,设想将存在四种或更多,优选五种或更多,更优选六种或更多或甚至七种或更多不同的香料组分。
在香料混合物中,优选15至25重量%是头香。头香由Poucher(Journal of theSociety of Cosmetic Chemists 6(2):80[1955])定义。优选的头香选自柑桔油、芳樟醇、乙酸里哪酯、薰衣草、二氢月桂烯醇、玫瑰氧化物和顺-3-己醇。
香料和头香可用于提示本发明的白度益处。
优选的是洗衣处理组合物不含过氧漂白剂,例如过碳酸钠、过硼酸钠和过酸。
聚合物
组合物可以含有一种或多种另外的聚合物。实例是羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸盐如聚丙烯酸盐、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
存在以防止染料沉积的聚合物,例如聚(乙烯基吡咯烷酮)、聚(乙烯基吡啶-N-氧化物)和聚(乙烯基咪唑),优选不存在于制剂中。
酶
一种或多种酶优选存在于本发明的洗衣组合物以及当实施本发明的方法时存在。
优选地,本发明的洗衣组合物中的每个酶的水平为0.0001重量%至0.1重量%蛋白质。
特别考虑的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化物酶/氧化镁、果胶酸裂合酶和甘露聚糖酶或其混合物。
合适的脂肪酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自以下的脂肪酶:腐质霉(Humicola)(同义词嗜热真菌(Thermomyces)),例如来自EP 258 068和EP 305 216中所述的H.lanuginosa(T.lanuginosus)或来自WO 96/13580中所述的H.insolens;假单胞菌脂肪酶,例如来自产碱假单胞菌(P.alcaligenes)或假产碱假单胞菌(P.pseudoalcaligenes)(EP 218 272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、施氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens),假单胞菌菌株SD 705(WO 95/06720和WO 96/27002)、P.wisconsinensis(WO 96/12012);芽孢杆菌脂肪酶,例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,1131,253-360)、嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO 91/16422)。
其他实例是脂肪酶变体,例如在WO 92/05249、WO 94/01541、EP 407 225、EP 260105、WO 95/35381、WO 96/00292、WO 95/30744、WO 94/25578、WO 95/14783、WO 95/22615、WO 97/04079和WO 97/07202、WO 00/60063中描述的那些。
优选的可商购脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和lipocleanTM(Novozymes A/S)。
本发明的方法可以在分类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶存在下进行。如在本文中所使用的,术语磷脂酶是对磷脂具有活性的酶。
磷脂,例如卵磷脂或磷脂酰胆碱,由在外部(sn-1)和中间(sn-2)位置被两个脂肪酸酯化,并在第三位置被磷酸酯化的甘油组成;磷酸反过来可以被酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分磷脂酶活性的多种类型,包括磷酸化酶A1和A2,其水解一个脂肪酰基(分别在sn-1和sn-2位置)以形成溶血磷脂;和溶血磷脂酶(或磷脂酶B),其可以水解溶血磷脂中剩余的脂肪酰基。磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基甘油或磷脂酸。
酶和光漂白剂可以显示一些相互作用,并且应该被选择使得这种相互作用不是负面的。通过在产品内将酶或光漂白剂中的一个或其他包封和/或其他隔离可以避免一些负面的相互作用。
合适的蛋白酶包括具有动物、植物或微生物来源的那些。微生物来源是优选的。包括化学修饰的或蛋白质工程化的突变体。蛋白酶可以是丝氨酸蛋白酶或金属蛋白酶,优选地是碱性微生物蛋白酶或胰蛋白酶样蛋白酶。优选的可商购蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTM和KannaseTM(Novozymes A/S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TM和FN3TM(Genencor International Inc.)。
本发明的方法可以在分类为EC 3.1.1.74的角质酶的存在下进行。根据本发明使用的角质酶可以具有任何来源。优选地,角质酶具有微生物来源,特别是细菌、真菌或酵母来源。
合适的淀粉酶(α和/或β)包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。淀粉酶包括例如从在GB1,296,839中更详细描述的芽孢杆菌获得的α-淀粉酶,如地衣芽孢杆菌的特殊菌株,或者WO 95/026397或WO 00/060060中公开的芽孢杆菌菌株。可商购的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自GenencorInternational Inc.)。
合适的纤维素酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。合适的纤维素酶包括来自以下的纤维素酶:芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、梭孢壳属、支顶孢属,例如从公开于US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、WO 96/029397和WO 98/012307的特异腐质霉、太瑞斯梭孢壳霉、嗜热毁丝霉和尖孢镰刀菌产生的真菌纤维素酶。可商购的纤维素酶包括CelluzymeTM、CarezymeTM、CellucleanTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.)和KAC-500(B)TM(KaoCorporation)。
合适的过氧化物酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自鬼伞属,例如来自灰盖鬼伞的过氧化物酶,及其变体,如在WO 93/24618、WO 95/10602和WO 98/15257中所述的那些。可商购的过氧化物酶包括GuardzymeTM和NovozymTM51004(Novozymes A/S)
另外的适用的酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
酶稳定剂
存在于组合物中的任何酶可以使用常规的稳定剂稳定,例如多元醇,如丙二醇或甘油;糖或糖醇;乳酸;硼酸或硼酸衍生物,例如芳族硼酸酯,或苯基硼酸衍生物,如4-甲酰基苯基硼酸,以及可以如例如WO 92/19709和WO 92/19708中所述配制的组合物。
当烷基足够长以形成支链或环状链时,烷基包括支链、环状和直链烷基链。烷基优选是直链或支链的,更优选直链的。
除非另有规定,如本文中所用不定冠词“一个/种(a或an)”及其对应的定冠词“所述/该(the)”指的是至少一个/种,或一个/种或多个/种。
实施例
(i)合成
根据方案1合成四氯刃天青化合物。亚硝基化合物通过2,4-氯间苯二酚与亚硝酸异戊酯在碱性乙醇溶液中的反应制备,最初在273K,然后在数小时内温热至室温。通过在273K的浓硫酸中混合,亚硝基化合物与2,4-氯间苯二酚反应,然后加热至353K达1小时。
(ii)洗衣沉积和色调
将一片10cm×10cm的白色的、经漂白的、未作丝光处理的编织棉布在基础洗涤剂(15.4重量%直链烷基苯磺酸盐,23.4重量%碳酸钠,41.9重量%硫酸钠,1.8重量%白云石,9.8重量%方解石,其余为次要成分和水分)的2g/L的水溶液(去矿物质水,液体:布为30:1)中在室温下搅动30分钟。将布移除、漂洗并滚动干燥。使用反射计测量布的颜色,并表示为CIE L*a*b*值。重复实验,向制剂中加入0.025重量%的染料的三甲胺盐。
添加到布的总颜色计算为ΔE值,使得
ΔE=(ΔL2+Δa2+Δb2)0.5
其中ΔL=L(对照)-L(染料);Δa=a(对照)-a(染料);Δb=b(对照)-b(染料)
布的实际颜色计算为色调角,其对于当前颜色范围通过下式给出
色调角=270+180/π×atan(-Δa/Δb)
360/0的色调角为红色,270为蓝色,180为绿色。
总结了经漂白的、未作丝光处理的编织棉片的结果。基于实验的3次独立重复,误差限度(±值)为95%置信区间。
包含酸性红51(食物红14)作为对照呫吨染料。
氯化吩噁嗪染料为调色提供最合适的色调(265-300)。
(iii)洗衣光漂白
从“Centre for Test materials BV,Stoomloggerweg,11,3133KT,Vlaardinger,NL”获得织物编号为E114的红葡萄酒着色的编织棉。以与沉积实验类似的方式洗涤色斑,并在漂洗后,在仍然湿润时,放置在老化试验机中2小时(设置为0.35W/m2@340nm)以模拟在自然阳光下挂干。光漂白的程度使用460nm处的反射率R460测量。然后将光漂白表示为ΔR460值,使得
ΔR460=R460(光漂白)-R460(对照)
实验重复3次,并且基于实验的这3次独立重复,误差限度(±值)为95%置信区间。
结果显示如下:
四氯试卤灵提供最大的光漂白效果,由最大的ΔR460值表示。
Claims (4)
1.一种洗衣处理组合物,其包含:
(i)2至70重量%的表面活性剂;和,
(ii)作为钠盐测量,0.0001至0.1重量%的下式的蓝色或紫色吩噁嗪染料及其N-氧化物:
其中R1至R6独立地选自H和Cl,并且其中R1至R6中的至少4个是Cl。
2.根据权利要求1所述的洗衣处理组合物,其中R1,R2,R3和R6是氯,并且R4和R5是H。
3.根据前述权利要求中任一项所述的洗衣处理组合物,其中所述制剂是颗粒状的。
4.一种处理纺织品的家用方法,所述方法包括以下步骤:用根据前述权利要求中任一项所述的洗衣洗涤剂组合物的0.5至20g/L的水溶液处理纺织品。
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2017
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- 2017-01-10 EP EP17700220.1A patent/EP3402868B1/en active Active
- 2017-01-10 BR BR112018014327A patent/BR112018014327A2/pt active Search and Examination
- 2017-01-10 CN CN201780006823.7A patent/CN108473920B/zh active Active
- 2017-01-13 AR ARP170100089A patent/AR107355A1/es active IP Right Grant
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2018
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US20060230547A1 (en) * | 2005-03-23 | 2006-10-19 | Fuji Photo Film Co., Ltd. | Hair-dyeing agent |
CN107109307A (zh) * | 2015-01-09 | 2017-08-29 | 荷兰联合利华有限公司 | 包含染料的洗衣处理组合物 |
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EP3402868A1 (en) | 2018-11-21 |
ZA201804329B (en) | 2019-09-25 |
WO2017121714A1 (en) | 2017-07-20 |
CN108473920B (zh) | 2020-03-10 |
EP3402868B1 (en) | 2020-04-08 |
AR107355A1 (es) | 2018-04-18 |
BR112018014327A2 (pt) | 2018-12-11 |
CL2018001882A1 (es) | 2018-08-31 |
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