CN102348769A - 染料-聚合物配方 - Google Patents
染料-聚合物配方 Download PDFInfo
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- CN102348769A CN102348769A CN2010800116262A CN201080011626A CN102348769A CN 102348769 A CN102348769 A CN 102348769A CN 2010800116262 A CN2010800116262 A CN 2010800116262A CN 201080011626 A CN201080011626 A CN 201080011626A CN 102348769 A CN102348769 A CN 102348769A
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- 238000000034 method Methods 0.000 claims description 8
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
-
- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
-
- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0052—Dyeing with polymeric dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
本发明提供包含2至70重量%表面活性剂和0.0001至10重量%分子量为至少500的染料-聚合物的洗衣处理组合物，其中该染料-聚合物可通过下列材料的聚合获得：（a）染料单体，其是共价键合到染料上的不带电烯烃，和（b）一种或多种其它烯烃共聚单体。还要求保护处理织物的家用方法。
Description
发明领域
本发明涉及将染料输送至织物。
发明背景
授予Unilever的WO2005/003274公开了在洗涤剂配方中可包括遮蔽染料以增强服装的白度。
授予Proctor and Gamble 的WO2006/055787描述在洗衣制剂中附着到纤维素醚上的反应性染料。该染料的反应性官能团通过产生共价键的加成或取代反应与该聚合物的OH、SH或NH2基团反应。该聚合物必须含有这些基团才能发生反应。所用反应性染料带负电荷。主要在纤维素服装上发现遮蔽益处。
WO2006/055843、WO2007/087252、WO2008/091524和WO2008/100445（都授予Milliken）描述用在洗衣制剂中的经由芳环侧面的胺基连接到聚醚基团上的染料。主要在纤维素服装上发现遮蔽益处。
WO2008/009579（Ciba）公开了用于染发的含侧接的带阳离子电荷的染料的聚合物链。
US
3926830公开了连接到聚合物上的染料指示剂；染料指示剂带电荷。聚合染料指示剂的用途是用于将水染色。
EP
0128619公开了不可溶苯乙烯染料聚合物的用途。
WO
2005/068598公开了用于洗衣的Liquitint Violet CT。Liquitint Violet CT仅在WO
2005/068598中作为聚合着色剂公开并根据实施例能将棉着色。
最好提供沉积到家庭洗涤负荷中存在的棉和聚酯织物上的聚合物染料。
发明概述
本发明的染料-聚合物沉积到棉和聚酯织物上。
一方面，本发明提供包含2至70重量%表面活性剂以及0.0001至10重量%，优选0.01至1重量%分子量为至少500的染料-聚合物的洗涤剂组合物，其中该染料-聚合物可通过下列材料的聚合获得：
（a）染料单体，该染料单体是共价键合到染料上的不带电烯烃，该染料单体具有至少1000
mol-1 L cm-1，优选大于4000
mol-1 L cm-1的在400至700nm波长下的摩尔消光系数，和
（b）一种或多种其它烯烃共聚单体，该烯烃单体具有小于100
mol-1 L cm-1，优选小于10
mol-1 L cm-1的在400至700nm波长下的摩尔消光系数。
该染料-聚合物优选通过如上详述的项目（a）和（b）的聚合获得（形成）。
另一方面，本发明提供处理织物的家用方法，该方法包括下列步骤：
（i）用染料-聚合物的水溶液处理织物，该水溶液包含10 ppb至100
ppm染料-聚合物；和0.0
g/L至3 g/L，优选0.3至2 g/L表面活性剂；
（ii）任选漂洗；和
（iii）干燥该织物。
如本文所述的洗涤剂组合物最优选是颗粒洗涤剂组合物。
染料单体
染料单体是溶解在有机溶剂中时具有1000 mol-1 L cm-1，优选大于4000 mol-1 L cm-1的在400-700nm，优选500-650nm，最优选540-600nm波长下的摩尔吸收消光系数的有机分子。
优选使用1、5或10厘米池在有机溶剂，优选丙-2-醇中测量摩尔吸收系数。
该染料单体在水溶液中在7至11的pH下不带电。该染料单体不含极性增溶基团。特别地，该染料单体不含任何磺酸（SO3 -）、羧酸（CO2 -）或季铵基团。
该染料优选选自有机染料，其选自下列发色团类别：蒽醌、偶氮和甲川，最优选蒽醌和单-偶氮。在Industrial Dyes (K.Hunger编辑,
Wiley VCH 2003, ISBN 3-527-30426-6)中描述了染料。
染料单体优选为下列形式：
其中Y是将染料共价连接到染料单体的烯烃部分上的有机桥连基，且R1选自：H；烷基；芳基；卤素；酯；酰胺；和CN。
当R1是苯基或苄基时，该芳基未被OH取代。
优选地，染料的芳基与带有R1的烯烃碳的最直接连接（Y）被1至8个原子，最优选3至6个原子隔开；该原子优选选自：C；N；O；和S。烯烃还可以直接连接至染料，在这种情况下不存在Y。
优选地，有机桥连基（Y）选自：-CONR4-、-NR4CO-、-COOR4-、-NR4-、-O-、-S-、-SO2-、-SO2NR4-、-N(COR4)-和-N(SO2R4)-，其中R4选自H、C1-C6支链或直链烷基、苯基和苄基，其中R4具有0至1个选自：-O-；-S-；-SO2-；-C(O)O-；-OC(O)-；和胺的间隔单元。有机桥连基最优选是-CONR4-。最优选地，R4选自H和Me。Y基团优选直接键合到染料的芳环的碳原子上。
R1优选选自：H；Me；Et；Pr；CO2C1-C4支链和直链烷基链；苯基；苄基；CN；Cl；和F。R1最优选是H或Me。
优选的染料-单体为下列形式：
其中Ar是芳基或杂芳基，且Z选自：H；CH3；Cl；和NHCOCH3，W选自H；CH3O；C2H5O；和Cl。
另一优选的染料-单体为下列形式：
,
其中A和B环被进一步取代。优选基团包括NH2、NHAr、NHR5、NR5R6、OH、Cl、Br、CN、OAr、NO2、SO2OAr、CH3和NHCOC(R1)=CH2，其中R5和R6独立地选自C1-C8支链、环状或直链烷基，其可以被OH、OMe、Cl或CN取代。
该染料最优选在4、5或8位置被至少一个选自NH2、NHAr和NHR5、NR5R6的基团取代。最优选地，当存在时，OH和NO2基团在4、5或8位置且存在不多于2个NO2基团。
可以通过优选选自：分散蓝1；分散蓝5；分散蓝6；分散蓝9；分散蓝19；分散蓝28；分散蓝40；分散蓝56；分散蓝60；分散蓝81；分散紫1；分散紫4和分散紫8的蒽醌分散染料的NH2的酰化制备合适的染料。
合适的染料的另一实例是分散蓝7。
该染料单体可以被具有小于400的总分子量的不带电有机基团进一步取代。优选的不带电有机基团选自：NHCOCH3；CH3；C2H5；CH3O；C2H5O；胺；Cl；F；Br；I；NO2；CH3SO2；和CN。
在US4943617 (BASF)、US5055602
(Bausch和Lomb)、WO2005/021663
(Eastman)、US5362812 (3M)中论述了各种染料单体的合成。
合适和优选的染料单体包括：
染料单体的另一些实例是：
烯烃共聚单体
该共聚单体优选为下列形式：
其中R2和R3独立地选自：
H、C1-C8支链、环状和直链烷基链、C(O)OH、CO2C1-C18支链和直链烷基链、-C(O)N(C1-C18)2；-C(O)N(C1-C18)H；-C(O)NH2；杂芳基、苯基、苄基、聚醚、氰基、Cl和F。在指定C1-C18时，优选范围是C1至C4。
该共聚单体的R2和R3可以被具有小于400的总分子量的带电和不带电有机基团进一步取代。优选的不带电有机基团选自：NHCOCH3、CH3、C2H5、OH、CH3O、C2H5O、胺、Cl、F、Br、I、NO2、CH3SO2和CN。
该苯基、苄基和烷基链可以被选自OH；F；Cl；烷氧基（优选OCH3）、SO3 -、COOH、胺、季胺、酰胺和酯的其它有机基团取代。当存在苯基或苄基时，芳基未被OH取代。
合适的共聚单体的实例包括。标出优选的共聚单体
可以使用共聚单体的混合物。优选>50重量%，更优选>80重量%的共聚单体选自具有小于300的分子量并含有胺、酰胺、OH、SO3 -或COO-基团的共聚单体。该共聚单体最优选含有胺基团。
染料聚合物
该染料聚合物优选是蓝色或紫色的。该染料聚合物优选赋予布色调角为250-345，更优选265至330，最优选270至300的蓝色或紫色。用于测定色调角的布是白色漂白的非丝光处理的棉织布料。
通过染料单体与合适的不饱和有机共聚单体的共聚制造该聚合物。
该聚合物优选含有0.1至30摩尔（Molar）%染料单体单元，优选2至15摩尔（Molar）%。
该聚合物内的单体可以以任何合适的方式排列。例如交替共聚物具有规则交替的单体残基；周期共聚物具有以重复序列排列的单体残基类型；无规共聚物具有单体残基类型的无规序列；统计共聚物具有根据已知统计规则排列的单体残基；嵌段共聚物具有由共价键连接的两个或更多个均聚物亚单元。该聚合物应具有500和更大，优选2000和更大，优选5000和更大的分子量。在本文中，分子量是数均分子量。这是各个大分子的分子量的普通算术平均值。其通过测量j个聚合物分子的分子量、合计这些分子量并除以j来测定。通过凝胶渗透色谱法测定分子量。
该染料-聚合物优选可溶于表面活性剂溶液。具体而言，在pH=7的1克/升十二烷基硫酸钠水溶液中，该染料聚合物具有大于1毫克/升，优选大于10毫克/升的溶解度。聚合物中羟基、氨基和带电基团，优选带阴离子电荷的基团的存在提高水溶性。
该聚合物优选为下列形式：
，其中X = Y-染料。
a优选大于b（a>b）。a:b的比率更优选为99.9:0.1至70:30。
该染料-聚合物优选具有500至500000，优选1000至100000，更优选5000至50000的数均分子量。
为了添加到颗粒制剂中，可以将该聚合物染料添加到要喷雾干燥的浆料中或优选通过后计量给料的颗粒添加。
在一个优选实施方案中，将由聚合物染料合成获得的聚合物染料粉末与Na2SO4或NaCl或预制的颗粒基料或完整洗涤剂配方混合以产生0.1至20聚合物染料重量%混合物。随后将这种干混合物混入颗粒制剂中。优选通过例如经真空干燥、冻干、在鼓式干燥机Spin Flash ®
(Anhydro)中干燥，但最优选经喷雾干燥法干燥染料的液体浆料或溶液来形成聚合物染料粉末。可以在制造该浆料之前、之中或之后研磨该聚合物染料粉末。优选在磨机，例如球磨机、摆锤磨机、珠磨机或砂磨机中或在捏合机中实现这种研磨。
可以将其它成分，如分散剂或碱金属盐添加到该液体浆料中。该聚合物染料粉末优选含有20至100重量%的染料。
该聚合物染料粉末优选具有0.1至300微米，优选10至100微米的平均粒度APS。这优选通过激光衍射粒度分析仪，优选带有100毫米透镜的Malvern HP测量。
表面活性剂
该组合物包含2至70重量%表面活性剂，最优选10至30重量%。通常，该表面活性剂体系的非离子型和阴离子型表面活性剂可以选自"Surface Active Agents"
第1卷,
Schwartz & Perry, Interscience 1949, 第2卷，Schwartz, Perry & Berch, Interscience 1958，"McCutcheon's Emulsifiers and Detergents"现行版，Manufacturing Confectioners Company出版或"Tenside-Taschenbuch", H. Stache, 第2版, Carl Hauser
Verlag, 1981中所述的表面活性剂。所用表面活性剂优选是饱和的。
可用的合适的非离子型洗涤剂化合物特别包括具有疏水基团和反应性氢原子的化合物，例如脂族醇、酸、酰胺或烷基酚与环氧烷，尤其是单独或与环氧丙烷一起的环氧乙烷的反应产物。具体的非离子型洗涤剂化合物是C6至C22烷基酚-环氧乙烷缩合物，通常每分子5至25 EO，即5至25个环氧乙烷单元，和脂族C8至C18伯或仲直链或支链醇与环氧乙烷，通常5至40 个EO的缩合产物。
可用的合适的阴离子型洗涤剂化合物通常是具有含有大约8至大约22个碳原子的烷基的有机硫酸酯和磺酸酯的水溶性碱金属盐，术语烷基用于包括高级酰基的烷基部分。合适的合成阴离子型洗涤剂化合物的实例是烷基硫酸钠和钾，尤其是通过硫酸化例如由牛脂油或椰子油制成的高级C8至C18醇获得的那些，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；和烷基甘油基醚硫酸钠，尤其是衍生自牛脂或椰子油的高级醇和衍生自石油的合成醇的那些醚。优选的阴离子型洗涤剂化合物是C11至C15烷基苯磺酸钠和C12至C18烷基硫酸钠。如EP-A-328
177 (Unilever)中所述的表现出抗盐析性的表面活性剂、EP-A-070 074中所述的烷基聚糖苷表面活性剂和烷基单糖苷也适用。
优选的表面活性剂体系是阴离子型与非离子型洗涤剂活性材料的混合物，特别是EP-A-346 995
(Unilever)中指出的阴离子型和非离子型表面活性剂集合和实例。尤其优选的是C16至C18伯醇硫酸酯的碱金属盐与C12至C15伯醇3至7 EO乙氧基化物的混合物形式的表面活性剂体系。
该非离子型洗涤剂优选以表面活性剂体系的大于10%，例如25至90重量%的量存在。阴离子型表面活性剂可以例如以该表面活性剂体系的大约5%至大约40重量%的量存在。
在也优选的另一方面中，该表面活性剂可以是阳离子型的，以使该制剂是织物调理剂。
阳离子型化合物
当本发明用作织物调理剂时，其需要含有阳离子型化合物。
最优选的是季铵化合物。
如果该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。
该季铵化合物优选具有下式：
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烷基链且X-是相容阴离子。这种类型的优选化合物是季铵化合物十六烷基三甲基溴化季铵。
用于本发明的第二类材料是上述结构的季铵，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烷基链且X-是相容阴离子。
根据权利要求1的洗涤剂组合物，其中（ii）阳离子型材料与（iv）阴离子型表面活性剂的比率为至少2:1。
在EP 0 239 910 (Proctor and Gamble)中公开了其它合适的季铵化合物。
阳离子型与非离子型表面活性剂的比率优选为1:100至50:50，更优选1:50至20:50。
该阳离子型化合物可以以该组合物总重量的1.5重量%至50重量%存在。该阳离子型化合物优选以2重量%至25重量%存在，更优选的组成范围为5重量%至20重量%。
该软化材料优选以总组合物的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。
该组合物任选包含聚硅氧烷(silicone)。
助洗剂或络合剂
助洗剂材料可选自1) 钙螯合剂材料，2) 沉淀材料，3) 钙离子交换材料和4) 它们的混合物。
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结晶或非晶硅铝酸盐，其中沸石是最已知的代表，例如如EP-A-0,384,070中所述的沸石A、沸石B（也称作沸石P）、沸石C、沸石X、沸石Y以及沸石P类型。
该组合物还可含有0-65%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、次氮基三乙酸或下面提到的其它助洗剂。许多助洗剂也是能够络合金属离子的漂白稳定剂。
沸石和碳酸盐（碳酸盐（包括碳酸氢盐和倍半碳酸盐）是优选助洗剂。
该组合物可含有结晶硅铝酸盐，优选碱金属硅铝酸盐，更优选硅铝酸钠作为助洗剂。这通常以小于15%w的量存在。硅铝酸盐是具有下列通式的材料：
0.8-1.5 M2O. Al2O3. 0.8-6 SiO2
其中M是一价阳离子，优选钠。这些材料含有一些结合水并要求具有至少50 mg
CaO/g的钙离子交换容量。优选的硅铝酸钠在上式中含有1.5-3.5个SiO2单元。它们容易通过如文献中充分描述的硅酸钠与铝酸钠之间的反应制备。表面活性剂与硅铝酸盐（如果存在）的比率优选大于5:2，更优选大于3:1。
代替或除硅铝酸盐助洗剂外，也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、三磷酸盐和膦酸盐物类。其它形式的助洗剂包括硅酸盐，如可溶硅酸盐、偏硅酸盐、层状硅酸盐（例如来自Hoechst的SKS-6）。
该洗衣剂配方优选是无磷酸盐助洗的洗衣剂配方，即含有少于1重量%磷酸盐。
荧光剂
该组合物优选包含荧光剂（荧光增白剂）。荧光剂是公知的，许多这样的荧光剂可购得。通常，这些荧光剂以它们的碱金属盐，例如钠盐形式供应和使用。该组合物中所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%。优选类型的荧光剂是：二-苯乙烯基联苯基化合物，例如Tinopal（商标）CBS-X，二-胺均二苯乙烯二-磺酸化合物，例如Tinopal DMS pure Xtra和Blankophor（商标）HRH和吡唑啉化合物，例如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}均二苯乙烯-2-2'二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉并-1,3,5-三嗪-2-基)]氨基}均二苯乙烯-2-2'二磺酸二钠和4,4'-双(2-磺基苯乙烯基)联苯基二钠。
该方法中所用的水溶液优选存在荧光剂。当该方法中所用的水溶液中存在荧光剂时，其优选为0.0001克/升至0.1克/升，优选0.001至0.02克/升。
香料
该组合物优选包含香料。香料优选为0.001至3重量%，最优选0.1至1重量%。在CFTA
Publications出版的CTFA (Cosmetic, Toiletry and Fragrance
Association) 1992 International Buyers Guide和Schnell
Publishing Co出版的OPD 1993 Chemicals Buyers Directory 80th
Annual Edition中提供香料的许多合适的实例。
在配方中通常存在多种香料组分。在本发明的组合物中，考虑存在四种或更多种，优选五种或更多种，更优选六种或更多种或甚至七种或更多种不同香料组分。
在香料混合物中，优选15至25重量%是头香。Poucher (Journal
of the Society of Cosmetic Chemists 6(2) : 80 [1955])定义了头香。优选的头香选自柠檬油、芳樟醇、乙酸里哪酯、薰衣草、二氢月桂烯醇、玫瑰醚和顺式-3-己醇。
香料和头香可用于提示本发明的增白益处。
该洗衣处理组合物优选不含过氧漂白剂，例如过碳酸钠、过硼酸钠和过酸。该洗衣处理组合物优选不含次氯酸盐漂白剂。
聚合物
该组合物可包含一种或多种聚合物。实例是羧甲基纤维素、聚(乙二醇）、聚(乙烯醇）、聚羧酸酯如聚丙烯酸酯、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
该配方中优选不存在用于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)。
酶
该洗衣处理组合物可含有酶。在WO 2007/087243和WO 2007/087257中公开了优选的酶。
实施例
实施例
1
染料单体的合成
反应图式：
1,4-二氨基蒽醌（DAQ）购自Aldrich（90%技术级）并按来样使用。
通过使DAQ（1,4-二氨基蒽醌）和Ac（丙烯酰氯）在碳酸氢钠存在下反应，制备染料单体。将150毫升无水THF、1克DAQ和0.6克碳酸氢钠的混合物装入配有冷凝器、滴液漏斗和磁搅拌棒的250毫升三颈圆底烧瓶。随后在从滴液漏斗添加溶解在5毫升无水THF中的0.38克Ac 3小时的同时使该烧瓶保持在室温下。将反应混合物在25℃下搅拌另外20小时。在20小时后过滤反应混合物以除去在反应过程中出现的不可溶固体，使用旋转蒸发减压计干燥该透明溶液，随后获得紫色粉末并用水洗涤三次，该粉末在真空下在60℃下完全干燥24小时。使用NMR证实DAQ-AC的结构并表明反应已达到大于88%完成。因此多于88%的蒽醌含有一个NHCOCH=CH2基团。
实施例
2
含染料的聚合物的合成：
反应图式：
将3克甲基丙烯酸二甲基氨基乙酯（DMAEMA）、0.03克DAQ-Ac和0.06克AIBN在10毫升甲苯中的溶液装入干N2气体吹扫过的带有冷凝器和磁搅拌棒的双颈管中。密封该管并在调节过的恒温浴中在65℃下放置24小时。该溶液在反应后在5倍过量的石油醚中沉淀三次，接着在真空下在40℃下干燥24小时。通过控制主要应用的染料单体和官能单体，调节该共聚物的组成。在该实验中，添加的染料单体的量分别为1重量%、2重量%、5重量%和10重量%。
实施例
3
染料聚合物的
UV-VIS
在软化水中在1克/升染料聚合物下记录实施例2的染料聚合物的UV-VIS谱，结果列在下表中。
实施例
4
：染料沉积实验
针织白色聚酯（微纤维）和白色纺织非丝光处理的棉织物一起用在含有15%直链烷基苯磺酸盐（LAS）表面活性剂、30% Na2CO3、40% NaCl（其余次要物包括方解石和荧光剂和水分）的4克/升洗涤剂中。在室温的6° French Hard水中用30:1的液/布比进行洗涤30分钟。洗涤后，布在水中漂洗两次，干燥，在反射计上测量它们的反射谱，颜色作为CIE L a b值表示。随后反复洗涤直至完成4次洗涤。
在添加实施例3的染料聚合物的情况下重复该实验。该染料聚合物以配方的0.125重量%定量给料。在第1、第2和第4次洗涤之前和之后，使用反射计（排除UV）记录该织物的CIE
L*a*b*值。以Δb值表示染料-聚合物沉积到织物上，以使
Δb = b(对照物)-b(染料聚合物)
+ve值表明由于染料-聚合物沉积，织物上蓝。
该染料-聚合物沉积到棉和聚酯上
附加优点在于，该染料-聚合物还促进去污和改变织物触感。
实施例
5
：染料沉积实验
使用下列聚合物重复实施例4的实验：
结果显示在下表中：
Claims (21)
1.包含2至70重量%表面活性剂以及0.0001至10重量%分子量为至少500的染料-聚合物的洗涤剂组合物，其中该染料-聚合物可通过下列材料的聚合获得：
（a）染料单体，该染料单体是共价键合到染料上的不带电烯烃，该染料单体具有至少1000
mol-1 L cm-1的在400至700nm波长下的摩尔消光系数，和
（b）一种或多种其它烯烃共聚单体，该烯烃单体具有小于100 mol-1
L cm-1的在400至700nm波长下的摩尔消光系数，
其中在pH=7的1克/升十二烷基硫酸钠水溶液中，该染料聚合物具有大于1毫克/升的溶解度。
2.根据权利要求1的洗涤剂组合物，其中该染料单体为下列形式：
其中Y是将染料共价连接到染料单体的烯烃部分上的有机桥连基，且R1选自：H；烷基；芳基；卤素；酯；酰胺；和CN。
3.根据权利要求2的洗涤剂组合物，其中该有机桥连基选自：-CONR4-；-NR4CO-；-COOR4-；-NR4-；-O-；-S-；-SO2-；-SO2NR4-；-N(COR4)-；和-N(SO2R4)-；其中R4选自：H、C1-C6支链或直链烷基；苯基和苄基；其中R4具有0至1个选自：-O-；-S-；-SO2-；-C(O)O-；-OC(O)-；和胺的间隔单元。
4.根据权利要求2的洗涤剂组合物，其中该有机桥连基是-CONR4-。
5.根据权利要求3或4任一项的洗涤剂组合物，其中R4选自：H和Me。
6.根据权利要求2至5任一项的洗涤剂组合物，其中Y基团直接键合到该染料的芳环的碳原子上。
7.根据前述权利要求任一项的洗涤剂组合物，其中该染料是选自下列发色团类别的有机染料：蒽醌；偶氮；和甲川。
8.根据权利要求7的洗涤剂组合物，其中该有机染料选自下列发色团类别：蒽醌和单-偶氮。
9.根据权利要求2至8任一项的洗涤剂组合物，其中R1选自：H；Me；Et；Pr；CO2C1-C4支链和直链烷基链；苯基；苄基；CN；Cl；和F。
10.根据权利要求9的洗涤剂组合物，其中R1选自：H；和Me。
11.根据前述权利要求任一项的洗涤剂组合物，其中该染料-单体选自：
其中Ar是芳基或杂芳基，且Z选自：H；Me；Cl；和NHCOCH3，W选自H；CH3O；C2H5O；和Cl。
12.根据权利要求2至10的洗涤剂组合物，其中该染料-单体选自：
。
13.根据权利要求12的洗涤剂组合物，其中A和B环被一个或多个选自：NH2；NHAr；NHR5；NR5R6；OH；Cl；Br、CN、OAr；NO2；SO2OAr；Me；和NHCOC(R1)=CH2的基团进一步取代，其中R5 和R6独立地选自C1-C8支链、环状或直链烷基，其可以被OH、OMe、Cl或CN取代。
14.根据权利要求13的洗涤剂组合物，其中A和B环在4、5或8位置被至少一个选自NH2、NHAr和NHR5、NR5R6的基团进一步取代。
15.根据前述权利要求任一项的洗涤剂组合物，其中该共聚单体选自：
其中R2和R3独立地选自：
H、C1-C8支链、环状和直链烷基链、C(O)OH、CO2C1-C18支链和直链烷基链、-C(O)N(C1-C18)2；-C(O)N(C1-C18)H；-C(O)NH2；杂芳基、苯基、苄基、聚醚、氰基、Cl和F。
16.根据权利要求1至14任一项的洗涤剂组合物，其中多于80重量%的共聚单体选自具有小于300的分子量并含有胺的共聚单体。
17.根据权利要求15的洗涤剂组合物，其中该共聚单体的R2和R3被选自带电和不带电有机基团的基团进一步取代，该进一步的基团具有小于400的总分子量。
18.根据权利要求2的洗涤剂组合物，其中该染料-单体选自：
19.根据前述权利要求任一项的洗涤剂组合物，其中洗涤剂组合物包含荧光剂。
20.处理织物的家用方法，该方法包括下列步骤：
（i）用如权利要求1至18任一项中所限定的染料-聚合物的水溶液处理织物，该水溶液包含10 ppb至100 ppm染料-聚合物；和0.0 g/L至3 g/L 表面活性剂；
（ii）任选漂洗；和
（iii）干燥该织物。
21.根据权利要求20的处理织物的家用方法，其中该水溶液包含0.3至2 g/L表面活性剂。
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| ES2435470T3 (es) | 2013-12-19 |
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