CN102015989A - 减少污斑的颗粒 - Google Patents
减少污斑的颗粒 Download PDFInfo
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- 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
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- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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Abstract
本发明提供一种粒状衣物洗涤剂组合物,其包括一种调整色光染料颗粒,所述颗粒包括调整色光染料、染料转印聚合物和任选成分。所述粒状衣物洗涤剂组合物还包括10-50重量%阴离子表面活性剂。
Description
技术领域
本发明涉及向织物递送调整色光染料(shading dyes)。
背景技术
Unilever的WO2005/003274公开了加入衣物洗涤剂以增加白度的调整色光染料。这些粉末的一种缺点是,在某些条件下会在用所述洗涤剂粉末处理的织物上产生局部污斑。
发明内容
衣物洗涤剂制剂中存在的调整色光染料容易给织物提供不希望有的污斑。
通过在调整色光染料颗粒中存在抗染料转印剂改善了该问题。
一方面,本发明提供一种调整色光染料颗粒,其包括:
(i)0.001-95重量%的调整色光染料;
(ii)0.1-99.999重量%的染料转印聚合物,其选自:聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基吡咯烷酮聚合物、聚乙烯基唑烷酮和聚乙烯基咪唑;
(iii)0-80重量%的非离子型表面活性剂;
(iv)0-20重量%的阴离子或阳离子表面活性剂;
(v)0-99.5重量%的载体;和
(vi)0-50重量%的粘合剂,其中染料转印聚合物和带电荷表面活性剂的重量比为1∶0-1∶1。
在另一方面,本发明提供一种粒状的衣物洗涤剂组合物,其包括:
(a)0.00005-10重量%如权利要求1-4中任一项限定的视觉上不同的(visually distinct)衣物洗涤剂颗粒;
(b)99.99995-90重量%的粒状基础粉末,其中所述粒状的衣物洗涤剂组合物包含10-50重量%的阴离子表面活性剂。
来自所述基础粉末的表面活性剂可以是不同类型表面活性剂的混合物,但是所述粒状衣物洗涤剂中的阴离子表面活性剂的总浓度是10-50重量%。来自所述基础粉末的表面活性剂优选是大于70%的阴离子表面活性剂。
具体实施方式
优选所述调整色光染料颗粒在视觉上不同于粒状背景粉末(background powder),以提供视觉指示。
所述调整色光染料颗粒用于加入基础粉末(主洗涤剂粉末)。
优选所述调整色光染料颗粒不包含阴离子表面活性剂。当所述调整色光染料颗粒与基础粉末(其必须包含阴离子表面活性剂)混合时,会有一些阴离子表面活性剂迁移到所述调整色光染料颗粒中。
染料转印聚合物与带电荷表面活性剂的比防止污斑玷污,同时使得直染染料(substantive dye)可以从洗涤液进行染料沉积。
调整色光染料
优选所述调整色光染料是蓝色或紫色的。优选所述调整色光染料的峰值吸收波长为550-650nm,优选570-630nm。可以使用染料的结合,所述染料们一起对人眼的视觉效应等同于在聚酯上的峰值吸收波长为550-650nm,优选570-630nm的一种单独染料。这例如通过混合红色染料与绿-蓝染料从而产生蓝色或紫色色光(shade)就可以实现。
染料是有色有机分子,其可溶于包含表面活性剂的含水介质。染料描述在“工业染料(Industrial Dyes)”中,Wiley VCH 2002,K.Hunger编。
染料列在“国际染料索引”中,其由英国染色家学会和美国纺织化学家与染色家协会出版。染料优选选自碱性染料、酸性染料和直接染料。
直接染料
优选直接紫和直接蓝染料。优选所述染料是双偶氮或三偶氮染料。不优选致癌性联苯胺染料。
可以使用包含双偶氮铜的染料如直接紫66。
最优选所述直接染料是以下结构的直接紫:
其中环D和E独立地是萘基或苯基,如上所示;
R1选自氢和C1-C4烷基,优选氢;
R2选自氢、C1-C4烷基、取代或未取代的苯基和取代或未取代的萘基,优选苯基;
R3和R4独立地选自氢和C1-C4烷基,优选氢或甲基;
X和Y独立地选自氢、C1-C4烷基和C1-C4烷氧基;优选所述染料的X为甲基,Y为甲氧基,并且
n是0、1或2,优选1或2。
优选的染料是直接紫7、直接紫9、直接紫11、直接紫26、直接紫31、直接紫35、直接紫40、直接紫41、直接紫51和直接紫99。
酸性染料
棉直染酸性染料给含棉衣服带来好处。优选的染料和染料混合物是蓝色或紫色的。优选的酸性染料是:
(i)吖嗪染料,其中所述染料为以下核心结构:
其中Ra、Rb、Rc和Rd选自H、支链或直链C1-C7烷基链、苄基、苯基和萘基;
所述染料被至少一个SO3 -或-COO-基团取代;
B环不带有带负电荷的基团或其盐;
A环可以进一步取代以形成萘基;
所述染料任选被选自以下的基团取代:胺、甲基、乙基、羟基、甲氧基、乙氧基、苯氧基、Cl、Br、I、F和NO2。
优选的吖嗪染料是酸性紫50和酸性蓝98。
(ii)以下核心结构的DANSA染料:
其中R选自H;支链或直链C1-C7烷基链;COR1,其中R1是支链或直链C1-C7烷基链;和-SO2Ar基团,其中Ar是苯基或甲基取代的苯基;
Y选自NO2;CN;I;Br;Cl;F;H;OCOR2;NHCOR3;R4;R5O和NR6R7,其中R2、R3、R4和R5独立地选自支链或直链C1-C7烷基链,R6和R7独立地选自H、支链或直链C1-C7烷基链,所述烷基链是未取代的或被独立选自以下的基团取代:OH;Cl;F;OCOCH3;COOCH3;OCOC2H5和COOC2H5;和
X选自H;SO2N(R8)COCH3;SO2N(R8)-Ar;SO2N(R8)-Ar和SO2-Ar,其中Ar是芳基,R8是H,CH3或C2H5,
条件是Y不带有带负电荷的基团或其盐。
(iii)以下核心结构的MAAD染料:
其中:
X选自-OH,CH3O-,CH3CH2O-和-NR1R2,其中R1和R2独立地选自H;支链或直链C1-C7烷基链;-COR3,其中R3是支链或直链C1-C7烷基链;和-SO2Ar基团,其中Ar是苯基或甲基取代的苯基;
Y是选自苯基和萘基的芳基,并且Y可以被R4O-、R4CONH-、R4-、Cl、Br、I、F、NO2和-NR4R5取代,其中R4和R5独立地选自H、支链或直链C1-C7烷基链或苯基。
其它优选的酸性染料是酸性紫17、酸性黑1、酸性红17和酸性蓝29。
优选所述酸性染料占所述制剂的量为0.001-0.006重量%。
疏水性染料
所述组合物可以包括选自苯并二呋喃、甲川、三苯甲烷、萘二甲酰亚胺、吡唑、萘醌、蒽醌和单偶氮或二偶氮染料发色团的一种或多种疏水性染料。疏水性染料是不包含任何带电荷的水增溶基团的染料。疏水性染料可以选自分散染料和溶剂染料。优选蓝色和紫色的蒽醌和单偶氮染料。
优选染料包括溶剂紫13、分散紫27、分散紫26、分散紫28、分散紫63和分散紫77。
优选所述疏水染料占所述制剂的0.0005-0.004重量%。
碱性染料
碱性染料是带净正电荷的有机染料。它们沉积在棉上。它们在主要包含阳离子表面活性剂的组合物中特别有用。染料可以选自国际染料索引中所列的碱性紫和碱性蓝染料。
优选的实例包括三芳基甲烷碱性染料、偶氮碱性染料、甲烷碱性染料、蒽醌碱性染料、碱性蓝16、碱性蓝65、碱性蓝66、碱性蓝67、碱性蓝71、碱性蓝159、碱性紫19、碱性紫35、碱性紫38、碱性紫48、碱性蓝3、碱性蓝75、碱性蓝95、碱性蓝122、碱性蓝124、碱性蓝141和噻唑染料。
活性染料
活性染料是包含能与纤维素反应并将所述染料以共价键连结到纤维素上的有机基团的染料。它们沉积在棉上。优选所述活性基团发生水解或所述染料的活性基团已与有机物种如聚合物起反应,以使所述染料连接到该物种上。染料可以选自国际染料索引中所列的活性紫和活性蓝染料。
优选的实例包括活性蓝19、活性蓝163、活性蓝182和活性蓝、活性蓝96。
抗染料转印聚合物
本发明的调整色光染料颗粒包含0.1-99.999重量%,优选0.5-18重量%,更优选0.5-2重量%的抗染料转印聚合物(ADTP),其选自聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基吡咯烷酮、聚乙烯基唑烷酮和聚乙烯基咪唑。
以上讨论的抗染料转印聚合物(ADTP)是本领域公知的并有市售,请参考US6833336和其中的参考文献。
优选的抗染料转印聚合物是聚乙烯基吡咯烷酮。
载体
所述调整色光染料颗粒优选包含载体,载体的优选实例是膨润土、氯化钠、沸石和硫酸钠。优选所述载体的量为80-99.8重量%。
粘合剂
粘合剂是用于粘合混合物中的两种或多种其它材料的一种材料。它的两个主要性质是粘合力和内聚力。所述粘合剂不是非离子型表面活性剂。粘合剂是衣物洗涤剂颗粒领域的标准组分,其实例是:SokalanCP45、SokalanCP 5、乙二醇、表面活性剂、阴离子表面活性剂、聚乙二醇、聚乙烯基吡咯烷酮、聚丙烯酸酯、柠檬酸和其混合物。
优选,所述粘合剂的熔点超过30℃。
优选所述粘合剂选自聚丙烯酸酯、聚乙二醇和聚丙烯酸酯/马来酸酯共聚物。
适用于本发明的聚合物是可水溶性的。可水溶性在本文中指的是,聚合物在20℃在软化水中的溶解度大于5克/升。
所述粘合剂优选是酸性聚合物。酸性聚合物在本文中指的是,所述聚合物的1%溶液的pH小于7,优选小于5.5。
适用于本发明的聚合物的分子量为1000-280000,优选1500-150000。
符合上述标准并因此特别适用于本发明的适合聚合物包括具有以下经验式I的那些聚合物:
其中X是O或CH2;Y是共聚单体或共聚单体混合物;R1和R2是漂白稳定性聚合物端基;R3是H、OH或Cl-4烷基;M是H以及其与碱金属、碱土金属、铵或取代的铵的混合物;P是0-2;和n至少是10,和其混合物。在这种聚合物中的M的比例优选确保所述聚合物具有足够酸性,以符合以上限定的酸度标准。
式I聚合物是衣物洗涤剂领域已知的,其一般用作螯合剂,如在GB-A-1597,756所述。优选的聚羧酸酯聚合物分成若干种类。第一种类属于共聚聚羧酸酯聚合物种类,其形式上至少由不饱和多羧酸如马来酸、柠康酸、衣康酸和中康酸作为第一单体和不饱和一元羧酸如丙烯酸或α-C1-C4烷基丙烯酸作为第二单体组成。因此,对于式I,这种类型优选的聚羧酸酯聚合物是那些聚合物,其中X是CHO;R3是H或C1-4烷基,尤其是甲基;p是约0.1-1.9,优选约0.2-1.5;n平均为约10-1500,优选约50-1000,更优选100-800,尤其是120-400;和Y包括式II的单体单元:
粘结剂材料很容易商购获得。优选BASF出售的Sokalan型水溶性聚合物。以下是一些这种适用的产品:Sokalan CP 10;Sokalan CP 10 S;Sokalan CP 12 S;Sokalan CP 13 S;Sokalan CP 45;Sokalan CP 5;Sokalan CP 7;Sokalan CP 9;Sokalan DCS;Sokalan HP 165;Sokalan HP 22 G;Sokalan HP 25;Sokalan HP 50;Sokalan HP 53;Sokalan HP 53 K;Sokalan HP 56;Sokalan HP 59;Sokalan HP 60;Sokalan HP 66;Sokalan PA 110 S;Sokalan PA 15;Sokalan PA 15 CL;Sokalan PA 20;Sokalan PA 20 PN;Sokalan PA 25 CL;Sokalan PA 30;Sokalan PA 40;Sokalan PM 70;和Sokalan SR 100。
颗粒
所述颗粒优选的尺寸为50-1800微米。所述颗粒尺寸是通过过网状筛而计算的。优选所述尺寸为100-800微米。
实施例
实施例1
将染料溶剂紫13混合在非离子型表面活性剂(7EO)中,以形成0.5重量%的溶液。向其中添加直接紫9的[硝基三(2,1-乙二氧基)]三[正丙醇]盐,DV 9,(Ciba Speciality Chemicals出品)。在高剪切混和器中将所述非离子型表面活性剂加入该载体。随后添加粘合剂Sokalam CP 5(BASF出品)。适当时将聚乙烯基吡咯烷酮(PVP)加如该非离子溶液。
所得颗粒在烘箱中在353K干燥,最后过筛得到尺寸为500-1400微米的颗粒。
所述颗粒有以下组成。所有百分比为干重百分比。
颗粒 | 膨润土 | 7EO | DV9 | PVP | CP5 |
1 | 69.93 | 20.56 | 0.20 | 0.00 | 9.41 |
2 | 69.71 | 20.68 | 0.20 | 0.21 | 9.51 |
3 | 69.41 | 20.65 | 0.08 | 0.21 | 9.83 |
4 | 69.38 | 20.93 | 0.08 | 0.00 | 9.58 |
实施例2
以2重量%将实施例1的颗粒分开加到洗涤剂粉末(20%直链烷基苯磺酸盐、30%碳酸钠、40%氯化钠、余量的微量成分包括荧光增白剂和水分)中。将10克粉末洒到浸于1cm软化水中的25*25cm白色棉布片碎片上。所述布浸90分钟,然后彻底冲冼和干燥。每个试验重复四次。将用颗粒1和2浸泡的布相比较,将用颗粒3和4浸泡的布相比较,因为它们有等量的DV 9。将来自每个比较的八块布根据染料污渍/污斑玷污程度分级。最少污渍/污斑玷污的布得分1,污渍玷污处于第二低水平的得分2,等等,而最多污斑/污斑玷污的布得分8。
对每种颗粒计算4块布的总得分,然后进行比较:
包含0.20重量%DV9的颗粒
颗粒1(没有PVP) 总分=24
颗粒2(PVP) 总分=12
包含0.08重量%DV9的颗粒
颗粒3(PVP) 总分=11
颗粒4(没有PVP) 总分=25
包含染料转印抑制聚合物的颗粒显示降低的污渍/污斑玷污水平。
实施例3
将实施例1的颗粒加入实施例2的基础洗衣粉中,使得当洗衣粉溶解成2克/升时,洗涤液包含200ppb的SV13。向所述洗涤液中添加织造棉和针织尼龙弹性织物的片,使得洗涤液与布的比是100∶1。所述洗涤液在293K搅拌60分钟,将所述布冲冼两次,并通过反射法测颜色变化,表示为CIE L*a*b*值。下面给出结果,表示为相对于不带染料洗涤的对照的ΔE值。
所有颗粒使染料对织物良好沉积,由所述ΔE值证实。
实施例4
示例基础粉末制剂A、B、C和D
制剂 | A | B | C | D |
NaLAS | 15 | 20 | 10 | 14 |
NI(7EO) | - | - | - | 1.0 |
三聚磷酸钠 | - | 15 | - | - |
皂 | - | - | - | 2 |
沸石A24 | 7 | - | - | 17 |
硅酸钠 | 5 | 4 | 5 | 1 |
碳酸钠 | 25 | 20 | 30 | 20 |
硫酸钠 | 40 | 33 | 40 | 22 |
羧甲基纤维素 | 0.2 | 0.3 | - | 0.5 |
氯化钠 | - | - | - | 5 |
脂酶 | 0.005 | 0.01 | - | 0.005 |
蛋白酶 | 0.005 | 0.01 | - | 0.005 |
淀粉酶 | 0.001 | 0.003 | - | - |
纤维素酶 | - | 0.003 | - | - |
荧光增白剂 | 0.1 | 0.15 | 0.05 | 0.3 |
水/杂质/微量成分 | 余量 | 余量 | 余量 | 余量 |
以1重量%将颗粒2和颗粒3各自被加到示例粉末制剂A、B、C和D中,以形成用于纺织物洗涤和色光调整的最终制剂。
Claims (5)
1.调整色光染料颗粒,其包括:
(i)0.001-95重量%的调整色光染料;
(ii)0.1-99.999重量%的染料转印聚合物,其选自:聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基吡咯烷酮聚合物、聚乙烯基唑烷酮和聚乙烯基咪唑;
(iii)0-80重量%的非离子型表面活性剂;
(iv)0-20重量%的阴离子或阳离子表面活性剂;
(v)0-99.5重量%的载体;和
(vi)0-50重量%的粘合剂,其中染料转印聚合物和带电荷表面活性剂的重量比为1∶0-1∶1。
2.根据权利要求1的调整色光染料颗粒,其中所述带电荷表面活性剂是阴离子表面活性剂。
3.根据权利要求1的调整色光染料颗粒,其中所述载体的量为80-99.8重量%。
4.根据在前权利要求任一项的调整色光染料颗粒,其中所述调整色光染料选自酸性染料、碱性染料和直接染料。
5.一种粒状衣物洗涤剂组合物,其包括:(a)0.00005-10重量%如权利要求1-4中任一项限定的视觉上不同的衣物洗涤剂颗粒;
(b)99.99995-90重量%的粒状基础粉末,其中所述粒状的衣物洗涤剂组合物包含10-50重量%的阴离子表面活性剂。
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- 2009-02-18 BR BRPI0910682-0A patent/BRPI0910682B1/pt active IP Right Grant
- 2009-02-18 MY MYPI2010005145A patent/MY153627A/en unknown
- 2009-02-18 WO PCT/EP2009/051893 patent/WO2009132870A1/en active Application Filing
- 2009-02-18 CN CN2009801153444A patent/CN102015989B/zh active Active
- 2009-04-29 AR ARP090101518A patent/AR071603A1/es active IP Right Grant
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106574212A (zh) * | 2014-08-22 | 2017-04-19 | 罗门哈斯公司 | 作为衣物染料转移抑制剂的咪唑改性碳水化合物聚合物 |
CN106574212B (zh) * | 2014-08-22 | 2020-03-20 | 罗门哈斯公司 | 作为衣物染料转移抑制剂的咪唑改性碳水化合物聚合物 |
CN111971372A (zh) * | 2018-04-03 | 2020-11-20 | 荷兰联合利华有限公司 | 染料颗粒 |
CN111971372B (zh) * | 2018-04-03 | 2022-03-11 | 联合利华知识产权控股有限公司 | 染料颗粒 |
Also Published As
Publication number | Publication date |
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MY153627A (en) | 2015-02-27 |
ZA201007320B (en) | 2012-01-25 |
EP2268784B2 (en) | 2015-10-28 |
BRPI0910682B1 (pt) | 2020-09-24 |
CN102015989B (zh) | 2012-07-04 |
CL2009001053A1 (es) | 2010-01-15 |
EP2268784A1 (en) | 2011-01-05 |
BRPI0910682A2 (pt) | 2015-09-29 |
ES2400204T3 (es) | 2013-04-08 |
AR071603A1 (es) | 2010-06-30 |
EP2268784B1 (en) | 2012-11-21 |
ES2400204T5 (es) | 2015-11-26 |
WO2009132870A1 (en) | 2009-11-05 |
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