CN1036975A - 洗涤剂用的光活性剂染料组合物 - Google Patents

洗涤剂用的光活性剂染料组合物 Download PDF

Info

Publication number
CN1036975A
CN1036975A CN89102154A CN89102154A CN1036975A CN 1036975 A CN1036975 A CN 1036975A CN 89102154 A CN89102154 A CN 89102154A CN 89102154 A CN89102154 A CN 89102154A CN 1036975 A CN1036975 A CN 1036975A
Authority
CN
China
Prior art keywords
composition
capsule material
photoactivator dye
mixture
photoactivator
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.)
Withdrawn
Application number
CN89102154A
Other languages
English (en)
Other versions
CN1015897B (zh
Inventor
比廷·托伦加德
戴维·威廉·约克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denmark Chemical Co Ltd
Procter and Gamble Co
Original Assignee
Denmark Chemical Co Ltd
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Denmark Chemical Co Ltd, Procter and Gamble Co filed Critical Denmark Chemical Co Ltd
Priority to CN 91111573 priority Critical patent/CN1027452C/zh
Publication of CN1036975A publication Critical patent/CN1036975A/zh
Publication of CN1015897B publication Critical patent/CN1015897B/zh
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001Post-treatment of organic pigments or dyes
    • C09B67/0014Influencing the physical properties by treatment with a liquid, e.g. solvents
    • C09B67/0016Influencing the physical properties by treatment with a liquid, e.g. solvents of phthalocyanines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0063Photo- activating compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)

Abstract

本发明涉及用于洗涤剂的光活性剂染料组合物, 它是由含有活性剂染料的微胶囊所组成。本发明也 涉及制备所述粒子的方法。本发明也涉及含有上述 粒子的洗涤剂组合物。

Description

本发明涉及特别适用于洗涤剂使用的光活性剂染料组合物、制备该光活性剂染料组合物的方法,以及包括此染料组合物的洗涤剂组合物。
美国专利us-3,927,967公开了采用光活性剂染料像酞菁染料那样应用于洗涤剂。该光活性剂染料在可见光范围内有吸收电磁辐射,並释放所吸收能量子的形式对织物起漂白作用。人们确此能量子形式是具有氧化活性作用的单态氧。像酞菁磺酸锌(ZPS)和酞菁磺酸铝(APS)之类的一些光活性剂已发现在颗粒洗涤剂组合物中的商业上应用。
但酞菁染料用在洗涤剂组合物上出现某些欠缺,直到现在还是不能适用。这些欠缺是在于被掺合在染料中的粒子当与水接触时不能很快的溶解来避免染料的着色。这种接触特别像在手洗的情况下,或将分散剂与衣服一起放入洗衣机的桶内就会出现。这种着色甚至可能当把分散有染料的洗涤剂组合物被典型的欧洲洗衣机的机械分散时也会发生。
人们已经试图把染料溶液喷雾到喷雾干燥的洗涤剂粒子上,但已发现经过这样处理过的粒子不能很快的溶解来避免染料对织物的着色。目前是倾向使用较高密度的洗涤剂粒子,但对于染料,此洗涤剂粒子很少有适合的载体。
目前加入光活性剂染料的最佳途径包括将染料溶液喷到低密度粒 子上,随后与洗涤剂组合物的基本粒子进行干混合。尽管这些低密度粒子比基本粒子溶解更快,但在各种洗涤条件下它们不能很快溶解来防止染料对织物的着色。
本发明涉及洗涤剂用的酞菁染料,其特征在于是此染料是包在胶囊物质中能很快的溶于冷水。较好地是胶囊物质不溶于非离子表面活性剂中。
优选的酞菁染料是酞菁磺酸锌(ZPS)和酞菁磺酸铝(APS)。优选的胶囊物质包括明胶,特别是低血化明胶,以及明胶和糖的混合物。
本发明也涉及制备胶囊光活化剂组合物的方法,包括下列步骤:
1.把光活性剂染料溶介在水介质中
2.把光活性剂染料溶液混合在胶囊物质的水溶液中
3.然后把所得的混合物转变成平均大小不超500微米的液滴
4.把所述粒子的水分含量降低到2%到12%重量。
本发明还涉及含有胶囊的酞菁染料的颗粒洗涤剂组合物。
根据本发明的光活性剂染料组合物含有在胶囊物质(溶剂)中的水溶性光活性剂染料(溶质)的固体溶液的微胶囊,能很快溶于水。所述微胶囊包有胶囊的重量为:
a)从1%到60%的光活性剂染料,优选为1%到40%,
b)从38%到97%的胶囊物质,和
c)从2%到12%的水,优选为2%到5%
术语“微胶囊”是指具有平均粒子大小不超过500微米的胶囊,优选的平均粒子大小为50微米到450微米的范围。
为了要评价物质很快溶介于冷水中的能力,进行了下面的实验
使用Sotax    AT6溶解仪,其中安装搅拌速度为150rpm的浆式搅拌器,把1000毫米PH为9.5的缓冲剂倒入到每一个聚碳酸酯的烧瓶中,並保持在20℃,再将0.05克物质加到缓冲剂溶液中,在特定条件下进行搅拌,在2分内每隔15秒钟取出3毫升等分溶液,在669nm下测量每一等分的吸收度,依照这一试验,适宜的物质具有下列溶解情况
≥80%在30秒溶解
≥95在60秒溶解
100%在120秒溶解
光活性剂染料组合物的胶囊物质,最好是不溶于非离子型表面活性剂。实际上、现在的洗涤剂组合物几乎是不变地含有非离子表面活性剂。典型的含量为1%到12%,在大多数情况下,将这种非离子型表面活性剂喷到洗涤剂组合物的基本粒子上,在储存时,如果是非离子型表面活性剂,在储存温度下是液体时,则非离子型表面活性剂能自由地迁移进入洗涤剂组合组的本体。
由于酞菁染料易溶于非离子型表面活性剂中,这些染料也同样迁移,並吸附在基本粒子上而不是吸附在低密度粒子上,结果,洗涤剂组合物的外观就变得具有相当非吸引性。此外,溶介的染料与溶介的基本粒子相缔合而不是与迅速溶介的低密度粒子相缔合。
如需要,可按下列实验来评价胶囊物质在非离子型表面活性剂中的不溶性。
把0.05克胶囊物质加到50毫升40℃的Dobanol45E7(是一种烷基醇环氧乙烷的缩合物,主要是线型的C14/C15的一元醇,含有平均7个环氧乙烷基团),温度维持40℃1小时,由 669nm时的吸收度确定其溶介作用,按照这样的测量在1小时后不应出现有溶介作用。
适宜的水溶性光活性剂的例子包括四碘荧光素钠玫瑰红、荧光生、叶绿素、不含金属的卟啉和磺化酞菁的多价金属离子络合物,特别是没有磺化酞菁的单质,多价金属离子的适宜例子包括Z++ n、Al3+、M++ n等,优选的光活性剂染料是酞菁磺酸锌(ZPS)、酞菁磺酸铝(APS)及其混合物,这些染料在工业上可以以钠盐的形式制得,在优选的实施例中,微胶囊含有5~30%重量的光活性剂染料。
合适的胶囊物质的例子包括明胶、水介明胶和成膜的碳水化合物。优选的胶囊物质是水介明胶和成膜的碳水化合物(包括糊精和阿拉伯树胶)。
上述的光活性剂染料组合物可由下列步骤来制备:
(1)把光活性剂染料溶介在水介质中
(2)把光活性剂与胶囊物质的水溶液相混合
(3)把由此所得的混合物转变成平均粒度不超过500微米的粒子,和
(4)把所述粒子的水分含量降低到2%到12%重量的范围,以便在胶囊物质中生成光活性剂染料的固体溶液。
优选的胶囊物质的分子量应比光活性剂染料的分子量高得多,故此,如果光活性剂染料的分子大小为胶囊物质的0.6还小时,得到一种间隙扩大的固体溶液,即得到一种溶质分子占据溶剂点阵间隙空间的固体溶液。
这样就出现了一种形成间隙的固体溶液,故当胶囊与水接触时,大大有助于把细分散形式的光活性剂染料释放出来。
混合物转变成粒子和降低粒子水分含量,最好是采用喷雾干燥技术。在本发明的方法中优选的实施例,是在低于100℃的高温下同时将细粉引入喷雾干燥区内,如在μS-2,756,177所述那样将混合物进行喷雾干燥。细粉可能是硅酸盐或细分散玉米淀粉,最好是细分散玉米淀粉。在另外的优选实施例中,混合物是在高于100℃的温度下进行喷雾干燥的。
在优选实施例中,可将蔗糖或葡萄糖浆加到要进行喷雾干燥的混合物中是为了要降低混合物的粘度,胶囊物质与蔗糖的重量比至少是35∶65,最好是50∶50。
最好将一种油,如椰子油掺入到要进行喷雾的干燥的混合中形成乳液的形式。油的使用量从3~20%重量,优选是从5~10%重量,最好为5%重量。
要进行喷雾干燥的混合物中,干物质的含量可在较大的范围内变化,但在60℃时,其粘度最好保持在70到200CP的范围。
本发明的洗涤剂组合物最好含有上述光活性剂染料组合物,其中纯的光活性剂染料的量为洗涤剂组合物重量的2到1,000PPM。
洗涤剂组合物还含有典型的洗涤剂组分,例如有机表面活性剂、洗涤剂增效助剂,一般洗涤剂添加剂等。有机表婊钚约量梢源嬖诘牧课艿淖楹衔锏?%到60%。
优选的洗涤剂组合物是含有1%到12%非离子型表面活性剂,尤以从3%到10%为佳。
优选的非离子表面活性剂最好含有分子通式为R(R′O)XOH的烷氧基化的醇,其中R是从12到20的碳原子的烃基,R′O代表烷氧基,优选的是乙氧基,及X是从4到12的数值。
参考下列实施例,详细地说明本发明
实施例
例1
将3,240克明胶(血化强度为0)和3,240克蔗糖,在搅拌下加到1,300克酞菁磺酸锌(溶于5200克水的溶液中)中,在所得的溶液中来乳化650克椰子油,因此,所制备混合物的干物质含量约为60%,酞菁磺酸锌约16%,在55℃时,粘度为96CP。
混合物在喷雾干燥塔中进行喷雾干燥,同时也导入作为糖状化组分的玉米淀粉,混合物进入干燥塔中的速率为2升/分,喷雾干燥区的温度约70℃,对最终产品(约9,200克)进行筛分,收集並分析30到120目的部分粒子(ASTM)。收集的部分含酞菁磺酸锌为14.1%,平均粒径约350微米。
例2
把2,388克明胶在搅拌下溶介在2,135克水中,加热到温度约60℃,再把126克氢氧化钠于215克水中所成的溶液中,在搅拌下于60℃加到明胶溶液中,搅拌20分钟后,于60℃下加入浓硫酸(96%)135克,调节PH值约5.5。这样制得的900克溶液(水介明胶)与100克酞菁磺酸锌于1150克水中所形成的溶液,再将450克喷雾干燥的葡萄糖浆(“monsweet    R    1924”)和50克椰子油,在搅拌下于55℃与之混合,当椰子油在水介质中被乳化后,再加入700克附加量的水。这样制得混合物的干物质含量约为30%,酞菁磺酸锌约为10%,混合物的粘度约为50CP(在60℃)。混合物在一般喷雾干燥塔中进行喷雾干燥,入口温度为240℃,出口温度为97℃。
对喷雾干燥过的产品(约900克)进行筛分,收集到的筛分粒子小于100目(ASTM)。
此节分部分含有9.7%酞菁磺酸锌,平均粒径约50微米。
例3
把1060克阿拉伯树脂和1010克蔗糖在搅拌下加到1375克酞菁磺酸锌于1850克水中所成溶液中,在此溶液中乳化138克椰子油,这样制得的混合物的干物质含量约45%,酞菁磺酸锌约11.4%,粘度在57℃时为108CP。
混合物在喷雾干燥塔中进行喷雾干燥,同时导入作为粉状化组分的玉米淀粉,混合物导入速度为1.5升/分,喷雾干燥区的温度约65℃,对最终产品(约3500克)进行筛分,收集並分析(ASTM)30~170目的筛分部份。收集到的部份含有8.2%酞菁磺酸锌,平均粒径约250微米。
例4
把1060克明胶(血化强度为0)和1010克蔗糖,在搅拌下加到1250克酞菁磺酸铝于850克水中所成溶液中,再将138克椰子油乳化在此所得的溶液中,这样制得的混合物中的干物质含量约53%,酞菁磺酸铝约6.3%,粘度在58℃时为106CP。
混合物在喷雾干燥塔中进行喷雾干燥,同时导入作为粉状化组分的玉米淀粉。混合物导入速度为1.5升/分,喷雾干燥区的温度约为70℃。
对最终产品(约2800克)进行筛分,收集並分析(ASTM)30到170目的节分部份,所收集部份含有5.2%酞菁磺酸铝。
例5
把1060克阿拉伯树脂和1010克喷雾干燥过的葡萄糖浆(“monsweet”
Figure 89102154X_IMG1
1924)在搅拌下加到1250克酞菁磺酸铝于2350克水所成溶液中,在此溶液中乳化138克椰子油,这样制得的混合物的干物质含量约为40%,酞菁磺酸铝为6.3%,粘度在58℃时为104CP。
混合物在喷雾干燥塔中进行喷雾干燥,同时导入作为粉椿榉值挠衩椎矸邸;旌衔锏牡既胨俣任?.5升/分,喷雾干燥区的温度约70℃。
在最终产品(约3100克)进行筛分,收集並分析(ASTM)30到170目的筛分部份,收集部份含有4.2%酞菁磺酸铝。
例6
制备的颗粒洗涤剂组合物含有下列组分:(%)
牛脂烷基硫酸酯    2.4
线型烷基苯磺酸    5.6
聚合物    2.0
硅酸盐    8.0
三聚磷酸钠    21.0
过硼酸钠    15.0
非离子型(DobanolR45E7) 5.0
酶(蛋白酶)    0.8
TAED    2.0
酞菁磺酸锌0.03
少量(荧光增白剂、螯合剂、CMC、
香料、抑泡剂)
无机盐(硫酸钠、碳酸钠、硫酸镁):和水    余量
*:如用血化为0的明胶包封,胶囊的ZPS含量为3.4%,胶囊的粒子大小为150-450微米;加入0.88%ZPS,结果在洗涤剂组合物中ZPS的含量为0.03。

Claims (17)

1、光活性剂染料组合物包括在易溶于水的胶囊物质中含有水溶性光活性剂染料的固体分布的微胶囊,所述微胶囊含有下列组份(以微胶囊重量计)
a)从1%到60%的光活性剂染料
b)从38%到97%的胶囊物质
c)从2%到12%的水。
2、根据权利要求1的组合物,其中胶囊物质是不溶于非离子型表面活性剂的。
3、根据权利要求1或2的组合物,其中包含具有平均粒径从50微米到450微米的微胶囊。
4、根据权利要求1或2的组合物,其中活性剂染料是一种磺化的酞菁的多价金属离子络合物。
5、根据权利要求4的组合物,其中光活性剂染料是酞菁磺酸锌、酞菁磺酸铝或其混合物。
6、根据权利要求2~5的组合物,其中胶囊物质是选自水介的胶,和包括有糊精和阿拉伯树胶的成膜碳水化合物。
7、根据权利要求1~6的组合物,其中微胶囊含有从1%到40%重量的光活性剂染料。
8、根据权利要求1~7的组合物,其中还含有蔗糖或葡萄糖浆,胶囊物质与蔗糖或葡萄糖浆的重量比至少是35∶65,优选的为50∶50。
9、根据权利要求1或2制备光活性剂组合物的方法,包括下列步骤:
(1)把光活约寥玖先苡谒橹手校?
(2)把光活性剂染料与胶囊物质的水溶液进行混合,
(3)把所得到的混合物转变成平均粒径不超过500微米的粒子,和
(4)把所述粒子的水分含量降低到2%到12%重量,以便在胶囊物质中形成活性剂染料的固体溶液。
10、根据权利要求9的方法,其中把混合物转变成粒子以及降低所述粒子的水分含量是由喷雾干燥来实现的。
11、根据权利要求10的方法,其中喷雾干燥的温度应低于100℃,同时导入细粉进入喷雾干燥区。
12、根据权利要求9的方法,其中喷雾干燥温度应在100℃以上。
13、根据权利要求9~12的方法,其中蔗糖或葡萄糖浆是加到光活性剂染料和胶囊物质的混合物中。
14、根据权利要求9~13的方法,其中油是在光活性剂染料和胶囊物质的混合物中进行乳化的。
15、洗涤剂组合物含有:
a)一种表面活性剂
b)根据权利要求1~6中的任一个权利要求的光活性剂染料组合物,纯的光活性剂染料的量为总的组合物量的2ppM到1,000ppM,和
c)其余量是包括一般的洗涤剂组分。
16、根据权利要求15的洗涤剂组合物,其中含有1%到12%的非离子表面活性剂。
17、根据权利要求16的洗涤剂组合物,其中非离子型表面活性剂是含有通式为R(R′O)XOH的烷氧基化的醇的混合物,其中R是从12到20个碳原子的烃基,R′O代表烷氧基,X为4到12的数值。
CN89102154A 1988-03-14 1989-03-14 洗涤剂用的光活性剂染料组合物 Expired CN1015897B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 91111573 CN1027452C (zh) 1988-03-14 1989-03-14 含光活性剂染料的洗涤剂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888806016A GB8806016D0 (en) 1988-03-14 1988-03-14 Encapsulated photoactivator dyes for detergent use
GB88-06016 1988-03-14

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN 91111573 Division CN1027452C (zh) 1988-03-14 1989-03-14 含光活性剂染料的洗涤剂组合物

Publications (2)

Publication Number Publication Date
CN1036975A true CN1036975A (zh) 1989-11-08
CN1015897B CN1015897B (zh) 1992-03-18

Family

ID=10633392

Family Applications (1)

Application Number Title Priority Date Filing Date
CN89102154A Expired CN1015897B (zh) 1988-03-14 1989-03-14 洗涤剂用的光活性剂染料组合物

Country Status (23)

Country Link
US (1) US4990280A (zh)
EP (1) EP0333270B1 (zh)
JP (1) JP2541652B2 (zh)
KR (1) KR960014750B1 (zh)
CN (1) CN1015897B (zh)
AU (1) AU605682B2 (zh)
BR (1) BR8901188A (zh)
CA (1) CA1321447C (zh)
DE (1) DE68917340T2 (zh)
DK (1) DK175476B1 (zh)
EG (1) EG19639A (zh)
ES (1) ES2059698T3 (zh)
FI (1) FI891204A (zh)
GB (1) GB8806016D0 (zh)
IE (1) IE890814L (zh)
IN (1) IN174384B (zh)
MA (1) MA21509A1 (zh)
MX (1) MX173260B (zh)
MY (1) MY103846A (zh)
NZ (1) NZ228315A (zh)
PH (1) PH24851A (zh)
PT (1) PT89983B (zh)
TR (1) TR24512A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104254592A (zh) * 2012-04-27 2014-12-31 宝洁公司 包含酞菁化合物颗粒的衣物洗涤剂组合物

Families Citing this family (138)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4961755A (en) * 1987-12-29 1990-10-09 Ciba-Geigy Corporation Coated active substances: dye coated with polyethylene oxide-propylene oxide or with ethoxylated stearyldi phenyloxyethyl diethylenetriamine
US5376288A (en) * 1989-06-21 1994-12-27 Noro Nordisk A/S Detergent additive granulate and detergent
EP0484027B1 (en) * 1990-11-02 1996-12-18 Zeneca Limited Polysubstituted phthalocyanines
DE4230655A1 (de) * 1992-09-14 1994-03-17 Ciba Geigy Verfahren zur Verbesserung von Weißgrad, Helligkeit und Farbort von Faserstoffen
DE4230656A1 (de) * 1992-09-14 1994-03-17 Ciba Geigy Verfahren zur Verbesserung von Weissgrad, Helligkeit und Farbort von Füllstoffen und Pigmenten
US5981719A (en) 1993-03-09 1999-11-09 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US6090925A (en) 1993-03-09 2000-07-18 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US5908821A (en) * 1994-05-11 1999-06-01 Procter & Gamble Company Dye transfer inhibiting compositions with specifically selected metallo catalysts
JPH10111697A (ja) * 1996-10-04 1998-04-28 Matsushita Electric Ind Co Ltd 音声反応装置と音声認識装置
WO1998016615A1 (en) * 1996-10-15 1998-04-23 The Procter & Gamble Company Colored particulate compositions
GB2329397A (en) * 1997-09-18 1999-03-24 Procter & Gamble Photo-bleaching agent
KR100497521B1 (ko) * 1998-04-08 2005-09-14 주식회사 엘지생활건강 캡슐형 세탁용 세제의 제조방법
ATE272104T1 (de) 1998-05-18 2004-08-15 Ciba Sc Holding Ag Wasserlösliche granulate von phthalocyaninverbindungen
EP1534814B1 (en) * 2002-09-04 2006-05-24 Ciba SC Holding AG Formulations comprising water-soluble granulates
KR100502955B1 (ko) * 2002-10-11 2005-07-21 씨제이라이온 주식회사 염착얼룩방지 세탁용 과립조성물
AU2004263673B2 (en) * 2003-08-06 2010-05-13 Basf Se Shading composition
US20070196502A1 (en) * 2004-02-13 2007-08-23 The Procter & Gamble Company Flowable particulates
BRPI0509679A (pt) 2004-04-09 2007-10-09 Unilever Nv granulado para uso em produto de limpeza particulado, processo de fabricação do mesmo e composição detergente
KR20080007325A (ko) * 2005-05-04 2008-01-18 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 캡슐화된 프탈로시아닌 과립
CN101370925B (zh) * 2006-01-23 2014-03-26 美利肯公司 含噻唑鎓染料的洗熨护理组合物
ES2960774T3 (es) 2006-01-23 2024-03-06 Procter & Gamble Composiciones que contienen enzima y agente de matizado de tejidos
BRPI0707215A2 (pt) * 2006-01-23 2011-04-26 Procter & Gamble composições de detergentes
AR059155A1 (es) * 2006-01-23 2008-03-12 Procter & Gamble Composiciones que comprenden enzimas y fotoblanqueadores
RU2479627C2 (ru) * 2006-01-23 2013-04-20 Дзе Проктер Энд Гэмбл Компани Композиции моющих средств
EP2007866A1 (en) * 2006-04-20 2008-12-31 The Procter and Gamble Company A solid particulate laundry detergent composition comprising perfume particle
US7629158B2 (en) * 2006-06-16 2009-12-08 The Procter & Gamble Company Cleaning and/or treatment compositions
US8021436B2 (en) 2007-09-27 2011-09-20 The Procter & Gamble Company Cleaning and/or treatment compositions comprising a xyloglucan conjugate
EP2071017A1 (en) * 2007-12-04 2009-06-17 The Procter and Gamble Company Detergent composition
JP5405488B2 (ja) * 2008-01-04 2014-02-05 ザ プロクター アンド ギャンブル カンパニー 酵素及び布地色調剤を含む組成物
EP2085070A1 (en) * 2008-01-11 2009-08-05 Procter & Gamble International Operations SA. Cleaning and/or treatment compositions
US8765170B2 (en) * 2008-01-30 2014-07-01 The Procter & Gamble Company Personal care composition in the form of an article
JP5804942B2 (ja) 2008-04-16 2015-11-04 ザ プロクター アンド ギャンブルカンパニー 物品の形態の非発泡性パーソナルケア組成物
EP2163605A1 (en) * 2008-08-27 2010-03-17 The Procter and Gamble Company A detergent composition comprising cello-oligosaccharide oxidase
JP5694186B2 (ja) * 2008-12-08 2015-04-01 ザ プロクター アンド ギャンブルカンパニー 使用時に溶解して界面活性剤を送達する物品の製造プロセス
WO2010077628A2 (en) 2008-12-08 2010-07-08 The Procter & Gamble Company Personal care composition in the form of an atricle having a porous, dissolvable solid structure
WO2010077650A2 (en) * 2008-12-08 2010-07-08 The Procter & Gamble Company Personal care composition in the form of an article having a porous, dissolvable solid structure
EP2355771B1 (en) * 2008-12-08 2015-02-25 The Procter and Gamble Company Porous, dissolvable solid substrates and surface resident cyclodextrin perfume complexes
WO2010077653A2 (en) * 2008-12-08 2010-07-08 The Procter & Gamble Company Personal care composition in the form of an article having a hydrophobic surface-resident coating
WO2011005943A1 (en) 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions containing benefit agent delivery particles
MX2012006247A (es) 2009-12-08 2012-06-19 Procter & Gamble Un sustrato solido soluble poroso y un recubrimiento fijo de superficie de acondicionador de surfactante cationico.
JP5678081B2 (ja) * 2009-12-08 2015-02-25 ザ プロクター アンド ギャンブルカンパニー パーソナルケア物品の製造方法
JP5639659B2 (ja) * 2009-12-08 2014-12-10 ザ プロクター アンド ギャンブルカンパニー 多孔質溶解性固体基材と、マトリックスミクロスフェアを含む表面残留コーティング
EP4159833A3 (en) 2009-12-09 2023-07-26 The Procter & Gamble Company Fabric and home care products
WO2011103152A1 (en) 2010-02-16 2011-08-25 The Procter & Gamble Company A porous, dissolvable solid substrate and surface resident coating comprising a zync pyrithione
US20130260438A1 (en) 2010-05-06 2013-10-03 Danisco Us Inc. Compositions and methods comprising serine protease variants (as amended)
JP5759544B2 (ja) 2010-07-02 2015-08-05 ザ プロクター アンド ギャンブルカンパニー 活性剤を送達する方法
RU2553295C2 (ru) 2010-07-02 2015-06-10 Дзе Проктер Энд Гэмбл Компани Моющий продукт и способы его изготовления
MX370147B (es) 2010-07-02 2019-12-03 Procter & Gamble Artículo con estructura soluble de trama fibrosa que comprende agentes activos.
US20180163325A1 (en) 2016-12-09 2018-06-14 Robert Wayne Glenn, Jr. Dissolvable fibrous web structure article comprising active agents
CA2803629C (en) 2010-07-02 2015-04-28 The Procter & Gamble Company Filaments comprising an active agent nonwoven webs and methods for making same
WO2011026154A2 (en) 2010-10-29 2011-03-03 The Procter & Gamble Company Cleaning and/or treatment compositions
WO2012057781A1 (en) 2010-10-29 2012-05-03 The Procter & Gamble Company Cleaning and/or treatment compositions comprising a fungal serine protease
EP2697352A1 (en) 2011-04-12 2014-02-19 The Procter and Gamble Company Metal bleach catalysts
EP2713989A2 (en) 2011-05-27 2014-04-09 The Procter and Gamble Company Soluble solid hair coloring article
JP5806396B2 (ja) 2011-05-27 2015-11-10 ザ プロクター アンド ギャンブルカンパニー 溶解性固体毛髪染色物品
US20140371435A9 (en) 2011-06-03 2014-12-18 Eduardo Torres Laundry Care Compositions Containing Thiophene Azo Dyes
EP2537918A1 (en) 2011-06-20 2012-12-26 The Procter & Gamble Company Consumer products with lipase comprising coated particles
SG11201400744XA (en) * 2011-09-23 2014-04-28 Emerald Hilton Davis Llc Self-assembled nano-structure particle and method for preparing
US10988618B2 (en) 2011-09-23 2021-04-27 Dystar Hilton Davis Corp. Self-assembled nano-structured particle and methods for preparing
CN104080902B (zh) 2012-02-03 2018-08-03 宝洁公司 具有脂肪酶的用于表面处理的组合物和方法
WO2013142486A1 (en) 2012-03-19 2013-09-26 The Procter & Gamble Company Laundry care compositions containing dyes
CN104204198B (zh) 2012-04-02 2018-09-25 诺维信公司 脂肪酶变体以及编码其的多核苷酸
JP2015519429A (ja) * 2012-04-27 2015-07-09 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se フタロシアニン粒子及びその使用
US20150132831A1 (en) 2012-05-16 2015-05-14 Novozymes A/S Compositions Comprising Lipase and Methods of Use Thereof
US8444716B1 (en) 2012-05-23 2013-05-21 The Procter & Gamble Company Soluble solid hair coloring article
US10246692B2 (en) 2012-07-12 2019-04-02 Novozymes A/S Polypeptides having lipase activity and polynucleotides encoding same
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye
EP2712915A1 (en) 2012-10-01 2014-04-02 The Procter and Gamble Company Methods of treating a surface and compositions for use therein
JP6158935B2 (ja) 2012-10-12 2017-07-05 ザ プロクター アンド ギャンブル カンパニー 溶解性物品の形態にあるパーソナルケア組成物
MX2015011690A (es) 2013-03-05 2015-12-07 Procter & Gamble Composiciones de azucares mezclados.
US9631164B2 (en) 2013-03-21 2017-04-25 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same
RU2712877C2 (ru) 2013-05-14 2020-01-31 Новозимс А/С Моющие композиции
EP3699256A1 (en) 2013-05-28 2020-08-26 The Procter & Gamble Company Surface treatment compositions comprising photochromic dyes
CN105339492A (zh) 2013-07-09 2016-02-17 诺维信公司 具有脂肪酶活性的多肽和编码它们的多核苷酸
US9834682B2 (en) 2013-09-18 2017-12-05 Milliken & Company Laundry care composition comprising carboxylate dye
MX2016003538A (es) 2013-09-18 2016-06-28 Procter & Gamble Composiciones para el cuidado de la ropa que contienen colorantes azoicos de tiofeno y carboxilato.
CA2921433A1 (en) 2013-09-18 2015-03-26 The Procter & Gamble Company Laundry care composition comprising carboxylate dye
WO2015042086A1 (en) 2013-09-18 2015-03-26 The Procter & Gamble Company Laundry care composition comprising carboxylate dye
WO2015112341A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Fabric treatment composition
EP3097173B1 (en) 2014-01-22 2020-12-23 The Procter and Gamble Company Fabric treatment composition
WO2015112340A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Method of treating textile fabrics
EP3097112B1 (en) 2014-01-22 2020-05-13 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same
WO2015112338A1 (en) 2014-01-22 2015-07-30 The Procter & Gamble Company Method of treating textile fabrics
US10111574B2 (en) 2014-01-24 2018-10-30 The Procter & Gamble Company Method for treating dishware
US10098519B2 (en) 2014-01-24 2018-10-16 The Procter & Gamble Company Lighted dispenser
US20150210963A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Systems and Methods for Treating a Surface
US9834740B2 (en) 2014-01-24 2017-12-05 The Procter & Gamble Company Photoactivators
US20150210964A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer Product Compositions
EP3117001B1 (en) 2014-03-12 2019-02-20 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same
US10030215B2 (en) 2014-04-15 2018-07-24 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same
WO2015164227A2 (en) 2014-04-22 2015-10-29 The Procter & Gamble Company Compositions in the form of dissolvable solid structures
WO2015171592A1 (en) 2014-05-06 2015-11-12 Milliken & Company Laundry care compositions
EP3760713A3 (en) 2014-05-27 2021-03-31 Novozymes A/S Lipase variants and polynucleotides encoding same
EP3256563A1 (en) 2014-11-17 2017-12-20 The Procter and Gamble Company Benefit agent delivery compositions
EP4067485A3 (en) 2014-12-05 2023-01-04 Novozymes A/S Lipase variants and polynucleotides encoding same
WO2016176296A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of laundering a fabric
WO2016176280A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of treating a fabric
EP3088506B1 (en) 2015-04-29 2018-05-23 The Procter and Gamble Company Detergent composition
DK3088503T3 (en) 2015-04-29 2018-08-20 Procter & Gamble PROCEDURE FOR TREATING A TEXTILE SUBSTANCE
CN112143591A (zh) 2015-04-29 2020-12-29 宝洁公司 处理织物的方法
CN111718806B (zh) 2015-05-04 2022-01-04 美利肯公司 在洗衣护理组合物中作为上蓝剂的隐色三苯甲烷着色剂
EP3317407B1 (en) 2015-07-01 2021-05-19 Novozymes A/S Methods of reducing odor
EP3950939A3 (en) 2015-07-06 2022-06-08 Novozymes A/S Lipase variants and polynucleotides encoding same
DE102015218190A1 (de) * 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Tensid-enthaltende Zusammensetzung zur Behandlung von Textilien mit einem Farbstoff
US11326152B2 (en) 2016-07-18 2022-05-10 Novozymes A/S Lipase variants, polynucleotides encoding same and the use thereof
US20180119056A1 (en) 2016-11-03 2018-05-03 Milliken & Company Leuco Triphenylmethane Colorants As Bluing Agents in Laundry Care Compositions
WO2018140675A1 (en) 2017-01-27 2018-08-02 The Procter & Gamble Company Compositions in the form of dissolvable solid structures comprising effervescent agglomerated particles
JP7028877B2 (ja) 2017-01-27 2022-03-02 ザ プロクター アンド ギャンブル カンパニー 溶解性固形構造体形態の組成物
EP3619304A1 (en) 2017-05-05 2020-03-11 Novozymes A/S Compositions comprising lipase and sulfite
EP3624765A1 (en) 2017-05-16 2020-03-25 The Procter and Gamble Company Conditioning hair care compositions in the form of dissolvable solid structures
US11332725B2 (en) 2017-09-27 2022-05-17 Novozymes A/S Lipase variants and microcapsule compositions comprising such lipase variants
EP3720954A1 (en) 2017-12-04 2020-10-14 Novozymes A/S Lipase variants and polynucleotides encoding same
WO2019154954A1 (en) 2018-02-08 2019-08-15 Novozymes A/S Lipase variants and compositions thereof
WO2019154951A1 (en) 2018-02-08 2019-08-15 Novozymes A/S Lipases, lipase variants and compositions thereof
JP1639110S (zh) 2018-07-16 2019-08-13
US11666514B2 (en) 2018-09-21 2023-06-06 The Procter & Gamble Company Fibrous structures containing polymer matrix particles with perfume ingredients
US20200140784A1 (en) 2018-11-07 2020-05-07 The Procter & Gamble Company Low ph detergent composition
JP2022505301A (ja) 2018-11-16 2022-01-14 ザ プロクター アンド ギャンブル カンパニー 布地から染みを除去するための組成物及び方法
CN114206307B (zh) 2019-06-28 2024-08-23 宝洁公司 包含阴离子表面活性剂的可溶性固体纤维制品
EP3994255A1 (en) 2019-07-02 2022-05-11 Novozymes A/S Lipase variants and compositions thereof
EP3993757A1 (en) 2019-07-03 2022-05-11 The Procter & Gamble Company Fibrous structures containing cationic surfactants and soluble acids
USD939359S1 (en) 2019-10-01 2021-12-28 The Procter And Gamble Plaza Packaging for a single dose personal care product
KR20220062613A (ko) 2019-10-14 2022-05-17 더 프록터 앤드 갬블 캄파니 고체 물품을 함유하는 생분해성 및/또는 가정 퇴비화가능 사셰
CA3157576A1 (en) 2019-11-20 2021-05-27 The Procter & Gamble Company Porous dissolvable solid structure
MX2022005532A (es) 2019-12-01 2022-06-08 Procter & Gamble Composiciones acondicionadoras para el cabello con un sistema de conservacion que contiene benzoato de sodio y glicoles y/o esteres de glicerilo.
USD941051S1 (en) 2020-03-20 2022-01-18 The Procter And Gamble Company Shower hanger
USD962050S1 (en) 2020-03-20 2022-08-30 The Procter And Gamble Company Primary package for a solid, single dose beauty care composition
USD965440S1 (en) 2020-06-29 2022-10-04 The Procter And Gamble Company Package
CN115867357A (zh) 2020-07-31 2023-03-28 宝洁公司 用于毛发护理的含有球粒的水溶性纤维小袋
EP4196234A1 (en) 2020-08-11 2023-06-21 The Procter & Gamble Company Clean rinse hair conditioner compositions containing brassicyl valinate esylate
MX2023001046A (es) 2020-08-11 2023-02-16 Procter & Gamble Composiciones acondicionadoras para el cabello de viscosidad baja que contienen esilato de valinato de brassicilo.
US11633338B2 (en) 2020-08-11 2023-04-25 The Procter & Gamble Company Moisturizing hair conditioner compositions containing brassicyl valinate esylate
JP2023538037A (ja) 2020-09-10 2023-09-06 ザ プロクター アンド ギャンブル カンパニー 抗細菌活性物質を含有する溶解性固体物品
WO2022090361A2 (en) 2020-10-29 2022-05-05 Novozymes A/S Lipase variants and compositions comprising such lipase variants
CA3201309A1 (en) 2020-12-01 2022-06-09 The Procter & Gamble Company Aqueous hair conditioner compositions containing solubilized anti-dandruff actives
USD1045064S1 (en) 2020-12-17 2024-10-01 The Procter & Gamble Company Single-dose dissolvable personal care unit
CA3228918A1 (en) 2021-08-10 2023-02-16 Nippon Shokubai Co., Ltd. Polyalkylene-oxide-containing compound
WO2023247664A2 (en) 2022-06-24 2023-12-28 Novozymes A/S Lipase variants and compositions comprising such lipase variants

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1408144A (en) * 1972-06-02 1975-10-01 Procter & Gamble Ltd Bleaching process
US3741121A (en) * 1971-09-03 1973-06-26 Olin Corp Fusee cover
US4033718A (en) * 1973-11-27 1977-07-05 The Procter & Gamble Company Photoactivated bleaching process
JPS5343523A (en) * 1976-10-01 1978-04-19 Canon Inc Finder construction for single lens reflex camera
US4417994A (en) * 1981-01-24 1983-11-29 The Procter & Gamble Company Particulate detergent additive compositions
DE3128336A1 (de) * 1981-07-17 1983-01-27 Henkel KGaA, 4000 Düsseldorf "verfahren zur herstellung umhuellter koerniger bleichaktivatoren"
CH654121A5 (de) * 1983-03-25 1986-01-31 Ciba Geigy Ag Verfahren zur herstellung von festen photoaktivatorpraeparaten.
CH654424A5 (de) * 1983-03-25 1986-02-14 Ciba Geigy Ag Verfahren zur verhinderung des gelierens von konzentrierten waessrigen photoaktivatorloesungen.
US4713079A (en) * 1985-12-31 1987-12-15 Lever Brothers Company Particles containing dihalohydantoin bleach in a diluted core
JPH0678559B2 (ja) * 1986-04-16 1994-10-05 株式会社資生堂 枠ねり石けん
DK690187A (da) * 1986-12-31 1988-07-01 Albright & Wilson Beskyttet system, som er egnet til anvendelse i rensemidler, samt produkter indeholdende systemet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104254592A (zh) * 2012-04-27 2014-12-31 宝洁公司 包含酞菁化合物颗粒的衣物洗涤剂组合物

Also Published As

Publication number Publication date
GB8806016D0 (en) 1988-04-13
PH24851A (en) 1990-12-26
PT89983B (pt) 1994-05-31
PT89983A (pt) 1989-11-10
EG19639A (en) 1995-08-30
MA21509A1 (fr) 1989-10-01
DE68917340T2 (de) 1995-04-06
FI891204A (fi) 1989-09-15
MY103846A (en) 1993-09-30
ES2059698T3 (es) 1994-11-16
TR24512A (tr) 1991-11-12
EP0333270B1 (en) 1994-08-10
EP0333270A2 (en) 1989-09-20
CN1015897B (zh) 1992-03-18
BR8901188A (pt) 1989-10-31
AU3127589A (en) 1989-09-14
JP2541652B2 (ja) 1996-10-09
IN174384B (zh) 1994-11-26
US4990280A (en) 1991-02-05
NZ228315A (en) 1992-04-28
DK175476B1 (da) 2004-11-08
DE68917340D1 (de) 1994-09-15
DK122889D0 (da) 1989-03-14
JPH0222398A (ja) 1990-01-25
KR960014750B1 (ko) 1996-10-19
FI891204A0 (fi) 1989-03-14
EP0333270A3 (en) 1990-06-27
MX173260B (es) 1994-02-14
KR890014693A (ko) 1989-10-25
AU605682B2 (en) 1991-01-17
DK122889A (da) 1989-09-15
CA1321447C (en) 1993-08-24
IE890814L (en) 1989-09-14

Similar Documents

Publication Publication Date Title
CN1036975A (zh) 洗涤剂用的光活性剂染料组合物
CN1034557C (zh) 以可吸性沉淀二氧化硅为基础的组合物
US6958362B2 (en) Method for manufacturing colloid aluminum silica gels
CN1184197C (zh) 荧光增白剂
CN1297370A (zh) 用于结构化非水液体组合物的表面活性剂
CN1027452C (zh) 含光活性剂染料的洗涤剂组合物
CN1233275A (zh) 自由流动的附聚的非离子表面活性剂洗涤剂组合物及其制备方法
CN1188143A (zh) 洗涤用的香料颗粒
CN1071376C (zh) 高分子活性固体洗涤剂组合物及其制造方法
RU2004115743A (ru) Способ получения гранул моющего средства
CN1096051A (zh) 衣物用无磷型防串色液体洗涤剂及其制备方法
JP3442753B2 (ja) 界面活性剤担持用顆粒群の製法
DE4128826A1 (de) Wasch- und/oder reinigungsverfahren
CN1049383A (zh) 固体管道疏通剂
CN1177922C (zh) 制备洗衣粉洗涤剂的方法
CN1326500A (zh) 含有季戊四醇酯类、膨润土和聚膦酸盐的织物柔软组合物
CN1177630A (zh) 颗粒状控泡剂
CN1346400A (zh) 溶解性改进的粒状洗涤剂组合物
BE544648A (zh)
TH6194B (th) สารผสมสำหรับทำให้สิ่งทอชนิดผงที่ไหลได้อย่างอิสระ
TH3095B (th) กระบวนการซักล้างผ้าและส่วนประกอบสารฟอกล้างที่ใช้เพื่อการนี้
TH1548A (th) กระบวนการซักล้างผ้าและส่วนประกอบสารฟอกล้างที่ใช้เพื่อการนี้
CN101724296A (zh) 一种染色皮革的活性染料组合物

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C13 Decision
GR02 Examined patent application
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee