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

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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
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photoactivator dye
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CN1015897B (zh
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比廷·托伦加德
戴维·威廉·约克
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Denmark Chemical Co Ltd
Procter and Gamble Co
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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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。
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DK175476B1 (da) 2004-11-08
MY103846A (en) 1993-09-30
BR8901188A (pt) 1989-10-31
DE68917340T2 (de) 1995-04-06
ES2059698T3 (es) 1994-11-16
AU3127589A (en) 1989-09-14
DE68917340D1 (de) 1994-09-15
PT89983A (pt) 1989-11-10
JPH0222398A (ja) 1990-01-25
KR890014693A (ko) 1989-10-25
FI891204A (fi) 1989-09-15
NZ228315A (en) 1992-04-28
EP0333270A3 (en) 1990-06-27
GB8806016D0 (en) 1988-04-13
CA1321447C (en) 1993-08-24
KR960014750B1 (ko) 1996-10-19
AU605682B2 (en) 1991-01-17
CN1015897B (zh) 1992-03-18
DK122889A (da) 1989-09-15
MX173260B (es) 1994-02-14
TR24512A (tr) 1991-11-12
FI891204A0 (fi) 1989-03-14
MA21509A1 (fr) 1989-10-01
PH24851A (en) 1990-12-26
PT89983B (pt) 1994-05-31
DK122889D0 (da) 1989-03-14
EG19639A (en) 1995-08-30
EP0333270A2 (en) 1989-09-20
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US4990280A (en) 1991-02-05
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JP2541652B2 (ja) 1996-10-09

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