CA1264504A - Coloured bleaching compositions - Google Patents
Coloured bleaching compositionsInfo
- Publication number
- CA1264504A CA1264504A CA000497014A CA497014A CA1264504A CA 1264504 A CA1264504 A CA 1264504A CA 000497014 A CA000497014 A CA 000497014A CA 497014 A CA497014 A CA 497014A CA 1264504 A CA1264504 A CA 1264504A
- Authority
- CA
- Canada
- Prior art keywords
- pigment
- coated
- blue
- green
- aqueous
- 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.)
- Expired - Fee Related
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Coloring (AREA)
Abstract
C 7044 (R) ABSTRACT OF THE DISCLOSURE
The invention provides an aqueous, coloured bleaching composition, particularly a thickened chlorine bleaching composition, in which as colouring agent a colloidally stable, coated pigment is used which has been coated with a bleach-resistant polymer, e.g.
polystyrene. These coated pigments are colloidally stable in the bleaching composition, in many cases more stable than uncoated pigments.
The invention provides an aqueous, coloured bleaching composition, particularly a thickened chlorine bleaching composition, in which as colouring agent a colloidally stable, coated pigment is used which has been coated with a bleach-resistant polymer, e.g.
polystyrene. These coated pigments are colloidally stable in the bleaching composition, in many cases more stable than uncoated pigments.
Description
C 7044 (R) ;4~S04 COLOURED BLEACHING COMPOSITIONS
. .
The present invention relates to aqueous, coloured, bleaching compositions, particularly alkali metal hypo-chlorite compositions.
By bleaching compositions are meant aqueous com-positions comprising an oxygen or chlorine bleaching agent, 5uch as hydrogen peroxide, organic or inorganic persalts (with or without a bleach precursor), organic or inorganic peracids, and alkali metal hypochlorites.
Hereinafter the invention will be describad and exem-plified with particular reference to alkali metal hypo-chlorite compositions, but it is to be understood that the present invention is also applicable to the above other bleaching compositions..
Aqueous solutions of alkali metal hypochlorites have been known and used since ages unknown. Normally, they consist of an alkali metal hypochlorite, dissolved in water, and are used for general bleaching and disin-fecting purposes. Such solutions are normally straw-coloured, and in order to ma~e them more attractive and more distinguishable from other household products, attempts have been made to impart to them a more dis-tinguishable, a~sthetically attractive colour.
The~e hypochlorite solutions, however, form a stronglyoxidizing environment, and consequently the choice of a colouring additive is very limited, restricted to only such colouring additives that are stable in these ~trongly oxidizing media~ Potassium permanganate and potassium di~hromate are such colouring a~ent~, bl~t they impart aesthetically less attractive colours (pur-ple and yellow). Ultramarine Blue has al80 been pro-posed, bu~ this pigment tends to settle out from the C 7044 (R) compositions during storage.
During the last decade, thickened aqueous hypochloritesolutions have become known and marketed. The~e are 5 aqueous solutions of an alkali metal hypochlorite which have been thickened by the inclusion therein of a mix-ture of two different detergent surfactants. The above problems accompanying colouring aqueous hypochlorite solutions also occur on colouriny such thickened com-positions, but the problem of storage stability ariseseven with such thickened compositions. Unless major changes are made in the thickening system, the pigment particles tend to settle out, and if major changes are made, this settling out can be reduced, but the thickening effect is significantly impaired.
It has also been proposed to use a floc system in such thickened hypochlorite compositions to prevent the par-ticulate colouring agent from settling out, such a floc system comprising, inter alia, a polymer latex. A1-though such a polymer latex may provide an improved physical stability of the particulate colouring agent in the hypochlorite compositions, it does not provide coloured products which are chemically stable over longer periods.
It has now been found that the chemical and physical stability of pigments as colouring agents in aqueous alkali metal hypochlorite compositions can be improved by coating the pigments with a coating of a bleach-resistant polymer.
It has already been proposed in US Patent Specifi-cation~ 3,666,680 (Briggs) and 3,655,566 (~vbinson) to include optical brighteners in liquid hypochlorite com-positions, whereby these optical brighteners are pro-tectively enclosed in the inner portion of a two-layer .. .. . ., . ... . ... . ... ,. . . . . . ~j .: . , ,., .. ,~.. . . .
C 704~
synthetic polymer particle. This is achieved by dis-solving the optical brightener in the oil-soluble mono-mer, copolymerizing the monomer-brightener solution with a vinyl acid, and subsequently performing a second polymerization with the hydrophobic monomer, whereby an impermeable film is formed around the previously ob-tained polymer-brightener particles. Although this prior proposal also mentions the possibility of using dyes and pigments such as Ultramarine Blue, Monastral Fast Green GWD, etc., it i8 primarily directed to optical brightening agents.
These polymer particles, however, contain a hydrophilic monomer as well, and in thickened liquid hypochlorite compositions they do not give a satisfactorily stable colour. Furthermore, these particles have an average particle siæe in ths range of 0.1-2 micron or O.S-2 micron, which is not suitable to produce compositions which are physically stable without the need of a sus-pending agent.
Recently, it has been described in GB-Al- 2 100 307 to include a hypochlorite solution stable, suspendable dye particle in a liquid bleaching and dyeing compo~ition.
These particles contain a dye which is resistant to attack by hypochlorous acid, which dye is incorporated in a hydrophobic latex. The dye is incorporated or "em-bedded" in a highly hydrophobic matrix, thus shielding it from actual contact with the hypochlorite.
Dyes, however, are discrete molecular units, whereas pigments are agglomerations of molecules into particles of microscopic rather than molecular (5-50 Angstroms~
dimensions. ~he dyes of the above propo~al mu~t be æoluble in the organic/monomeric phas In addition, low chromophore to polymer ratios are required to get a high proportion of the finished particles to be polymer to get some effective physical entrapment.
We have now found that pigments, i.e. colourants which are insoluble in the organic and a~ueous pha~e, which have been coated with a pxotective coating in a ~ingle-stage process have an improved stability against attack by hypochlorite and do not cause any significant physical storage stability problems when used in an aqueous bleaching composition.
In its broadest aspect, therefore, the present inven-tion relates to coloured aqueous alXali metal hypo-chlorite compositions, comprising as colouring agent a colloidally stable, coated pigmen~ which has been coatad with a bleach-resistant polymer.
Surprisingly, the~e coated pigments are colloidally at least as stable, or in many cases more ~table than the uncoated pigments. In addition, often less coated pigment particles than dyed latices are required to colour the aqueous hypochlorite 601ution to the same inten~ity.
The invention will hereafter be described in more detail.
The pigments which can be used in the present invention can be of any type, as long as they are insoluble in the organic and aqueous phase and are of a relatively small av~rage particle size (e.g.rV 1000 A). They can include metallated and non-metallated synthetic pig-ments a6 well as organic and inorganic pigments.
Typical examples are given in the following list.
C 7044 (R) 15~
Blue Pigment C.I N ~ue Type/
Name Structure Blue 1 42595O2bright reddi~h blue TAM/PTMA
5 2 44045:2bright blue PTMA
3 42140:1bright blue TPM/PTMA
4 - bright blue TPM/PTMA
6 - greeni~h blue ~PM/PTMA
8 42140:1 + bright greenish blue PTMA
4~041:1 9 42025:1bright greenish blue TPM/PTMA
12 42130bright blue TPM/PMA
13 - blue PTA
1~ 42600:1bright reddish blue TAM/PTA
1518 42770:1bright blue + TAM
bright reddish navy 19 42750:1bright blue ~ TAM
bright reddish navy - bright na~y Organic pigment 21 69835reddish navy Anthra-quinone 23 - blue Organic pigment 2524 42090:1bright greenish blue TPM
52 - navy Anthra-quinone 53 -blue + greenish blue PTMA
56 42800yreenish blue TAM
3063 73015 blue Indigoid 66 73000 blue Indigoid TAM = triarylmethane PTMA = phosphotung~tomolybdic acid TPM = triphenylmethane PMA - pho~phomolybdic acid PTA = pho~photungstic acid . ~ , . .. ... .. .... , . ~ . .. . ... . ... ..... ... . . .
C 7044 ~R~
Green Pigment C.I. N ~ue Type/
Name Structure Green 1 42040:1bright hlui~h green TAM/PTMA
. .
The present invention relates to aqueous, coloured, bleaching compositions, particularly alkali metal hypo-chlorite compositions.
By bleaching compositions are meant aqueous com-positions comprising an oxygen or chlorine bleaching agent, 5uch as hydrogen peroxide, organic or inorganic persalts (with or without a bleach precursor), organic or inorganic peracids, and alkali metal hypochlorites.
Hereinafter the invention will be describad and exem-plified with particular reference to alkali metal hypo-chlorite compositions, but it is to be understood that the present invention is also applicable to the above other bleaching compositions..
Aqueous solutions of alkali metal hypochlorites have been known and used since ages unknown. Normally, they consist of an alkali metal hypochlorite, dissolved in water, and are used for general bleaching and disin-fecting purposes. Such solutions are normally straw-coloured, and in order to ma~e them more attractive and more distinguishable from other household products, attempts have been made to impart to them a more dis-tinguishable, a~sthetically attractive colour.
The~e hypochlorite solutions, however, form a stronglyoxidizing environment, and consequently the choice of a colouring additive is very limited, restricted to only such colouring additives that are stable in these ~trongly oxidizing media~ Potassium permanganate and potassium di~hromate are such colouring a~ent~, bl~t they impart aesthetically less attractive colours (pur-ple and yellow). Ultramarine Blue has al80 been pro-posed, bu~ this pigment tends to settle out from the C 7044 (R) compositions during storage.
During the last decade, thickened aqueous hypochloritesolutions have become known and marketed. The~e are 5 aqueous solutions of an alkali metal hypochlorite which have been thickened by the inclusion therein of a mix-ture of two different detergent surfactants. The above problems accompanying colouring aqueous hypochlorite solutions also occur on colouriny such thickened com-positions, but the problem of storage stability ariseseven with such thickened compositions. Unless major changes are made in the thickening system, the pigment particles tend to settle out, and if major changes are made, this settling out can be reduced, but the thickening effect is significantly impaired.
It has also been proposed to use a floc system in such thickened hypochlorite compositions to prevent the par-ticulate colouring agent from settling out, such a floc system comprising, inter alia, a polymer latex. A1-though such a polymer latex may provide an improved physical stability of the particulate colouring agent in the hypochlorite compositions, it does not provide coloured products which are chemically stable over longer periods.
It has now been found that the chemical and physical stability of pigments as colouring agents in aqueous alkali metal hypochlorite compositions can be improved by coating the pigments with a coating of a bleach-resistant polymer.
It has already been proposed in US Patent Specifi-cation~ 3,666,680 (Briggs) and 3,655,566 (~vbinson) to include optical brighteners in liquid hypochlorite com-positions, whereby these optical brighteners are pro-tectively enclosed in the inner portion of a two-layer .. .. . ., . ... . ... . ... ,. . . . . . ~j .: . , ,., .. ,~.. . . .
C 704~
synthetic polymer particle. This is achieved by dis-solving the optical brightener in the oil-soluble mono-mer, copolymerizing the monomer-brightener solution with a vinyl acid, and subsequently performing a second polymerization with the hydrophobic monomer, whereby an impermeable film is formed around the previously ob-tained polymer-brightener particles. Although this prior proposal also mentions the possibility of using dyes and pigments such as Ultramarine Blue, Monastral Fast Green GWD, etc., it i8 primarily directed to optical brightening agents.
These polymer particles, however, contain a hydrophilic monomer as well, and in thickened liquid hypochlorite compositions they do not give a satisfactorily stable colour. Furthermore, these particles have an average particle siæe in ths range of 0.1-2 micron or O.S-2 micron, which is not suitable to produce compositions which are physically stable without the need of a sus-pending agent.
Recently, it has been described in GB-Al- 2 100 307 to include a hypochlorite solution stable, suspendable dye particle in a liquid bleaching and dyeing compo~ition.
These particles contain a dye which is resistant to attack by hypochlorous acid, which dye is incorporated in a hydrophobic latex. The dye is incorporated or "em-bedded" in a highly hydrophobic matrix, thus shielding it from actual contact with the hypochlorite.
Dyes, however, are discrete molecular units, whereas pigments are agglomerations of molecules into particles of microscopic rather than molecular (5-50 Angstroms~
dimensions. ~he dyes of the above propo~al mu~t be æoluble in the organic/monomeric phas In addition, low chromophore to polymer ratios are required to get a high proportion of the finished particles to be polymer to get some effective physical entrapment.
We have now found that pigments, i.e. colourants which are insoluble in the organic and a~ueous pha~e, which have been coated with a pxotective coating in a ~ingle-stage process have an improved stability against attack by hypochlorite and do not cause any significant physical storage stability problems when used in an aqueous bleaching composition.
In its broadest aspect, therefore, the present inven-tion relates to coloured aqueous alXali metal hypo-chlorite compositions, comprising as colouring agent a colloidally stable, coated pigmen~ which has been coatad with a bleach-resistant polymer.
Surprisingly, the~e coated pigments are colloidally at least as stable, or in many cases more ~table than the uncoated pigments. In addition, often less coated pigment particles than dyed latices are required to colour the aqueous hypochlorite 601ution to the same inten~ity.
The invention will hereafter be described in more detail.
The pigments which can be used in the present invention can be of any type, as long as they are insoluble in the organic and aqueous phase and are of a relatively small av~rage particle size (e.g.rV 1000 A). They can include metallated and non-metallated synthetic pig-ments a6 well as organic and inorganic pigments.
Typical examples are given in the following list.
C 7044 (R) 15~
Blue Pigment C.I N ~ue Type/
Name Structure Blue 1 42595O2bright reddi~h blue TAM/PTMA
5 2 44045:2bright blue PTMA
3 42140:1bright blue TPM/PTMA
4 - bright blue TPM/PTMA
6 - greeni~h blue ~PM/PTMA
8 42140:1 + bright greenish blue PTMA
4~041:1 9 42025:1bright greenish blue TPM/PTMA
12 42130bright blue TPM/PMA
13 - blue PTA
1~ 42600:1bright reddish blue TAM/PTA
1518 42770:1bright blue + TAM
bright reddish navy 19 42750:1bright blue ~ TAM
bright reddish navy - bright na~y Organic pigment 21 69835reddish navy Anthra-quinone 23 - blue Organic pigment 2524 42090:1bright greenish blue TPM
52 - navy Anthra-quinone 53 -blue + greenish blue PTMA
56 42800yreenish blue TAM
3063 73015 blue Indigoid 66 73000 blue Indigoid TAM = triarylmethane PTMA = phosphotung~tomolybdic acid TPM = triphenylmethane PMA - pho~phomolybdic acid PTA = pho~photungstic acid . ~ , . .. ... .. .... , . ~ . .. . ... . ... ..... ... . . .
C 7044 ~R~
Green Pigment C.I. N ~ue Type/
Name Structure Green 1 42040:1bright hlui~h green TAM/PTMA
2 42040~1 ~ bright green TAM/PTMA
49005:1
49005:1
3 41000:2 + bright green TAM/PTMA
42040:1
42040:1
4 42000bright green TAM
10 7 74~60 green Phthalo-cyanine 9 49415 green Naphthalene ~ulphonic acid 11 green Organic pigment 14 77199 +green In,organic 77346 plgment 18 -green ~ bluish green Chromium salt~
2047 59825bluish green Anthra-quinone Other colours Pi~ment Name C.I. N Type/Structure Red 5 12490 Monoazo Red 48:1 15865:1 Monoazo Red 48:2 15865:2 Monoazo Red 48:3 15865:3 Monoazo Red 49:1; 49:2: 15630 Monoa~o 49:3 Red 52:1 15860 Monoazo Red 53:1 15585:1 Monoazo Red 57:1 15850:1 Monoazo Red 81 45160:1 Xanthene/PTMA
Red 82 45150:1 Xanthene/PTMA
Red 83 58000:1 Anthraquinone Red 90:1 45380:1 Xanthene/Al C 70~4 (~) ~6~504 Other colour~
Pigment Name C.I. N Type/Structure ~iolet 3 42535:1 TAM/PTMA
Violet 5:1 58055:1 Anthraquinone/Al Violet 19 46500 ~uinacridonP
Yellow 14 21095 Di~azo Brown 3 21310 Disa~o/DPTMA
Brown 23 Disazo Brown 25 - Monoazo 10 Black 3 - Organic~PTMA
BlacX 5 - Mordant/Metal Mixtures of various pigments can equally be used. Pre-ferably, non-metallated pigments are used in bleaching compositions which are susceptible to decomposition by metal ion catalysis, but metallated pigments when used according ~o the present invention show already a sig-nificant improvement in thi~ respect in comparison with the uncoated pigments, without any significant physical stability problem. Thu6 it has been found that a copper-containing halogenated phthalocyanine, when used ac-cording to the present inven~ion, causes substantially less decomposition o~ the bleaching composition than the ~ame uncoated pigment, and less settling out of the pigment particles. When metallated pigments are used, it is sometimes advantageous to use a metal ~ques-tering agent in the composition, such as a periodate or other suitable metal-chelating agent which is stable in the bleaching composition in amounts of up to about 5%
by weight o the coated pigment added, to reduce the decomposition even further.
The coating The coating material to be used in the present inven-tion should be bleach-resi~tantO Any organic material can be u~ed, as long a~ the pigment is no~ soluble ~ 5~ C 7044 (R) therein. Preferably, organic materials are used in which the pigment is readily dispersible. ~uitable materials are (co)polymers prepared from a hydrophobic monomer which is capable of undergoing emulsion poly-merization.
Typical examples are styrene, alkyl styrene3 with one to four carbon a~oms in the alkyl group, monohalogen-ated styrenes, acrylates, methacrylates, vinylesters, ethylene and vinylchloride. A particularly suitable material is polystyrene.
The coating process is carried out in a manner known per se, by introducing the pigment particles into an aqueous emulsion polymerization of styrene, using a common i~itiator such as potassium persulphate, a~obi~-(isobutyramidine hydrochloride) or 4,4'-azobis-(4-cyanovaleric acid). It has ~een found that higher con-centrations of initiator than are usual for convention-al emulsion polymerization favour the coating of thepigment particles.
The concentration ratio of monomer to pigment should be such that there i8 sufficient monomer present to just coat all the particles to avoid the formation of un-coloured polymeric latices. For e.g. styrene and Pig-ment Green 7 (C.I. N 74260), the most eff ctive styrene/pigment ratio was found to be 5:1.
To aid the dispersal of the pigment in the polymer-ization reaction mixture, a suitable surfactant, such as a nonionic or an anionic synthetic detergent, can be advantageously added.
The com~osition The coated pigments of the present invention are suit-C 7044 (R) 50~
able for colouring aqueous bleaching compositions, both thickened and non-thickened ones. These compositions may contain other ingredients, which are governed by the purpose for which these compo~itions are u~ed, such as heavy-duty liquid fabric-bleaching and -washing com-positions, liquid fabric~softening compositions, hair-bleaching compositions, hygienic cleaning compositions, hard-surface-cleaning compositions, etc. Thu~, they preferably contain one or more detergent-active com-pounds. Further ingredients commonly encountered in such products may be included in the compositions of the inven~ion. As said before, the bleaching agent can comprise both oxygen and chlorine ~leaching agants, as well a~ reducing bleaches.
The coated pigments of the present invention are par-ticularly suitable for thickened aqueous alkali hypo-chlorite compositions such a~ described in GB-A-1 329 086, EP-Al- 00 30401, GB-A- 1 548 379, GB-A-1 466 560, GB-Al- 2 003 522, GB-Al- 2 041 162, GB-Al-2 076 010 and GB-Al- 2 046 321.
The amount of coated pigments used in the bleach com-position varies from 0.0005 to 10% by weight, prefer-ably ~rom O.OOl to 1% by weight.
The invention will now further be illustrated by way of example.
In the following examples, the bleaching composition was a current commercial thickened h~pochlorite bleaching composition, Domestos~ manufactured and sold by Lever Brothers Ltd. This product is a prcduct ac-cording to GB Patent l 329 086.
The colour and phy~ical stability were asses~ed spectrophotometrically and visually, respectively, and C~e~o74s ~e ~ark , .. .. .... . ~ . . . . . . , ~ i ,. .
C 7044 ~R) the hypochlorite decomposition ("gas~ing") was ~ea ured by collecting the volume of gas evolvedO
Example 1 - Coated Colanyl Green GG
Pigment Encapsulation Styrene 5 0 g Colanyl Green GG* (Pigment Green 7 C.I. ~ 74260) 2.0 g 4,4'-azobis-(4-cyanovaleric acid) (CVA) 2.0 g 10 Distilled water 1000 g * A copper phthalocyanine pigment supplied as a 50% solids aqueous paste by Hoechst (U.K.).
_thod Colanyl Green GG was dispersed in water (970 g) and heated to 82C. The dispersion was purged with nitrogen for 15 minutes and styrene was added with vigorous s~irring. 4,4'-a~obis-(4-cyanovaleric acid) was slurried in the remaining water and added to the re-actants. Polymerization was continued for 6 hours at82C. The latex was steam-stripped to remove any un-converted monomer and filtered through glase wool.
Transmi~sion ~lectron Microscopy ~howed that the pig-ment particles were encapsulated within a sheath of polystyrene, and that the average size of the~e particles was 900 A.
Stability in Thickened ~ypochlorite A sample of the above dispersion was added to Domestos at 200 ppm to give a clear, green colouration. Both colour and colloidal stability were maintained for 8 weeks at 37C. In gassing studies hypochlorite con-taining polymer-protected pigment s~owed dramatically 35 less gassing than a sample containing Colanyl Green (order 100 times less gassing).
C 7044 (R) l.~g;45~)4 Example 2 - Coated Colanyl Green GG
Pigment Encapsulation ~tyrene 5.0 g
10 7 74~60 green Phthalo-cyanine 9 49415 green Naphthalene ~ulphonic acid 11 green Organic pigment 14 77199 +green In,organic 77346 plgment 18 -green ~ bluish green Chromium salt~
2047 59825bluish green Anthra-quinone Other colours Pi~ment Name C.I. N Type/Structure Red 5 12490 Monoazo Red 48:1 15865:1 Monoazo Red 48:2 15865:2 Monoazo Red 48:3 15865:3 Monoazo Red 49:1; 49:2: 15630 Monoa~o 49:3 Red 52:1 15860 Monoazo Red 53:1 15585:1 Monoazo Red 57:1 15850:1 Monoazo Red 81 45160:1 Xanthene/PTMA
Red 82 45150:1 Xanthene/PTMA
Red 83 58000:1 Anthraquinone Red 90:1 45380:1 Xanthene/Al C 70~4 (~) ~6~504 Other colour~
Pigment Name C.I. N Type/Structure ~iolet 3 42535:1 TAM/PTMA
Violet 5:1 58055:1 Anthraquinone/Al Violet 19 46500 ~uinacridonP
Yellow 14 21095 Di~azo Brown 3 21310 Disa~o/DPTMA
Brown 23 Disazo Brown 25 - Monoazo 10 Black 3 - Organic~PTMA
BlacX 5 - Mordant/Metal Mixtures of various pigments can equally be used. Pre-ferably, non-metallated pigments are used in bleaching compositions which are susceptible to decomposition by metal ion catalysis, but metallated pigments when used according ~o the present invention show already a sig-nificant improvement in thi~ respect in comparison with the uncoated pigments, without any significant physical stability problem. Thu6 it has been found that a copper-containing halogenated phthalocyanine, when used ac-cording to the present inven~ion, causes substantially less decomposition o~ the bleaching composition than the ~ame uncoated pigment, and less settling out of the pigment particles. When metallated pigments are used, it is sometimes advantageous to use a metal ~ques-tering agent in the composition, such as a periodate or other suitable metal-chelating agent which is stable in the bleaching composition in amounts of up to about 5%
by weight o the coated pigment added, to reduce the decomposition even further.
The coating The coating material to be used in the present inven-tion should be bleach-resi~tantO Any organic material can be u~ed, as long a~ the pigment is no~ soluble ~ 5~ C 7044 (R) therein. Preferably, organic materials are used in which the pigment is readily dispersible. ~uitable materials are (co)polymers prepared from a hydrophobic monomer which is capable of undergoing emulsion poly-merization.
Typical examples are styrene, alkyl styrene3 with one to four carbon a~oms in the alkyl group, monohalogen-ated styrenes, acrylates, methacrylates, vinylesters, ethylene and vinylchloride. A particularly suitable material is polystyrene.
The coating process is carried out in a manner known per se, by introducing the pigment particles into an aqueous emulsion polymerization of styrene, using a common i~itiator such as potassium persulphate, a~obi~-(isobutyramidine hydrochloride) or 4,4'-azobis-(4-cyanovaleric acid). It has ~een found that higher con-centrations of initiator than are usual for convention-al emulsion polymerization favour the coating of thepigment particles.
The concentration ratio of monomer to pigment should be such that there i8 sufficient monomer present to just coat all the particles to avoid the formation of un-coloured polymeric latices. For e.g. styrene and Pig-ment Green 7 (C.I. N 74260), the most eff ctive styrene/pigment ratio was found to be 5:1.
To aid the dispersal of the pigment in the polymer-ization reaction mixture, a suitable surfactant, such as a nonionic or an anionic synthetic detergent, can be advantageously added.
The com~osition The coated pigments of the present invention are suit-C 7044 (R) 50~
able for colouring aqueous bleaching compositions, both thickened and non-thickened ones. These compositions may contain other ingredients, which are governed by the purpose for which these compo~itions are u~ed, such as heavy-duty liquid fabric-bleaching and -washing com-positions, liquid fabric~softening compositions, hair-bleaching compositions, hygienic cleaning compositions, hard-surface-cleaning compositions, etc. Thu~, they preferably contain one or more detergent-active com-pounds. Further ingredients commonly encountered in such products may be included in the compositions of the inven~ion. As said before, the bleaching agent can comprise both oxygen and chlorine ~leaching agants, as well a~ reducing bleaches.
The coated pigments of the present invention are par-ticularly suitable for thickened aqueous alkali hypo-chlorite compositions such a~ described in GB-A-1 329 086, EP-Al- 00 30401, GB-A- 1 548 379, GB-A-1 466 560, GB-Al- 2 003 522, GB-Al- 2 041 162, GB-Al-2 076 010 and GB-Al- 2 046 321.
The amount of coated pigments used in the bleach com-position varies from 0.0005 to 10% by weight, prefer-ably ~rom O.OOl to 1% by weight.
The invention will now further be illustrated by way of example.
In the following examples, the bleaching composition was a current commercial thickened h~pochlorite bleaching composition, Domestos~ manufactured and sold by Lever Brothers Ltd. This product is a prcduct ac-cording to GB Patent l 329 086.
The colour and phy~ical stability were asses~ed spectrophotometrically and visually, respectively, and C~e~o74s ~e ~ark , .. .. .... . ~ . . . . . . , ~ i ,. .
C 7044 ~R) the hypochlorite decomposition ("gas~ing") was ~ea ured by collecting the volume of gas evolvedO
Example 1 - Coated Colanyl Green GG
Pigment Encapsulation Styrene 5 0 g Colanyl Green GG* (Pigment Green 7 C.I. ~ 74260) 2.0 g 4,4'-azobis-(4-cyanovaleric acid) (CVA) 2.0 g 10 Distilled water 1000 g * A copper phthalocyanine pigment supplied as a 50% solids aqueous paste by Hoechst (U.K.).
_thod Colanyl Green GG was dispersed in water (970 g) and heated to 82C. The dispersion was purged with nitrogen for 15 minutes and styrene was added with vigorous s~irring. 4,4'-a~obis-(4-cyanovaleric acid) was slurried in the remaining water and added to the re-actants. Polymerization was continued for 6 hours at82C. The latex was steam-stripped to remove any un-converted monomer and filtered through glase wool.
Transmi~sion ~lectron Microscopy ~howed that the pig-ment particles were encapsulated within a sheath of polystyrene, and that the average size of the~e particles was 900 A.
Stability in Thickened ~ypochlorite A sample of the above dispersion was added to Domestos at 200 ppm to give a clear, green colouration. Both colour and colloidal stability were maintained for 8 weeks at 37C. In gassing studies hypochlorite con-taining polymer-protected pigment s~owed dramatically 35 less gassing than a sample containing Colanyl Green (order 100 times less gassing).
C 7044 (R) l.~g;45~)4 Example 2 - Coated Colanyl Green GG
Pigment Encapsulation ~tyrene 5.0 g
5 Colanyl Green GG 2.0 g 2,2'~azobis-(2-amidino propane) HCl 2.0 g Distilled water 1000 g Method As Example 1.
Stability in Thickened Hypochlorite A sample of the above dispersion was added to Domestos at 20Q ppm to give a clear, green colouration. The pro-duct retained a colour and colloidal stability for greater than 6n days.
E~ample 3 - Coated Colanyl Green GG
20 Pigment ~ncapsulation Styrene 9.0 g Colanyl Green GG 2.0 g Potassium persulphate 0.5 g Distilled water 1000 g Method As Example 1.
Stability in Thickened H~pochlorite A sample of the above dispersion was added to Domestos at 150 ppm to give a translucent green colouration. The product remained coloured after 60 days storage at 37C.
C 7044 (R) Example 4 Coated Colanyl Green Pigment Encapsulation Styrene 17.1 g 5 Colanyl Green 2.8 g 2,2'-a~obis-~2-amidino propane) HCl~ 0.5 g Sodium dodecyl sulphate 1.73 g Distilled water 250 g Method The sodium dodecyl sulphate was dissolved in the water and the encapsulation effected as in Example 1.
Stability in Thickened Hypochlorite A sample of the above dispersion was added to Domestos at lS0 ppm to give a translucent green colouration. The product remained coloured after 60 days storage at , . .. .. . ~
G 7044 (R) 50~
Example 5 - Coated Pigment Blue 1 Pigment Encapsulation Styrene 5.0 g 5 Eljon Blu~ Toner* 1.0 g Arylan SNS** (20~ w/w/ aqueou~ solution~ 1.72 g CVA 2.0 g Diætilled water 1000 g * Eljon Blue Toner MGS55~30 obtain~d from Allis Joneæ ~ Co.
Used as Pigment Blue 1 (C~I~ N 42595:2), i.e. a phosho-tungstomolybdic acid (PTMA~ salt of a triarylmethane dye derivative:
~ C2H5 ~ N ~
/--'\ ,~J C2H5 C2H5 - ~H ~ ~ N ~C2H5 ** Arylan SNS is a naphthalene sulphonic acid formalde-hyde condensate obtained from Lankro.
Method The Arylan SNS æolution was mixed with the pigment and the encapsulation effected aæ in Example 1.
Stability of ThicXened Hypochlorite A sample of the above dispersion was added to Domestos at 550 ppm to give a clear blue colouration. Encapsu-lation enhanced the colour stability eightfold over that of the untreated pigment (120 min. vs 15 min.).
.. , . .. . ~ . ...... .. .. .. .. . .
C 704~ (R) Exam le 6 - Coated Pigment Violet 3 P
Pigment Encapsulation Styrene 5,0 g ljon Violet Toner* 1.0 g CVA 2.0 g Arylan SNS (20~ w/w aq. solution) 1. 43 g Distilled water 1000 g * Eljon Violet Toner 55051 obtained from Allis Jones Co. Used as Pigment Violet 3 (C.I. N 42535:2), i.e.
a PTM~ ~alt of mixed methylated pararosanilines.
Method As for Example 5.
Stability in Thickened Hy~ochlorite A sample of the above dispersion was added to Domestos at 500 ppm to give a clear violet colouration. Encapsu-lation enhanced the colour stability threefold over that of ~he untreated pigment (15 min. vs 5 min.).
Exam le 7 - Coated Pigment Blue 66 P
~ nt Encal@sulation 25 Styrene 5.0 9 CVA 2.0 g Monolite Blue A-Ru* 1.0 g Axylan S~S (20% w/w aqueous solution) 106 g Distilled water 1000 g * Monolite Blue A-Ru obtained from ICI. Used as Pigment Blue 66 (C.I. ~ 73000), i.e.:
O O
CX'~ '\~X~
~ 5 ~ C 7044 (R) Method As Example 5.
Stability in Thickened Hypochlorite A sample o the above dispersion was added to Domesto~
at 500 ppm to give a blue colouration. Encapsulation enhanced the colour ~tability of the pigment (up to 1 hour).
10 Example 8 - Coated Pigment Green 1 Pigment Encapsulation Styrene 5,0 g Fanal Green* 1.0 g 15 CVA 2.0 g Arylan SNS 120~ w/w aq. solution) 1.09 g ~istilled wa~er 1000 g * Fanal Green D8330 obtained from BASF. Used as Pigment Green 1 (C.I. N 42040:1), i.e. an acid salt of tri-arylmethane dye:
a~
¦ ~ ~ PTMA
N ~ - C2H5 Stability in Thickened Hy~ochlorite A sample of the above dispersion was added to Domestos at 500 ppm to give a green colouration. ~ncap~ulation enhanced the colour ~tability of the pigment (up to 20 minute 8 ) .
i4504 c 7044 (R) Example 9 - Coated Pigment Blue 16 Pigment Encapsulation Styrene 2.5 g 5 Irgazin Blue 3GT 0O4 g CVA 1.0 g Arylan SNS (20% w/w aq. solution~ 0.7 g Distilled water 500 g * Irgazin Blue 3GT suppliPd by Ciba Geigy. Used as Pig-ment Blue 16 (C.I. N 74100), i.e. unmetallated phthalocyanine.
Method As Example 5.
Stability in Thickened Hypochlorite A sample of the above dispersion was added to Domestos at 500 ppm to give a blue colouration. Colour was re-tained for 1 week (cf. unencapsulated pigment 3 days).
Example 10 ~ Coated Pigment Brown 25 Pigment Encap~ulation Styrene 5.0 g 25 Ho~taperm Brown* 1.0 g Arylan S~S (20% w/w aqueous solution) 1.52 g CVA
Distilled water 1000 g * Hostaperm Brown ~FR supplied by Hoechst. Used as Pig-ment Brown 25 (C.I. ~ 1~510(S)), i,e a monoazo pigment:
H
C = O
Cl <
C 7044 ~R) 50~
Method As Example 5.
Stability in Thickened Hypochlorite A sample of the dispersion was added to Domestos at S00 ppm to give a brown colouration. Colour was retained for 5 hour~ at room temperature (cf. 5 minutea for the uncoated pigment~.
~xample 11 - Coated Pigment Brown 23 Pigment Encapsulation Styrene 5.0 g Cromophtal Brown* 1.0 g Arylan S~S (20% w/w aq. solution) 0.27 g CVA 2.0 g Distilled water 1000 g * Cromophtal Brown 5R supplied by Ciba Geigy. Used as Pigment Brown 23, i.e. a diazo pigment.
Method As Example 5.
Stability in Thickened Hypochlorite A sample of the dispersion wae added to Domestos at 500 ppm to give a brown colouration. Colour wa~ retained ~or 45 minutes at room temperature.
Example 12 - Coated Remazol Green -Pigment Encapsulation Styrene ~.~ g Remazol Brilliant Green Vinyl Sulphone* O.9S g Sodium Dodecyl Sulphate 0.863 g 2,2'-azobis-~amidino pxopane) HCl 0.25 g Distilled water 125 g * Remazol Brilliant Green 6B (ex Hoechst) was used as ~45~4 C 7044 (R) C.I. Reactive Blue 38, i.e. a phthalocyanine reactive dye.
Method S The vinyl sulphone derivative of Remazol Brilliant Green was generated by treating the -sulphatoethyl-sulphone form of the dye with 2M aq. sodium hydroxide ~e.g. see Robinson, C. et al., Proc. R. Soc. (A) 31, 576, (1931)~. The dye and surfactant were dissolved in the water, and concentrated hydrochloric acid wa~ added until the pH of the aqueous phase was less than 1. The resulting precipitated pigment was coated as in Example 4.
Stability in Thickened HypochloritP
A sample of the above dispersion was added to Domestos at 500 ppm to give a green colouration, which per~isted for over 2 hours (cf. immediate colour loss for original dye).
Example 13 - Coated Remastral Blue 3G
Pigment Encapæulation Styrene 8.6 g 25 Remastral Blue 3G* 0.95 g 2,2'-azobi~ (amidino propane) HCl 0.25 g Sodium dodecyl sulphate 0.863 g Distilled water 125 5 * Remastral Blue 3G is an example of a Direct dye (ex Hoechst).
Method Aæ Example 4.
Stability in Thickened Hypochlorlte A sample of the above dispersion was added to Domestos at 500 ppm concentration, to qive a coloured product which retained colour overnight.
Stability in Thickened Hypochlorite A sample of the above dispersion was added to Domestos at 20Q ppm to give a clear, green colouration. The pro-duct retained a colour and colloidal stability for greater than 6n days.
E~ample 3 - Coated Colanyl Green GG
20 Pigment ~ncapsulation Styrene 9.0 g Colanyl Green GG 2.0 g Potassium persulphate 0.5 g Distilled water 1000 g Method As Example 1.
Stability in Thickened H~pochlorite A sample of the above dispersion was added to Domestos at 150 ppm to give a translucent green colouration. The product remained coloured after 60 days storage at 37C.
C 7044 (R) Example 4 Coated Colanyl Green Pigment Encapsulation Styrene 17.1 g 5 Colanyl Green 2.8 g 2,2'-a~obis-~2-amidino propane) HCl~ 0.5 g Sodium dodecyl sulphate 1.73 g Distilled water 250 g Method The sodium dodecyl sulphate was dissolved in the water and the encapsulation effected as in Example 1.
Stability in Thickened Hypochlorite A sample of the above dispersion was added to Domestos at lS0 ppm to give a translucent green colouration. The product remained coloured after 60 days storage at , . .. .. . ~
G 7044 (R) 50~
Example 5 - Coated Pigment Blue 1 Pigment Encapsulation Styrene 5.0 g 5 Eljon Blu~ Toner* 1.0 g Arylan SNS** (20~ w/w/ aqueou~ solution~ 1.72 g CVA 2.0 g Diætilled water 1000 g * Eljon Blue Toner MGS55~30 obtain~d from Allis Joneæ ~ Co.
Used as Pigment Blue 1 (C~I~ N 42595:2), i.e. a phosho-tungstomolybdic acid (PTMA~ salt of a triarylmethane dye derivative:
~ C2H5 ~ N ~
/--'\ ,~J C2H5 C2H5 - ~H ~ ~ N ~C2H5 ** Arylan SNS is a naphthalene sulphonic acid formalde-hyde condensate obtained from Lankro.
Method The Arylan SNS æolution was mixed with the pigment and the encapsulation effected aæ in Example 1.
Stability of ThicXened Hypochlorite A sample of the above dispersion was added to Domestos at 550 ppm to give a clear blue colouration. Encapsu-lation enhanced the colour stability eightfold over that of the untreated pigment (120 min. vs 15 min.).
.. , . .. . ~ . ...... .. .. .. .. . .
C 704~ (R) Exam le 6 - Coated Pigment Violet 3 P
Pigment Encapsulation Styrene 5,0 g ljon Violet Toner* 1.0 g CVA 2.0 g Arylan SNS (20~ w/w aq. solution) 1. 43 g Distilled water 1000 g * Eljon Violet Toner 55051 obtained from Allis Jones Co. Used as Pigment Violet 3 (C.I. N 42535:2), i.e.
a PTM~ ~alt of mixed methylated pararosanilines.
Method As for Example 5.
Stability in Thickened Hy~ochlorite A sample of the above dispersion was added to Domestos at 500 ppm to give a clear violet colouration. Encapsu-lation enhanced the colour stability threefold over that of ~he untreated pigment (15 min. vs 5 min.).
Exam le 7 - Coated Pigment Blue 66 P
~ nt Encal@sulation 25 Styrene 5.0 9 CVA 2.0 g Monolite Blue A-Ru* 1.0 g Axylan S~S (20% w/w aqueous solution) 106 g Distilled water 1000 g * Monolite Blue A-Ru obtained from ICI. Used as Pigment Blue 66 (C.I. ~ 73000), i.e.:
O O
CX'~ '\~X~
~ 5 ~ C 7044 (R) Method As Example 5.
Stability in Thickened Hypochlorite A sample o the above dispersion was added to Domesto~
at 500 ppm to give a blue colouration. Encapsulation enhanced the colour ~tability of the pigment (up to 1 hour).
10 Example 8 - Coated Pigment Green 1 Pigment Encapsulation Styrene 5,0 g Fanal Green* 1.0 g 15 CVA 2.0 g Arylan SNS 120~ w/w aq. solution) 1.09 g ~istilled wa~er 1000 g * Fanal Green D8330 obtained from BASF. Used as Pigment Green 1 (C.I. N 42040:1), i.e. an acid salt of tri-arylmethane dye:
a~
¦ ~ ~ PTMA
N ~ - C2H5 Stability in Thickened Hy~ochlorite A sample of the above dispersion was added to Domestos at 500 ppm to give a green colouration. ~ncap~ulation enhanced the colour ~tability of the pigment (up to 20 minute 8 ) .
i4504 c 7044 (R) Example 9 - Coated Pigment Blue 16 Pigment Encapsulation Styrene 2.5 g 5 Irgazin Blue 3GT 0O4 g CVA 1.0 g Arylan SNS (20% w/w aq. solution~ 0.7 g Distilled water 500 g * Irgazin Blue 3GT suppliPd by Ciba Geigy. Used as Pig-ment Blue 16 (C.I. N 74100), i.e. unmetallated phthalocyanine.
Method As Example 5.
Stability in Thickened Hypochlorite A sample of the above dispersion was added to Domestos at 500 ppm to give a blue colouration. Colour was re-tained for 1 week (cf. unencapsulated pigment 3 days).
Example 10 ~ Coated Pigment Brown 25 Pigment Encap~ulation Styrene 5.0 g 25 Ho~taperm Brown* 1.0 g Arylan S~S (20% w/w aqueous solution) 1.52 g CVA
Distilled water 1000 g * Hostaperm Brown ~FR supplied by Hoechst. Used as Pig-ment Brown 25 (C.I. ~ 1~510(S)), i,e a monoazo pigment:
H
C = O
Cl <
C 7044 ~R) 50~
Method As Example 5.
Stability in Thickened Hypochlorite A sample of the dispersion was added to Domestos at S00 ppm to give a brown colouration. Colour was retained for 5 hour~ at room temperature (cf. 5 minutea for the uncoated pigment~.
~xample 11 - Coated Pigment Brown 23 Pigment Encapsulation Styrene 5.0 g Cromophtal Brown* 1.0 g Arylan S~S (20% w/w aq. solution) 0.27 g CVA 2.0 g Distilled water 1000 g * Cromophtal Brown 5R supplied by Ciba Geigy. Used as Pigment Brown 23, i.e. a diazo pigment.
Method As Example 5.
Stability in Thickened Hypochlorite A sample of the dispersion wae added to Domestos at 500 ppm to give a brown colouration. Colour wa~ retained ~or 45 minutes at room temperature.
Example 12 - Coated Remazol Green -Pigment Encapsulation Styrene ~.~ g Remazol Brilliant Green Vinyl Sulphone* O.9S g Sodium Dodecyl Sulphate 0.863 g 2,2'-azobis-~amidino pxopane) HCl 0.25 g Distilled water 125 g * Remazol Brilliant Green 6B (ex Hoechst) was used as ~45~4 C 7044 (R) C.I. Reactive Blue 38, i.e. a phthalocyanine reactive dye.
Method S The vinyl sulphone derivative of Remazol Brilliant Green was generated by treating the -sulphatoethyl-sulphone form of the dye with 2M aq. sodium hydroxide ~e.g. see Robinson, C. et al., Proc. R. Soc. (A) 31, 576, (1931)~. The dye and surfactant were dissolved in the water, and concentrated hydrochloric acid wa~ added until the pH of the aqueous phase was less than 1. The resulting precipitated pigment was coated as in Example 4.
Stability in Thickened HypochloritP
A sample of the above dispersion was added to Domestos at 500 ppm to give a green colouration, which per~isted for over 2 hours (cf. immediate colour loss for original dye).
Example 13 - Coated Remastral Blue 3G
Pigment Encapæulation Styrene 8.6 g 25 Remastral Blue 3G* 0.95 g 2,2'-azobi~ (amidino propane) HCl 0.25 g Sodium dodecyl sulphate 0.863 g Distilled water 125 5 * Remastral Blue 3G is an example of a Direct dye (ex Hoechst).
Method Aæ Example 4.
Stability in Thickened Hypochlorlte A sample of the above dispersion was added to Domestos at 500 ppm concentration, to qive a coloured product which retained colour overnight.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS
1. An aqueous, coloured bleaching composition comprising an aqueous solution of an oxygen or chlorine bleaching agent and a colouring agent, in which the colouring agent is a colloidally stable, coated pigment which has been coated with a bleach-resistant polymer prepared from a hydrophobic monomer which is capable of undergoing emulsion polymerisation.
2. The composition of claim 1, in which the polymer is polystyrene.
3. The composition of claim 1, in which the pigment is a metallated pigment.
4. The composition of claim 3, in which the pigment is a copper-containing halogenated phthalocyanine.
5. A thickened, aqueous coloured alkali metal hypochlorite composition comprising as colouring agent from 0.0005-10% by weight of a colloidally stable, coated pigment which has been coated with a bleach-resistant polymer prepared from a hydrophobic monomer which is capable of undergoing emulsion polymerisation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8431256 | 1984-12-11 | ||
| GB848431256A GB8431256D0 (en) | 1984-12-11 | 1984-12-11 | Coloured bleaching compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1264504A true CA1264504A (en) | 1990-01-23 |
Family
ID=10571024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000497014A Expired - Fee Related CA1264504A (en) | 1984-12-11 | 1985-12-06 | Coloured bleaching compositions |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0184888A3 (en) |
| JP (1) | JPS61141800A (en) |
| AU (1) | AU584952B2 (en) |
| BR (1) | BR8506183A (en) |
| CA (1) | CA1264504A (en) |
| ES (1) | ES8608036A1 (en) |
| GB (1) | GB8431256D0 (en) |
| GR (1) | GR852964B (en) |
| ZA (1) | ZA859430B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5075029A (en) * | 1984-01-27 | 1991-12-24 | The Clorox Company | Stable emulsified bleaching compositions |
| US4800066A (en) * | 1986-07-21 | 1989-01-24 | The Drackett Company | End of life indicator for automatic toilet cleaning devices |
| US4917814A (en) * | 1988-08-11 | 1990-04-17 | The Drackett Company | Pigmented hypochlorite compositions |
| DE19810885A1 (en) * | 1998-03-13 | 1999-10-07 | Henkel Kgaa | Process for the gentle bleaching of textile fabrics |
| DE29903535U1 (en) * | 1999-02-27 | 1999-06-10 | Henkel KGaA, 40589 Düsseldorf | Preparations containing active chlorine with colorants in microcapsules |
| AR049537A1 (en) * | 2004-06-29 | 2006-08-09 | Procter & Gamble | DETERGENT COMPOSITIONS FOR LAUNDRY WITH DYING COLOR |
| ATE492624T1 (en) * | 2007-05-18 | 2011-01-15 | Unilever Nv | TRIPHENYLMETHANE AND XANTHENE PIGMENTS |
| JP6790257B2 (en) * | 2016-11-01 | 2020-11-25 | ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ | Leuco colorants as bluish agents in laundry care compositions, their packaging, kits and methods |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666680A (en) * | 1970-03-05 | 1972-05-30 | Purex Corp Ltd | Method of combining optical brighteners with polymers for stability in bleach and encapsulated product |
| US3655566A (en) * | 1970-03-05 | 1972-04-11 | Purex Corp Ltd | Bleach having stable brighteners |
| AU453910B2 (en) * | 1971-12-16 | 1974-10-17 | Purex Corporation | Bleach having stable brighteners |
| US3956163A (en) * | 1973-08-20 | 1976-05-11 | The Dow Chemical Company | Pigmented detergents |
| AU519631B2 (en) * | 1977-11-18 | 1981-12-17 | Unilever Ltd. | Liquid bleach compositions |
| US4457855A (en) * | 1981-06-08 | 1984-07-03 | The Clorox Company | Stable hypochlorite solution suspendable dyes |
| GB8315838D0 (en) * | 1983-06-09 | 1983-07-13 | Unilever Plc | Coloured bleaching compositions |
| EP0156438B1 (en) * | 1984-03-30 | 1992-01-29 | THE PROCTER & GAMBLE COMPANY | Stable suspension of pigments in aqueous hypochlorite bleach compositions |
-
1984
- 1984-12-11 GB GB848431256A patent/GB8431256D0/en active Pending
-
1985
- 1985-12-03 EP EP85202011A patent/EP0184888A3/en not_active Withdrawn
- 1985-12-05 AU AU50799/85A patent/AU584952B2/en not_active Ceased
- 1985-12-06 CA CA000497014A patent/CA1264504A/en not_active Expired - Fee Related
- 1985-12-10 GR GR852964A patent/GR852964B/el unknown
- 1985-12-10 ZA ZA859430A patent/ZA859430B/en unknown
- 1985-12-10 JP JP60277781A patent/JPS61141800A/en active Pending
- 1985-12-10 ES ES549786A patent/ES8608036A1/en not_active Expired
- 1985-12-10 BR BR8506183A patent/BR8506183A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8608036A1 (en) | 1986-06-01 |
| ES549786A0 (en) | 1986-06-01 |
| EP0184888A2 (en) | 1986-06-18 |
| AU5079985A (en) | 1986-06-19 |
| ZA859430B (en) | 1987-08-26 |
| AU584952B2 (en) | 1989-06-08 |
| GB8431256D0 (en) | 1985-01-23 |
| JPS61141800A (en) | 1986-06-28 |
| GR852964B (en) | 1986-04-07 |
| BR8506183A (en) | 1986-08-26 |
| EP0184888A3 (en) | 1989-04-19 |
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