EP0156438B1 - Suspension stable de pigments dans des compositions de blanchiment de hypochloride aqueuses - Google Patents

Suspension stable de pigments dans des compositions de blanchiment de hypochloride aqueuses Download PDF

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Publication number
EP0156438B1
EP0156438B1 EP85200422A EP85200422A EP0156438B1 EP 0156438 B1 EP0156438 B1 EP 0156438B1 EP 85200422 A EP85200422 A EP 85200422A EP 85200422 A EP85200422 A EP 85200422A EP 0156438 B1 EP0156438 B1 EP 0156438B1
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Prior art keywords
composition
bleach
pigment
weight
surfactant
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EP85200422A
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German (de)
English (en)
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EP0156438A3 (en
EP0156438A2 (fr
Inventor
Bala Chandran Nayar
Kathleen Grieshop Baier
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • 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
    • C11D3/42Brightening agents ; Blueing agents
    • 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
    • C11D3/395Bleaching agents
    • C11D3/3956Liquid compositions
    • 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

Definitions

  • the invention pertains to an aqueous hypochlorite laundry bleach product which contains suspended pigments, and to the process for making same.
  • optical brighteners or bluing agents are not present in bleach, particularly liquid bleach, since the liquid bleach has a strong tendency to oxidize and destroy the dyes with concurrent reduction in bleaching strength.
  • Alternative approaches involving addition of bleach stable inorganic pigments to liquid hypochlorite bleach to effect bluing have also been unsuccessful generally because the pigment particles have a tendency to settle out of suspension.”
  • German Patent Document DE-C-2849225 discloses a colored liquid hypochlorite bleach composition primarily designed for cleaning lavatory pans.
  • the composition contains Ultramarine Blue (UMB) suspended in a flocculate, which is preferably made by reacting a soap or synthetic surfactant with calcium ions.
  • UMB Ultramarine Blue
  • Such a composition which contains a calcium floc is undesirable for laundry cleaning because the calcium floc will deposit on the fabric.
  • Also a linear alkylbenzene sulfonate (LAS)/hypochlorite floc alone will not support an effective amount of Ultramarine Blue pigment at an LAS level desirable for an aqueous laundry bleach composition.
  • This patent does not teach the essential optical brightener of the present invention.
  • EP-A-0142883 published on May 29 1985.
  • This document discloses aqueous hypochlorite bleach compositions containing from 0.025% to 0.2% of 4, 4' bis (4 phenyl-2H-1,2,3, triazol-2-yl)-2, 2' stilbene disulfonic acid, from 0.05% to 2% of a bleach stable alkyl aryl sulfonate surfactant, form 0% to 0.5% of a bleach stable organic oil and a bleach stable pigment such as Ultramarine Blue.
  • the bleach stable pigment selected from 3,31-dichloro indanthrone and Ultramarine Blue, Na7Al6Si6O24S2 can be stably dispersed in an aqueous sodium hypochlorite laundry bleach containing LAS and a special optical brightener.
  • the pigment is mixed with the LAS/optical brightener before they are salted out as a fine dispersion
  • the blue pigment particles settle very slowly. When settling does occur, the settled layer of particles is very loose and occupies a substantial volume of the composition. The settled particles can be readily redispersed throughout the composition by gentle shaking of the bottle or other container from which the composition is to be dispensed. If an organic oil such as perfume is included in the formulation, the blue composition is very stable and very little settling occurs.
  • sodium hypochlorite is commercially available in aqueous solutions having a concentration of from 5% to about 15%. These solutions typically contain an amount of sodium chloride about equal, (on a mole basis) to the amount of sodium hypochlorite.
  • the aqueous sodium hypochlorite source chosen for preparing a composition of the invention should be one which has a sodium hypochlorite concentration such that it can be mixed with the aqueous pigment/brightener/surfactant solution within these volume proportions to produce the desired amounts of sodium hypochlorite, pigment, brightener and surfactant in the finished product.
  • Sodium hypochlorite is present in the compositions of the invention at levels of from 3% to 8%, preferably from 4% to 6%.
  • a preferred pigment used in this invention is Ultramarine Blue. It is sold as "C.I. Pigment Blue 29; C.I. 77007". It is a blue pigment occurring naturally as the mineral lapis lazuli. It is made by igniting a mixture of kaolin, Na2CO3 (or Na2SO4), S and carbon. The resulting product is believed to have the formula Na7Al6Si6O24S2. It is insoluble in water and readily decomposed by acids, even carbonic acid, with liberation of H2S.
  • C.I. 69825 is known under the names of C.I. Vat Blue 6 and C.I. Pigment Blue 64. They have the following chemical formula.
  • This C.I. 69825 pigment is available from Crompton & Knowles Corporation under the name Intravat Blue.
  • the pigment is present in the composition of this invention at levels of from 0.01% to 0.3%, preferably from 0.01% to 0.1% and more preferably from 0.02% to 0.05%.
  • the brightener used in the compositions made by the process of the invention herein is 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonic acid, or its alkali metal (e.g. sodium or potassium) salts.
  • alkali metal e.g. sodium or potassium
  • This optical brightener is available from Mobay Chemical Corporation, a subsidiary of Bayer AG, under the name Phorwite® CNA.
  • the optical brightener is present at levels of from 0.025% to 0.2%, preferably from 0.05% to 0.075%.
  • the surfactants used in the present invention are alkylaryl sulfonates of the following formulas: wherein R1 is an alkyl group of from 8 to 20 (preferably 11 to 13) carbon atoms, R2 and R3 are alkyl groups of 6 to 16 (preferably 10-12) carbon atoms and M is an alkali metal, e.g., sodium or potassium, and n is 0 or 1.
  • Surfactants of Formula 1 are called alkylbenzene sulfonates and are available under various tradenames, e.g., Calsoft® L-60, F-90 and L-40 from Pilot Chemical Company, and Naccanol® 35SL and 90F from Stephan Chemical Company.
  • Surfactants of Formula 2 are alkyl diphenyloxide sulfonates and are available under the Dowfax® name from Dow Chemical Company.
  • the surfactants are present in the compositions herein at levels of from 0.05% to 2.0%, preferably from 0.2% to 1.0%. In aqueous laundry bleach products a most preferred range is from 0.2% to 0.5%.
  • surfactant in the compositions of the invention has been found to be essential to creating dispersed particles of brightener having a small particle size. If surfactant is not used, the particles are much larger. These larger particles have the appearance of curd and render the product less appealing from an aesthetic standpoint.
  • the UMB pigment will settle quickly if only surfactant or only brightener is used.
  • the surfactant/brightener dispersion must be present for a uniform UMB bleach in the practice of this invention.
  • Preferred processes in accordance with the invention employ an organic oil which has a density of from 0.8 to 1.05 g/cm3.
  • the oil is present at levels of from 0.01% to 0.5%, preferably from 0.05% to 0.3%.
  • Preferred oils are perfume materials which have a high degree of stability to sodium hypochlorite.
  • Some preferred materials for use as perfume ingredients in the compositions herein are patchouli oil, cyclopentadecanolide, p-tertiarybutyl cyclohexyl acetate, tetrahydromycenol, tetrahydrolinalool, phenylacetaldehyde dimethylacetal, methylphenyl carbinol, and mixtures thereof.
  • Another preferred organic oil is linear alkyl benzene (LAB) having alkyl chains of from 10 to 14 carbon atoms.
  • organic oils When organic oils are used in the process of the invention they are mixed into the pigment, brightener and surfactant solution prior to the addition of aqueous sodium hypochlorite to the solution.
  • the preferred bleach stable organic oils are selected from:
  • organic oil materials are also perfume ingredients.
  • the following organic oil materials can also be used as perfume ingredients:
  • organic oil usage is toward the upper end of the usage range (i.e., 0.3% to 0.5%) then it is usually necessary to use an amount of surfactant which is also at the higher end of the 0.05% to 2% surfactant usage range hereinbefore disclosed.
  • the process of the invention comprises
  • the aqueous solution of Step 1 is preferably prepared with deionized water. This minimizes the presence of heavy metal ions, which tend to cause decomposition of sodium hypochlorite. At the higher end of the brightener concentration ranges, heating of the solution may be necessary to get all of the brightener into solution.
  • the organic oil (if used) is added after the surfactant has been added. Higher levels of oil generally require surfactant usage to be at the high end of the above stated concentration range.
  • the hypochlorite When adding concentrated sodium hypochlorite to the aqueous composition of Step 1 the hypochlorite should be added slowly and with gentle mixing. The rate of addition should be sufficiently slow to allow maintenance of substantial uniformity of hypochlorite throughout the system, notwithstanding the gentle mixing. As the hypochlorite is added, brightener and surfactant will be salted out as a fine dispersion. Mixing should be gentle throughout the addition of the hypochlorite. High shear mixing and other forms of mixing which produce a high degree of agitation should be avoided since they will lead to formation of larger particles which have poor suspension properties in the solution. The dispersion is best described as loose aggregates of very small brightener and surfactant particles. The insoluble UMB is uniformly dispersed in the system and thereby provides uniform color.
  • the particles of pigment/brightener/surfactant will typically remain more or less homogeneously suspended in the compositions for at least fifteen minutes, and in most cases an hour or more.
  • the length of time depends on the amount of pigment present. A smaller amount can remain suspended for days. Even after the composition eventually becomes nonhomogeneous, most of the particles do not settle to the bottom of the composition, but remain suspended in the bottom one third to two thirds of the composition volume. With a very minor amount of agitation (such as by inverting a bottle and returning it to its upright position) a homogeneous composition is quickly restored. When an organic oil is used the pigment is stably suspended for days.
  • the present invention provides compositions whereby consistent dosages of a combination of sodium hypochlorite, pigment and optical brightener in a concentrated aqueous medium can be easily obtained.
  • compositions herein should have a pH above 12, preferably about 12.5.
  • the pH of the composition should be tested after preparation is complete. If needed, pH adjustment can be made with acid or base (e.g., HCl or NaOH).
  • a composition consisting of: Ingredient Wt. % Ultramarine Blue 0.02 Brightener 0.05 Surfactant (NaLAS) 0.25 Perfume* 0.15 NaOCl ( ⁇ 13%) 44.25 Water to 100.00 *
  • the perfume has a density of about 1.03 g/cm3 and contains about about 15% 2,6-dimethyloctan-2-ol, about 15% of 3,7-dimethyloctan-3-ol and balance made of one or more components listed in Table A.
  • a bleach stable organic oil perfume (2.4 g) and then Ultramarine Blue (0.32 g, grade 5017, Whittaker, Clark & Daniels, Inc.) were added and the mixture was stirred for 30 minutes.
  • 708 g of bleach solution ( ⁇ 13% NaOCl content) were gradually added to the brightener/surfactant/perfume/pigment mixture over a 20 minute period.
  • the brightener and surfactant were salted out and were dispersed uniformly throughout the vessel.
  • 500 ml of this bleach composition were taken in a graduated 500 ml glass cylinder for settling studies.
  • the pH of the final composition was determined to be 12.57 at 24°C. After 7 days of storage at ambient conditions, there was only 2% settling.
  • the pigment was uniformly dispersed in 98% of the composition volume providing a uniform coloration.
  • a composition consisting of: Ingredient Wt. % Ultramarine Blue 0.02 Surfactant (NaLAS) 0.25 NaOCl ( ⁇ 13%) 44.25 Water to 100.00
  • Example II The procedure for making the composition of Example II was the same as that of Example I, except that in Example II the brightener and perfume were not included.
  • the surfactant was precipitated by addition of the bleach solution.
  • the pigment was gently stirred into the surfactant precipitate. The pigment settled down entirely within about 3 hours.
  • This example shows that it is not possible to get a stable suspension of the pigment in a bleach composition by surfactant alone.

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  • 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)

Claims (7)

  1. Procédé de fabrication d'une composition de blanchiment aqueuse comprenant :
    (a) de 3% à 8%, en poids de la composition, d'hypochlorite de sodium;
    (b) de 0,01% à 0,3%, en poids de la composition, d'un pigment stable à l'agent de blanchiment, choisi parmi le Bleu Outremer et la 3,3'-dichloroindanthrone;
    (c) un tensioactif sulfonate anionique stable à l'agent de blanchiment;
    (d) de 0% à 0,5%, en poids de la composition, d'une huile organique stable à l'agent de blanchiment, ayant une masse volumique de 0,8 à 1,05 g/ml; et
    (e) au moins 80%, en poids de la composition, d'eau;
    caractérisé en ce que le procédé comprend les étapes de :
    1) préparation d'un système aqueux contenant ledit pigment, ledit tensioactif et, le cas échéant, ladite huile organique stable à l'agent de blanchiment, avec un azurant optique de formule :
    Figure imgb0015
    ou ses sels de métaux alcalins;
    ledit azurant optique étant ajouté en une quantité fournissant de 0,025% à 0,2% en poids de celui-ci dans la composition de blanchiment, ledit tensioactif étant choisi parmi les alkylarylsulfonates de formules :

    et
    Figure imgb0016
    dans lesquelles R₁ est un groupe alkyle en C₈-C₂₀, R₂ et R₃ sont des groupes alkyle en C₁₀-C₁₆, M est un métal alcalin et n est nul ou égal à 1;
    ledit pigment étant uniformément disperse dans ledit système aqueux;
    2) addition lente, avec mélange à faible cisaillement, au système de l'étape 1, d'une quantité suffisante d'hypochlorite de sodium aqueux pour produire la composition de blanchiment.
  2. Procédé selon la revendication 1, dans lequel ladite huile organique est ajoutée au système aqueux de l'étape 1 après que l'on ait mélangé le tensioactif et l'azurant et avant que l'on ait ajouté le pigment.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel la quantité de pigment dans la composition finie est de 0,01% à 0,1% en poids.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité d'hypochlorite de sodium dans la composition finie est de 4% à 6% en poids.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité d'azurant optique dans la composition finie est de 0,05% à 0,075% en poids.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de tensioactif dans la composition finie est de 0,2% à 1% en poids.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité d'huile organique dans la composition finie est de 0,05% à 0,35% en poids.
EP85200422A 1984-03-30 1985-03-20 Suspension stable de pigments dans des compositions de blanchiment de hypochloride aqueuses Expired - Lifetime EP0156438B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59517184A 1984-03-30 1984-03-30
US595171 1984-03-30

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EP0156438A2 EP0156438A2 (fr) 1985-10-02
EP0156438A3 EP0156438A3 (en) 1989-05-03
EP0156438B1 true EP0156438B1 (fr) 1992-01-29

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5075029A (en) * 1984-01-27 1991-12-24 The Clorox Company Stable emulsified bleaching compositions
US4929383A (en) * 1984-01-27 1990-05-29 The Clorox Company Stable emulstified bleaching compositions
GB8431256D0 (en) * 1984-12-11 1985-01-23 Unilever Plc Coloured bleaching compositions
US4764302A (en) * 1986-10-21 1988-08-16 The Clorox Company Thickening system for incorporating fluorescent whitening agents
US4900469A (en) * 1986-10-21 1990-02-13 The Clorox Company Thickened peracid precursor compositions
JPH08503013A (ja) 1992-11-03 1996-04-02 ザ、プロクター、エンド、ギャンブル、カンパニー 短鎖界面活性剤によるクリーニング
EP0905224A1 (fr) * 1997-09-19 1999-03-31 The Procter & Gamble Company Compositions de blanchiment
DE19858238A1 (de) * 1998-12-17 2000-06-21 Henkel Kgaa Viskoelastische Bleich- und Desinfektionsmittel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4271030A (en) * 1977-11-18 1981-06-02 Lever Brothers Company Pourable liquid compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS591438B2 (ja) * 1976-10-09 1984-01-12 ライオン株式会社 漂白剤組成物
JPS53124182A (en) * 1977-04-06 1978-10-30 Dainichi Seika Kogyo Kk Granular additives for bleaching agent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4271030A (en) * 1977-11-18 1981-06-02 Lever Brothers Company Pourable liquid compositions

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EP0156438A3 (en) 1989-05-03
DE3585293D1 (de) 1992-03-12
CA1232410A (fr) 1988-02-09
EP0156438A2 (fr) 1985-10-02

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