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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments
  • C11D3/42—Brightening agents ; Blueing agents
• • 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

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.
• U.S. Pat. No. 4,271,030 Brierley et al., issued June 2, 1981, 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 '030 patent does not . teach the essential optical brightener of the present invention.
• the present invention is directed to the formulation of aqueous sodium hypochlorite laundry bleach compositions containing a dispersion of bleach stable inorganic pigment, an optical brightener and LAS (linear alkylbenzene sulfonate).
• the preferred compositions comprise a uniform mixture of from 3% to 8% sodium hypochlorite, from 0.01% to 0.3% of the Ultramarine Blue pigment, from - 0.025% to 0.2% of the optical brightener 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'- stilbenedisulfonate, from 0.05% to 2% of a certain alkylaryl sulfonate surfactants, and preferably from 0.01% to 0.5% of a bleach stable organic oil, and at least 80% water.
• the bleach stable pigment selected from the group consisting of chlorinated indanthrone (and its equivalents) and Ultramarine Blue, Na 7 Al 6 Si 6 O 24 S 2 (and its equivalents), can be stably dispersed in an aqueous sodium hypochlorite laundry bleach containing LAS and a special optical brightener.
• the pigment can be mixed with the LAS/optical brightener before they are salted out as a fine dispersion or it can be mixed into the LAS/optical brightener/hypochlorite.
• 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.
• compositions of the invention comprise:
• composition of this invention prepared by either admixing the pigments prior to or after mixing the brightener/surfactant solution with the aqueous sodium hypochlorite.
• sodium hypochlorite is commercially available in aqueous solutions having a concentration of from about 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.l. 77007". It is a blue pigment occurring naturally as the mineral iapis lazuti. It is made by igniting a mixture of kaolin, Na 2 CO 3 (or Na 2 SO 4 ), S and carbon. The resulting product is believed to have the formula Na 7 Al 6 Si 6 O 24 S 2 . it is insoluble in water and readily decomposed by acids, even carbonic acid, with liberation of H 2 S.
• C.l. 69825 is known under the names of C.l. Vat Blue 6 and C.l. 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 0.02% to 0.05% and more broadly 0.01% to 0.1%.
• the brightener used in the compositions herein is 4,4- bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonic said, its alkali metal (e.g., sodium or potassium) salts.
• alkali metal e.g., sodium or potassium
• the structure of the sodium salt is: .
• This optical brightener is available from Mobay Chemical Corporation, a subsidiary of Bayer AG, under the name Phorwite® CNA.
• optical brightener is present in the compositions of the invention 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 R 1 is an alkyl group of from 8 to 20 (preferably 11 to 13) carbon atoms, R 2 and R 3 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 alkytbenzene 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.
• compositions contain an organic oil which has a density of from 0.8 to 1.05.
• the oils are present in the compositions of the invention 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, cyclo- pentadecanolide, p-tertiarybutyl cyclohexyl acetate, tetrahydro- mycenol, 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 compositions herein 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 the group consisting of:
• 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.
• compositions of the invention are preferably prepared by the following steps:
• 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 pigmentlbrightenerlsurfactant 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., HCI or NaOH).
• composition consisting of:
• the perfume has a density of about 1.03 g/cc 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% NaOCI content) were gradually added to the brightenerlsur- factant/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.
• Example 2 Same as Example 1, except that the pigment was added to the system after the hypochtorite was added to the perfumel brightenerlsurfactant solution. A homogeneous blue product was formed which also remained stable for several days.
• composition consisting of:
• Example III The procedure for making the composition of Example III was the same as that of Example 1, except that in Example III 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.
• compositions were made consisting of:
• compositions were made consisting of:
• Example V The procedure was the same as described in Example I, except that in Example V the UMB was added as a 10% dispersion in water after the brightener/surfactant dispersion was formed by the addition of NaOCI.
• 500 ml of Compositions A and B were stored in 500 ml graduated glass cylinders. The pigment was uniformly suspended throughout the composition and did not settle down.
• composition consisting of:
• the pigment was added after precipitation of the brightener and surfactant. Pigment levels were varied from 0.02% to 0.1% to get different shades of blue color. In all cases, the pigment was dispersed uniformly throughout the composition and had excellent physical stability for several days. There was also good chemical stability as evidenced by the retention of color and % NaOCI.
• composition consisting of:
• composition consisting of:
• Example VIII 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)
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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
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• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (8)

Citations (3)

• 1985
  • 1985-03-20 EP EP85200422A patent/EP0156438B1/de not_active Expired - Lifetime
  • 1985-03-20 DE DE8585200422T patent/DE3585293D1/de not_active Expired - Fee Related
  • 1985-03-28 CA CA000477785A patent/CA1232410A/en not_active Expired

Patent Citations (4)

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