EP0206718B1 - Bleaching and brightening composition and method - Google Patents

Bleaching and brightening composition and method Download PDF

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Publication number
EP0206718B1
EP0206718B1 EP19860304625 EP86304625A EP0206718B1 EP 0206718 B1 EP0206718 B1 EP 0206718B1 EP 19860304625 EP19860304625 EP 19860304625 EP 86304625 A EP86304625 A EP 86304625A EP 0206718 B1 EP0206718 B1 EP 0206718B1
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Prior art keywords
polymer
whitening agent
aqueous solution
fluorescent whitening
polyethylene
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German (de)
French (fr)
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EP0206718A3 (en
EP0206718A2 (en
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Randall J. Cramer
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Clorox Co
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Clorox Co
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    • 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
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
    • C11D3/395Bleaching 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
    • C11D3/42Brightening agents ; Blueing agents

Definitions

  • the present invention provides liquid compositions which include a dispersed polymer forming a matrix in which substantially water insoluble particles, including brighteners and, if desired, bluing agents, are entrapped.
  • the particles are substantially evenly distributed throughout the composition and are suspended therein by means of the polymer.

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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)

Description

  • The present invention generally relates to liquid compositions useful in treating fabrics, and particularly relates to liquid bleaching solutions having stably suspended fluorescent whitening agents therein and preferably also bluing agents.
  • A variety of substantially water insoluble particulates are known and useful in treating fabrics. For example, fluorescent whitening agents, also known as optical brighteners, or brighteners, which are adsorbed onto textile fibers and impart to the fabric an improved degree of whiteness or brightness (fluorescence) by means of their chemical ability to absorb ultraviolet radiation and re-emit visible radiation, have found widespread use as components of household detergent compositions. In order to provide substantial fabric whitening, it is desirable to combine the optical brightening capacity of fluorescent whitening agents with an effective bleach. Fluorescent whitening agents are, however, very reactive and generally unstable in liquid chlorine bleaches. The prior art has failed to provide a stable product incorporating fluorescent whitening agents in a liquid chlorine bleach.
  • U.S. Pat. No. 3,393,153 to Zimmerer et al. discloses the use of an oxidize polyethylene emulsion as a stabilizing agent for dispersions of fluorescent whitening agents in bleach. These emulsions, however, have been shown to substantially lack both physical and chemical stability.
  • Problems of physical and chemical stability are compounded when particulate pigments, or bluing agents, such as ultramarine blue, are also incorporated into the bleach composition. Bluing agents deposit on a fabric surface, and in contrast to optical brighteners, reflect blue light while absorbing yellow light. Although addition of bluing agents in conjunction with laundering additives is a desirable means of treating fabrics, it has been difficult to sufficiently stably suspend the bluing agents, particularly in a strongly oxidizing environment such as hypochlorite bleach, while retaining water dispersibility of the solution.
  • U.S. Pat. No. 4,271,030, issued June 2, 1981, inventors Brierley et al., discloses a liquid hypochlorite bleach having a particulate pigment, such as ultramarine blue, which is said to be stably suspended in the composition by means of a flocculant, such as calcium soap flocs and amine oxides, filling at least 50% of the volume of the composition; and, U.S. Patent No. 3,663,442, issued May 16, 1972, inventor Briggs, discloses liquid bleaching compositions having a finely particulate terpolymer which imparts opacity to the compositions.
  • Generally, prior known compositions with particulates in aqueous solutions have posed sedimentation, coagulation or stability problems or have not found commercial acceptability as dual bleaching and bluing compositions. JP-A-60 179 465 is addressed to stabilizing bluing agents in chlorine bleach compositions; this application relates to stabilizing optical brighteners and preferably also bluing agents in chlorine bleach compositions.
  • Accordingly, it is an object of the present invention to provide a simple and efficient method for stably suspending fluorescent whitening agents, and preferably also being able stably to suspend substantially inert and water insoluble particulate agents such as bluing agents, for treating fabrics in aqueous bleaching solutions, with the solutions being readily dispersed during laundering to provide both bleaching and brightening, as well as coloring or bluing of the fabrics treated.
  • In one aspect of the present invention, a composition useful for treating fabrics is provided which comprises an aqueous bleaching solution, a fluorescent whitening agent, and a polymer dispersed in the aqueous solution which forms a matrix in which the fluorescent whitening agent is entrapped. The amount of fluorescent whitening agent is present in an amount of 0.01 wt.% to 1.0 wt.%, preferably 0.01 wt.% to 0.2 wt.%. The polymer is present in an amount of from 0.015 wt.% to 11.0 wt.%, preferably in an amount ranging from 0.3 wt.% to 2.0 wt.%. The aqueous solution has from 0.1 wt.% to 15 wt.% of a hypochlorite salt, preferably from 1 wt.% to 10 wt.% of a hypochlorite salt, and the polymer is an oxidized polyethylene or a polyethylene-acrylic acid copolymer. A bluing agent such as ultramarine blue may also be added, which together with the fluorescent whitening agent, is entrapped within the polymer matrix. The amount of bluing agent is preferably from 0.1 wt.% to 1.0 wt.%, and more preferably, ranges from 0.01 wt.% to 0.2 wt.%.
  • The polymer used according to the invention is a modified polyethylene compound selected from the group consisting of oxidized polyethylenes having a molecular weight of from 400 to 3,000, polyethylene -acrylic acid copolymers having a molecular weight of below 10,000 and mixtures thereof.
  • In another aspect of the present invention, a method for producing a bleaching, brightening, and optionally bluing composition is provided which comprises the steps of admixing a quantity of the molten polymer cited hereinbefore with sufficient base to saponify and neutralize said oxidized polyethylene or to neutralize said polyethylene-acrylic acid copolymer, contracting the molten polymer in the presence of an anionic or a nonionic surfactant with sufficient of an aqueous solution to form an emulsion, dispersing a quantity of a fluorescent whitening agent and optionally a quantity of particulate ultramarine blue in the emulsion said whitening agent being in a weight ratio with respect to the emulsified polymer of from 1:15 to 1:3, and slowly adding a water soluble salt, which includes a hypochlorite salt, such as sodium hypochlorite and sodium chloride, at least until the emulsion collapses, wherein the polymer forms a matrix in which particles of brightener and optionally ultramarine blue are entrapped.
  • A preferred liquid composition of the invention has sodium hypochlorite in an amount of from 3.5 wt.% to 6.2 wt.%, an anionic or nonionic surfactant in an amount of from 0.03 wt.% to 0.3 wt.%, a polymer derived from oxidized polyethylene or polyethylene-acrylic acid copolymer in an amount of from 0.3 wt.% to 20 wt.%, fluorescent whitening agent in an amount of from 0.01 wt.% to 0.2 wt.%, and ultramarine blue particles in an amount of from 0.01 wt.% to 0.2 wt.%. The polymer stably suspends and disperses the fluorescent whitening agent and the ultramarine blue particles in the liquid composition. When the preferred composition is used, as by adding to wash water, then the polymer releases the fluorescent whitening agent and ultramarine blue particles, which deposit on clothing being washed to mask undesirable yellowing following laundering.
  • Best Mode of Carrying Out the Invention
  • Broadly, the present invention provides liquid compositions which include a dispersed polymer forming a matrix in which substantially water insoluble particles, including brighteners and, if desired, bluing agents, are entrapped. The particles are substantially evenly distributed throughout the composition and are suspended therein by means of the polymer.
  • Suitable brighteners which can be used in the practice of the present invention include compounds which are substantially resistant to chlorine bleaches and which will deposit onto cotton fabric. Particularly suitable compounds include the disodium salt of 2,2-(4,4'-biphenylene divinylene)-dibenzenesulfonic acid (manufactured and sold under the name Tinopal® CBS-X by Ciba-Geigy Corporation of Greensboro, North Carolina; "Tinopal" is a registered trademark of Ciba-Geigy) having the structure
    Figure imgb0001
    and Phorwite BHC 766 (manufactured by Mobay Corporation of Union, New Jersey; "Phorwite" is a registered trade-mark of Mobay Corporation) which has the following structure:
    Figure imgb0002
    Alkaline earth, alkali metal, zinc, and other multivalent salts (such as the metals of Group IIIA of the periodic table of the elements (e.g., AL+3)) of these compounds are also suitable brightening agents, as are the fluorescent whitening agents disclosed in U.S. Pat. No. 3,393,153 to Zimmerer, et al.
  • Concentration of brightener in the bleach composition is paticularly preferably between 0.01 wt.% and 0.2 wt.%; an especially preferred concentration is approximately 0.1 wt.%.
  • It had previously been believed that stable suspension of fluorescent whitening agents in hypochlorite solution was not possible (see, e.g., W. R. Findley, Whitener Selection for Today's Detergents, J. Amer. Oil Chem. Soc. 60(7), p. 1369 (July 1983)). In fact, none of the methods disclosed in the prior art have been successful in providing a stable suspension of brightener in hypochlorite solution. For example, U.S. Pat. No. 3,393,153 to Zimmerer, et al., sets forth liquid bleaching agents which are stated to include stably suspended fluorescent whitening agents. However, comparative testing conducted by the inventor of the instant invention illustrated that substantial chemical stability is not achieved by the Zimmerer et al. methodology. The present invention, in surprising contrast to the prior art, provides a composition which is substantially chemically stable.
  • The bleach composition of the present invention, may include stably suspended bluing agents or related compounds in addition to optical brighteners. Suitable compounds for suspending in compositions of the present invention are substantially inert in the liquid solution, and include various known pigments. For example, suitable pigments include aluminosilicates, such as the ultramarines (red, green, violet and blue), zeolites, and simple metal oxides (such as titanium dioxide and chromium dioxide).
  • Bluing agents useful in the present invention are substantially water insoluble and often have a higher density than the aqueous solutions in which they are desirably dispersed for fabric treatment. For example, ultramarine blue has a density of 2.35 g/cc, and ultramarine blue particles settling out of aqueous solution within about four hours, even when the particles are of very small size.
  • Density of bluing agent in the bleach solution, however, is not believed to be a critical factor in the present invention, as the inventive compositions do not rigorously follow Stokes' law. Thus, bluing agents suitable for the present invention may have densities which are either higher or lower than the liquid solution. Particle size will generally be from 0.5 to 50 urn, preferably from 0.5 to 2 µm. Compositions of the invention will typically have relatively low viscosity (20 to 60 centipoise, or 0.02 to 0.06 pascal second) and thus are readily poured or dispensed for use. Preferred compositions have a pH of at least 11, preferably a pH of at least 12.5. These high pH's appear necessary to promote optimum physical and chemical stability of these bleach compositions. To achieve these high pH's, it is preferred to add a source of caustic, preferably sodium hydroxide. Preferred amounts are from 0.1 to 5.0 wt.%, more preferably from 0.5 wt.% to 2.0 wt.%., and most preferably from 1.0 to 1.75 wt.%. While sodium hydroxide is preferred, other alkali metal hydroxides (e.g., potassium hydroxide, lithium hydroxide) are suitable. Alkali metal carbonates and silicates may also provide the proper high pH.
  • Particularly preferred concentration of bluing agent ranges from 0.01 wt.% to 0.2 wt.%, and an especially preferred concentration is about 0.05 wt.%. Bluing agents for use in the practice of the present invention are effective as composition colorants in addition to providing effective masking of the yellow cast of laundered fabric. Thus, in addition to the pigments listed above, suitable compounds that may be substituted for functional bluing agents include non-functional colorants such as anthraquinone dyes.
  • Suitable polymers for practice of the present invention form a matrix which is dispersed in an aqueous solution and which entraps the particulate. These polymers are oxidized polyethylenes and polyethylene-acrylic acid copolymers, which have e.g., melting points in the range of 90°C to 120°C.
  • Oxidized polyethylenes suitable for the present invention may vary considerably in structure. One suitable oxidized polyethylene has the general formula shown by Formula 3, below, where "R" may be hydrogen or alkyl groups. The ether and ester functionalities may be linear (as illustrated by Formula 3) or be intramolecularly bonded ring structures. The oxidized polyethylenes have a molecular weight of 400 to 3000 and have preferably acid numbers from 30 to 120.
    Figure imgb0003
    wherein the total of x, y and z, is from 35 to 250.
  • It is particularly preferred to use polyethylene-acrylic acid copolymers which are slightly branched polyethylene chains containing no oxygen functionality other than carboxy groups, and have the general structure illustrated by Formula 4, below. Molecular weight is below 10,000, and more preferably ranges from 500 to 6000, and the copolymers have preferably acid numbers ranging from 25 to 160. Particularly preferred copolymers have acid numbers ranging from 30 to 70.
    Figure imgb0004
    wherein the total of x and y is from 12 to 195, and R may be hydrogen or carboxyl.
  • Preparation of compositions in accordance with the present invention includes forming an emulsion of suitable polymer with an anionic or a nonionic surfactant. The amount of surfactant used is preferably from 0.01 wt.% to 6.0 wt.%, more preferably from 0.03 wt.% to 0.3 wt.%. The emulsified polymer forms a discontinuous, internal phase which is dispersed in the continuous, external aqueous phase.
  • Suitable anionic surfactants, or emulsifying agents, include soaps (such as are produced from reacting fatty acids with alkalis or amine compounds), sulfates, sulfonates and phosphates. Suitable nonionic surfactants include polyoxyethylene and polyoxypropylene derivatives, fatty alkanol amides and fatty amine oxides.
  • The emulsion is preferably prepared by melting the oxidized polyethylene or polyethylene acid copolymer with a solution of the surfactant and with base, and then slowly adding boiling water to the melt. At emulsion inversion point, the viscosity of the composition drops and additional boiling water may be added to adjust the emulsion to a desired weight percent of total solids. A quantity of either fluorescent whitening agent or both fluorescent whitening agent and bluing agent is then dispersed into the emulsion, preferably with the dispersed bluing agent and brightener being in a weight ratio with respect to the emulsified polymer of from 1: 1.5 to 1:8. If fluorescent whitening agent only is dispersed, a ratio of 1:1.5 to 1:3, preferably about 1:2.5, is used.
  • Saponification and/or neutralization of the molten polymer is performed prior to formation of the emulsion, preferably with elevated pressure. (The oxidized polyethylene is both saponified and neutralized. The polyethylene-acrylic acid copolymer is neutralized.) Smooth addition of boiling water preceding the emulsion inversion point provides a uniform dispersion. Cooling of the emulsion to room temperature is preferably at a rapid rate (by means, for example, of a cooling jacket on the emulsion kettle).
  • Following preparation of a suitable emulsion, the selected particulate is then admixed, preferably at a mix rate of about 100 to 300 rpm, forming a simple, physical mixture. A water soluble salt is added until the emulsion collapses (due to increased ionic strength of the solution). Addition of the water soluble salt is preferably by adding a hot (21°C to 40°C) aqueous solution in which the salt is dissolved, preferably at a mix rate of 100 to 300 rpmin. Further additions of the salt solution may be used following collapse of the emulsion to adjust the final, inventive composition to desired solids ranges, and additional surfactant may be added if desired.
  • Suitable water soluble salts include: alkali metal carbonates, such as sodium carbonate; alkali metal halides, such as sodium chloride; alkaline earth halides, such as calcium chloride; alkali metal hypohalites, such as sodium hypochlorite and lithium hypochlorite; alkaline earth hypohalites, such as calcium hypochlorite; alkali metal sulfates, such as sodium sulfate; and alkaline earth and multivalent sulfate salts, such as magnesium and aluminum sulfate. Particularly preferred is sodium hypochlorite.
  • It has been found that the salt should be slowly added into the emulsion. Too rapid addition tends to precipitate polymer in a curd-like form.
  • The following experimental methods, materials and results are described for purposes of illustrating the present invention. However, other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.
  • Experimental
  • Cardipole LPO-25 (available from Bareco Co.) was utilized in preparing embodiments of the invention in which the polymer was an oxidized polyethylene. Cardipol was found to have a relatively low molecular weight, and samples with a range of saponification numbers 52-91 mg KOH/g and melting points 98-115°C were used.
  • Polyethylene-acrylic acid copolymers ("A―C"* polyethylenes available from Allied) were found to have higher molecular weights with acid numbers ranging 40-120 mg KOH/g and melting points 92-108°C. _
  • The water soluble salt was provided by a liquid hypochlorite bleach containing sodium hypochlorite, and the surfactants chosen were stable to hypochlorite. Aqueous solutions of sodium hypochlorite are inherently basic, as sodium hypochlorite is the salt of a weak acid (hypochlorous acid) and a strong base (sodium hydroxide). Since it is well known that hypochlorite ion is stabilized by basic solutions, conventional aqueous hypochlorite bleach usually incorporates small amounts of sodium hydroxide or sodium carbonate, which adjust the solution to a pH of 10.5 to 12.0. Aqueous hypochlorite bleaches can also include additional components and be of higher pH. However, it has been found that higher amounts of caustic, e.g., sodium hydroxide, will impart good chemical and physical stability to the compositions of the invention.
  • Examples I―VII illustrate suitable emulsions as precursors in making compositions in accordance with the present invention, and examples VIII through XVI illustrate preferred embodiments.
  • Example I
  • Into a 1 liter three-neck flask equipped with condensor and mechanical stirrer was placed 100 g Cardipol LPO-25, 83 g sodium lauryl sulfate (30% active solution) and 6.8 g NaOH for saponification and neutralization. The mixture was stirred and heated on an oil bath at 120°C until the polymer was melted and homogeneous. Boiling water was added in small portions (25 ml) with rapid stirring until there was a drop in viscosity. Additional hot water was added to bring the volume to 500 ml. The emulsion was allowed to cool to room temperature with stirring, filtered through a cheese cloth and stored.
  • Preferred ranges for the emulsion are:
    Figure imgb0005
  • Example II
  • Three compositions (with varying amount of an anionic surfactant) were prepared in a manner analogous to the preparation of Example I. Component weight percentages of the three emulsions were as follows:
    Figure imgb0006
  • Example III
  • Another three emulsion compositions were prepared having the component weight percentages as follows:
    Figure imgb0007
  • Example IV
  • Similarly, two compositions having different ranges of a surfactant were prepared with the emulsion components as follows.
    Figure imgb0008
  • Example V
  • In an analogous manner, another emulsion was prepared with lauric acid as surfactant and having the following weight percentages.
    Figure imgb0009
  • Example VI
  • Another emulsion (with a nonionic surfactant was prepared having the component weight percentages as follows.
    Figure imgb0010
  • In a manner similar to emulsification of oxidized polyethylenes (as in Example I), stable emulsions utilizing polyethylene-acrylic acid copolymers were prepared from neutralized A-C580 polymer with equivalents of NaOH (1.3 mgNaOH/g A-C580) added for neturalization. Examples VII and VIII characterize emulsions with neutralized polyethylene-acrylic acid copolymer and two different surfactants.
    Figure imgb0011
    Figure imgb0012
  • Example VIII Preparation of a Stable Suspension of Brightener in Chlorine Bleach Solution
  • An emulsion was first prepared as follows. To a flask equipped with a condenser and a paddle-blade stirrer was added 10 g. A-C 580 polymer (Allied Chemical Corp., Morristown, New Jersey), 0.5 g NaOH and 5.3 g Dowfax 2AI (sodium dodecyl diphenyloxide disulfonate, an anionic surfactant obtained from Dow Chemical Co., Midland, Michigan). The contents were then heated with an oil bath set at 120°C until, after about fifteen minutes, there was a viscous melt. Slowly and with continuous agitation, 84.2 g boiling water was added. The oil bath was then replaced with an ice bath and the emulsion was stirred until it cooled to room temperature. The emulsion was filtered through cheese cloth, bottled and stored.
  • To 0.2 g Tinopal CBS-X (a fluorescent whitening agent obtained from Ciba-Geigy Corporation in Greensboro, North Carolina; "Tinopal" is a registered trademark of Ciba-Geigy) dissolved in 6.0 g water was added 5.0 g of the above emulsion. In a separate beaker, 4.0 g of a 50 wt.% NaOH solution was mixed with 184.8 g of a liquid hypochlorite bleach solution (having a sodium hypochlorite concentration of about 5.25 wt.%). This bleach solution was then added slowly with agitation to the emulsion and brightener precipitate upon addition of the bleach leading to a stable yellow, opaque colloid. This resultant solution is thus a stable suspension of a fluorescent whitening agent in chlorine bleach.
  • Example IX Preparation of a Stable Suspension of Bluing Agents and Brightener in Chlorine Bleach Solution
  • An emulsion was prepared in the same manner as described in Example I, with 10.0 g A-C 580, 0.5 g NaOH and 4.4 g Dowfax 2AI and 85.1 g water.
  • Tinopal CBS-X (0.2 g was dissolved in 6.0 g water and 0.2 g ultramarine blue was added and dispersed in the solution with the aid of sonication. The emulsion, 17.0 g, was then mixed well with the ultramarine blue and CBS-X mixture, followed by the addition of 176.6 g of liquid hypochlorite bleach solution containing 0.5 wt.% NaOH. A stable light blue colloid was formed, indicating a stable suspension of both brightener and bluing agent in chlorine bleach.
  • Example X
  • Brightener may also be added during emulsification of the polymer resulting in an emulsion containing CBS-X. This emulsion can then be used in dispersing the ultramarine blue in liquid hypochlorite bleach solution.
  • The emulsion was prepared in the same manner as described in Example II with the exception that 1.3 g of CBS-X were added to the polymer melt before the addition of water.
  • The liquid hypochlorite bleach dispersion was then prepared in the same manner as described in Example II using the above emulsion with the exception of omitting the addition of 0.2 g of CBS-X.
  • As noted earlier, compositions prepared in accordance with the present invention may include alkaline earth or alkaline metal salts of brighteners. These salts may be prepared as follows.
  • Example XI
  • The calcium salt of CBS-X was prepared by adding 10 ml of 10 wt.% CaCI2 solution to 5 g CBS-X dissolved in 150 ml of water. The precipitate that was formed was filtered and dried.
  • Example XII
  • The zinc salt of CBS-X was prepared by adding 25 ml of a 5 wt.% ZnCI2 solution to 5 g CBS-X in 150 ml water. The precipitate was filtered and dried.
  • Example XIII
  • The magnesium salt of CBS-X was prepared by adding 11 ml of a 5 wt.% MgS04 solution to 5.0 g CBS-X in 150 ml water. The precipitate was filtered and dried.
  • Example XIV
  • The barium salt of CBS-X was prepared by adding 27 ml of a 5 wt.% BaCI2 solution to 3.0 g CBS-X in 100 ml water. The precipitate was filtered and dried.
  • Example XV
  • The aluminum salt of CBS-X was prepared by adding 14 ml of a 10 wt.% solution of Al2(SO4)3·18H2O solution to 2 g CBS-X in 75 ml H20. The precipitate was filtered and dried.
  • Example XVI
  • Testing of physical and chemical stability was done on a bleach composition containing both brightener and ultramarine blue. The composition was composed of the following: 0.1 wt.% ultramarine blue, 0.1 wt.% Tinopal CBS-X, 0.60 wt.% A-C 580 polymer, 0.12 wt.% Dowfax 2AI surfactant, 1.0 wt.% NaOH, 5.2 wt.% NaOCI, 4.1 wt.% NaCi,a nd 88.78 wt.% water.
  • The sample was physically stable for 9 weeks at 48.5°C (120°F). It was unstable, i.e. showed some signs of irreversible phase separation, when measured at 12 weeks at 48.5°C (120°F); Measurements were not made after 12 weeks. However, the composition was stable for 12 weeks at both 22°C (70°F) and 37.5°C (100°F). An approximation based on previous work estimates physical stability as between about 6 months and 1 year at 22°C (70°F).
  • Chemical stability was evaluated as follows. After twelve weeks of storage, the percentage of original sodium hypochlorite remaining in solution was measured at various temperatures. At 4°C (40°F), 98.0% was retained; at 22°C (70°F) 92.9%; at 37.5°C (100°F), 62.2%; and at 48.5°C (120°F) 23.9%. Thus, the composition shows substantial chemical stability at ordinary and even at slightly elevated temperatures.
  • Chemical stability was also evaluated in terms of fluorescence stability. After 12 weeks of storage, the percentage of the original intensity remaining was calculated: at 4°C (40°F) and at 22°C (70°F), 100% was retained; at 37.5°C (100°F), 64%; and at 48.5°C (120°F) 0%. Thus, fluorescence stability is also maintained at ordinary as well as at somewhat elevated temperatures.

Claims (22)

1. A bleaching and brightening composition comprising a hypochlorite bleach, a fluorescent whitening agent and a stabilizing agent characterized in that the composition comprises
an aqueous solution, said aqueous solution having from 0.1 wt.% to 15 wt.% of a hypochlorite salt dissolved therein;
a fluorescent whitening agent, said agent being in an amount of from 0.01 wt.% to 1.0 wt.% with respect to the aqueous solution; and
a polymer dispersed in the aqueous solution, said polymer forming a matrix in which fluorescent whitening agent is entrapped and stably suspended in the aqueous solution, the polymer being in an amount of from 0.015 wt.% to 11.0 wL% with respect of the aqueous solution, the polymer being a
modified polyethylene compound selected from the group consisting of oxidized polyethylenes having a molecular weight of from 400 to 3,000, polyethylene-acrylic acid copolymers having a molecular weight of below 10,000, and mixtures thereof.
2. A bleaching and brightening composition as claimed in claim 1 characterized in that when the mofified polyethylene compound is oxidized polyethylene this is saponified and neutralized and when the modified polyethylene compound is a polyethylene-acrylic acid copolymer, and it is neutralized and has a molecular weight of from 500 to 6,000.
3. A bleaching and brightening composition as claimed in claim 1 or claim 2 characterized in the oxidized polyethylene has an acid number from 30 to 120 and the polyethylene-acrylic acid copolymer has an acid number of from 25 to 160.
4. A bleaching and brightening composition as claimed in any of claims 1 to 3 characterized in that it further contains a nonionic or anionic surfactant.
5. A bleaching and brightening composition as claimed in claim 4 characterized in that the surfactant is present in an amount of from 0.01 wt.% to 6 wt.% with respect of said aqueous solution.
6. A bleaching and brightening composition as claimed in any of the preceding claims characterized in that it further includes a particulate pigment, said pigment being present in an amount of from 0.01 wt.% to 1.0 wt.% with respect to the aqueous solution, and preferably being ultramarine blue.
7. A bleaching and brightening composition as claimed in any of the claims 1 to 6 characterized in that it further comprises a caustic material in an amount of from 0.01 wt.% to 5.0 wt.%.
8. A bleaching and brightening composition as claimed in any of claims 1 to 6 characterized in that said aqueous solution has a pH of at least about 11.
9. A composition as claimed in any of the preceding claims characterized in that the fluorescent whitening agent is selected from the group consisting of distyrylbiphenyl derivatives, stilbene derivatives, the alkali metal salts thereof, the multivalent salts thereof, and mixtures thereof.
10. A liquid composition as claimed in claim 9 characterized in that the flurescent whitening agent is at least one multivalent salt of a distyrylbiphenyl derivative, said salt selected from the group consisting of alkaline earth, zinc, Group IIA metal salts and mixtures thereof.
11. A liquid bleaching and brightening composition according to claim 1 comprising:
an aqueous solution having sodium hypochlorite in an amount of from 3.5 wt.% to 6.2 wt.%, an anionic or nonionic surfactant in amount of from 0.03 wt.% to 0.3 wt.%, a polymer which is a modified polyethylene compound selected from the group consisting of oxidized polyethylenes having a molecular weight of from 400 to 3,000, polyethylene-acrylic acid copolymers having a molecular weight of below 10,000 and mixtures thereof so that it forms a matrix in the aqueous solution and in an amount of from 0.3 wt.% to 2.0 wt.% and a fluorescent whitening agent in an amount of from 0.01 wt.% to 0.2 wt.%, the fluoorescent whitening agent being stably suspended and dispersed in the aqueous solution via the polymer.
12. A composition as claimed in claim 11 characterized in that it further includes ultramarine blue particles in an amount of from 0.01 wt.% to 0.2 wt.% with respect of said aqueous solution.
13. A composition as claimed in claim 12 characterized in that the amount of said fluorescent whitening agent is approximately 0.1 wt.% and the amount of the ultramarine blue particles is approximately 0.05 wt.%.
14. A process for the preparation of a liquid composition, useful for bleaching and brightening fabric, which comprises:
admixing a quantity of a molten polymer selected from the group consisting of oxidized polyethylene having a molecular weight of from 400 to 3,000, polyethylene-acrylic acid copolymer having a molecular weight of below 10,000; and mixtures thereof; with sufficient base to saponify and neutralize said oxidized polyethylene or to neutralize said polyethylene-acrylic acid copolymer;
contacting said molten polymer in the presence of a anionic or a nonionic surfactant with sufficient of an aqueous solution to form an emulsion;
dispersing a quantity of fluorescent whitening agent in said emulsion, said agent being in a weight ratio with respect to the emulsified polymer of from 1:1.5 to 1:3; and,
slowly adding a water soluble salt which includes a hypochlorite salt to the dispersed fluorescent whitening agent and emulsified polymer at least until the emulsion collapses, wherein the polymer forms a matrix in which particles of the fluorescent whitening agent are entrapped.
15. A process as claimed in claim 14 characterized in that the ratio of said fluorescent whitening agent to said emulsified polymer is approximately 1:2.5.
16. A process as claimed in claim 14 or claim 15 characterized in that the dispersing step further includes dispersing a quantity of particulate pigment in said emulsion, said pigment being in a weight ratio with respect of the emulsified polymer of from 1:2 to 1:8.
17. A process as claimed in claim 16 characterized in that the particulate pigment includes ultramarine blue.
18. A process as claimed in any of claims 14 to 17 characterized in that the water soluble salt is selected from the group consisting essentially of: alkali metal carbonates; alkali metal; alkaline earth and multivalent sulfates; alkali metal and alkaline earth halides; alkali metal and alkaline earth hypohalites; and mixtures thereof.
19. A process as claimed in any of claims 14 to 18 characterized in that the water soluble salt includes sodium hypochlorite in an aqueous solvent.
20. A process as claimed in any of claims 14 to 19 characterized in that the fluorescent whitening agent is selected from the group consisting of distyrylbiphenyl derivatives, stilbene derivatives, the alkali metal salts thereof, the multivalent salts thereof, and mixtures thereof.
21. A process as claimed in claim 20 characterized in that the fluorescent whitening agent is at least one multivalent salt of distryrylbiphenyl derivative, said salt selected from the group consisting of alkaline earth, zinc, Group IIIA metal salts and mixtures thereof.
22. A method according to claim 14 wherein sodium hypochlorite dissolved in an aqueous solution is slowly added to the dispersed fluorescent whitening agent and emulsified polymer until the emulsion collapses, wherein the polymer forms a matrix in which particles of the fluorescent whitening agent are entrapped.
EP19860304625 1984-01-27 1986-06-16 Bleaching and brightening composition and method Expired EP0206718B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86304625T ATE55408T1 (en) 1985-06-24 1986-06-16 BLEACHING AND OPTICAL BRIGHTENING PROCESS AND COMPOSITION.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US57456584A 1984-01-27 1984-01-27
US74830685A 1985-06-24 1985-06-24
US748306 1996-11-13

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EP0206718A2 EP0206718A2 (en) 1986-12-30
EP0206718A3 EP0206718A3 (en) 1987-04-01
EP0206718B1 true EP0206718B1 (en) 1990-08-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6991747B2 (en) 1999-10-19 2006-01-31 Procter & Gamble Company Radical scavenger

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK690187A (en) * 1986-12-31 1988-07-01 Albright & Wilson PROTECTED SYSTEM SUITABLE FOR USE IN CLEANING AGENTS AND PRODUCTS CONTAINING THE SYSTEM
US4714562A (en) * 1987-03-06 1987-12-22 The Procter & Gamble Company Automatic dishwasher detergent composition
US5227366A (en) * 1987-08-07 1993-07-13 The Clorox Company Mitigation of stress-cracking in fragranced bleach-containing bottles
US5080826A (en) * 1987-08-07 1992-01-14 The Clorox Company Stable fragranced bleaching composition
US4863633A (en) * 1987-08-07 1989-09-05 The Clorox Company Mitigation of stress-cracking in stacked loads of fragranced bleach-containing bottles
GB8816443D0 (en) * 1988-07-11 1988-08-17 Albright & Wilson Liquid enzymatic detergents
ES2007221A6 (en) * 1988-05-05 1989-06-01 Henkel Iberica Bleaching composition containing alkaline hypochlorite and process for its manufacture.
US4946619A (en) * 1988-07-19 1990-08-07 The Clorox Company Solubilization of brighter in liquid hypochlorite
MX173174B (en) * 1989-11-06 1994-02-04 Bio Lab Inc N-HALOGEN COMPOSITIONS WITH STABLE BLUE PIGMENT
EP0663438A1 (en) * 1994-01-13 1995-07-19 The Procter & Gamble Company Use of polymers in liquid detergent compositions containing brighteners for preventing fabric spotting
EP0905224A1 (en) * 1997-09-19 1999-03-31 The Procter & Gamble Company Bleaching compositions
US6566320B1 (en) 1999-10-19 2003-05-20 The Procter & Gamble Company Bleaching composition containing chromotropic compound
DE10029697A1 (en) * 2000-06-16 2001-12-20 Basf Ag Binding composition, useful e.g. in paints and inks, or for pigmentation, comprises radical-polymerized block copolymer and non-magnetic filler
WO2002079327A1 (en) 2001-03-30 2002-10-10 Council Of Scientific And Industrial Research A natural fluorescent dye obtained from a marine invertebrate, compositions containing the said dye and their uses
US6689391B2 (en) 2001-03-30 2004-02-10 Council Of Scientific & Industrial Research Natural non-polar fluorescent dye from a non-bioluminescent marine invertebrate, compositions containing the said dye and its uses
US6916492B2 (en) 2001-03-30 2005-07-12 Council Of Scientific & Industrial Research Natural nontoxic multicolor fluorescent protein dye from a marine invertebrate, compositions containing the said dye and its uses
US6956122B2 (en) 2001-09-05 2005-10-18 Council Of Scientific & Industrial Research Multiple fluorescent natural dye compound from a marine organism
US7214652B1 (en) 2005-12-30 2007-05-08 3M Innovative Properties Company Anionic surfactant-containing hypochlorite bleach composition and methods of making and use
PT1865051T (en) * 2006-06-08 2019-06-12 Procter & Gamble Bleaching compositions
CN104232359A (en) * 2014-09-28 2014-12-24 山西青山化工有限公司 Stilbene bistriazine liquid whitening agent and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3393153A (en) * 1965-12-20 1968-07-16 Procter & Gamble Novel liquid bleaching compositions
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
US4457855A (en) * 1981-06-08 1984-07-03 The Clorox Company Stable hypochlorite solution suspendable dyes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6991747B2 (en) 1999-10-19 2006-01-31 Procter & Gamble Company Radical scavenger

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EP0206718A2 (en) 1986-12-30

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