GB2213161A - Vividly colored laundry or cleaning products - Google Patents

Abstract

Daylight fluorescent pigments or dyes are included in cleaning or laundry compositions to achieve a vividly colored product.

Description

VIVIDLY COLORED LAUNDRY OR CLEANING PRODUCTS TECHNICAL FIELD AND BACKGROUND ART The present invention relates to laundry or cleaning compositions which exhibit daylight fluorescent coloring.

Colored laundry or cleaning products and processes for producing them are well-known, including those described in U.S.

Patent 3,544,473 to Kitchen et al. (Dec. 21, 1970), U.S. Patent 3,630,923 to Simmons et al. (Dec. 28, 1971), U.S. Patent 3,931,037 to Hall (Jan. 6, 1976), U.S. Patent 4,097,418 to Rolfes (Jan. 27, 1978), U.S. Patent 4,162,228 to Robles (July 24, 1979), U.S. Patent 4,427,417 to Porasik (Jan. 24, 1984), and European Patent Application 0138410 to Davies et al., published Apr. 24, 1985. In the paint, plastics, inks and coating composition industries, the use of daylight fluorescent pigments is also known. However, until the present invention, the use of daylight fluorescent pigments to produce vividly colored compositions useful in or as laundry or cleaning products was unknown.

Fluorescent whitening and brightening agents are well known in the laundry detergent industry. Fluorescent whiteners and brighteners typically do not add noticeable coloration to the product. Instead, they help produce a whiter or brighter looking product. In addition to the lack of coloration they impart to the product, fluorescent whiteners and brighteners are highly substantive on fabrics and are highly soluble in the wash water.

They are designed to solubilize into the wash water and deposit onto the fabrics being washed, whereby they tend to brighten the fabric in much the same way they brighten the laundry product.

When fluorescent whiteners or brighteners are included in a colored laundry product, the whitener or brightener can impart some enhancement to the coloration of the product, though generally the effect is minimal. In any event, fluorescent whiteners and brighteners do not add vivid coloring to the product.

Laundry or cleaning products which contain only common, non-fluorescent pigments do not have the vivid brilliance or glow associated with daylight fluorescent pigments. Laundry or cleaning products that contain common pigments in combination with fluorescent whiteners or brighteners may show some enhanced coloring effects and have brighter common colors. However, the effect is minimal and the fluorescent whitening or brightening agent itself imparts little or no actual color to the laundry or cleaning product.

SUMMARY OF THE INVENTION The present invention relates to laundry or cleaning compositions which exhibit vivid daylight fluorescent coloring.

The compositions comprise from about 0.0018 to about 2% by weight of a daylight fluorescent pigment.

The compositions herein can be laundry detergents, bleaches, laundry additives, fabric softeners, rinse aids, hard surface cleaners, dishwashing products, and, in general, any laundry or cleaning product for which a vivid coloration is desired. Preferably the compositions are laundry detergent compositions. The compositions herein can also be in any physical torm. Although granular compositions are preferred, gelled, paste and liquid products, particularly with suspended solids, can also benefit from the addition of the fluorescent pigments of this invention.

Cleaning or laundry products containing these compositions can be completely colored, multi-colored, white or light colored base products with vividly colored interspersed granules or speckles, or vividly colored base products with white or light colored interspersed granules or speckles. It has been discovered that daylight fluorescent pigments alone, or in combination with certain maximum amounts of common pigments, will produce the desired vivid fluorescent coloration. In a laundry composition, they will have low potential for fabric staining at the levels described below, and will be of low solubility in the wash water.

DETAILED DESCRIPTION OF THE ll4VENTlON The term "dyestuffs", as used herein, applies to any organic or inorganic substance that exhibits strong absorption of light in either the visible or ultraviolet regions of the spectrum, whether or not reemission occurs.

Thus, dyestuffs include common dyes, i.e. those substances which absorb most wavelengths, reflect some visible wavelengths to produce a color, and dissipate the absorbed energy as heat.

Dyestuffs also include fluorescent whiteners and brighteners, i.e. substances which absorb ultraviolet light or short wavelength blue or violet light, and reemit some of the absorbed energy as a barely noticeable, faint blue or blue-violet visible light. Fluorescent whiteners and brighteners add little or no color to laundry or cleaning compositions. In laundry compositions, they deposit onto the fabric and mask any undesirable yellowish tint, thereby producing a whiter looking fabric. Fluorescent whiteners and brighteners are used in such laundry compositions at levels from about 0.018 to about 0.75% by weight of the total compo sition.

Dyestuffs also include daylight fluorescent dyestuffs, i.e.

those substances that exhibit vivid, brilliant colors due to reflectance in the visible region, absorption of some visible or ultraviolet light, and reemission of some of the absorbed energy as visible light. The daylight fluorescent dyestuffs of concern to this invention exhibit bright visible coloration, and thus impart vivid coloring to the laundry or cleaning product itself. Of particular interest to the present invention are those daylight fluorescent dyestuffs which have been matrixed with a resinous binder to form a fluorescent pigment which has a low potential for fabric staining at the levels described below and low wash water solubility.

The term "pigment", as used herein, means the combination of dyestuff, whether fluorescent or common, and any binders, resins, or compositional matrices containing the dyestuff.

Fluorescent whiteners and brighteners differ from daylight fluorescent dyestuffs for purposes of this invention in several key ways. First, whiteners and brighteners impart little or no visible color to the laundry or cleaning product. Instead, they function to add faint blue or blue-violet hues to an otherwise dull, yellow-white material. The addition of the bluish tone does not cause the material to appear blue, nor does it cause the product to appear "fluorescent". Rather, the blue tone masks the dull tints by adding the missing or weak colors which the material has absorbed from the visible spectrum, thus causing the viewer to perceive the full spectrum of visible light, i.e. an optically complete white color.Second, whiteners and brighteners are highly cloth substantive, that is, they are designed to deposit onto the fabrics being washed or conditioned and impart the same faint tint to the fabric. Third, whiteners and brighteners are highly soluble in the wash water, enabling them to deposit easily onto the fabrics. Fourth, mechanistically, whiteners and brighteners generally absorb in the short wavelength ultraviolet and visible blue regions of the spectrum and reemit very faint blue or blue-violet visible light.

Daylight fluorescent dyestuffs, on the other hand, impart strong degrees of visible coloration to the cleaning or laundry product. The color imparted differs from a common dye in that it consists of both reflected and reemitted visible light whereas the color due to a common dye consists only of reflected light. The combination of the reflected and reemitted light produces the characteristic "glow" of fluorescent materials.

Pigments containing daylight fluorescent dyestuffs of interest to this invention are at best only slightly soluble in the wash water. This ensures that the dyestuff does not cause staining or dyeing of laundered fabrics. Daylight fluorescent dyestuffs absorb energy in either the ultraviolet or visible regions of the spectrum, but reemit large amounts of visible light that can range from one end of the visible spectrum to the other. The selection of the correct daylight fluorescent pigment depends on the product color desired.

The fluorescent effect of synthetic dyes is explained in general in Venkataraman, K., ed., The Analytical Chemistry of Synthetic Dyes, N.Y., John Wiley s Sons, 1977, p. 165, TP 910.V46, as the phenomenon of immediate reemission of radiant energy after absorption by a material.According to Adams, D.A.W. "Optical Whitening Agents" in: Gore, T.S., Joshi, B.S., Sunthankar, S.V., and Tilak, B.D., ed., Recent Progress in the Chemistry of Natural and Synthetic Colouring Matters and Related Fields, N.Y., Academic Press, 1962, p. 615-620, Library of Congress Catalog Card Number: 62-13130, on page 617, "(s)ome general rules can be laid down regarding the molecular requirements to give high fluorescent activity: (i) the molecule must contain a system of conjugated double bonds, (ii) it must be essentially planar, (iii) it should contain electron-donating groups (OH,NH2, etc.) and be free of electron-accepting groups (NO2,-N: N-, etc.)." Daylight fluorescent pigments useful herein are also described in Ward, R.A. and Kimmel, E.L. "Luminescent Materials (Fluorescent Daylight)", in:Encyclopedia of Chemical Technology (1981 ed.), vol. 14, pp. 546-569, Ref. TP9.E685, which is incorporated herein by reference. According to this article, daylight fluorescent pigments "require no artificially generated energy. Daylight, or an equivalent white light, can excite these unique materials not only to reflect colored light selectively, but to give off an extra glow of fluorescent light, often with high efficiency and surprising brilliance." The colorful daylight fluorescent dyestuffs are generally contained in colorless binders, resins, or matrices. It is preferred, although not necessary, for the dyestuff to be in a resinous matrix. The resin/dyestuff combinations tend to have the desired qualities of low solubility in water, low fabric substantivity, and a high degree of visible daylight fluorescence.

Thus, such pigments are particularly well-suited to laundry products because they will not cause staining of fabrics.

Commercially available daylight fluorescent pigments that have been used for paints, coatings, inks, and as colorants in molded and extruded plastics, can be used in the present invention.

Commercially available daylight fluorescent pigments can be obtained from Day-Glo Color Corporation, Cleveland, Ohio, USA and Radiant Color Company, a division of Magruder Color Company, as well as several other producers.

The methods of producing such pigments are not critical to this invention. In fact, methods of preparing resinous pigments containing fluorescent dyestuffs for uses in paints, plastics, and inks are well-known to those skilled in the art. For example, daylight fluorescent pigments can be prepared by dissolving the daylight fluorescent dyestuff in a solution of molten butanol-modified urea-formaldehyde resin, heating the solution, gelling the solution through the addition of acid, and thermosetting the resin mass with heat. Upon thermosetting, the resin mass can be hammermilled, ballmilled, or ground to the required particle size pigment. See U.S. Patent 2,498,592, Switzer et al. (1950), which patent is hereby incorporated by reference.

In addition to thermosetting resins, thermoplastic resins are also available. See U.S. Patent 2,938,873, Kazenas (1960), which patent is hereby incorporated by reference. A mixture of o- and p-toluenesulfonamide, paraformaldehyde, and a 13-stage-unmodified melamine-formaldehyde resin are heated at about 170 degrees Centigrade for about 15 minutes. The daylight fluorescent dyestuff is added and heating is continued. Upon cooling, the completely condensed resin solidifies into a clear, brittle, colored resin. The resin can be impact milled to the proper particle size pigment.

For safety reasons, it is desirable to formulate the pigments so that hazardous or toxic substances (such as free formaldehyde) are effectively dealt with according to the applicable laws and regulations concerning their use.

Preferred daylight fluorescent pigments herein provide at least about a 10%, preferably at least about a 15%, more preferably at least about a 20%, increase in intensity of fluorescence (as measured hereinafter) when included in a cleaning or laundry composition herein, at a level of from about 0.001% to about 2%, preferably from about 0.05% to about 1%, more preferably from about 0.10E to about 0.25%, by weight of the composition, versus the corresponding common pigment in the same composition. The fluorescence of pigmented compositions herein is measured using the following equipment:Aminco-Bowan spectrophotofluorometer Model No. 4-8202; American Instrument Co. ratio photometer Model No. D68-70034; Houston Instrument aphic 2000 chart recorder; and Beckman quartz cuvette (1.875" x 0.5" x 0.5"). In addition, the intensity of fluorescence is measured at ambient relative humidity, with cell slits for No.

2-5 of 0.5:0.5:0.5:0.5 (slits 1 and 6 are not used), a Y range of 0.5-1 ratio mode, and an X range of 10-20 ratio mode-.

Finely divided particulate pigments are preferred for use in granular compositions of this invention and should have ultimate particle sizes of from about 0.1 to about 50 microns, preferably from about 1 to about 10 microns. If the fluorescent dyestuff is contained in a resinous matrix, the pigment should contain from about 0.2% to about 10% daylight fluorescent dyestuff, preferably from about 0.5% to about 5% daylight fluorescent dyestuff.

Concentrations of fluorescent dyestuff in the resin matrix above these percentages can lead to a phenomenon called "concentration quenching", which results in an excessive dulling effect on the fluorescence of the dyestuff.

The compositions useful herein can contain from about 0.001% to about 2.0% of common pigments, either as separate pigments, or as integral components of the fluorescent pigments of approximately the same particle size, in a weight ratio of fluorescent pigment to common pigment of from about 1:1 to about 1000:1, preferably from about 10:1 to about 50:1. If separate, the common pigments should have ultimate particle sizes in the same ranges as the fluorescent pigments. Common pigments generally consist of colorless binders, resins, or matrices which contain the common dyestuffs. Particularly well-suited common pigments include, but are not limited to, the following (referred to by the Food and Drug Administration official name with the Color Index, 1971, given thereafter in parenthesis): Titanium Dioxide (C. 1. 77891) FD & Blue No. 2 Aluminum Lake (C.l. 73015) FD & Red No. 2 Aluminum Lake (C.I. 16185:1) FD & Red No. 3 Aluminum Lake (C.I. 45430:1) FD & Yellow No. 5 Aluminum Lake (C.I. 19140:1) FD & Yellow No. 6 Aluminum Lake (C.l. 15985::1) Alumina (C.l. 77002) Calcium Carbonate (C.l. 77220) Ultramarine Blue (C.l. 77007) Ultramarine Green (C.I. 77013) Ultramarine Red (C.I. 77007) Ultramarine Violet (C.l. 77007) Talc (C.l. 77019) Tin Oxide (C. I. 77861), and FD & Blue No. 6 (C.l. 73000).

However, the daylight fluorescent pigments are preferably not used in combination with the common pigments.

Any standard method of adding the pigments to the product is acceptable. It is preferred that, before adding the pigments to the preferred granular products l1erein, the pigments are mixed with a diluent to produce a premix.

Suitable non-agglomerating granular diluents include: sodium, potassium, lithium, magnesium, and/or calcium, sulfates, carbonates, fluorides, borates, orthophospllates, pyrophosphates, tripolyphosphates, and mixtures thereof. Sodium sulfate and sodium carbonate are especially preferred. Sodium sulfate is more effective at breaking up lumps titan sodium carbonate and colors faster.

The diluent should have a particle size of from about 10 microns to about 600 microns, preferably from about 10 microns to about 100 microns, be relatively nonhygroscopic, have essentially no tendency to agglomerate, and, preferably, be compatible with the end product.

Weight ratios of pigment to diluent of from about 1:1 to about 1:1000, preferably from about 1:2 to about 1:100, more preferably from about 1:3 to about 1:50, most preferably from about 1:5 to about 1:20, can be used.

Any granular, non-agglomerating material can be used as a diluent. However, the diluent should be compatible with the end product and preferably will be desirable in the end product.

When more diluent is used, more time is required to form the premix, but high energy mixers can be used to shorten the time it takes to break up the visible agglomerates.

Particularly preferred procedures and materials for preparing the premix are disclosed in U.S. Patent 4,671,886 to Mueller (June 9, 1987), which patent is hereby incorporated by reference. Once formed, the premix is added to the remainder of the product composition.

In formulating a vividly colored laundry or cleaning product, the end product can contain from about 1% to about 95% by weight of a detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. The surfactant preferably represents from about 5% to about 60%, more preferably from about 10% to about 50%, by weight of the composition. Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. Halo. 3,919,678, Laughlin, et al, issued Dec. 30, 1975, both incorporated herein by reference. Useful cationic surfactants also include those described in U.S. Pat. No.

4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. No.

4,239,659, Murphy, issued Dec. 16, 1980, both incorporated herein by reference.

II Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and substituted ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal1 ammonium and substituted ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat.Nos. 2,220,099 and 2,477,383, both of which are incorporated herein by reference. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13LAS.

Other anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates, containing from about 1 to about 10 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and sodium or potassium salts of alkyl ethylene oxide ether sulfates, containing from about 1 to about 10 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.

Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a watersoluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.

Preferred nonionic surfactants are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.

Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.

Semi-polar nonionic surfactants useful herein include watersoluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.

Ampholytic surfactants include aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to about 18 carbon atoms.

Cationic surfactants can also be included in laundry compositions of the present invention. Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.

Cationic surfactants are often used in detergent compositions to provide fabric softening andlor antistatic benefits. Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976, which is incorporated herein by reference. Such materials will normally be present in an amount from about 1% to about 10% by weight of the detergent composition.

Particularly preferred surfactants herein are anionic surfactants selected from the group consisting of the alkali metal salts of C 11-13 alkylbenzene sulfonates, C14-18 alkyl sulfates, C14-l alky linear polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.

The compositions of the present invention can also contain from 0% to about 75%, preferably from about 5% to about 60%, and more preferably from about 10% to about 50%, by weight of one or more water-soluble neutral or alkaline salts. Neutral or alkaline salts have a pH in solution of about seven or greater, and can be either organic or inorganic in nature. While some of the salts are inert, many of them also function as detergency builder materials in solution. Preferably, the salts are inorganic.

Examples of neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides and sulfates.

The alkali metal, and especially sodium, salts of the above are preferred. Sodium sulfate and sodium carbonate are typically found in detergent granules and are preferred salts herein.

The water-soluble salts herein preferably include the compounds commonly known as detergent builder materials. Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above.

The compositions of the instant invention may contain a detergent builder in an amount from about 5% to about 85% by weight, preferably from about 10% to about 608 by weight, and most preferably from about 158 to about 40% by weight of the entire composition.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3, 422,137; 3,400,176; and 3,400,148, incorporated herein by reference.

Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.

Water-soluble, non phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxy!ates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Salts of nitrilotriacetic acid, such as sodium nitrilotriacetate, are particularly preferred.

Polymeric polycarboxylate builders are set forth in U.S.

Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexaca rboxy late, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution and converted to the corresponding salt. Preferred polycarboxylate builders herein are described in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, incorporated herein by reference.

The neutral or alkaline salt of the present invention is preferably selected from alkali metal polyphosphates, poiycarboxylates, carbonates, silicates, sulfates, and mixtures thereof.

An optional builder herein is a water-insoluble crystalline or amorphous aluminosilicate ion exchange material. The preferred crystalline material useful herein is of the formula Naz l O2)(SiO2)yixH2O wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.5 and x is from about 10 to about 264.

Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M ( (zAlO 2,ySi02) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of Cacao3 hardness per gram of anhydrous aluminosilicate. Such aluminosilicate materials are described in more detail in the above incorporated U.S. Patent 4,663,071, Bush et al.

Other ingredients commonly used in laundry or cleaning products can be included in the compositions of the present invention. These include auxiliary detergent surfactant and builder materials, bleaching agents and bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, fillers, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. Bleaching agents and activators are described in U,S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference.

The following ingredients are preferably Included in granular detergent compositions of the present invention: a. Detergency builder in an amount from about 5% to about 85% by weight, preferably from about 15% to about 60% by weight, and most preferably from about 20% to about 40% by weight of the detergent composition; b. Percarboxylic acid bleaching agents or bleaching compositions containing peroxygen bleaches capable of yielding hydrogen peroxide in an aqueous solution and bleach activators, in an amount from about 1% to about 20%, and preferably from about 1% to about 10% by weight of the detergent composition; c. Enzyme in an amount from about 0.1% to about 1.0% by weight of the detergent composition; d.Smectite clay in an amount from about 4% to about 15% by weight of the detergent composition, selected from the group consisting of sodium hectorite, potassium hectorite, lithium hectorite, magnesium hectorite, calcium hectorite, sodium montmorillonite, potassium montmorillonite, magnesium montmorillonite, calcium montmori Ilonite, sodium saponite, potassium saponite, lithium saponite, magnesium saponite, calcium saponite, and mixtures thereof; and/or e. Fabric softener andlor antistatic agent in an amount from about 1% to about 10% by weight of the detergent composition.

These are in addition to the two ingredients previously described for use in the composition of the present invention: surfactant and daylight fluorescent pigment.

The level of total pigment in the laundry or cleaning composition of the present invention can range from about 0.001% to about 2.0%, preferably from about 0.05% to about 1.0%, most preferably from about 0.10% to about 0.25%. If the common pigments are added as separate finely divided pigments, the weight ratio of common pigments to daylight fluorescent pigments in the composition should be from about 1:1 to about 1:1000, preferably from about 1:10 to about 1:50. If added as an integral component of a fluorescent pigment, the fluorescent pigment should contain a weight ratio of common dyestuff to daylight fluorescent dyestuff of from about 1:1 to about 1:1000, preferably from about 1:10 to about 1:50.

For the preferred laundry detergent compositions of the invention, typical laundry wash water solutions comprise from about 0.1% to about 2% by weight of the composition. Fabrics to be laundered are agitated in these solutions to effect cleaning, stain removal, and optional fabric care benefits. The pH of a 0.18 by weight aqueous solution of this composition will be in the range of from about 7.0 to about 11.0, preferably from about 8.0 to about 11.0, and most preferably from about 9.0 to about 10.5.

The following nonlimiting examples illustrate the compositions of the present invention.

All parts, percentages and ratios herein are by weight unless otherwise specified.

EXAMPLE I A granular laundry detergent composition of the present invention is as follows.

Ingredient Weight Percent 1. Spray-dried detergent base granules: Sodium C13 linear alkylbenzene sulfonate 12.6 Sodium tripolyphosphate 25.5 Sodium silicate (1.6 ratio) 5.0 Brightener 0.049 Real soap 1.1 Water 5.9 Sodium sulfate 27.56 2. Spray on base granules: Perfume 0.24 C 12 13 alcohol polyethoxylate (6.5)* 0.3 3. Admix with base granules: Sodium carbonate 10.5 Distearyl dimethylammonium chloride 3.2 Smectite clay 5.2 Enzyme-Savinase (Novo) 0.7 Dextrin 0.26 4. Mix finished detergent with: Blue daylight fluorescent pigment 0.09 Sodium sulfate 1.8 *Alcohol and monoethoxylated alcohol removed.

The above granular detergent composition is made as follows.

Spray-dried detergent base granules are formed by adding the above-named ingredients in step 1 to a crutcher, mixing, and then spray-drying by conventional methods. The perfume and nonionic surfactant of step 2 are then sprayed onto the detergent base granules. This product is admixed with the above-named ingredients in step 3 to form a finished detergent composition.

Blue daylight fluorescent pigment (0.09% of the total composition) is premixed with sodium sulfate (1.89w of the total composition) in a 20:1 pigment: diluent ratio. This blend is mixed in step 4 in a rotating drum with the finished detergent composition to form a vividly colored blue product.

Fluorescence and intensity are measured as previously described and as follows.

Settings: Excitation Frequency 350 nm.

Meter (coarse) 10 Meter (fine) 50 The above composition has a peak fluorescence of 433 nanometers (nm.).

The blue daylight fluorescent pigment has about a 28% higher intensity level than blue common pigment substituted in the same composition.

EXAMPLE I I A granular laundry detergent composition of the present invention is as follows.

Ingredient Weight Percent 1. Spray-dried detergent base granules: Sodium C13 linear alkylbenzene sulfonate 8.75 Sodium C14-15 alkyl sulfate 8.75 Sodium tripolyphosphate 27.1 Sodium silicate (1.6 ratio) 5.8 Real soap 0.1 Water 3.0 Brightener 0.15 Sodium polyacrylate (MW 4500) 1.2 Polyethylene glycol 0.5 Sodium sulfate 25.8 2. Spray on base granules: Perfume 0.16 C12- 13 a alcohol polyethoxylate (6.5)* 0.5 3. Admix with base granules: Sodium carbonate 15.8 Enzyme s carrier 0.5 4. Mix finished detergent with: Blue daylight fluorescent pigment 0.09 Sodium sulfate 1.8 *Alcohol and monoethoxylated alcohol removed.

The above granular detergent composition is made as described in Example I except that the above-named ingredients are used. The final product is a vivid blue color.

Fluorescence and intensity are measured as previously described and as follows.

Settings: Excitation Frequency 365 nm.

Meter (coarse) 30 Meter (fine) 66 The above composition has a peak fluorescence of 442 nm.

(wavelength).

The blue daylight fluorescent pigment has about a 32% higher intensity level than blue common pigment substituted in the same composition.

EXAMPLE Ill A granular laundry detergent composition of the present invention is as follows.

Ingredient Weight Percent 1. Spray-dried detergent base granules: Sodium C13 linear alkylbenzene sulfonate 3.84 Sodium C14-15 alkyl sulfate 6.08 Sodium C14 15 ethoxy (2.25) sulfate 6.08 Sodium tripolyphosphate 34.5 Sodium silicate (1.6 ratio) 5.6 Real soap 0.1 Brightener 0.22 Carboxymethylcellulose 0.6 Polyethylene glycol (MW 8000) 0.5 Water 9.1 Sodium sulfate 13.29 2. Spray on base granules: Perfume 0.14 C 12-13 alcohol polyethoxylate (6.5)* 0.25 3. Admix with base granules: Sodium carbonate 11.4 Sodium perborate tetrahydrate 3.5 4. Mix finished detergent with: Green daylight fluorescent pigment 0.24 Sodium sulfate 4.56 *Alcohol and monoethoxylated alcohol removed.

The above granular detergent composition is made as described in Example I except that the above-named ingredients are used. The final product is a vivid green color.

Fluorescence and intensity are measured as previously described and as follows.

Settings: Excitation Frequency 395 nm.

Meter (coarse) 30 Meter (fine) 89 The above composition has a peak fluorescence of 503 nm.

(wavelength).

The green daylight fluorescent pigment has about a 38% higher intensity level than green common pigment substituted in the same composition.

EXAMPLE IV A granular laundry detergent composition of the present invention is as follows.

Ingredient Weight Percent 1. Spray-dried detergent base granules: Sodium C13 linear alkylbenzene sulfonate 4.1 Sodium C14-15 alkyl sulfate 6.4 Sodium C14 15 ethoxy (2.25) sulfate 6.4 Sodium tripolyphosphate 26.1 Sodium silicate (1.6 ratio) 8.8 Brightener 0.14 Carboxymethylcellulose 0.27 Water 6.5 Sodium sulfate 37.68 2. Spray on base granules: Perfume 0.56 C12- 13 a alcohol polyethoxylate (6.5)* 0.25 3. Mix finished detergent with: Green daylight fluorescent pigment .07 Yellow daylight fluorescent pigment .07 Sodium sulfate 2,66 *Alcohol and monoethoxylated alcohol removed.

The above granular detergent composition is made as described in Example I except that the above-named ingredients are used. The final product is a vividly colored yellow-green granular composition which is an excellent laundry detergent.

Fluorescence and intensity are measured as previously described and as follows.

Settings: Excitation Frequency 395 nm.

Meter (coarse) 30 Meter (fine) 80 The above composition has a peak fluorescence of 495 nm.

(wavelength).

This yellow-green daylight fluorescent pigment has about a 23% higher intensity level than yellowish green common pigment substituted in the same composition.

EXAMPLE V A granular laundry detergent composition of the present invention is as follows.

Ingredient Weight Percent 1. Spray-dried detergent base granules: Sodium C13 linear alkyl benzene sulfonate 17.5 Sodium aluminosilicate (Zeolite A, avg. dia.

3 microns) 18.3 Sodium silicate (1.6 ratio) 2.1 Brightener .05 Real soap 1.1 Water 6.4 Sodium polyacrylate (MW 4500) 3.2 Sodium sulfate 23.42 Blue daylight fluorescent pigment .09 2. Spray on base granules: Perfume .24 C12~13 alcohol polyethoxylate (6.5)* .3 3. Admix with base granules: Sodium carbonate 15.9 Distearyl dimethylammonium chloride 4.0 Smectite clay 6.4 Enzyme-Savinase (Novo) .74 Dextrin .26 *Alcohol and monoethoxylated alcohol removed.

The above granular detergent composition is made as described in Example I except that the above-named Ingredients are used and the daylight fluorescent pigment of Example I is incorporated into the spray-dried detergent base granules. The final product contains white detergent granules mixed with pigmented (daylight fluorescent) detergent granules which are vivid blue speckles. This laundry detergent exhibits excellent cleaning performance.

EXAMPLE VI The phenomenon of "concentration quenching" is illustrated by the following example. Four granular laundry detergent compositions are made according to Example II above except that different levels of blue daylight fluorescent pigment are substituted in each formulation. An identical granular detergent composition is made which contains blue common pigment rather than blue daylight fluorescent pigment.

Fluorescence and intensity of the compositions are measured as previously described and as follows.

Settings: Excitation Frequency 365 nm.

Meter (coarse) 30 Meter (fine) 68 Fluorescence: Wavelength 442-446 nm.

Below are shown the amount of blue daylight fluorescent pigment incorporated into each of the four compositions and the percent increase in intensity of that sample over the composition containing the blue common pigment.

1.0% - 20% higher intensity 0.4% - 33% higher intensity 0.19% - 35% higher intensity 0.09% - 37% higher intensity The granular detergent composition containing 0.09% of blue daylight fluorescent pigment has the most intense color. Raising the amount of blue daylight fluorescent pigment above 0.09% "quenches" or reduces the effect provided by the pigment.

EXAMPLE VII 0.50 grams (about 0.14 parts) of chartreuse yellow daylight fluorescent pigment is added to approximately 383 grams of a liquid automatic dishwashing detergent composition having the following formula: Ingredient Weight Percent Sodium hypochlorite 1.05 Monostearyl acid phosphate 0.03 Sodium carbonate 6.0 Sodium silicate (2.4 ratio) 7.0 Sodium phosphate solids (hexahydrate) 26.30 Sodium mono and didecyl disulfonated diphenyl oxide 0.36 Perfume 0.04 Phthalocyanine green 0.0034 Ultramarine blue dye 0.0065 Aluminum tristearate 0.15 Sodium hydroxide ç 0.65 Smectite clay 0.70 Water Balance After stirring, the homogeneous, milky blue liquid changes to a homogeneous, milky green fluorescent color.

EXAMPLE VIII 0.47 grams (about 0.14 parts) of chartreuse yellow daylight fluorescent pigment is added to 343 grams of a light duty liquid dishwashing detergent composition having the following formula: Ingredient Weight Percent Magnesium coconutalkyl sulfate 5.0 Magnesium coconutalkyl ethoxy(1) sulfate 15.1 Ammonium coconutalkyl ethoxy (1) sulfate 8.1 Coconutalkyl dimethyl amine oxide 2.7 Ammonium xylene sulfonate 2.0 Ethanol 4.8 Sodium diethylenetriamine pentaacetate 0. 1 Ammonium chloride 3.4 Ammonium sulfate 0.1 Perfume 0.2 Water s miscellaneous Balance After stirring, the clear pale yellow liquid changes to an opaque, fluorescent yellow liquid.

Claims (22)

1. A laundry or cleaning composition comprising from about 0.001% to about 2.0% by weight of a daylight fluorescent pigment.

2. The composition of Claim 1 wherein the daylight fluorescent pigment provides at least about a 108 increase in intensity of fluorescence versus the corresponding common pigment.

3. The composition of Claim 2 wherein the daylight fluorescent pigment provides at least about a 20% increase in intensity of fluorescence versus the corresponding common pigment.

4. The composition of Claim 2 wherein the daylight fluorescent pigment is selected from the group consisting of blue, green, and yellow-green daylight fluorescent pigments, and mixtures thereof.

5. The composition of Claim 1 wherein the daylight fluorescent pigment is premixed with a diluent selected from the group consisting of sodium, potassium, lithium, magnesium, or calcium, sulfates, carbonates, fluorides, borates, orthophosphates, pyrophosphates, tripolyphosphates, and mixtures thereof, in a weight ratio of pigment: diluent of from about 1:1 to about 1:1000.

6. The composition of Claim 1 further comprising about 0.001% to about 2.0% by weight of a common pigment.

7. The composition of Claim 6 wherein said common pigment is selected from the group consisting of Titanium Dioxide (C.l.

77891); FD & Blue No. 2 Aluminum Lake (C.I. 73015); FD & Red No. 2 Aluminum Lake (C.l. 16185:1); FD & Red No. 3 Aluminum Lake (C.l. 45430:1); FD & Yellow No. 5 Aluminum Lake (C.l. 19140:1); FD & Yellow No. 6 Aluminum Lake (C.l. 15985:1); Alumina (C.l. 77002); Calcium Carbonate (C.l. 77220); Ultramarine Blue (C.l. 77007); Ultramarine Green (C.l. 77013); Ultramarine Red (C.l. 77007); Ultra marine Violet (C.l. 77007); Talc (C.l. 77019); Tin Oxide (C.l. 77861); FDC Blue No. 6 (C.l. 73000); and mixtures thereof.

8. The composition of Claim 7 wherein the weight ratio of said common pigment to said daylight fluorescent pigment is from about 1:1 to about 1:1000.

9. The composition of Claim 1 further comprising from about 0.01% to about 0.75% by weight of a fluorescent brightener.

10. The composition of Claim 9 comprising from about 0.05% to about 1.0% by weight of the daylight fluorescent pigment.

11. A granular detergent composition comprising, by weight: a. from about 58 to about 60% of a detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic, and cationic surfactants, and mixtures thereof; and b. from about 0.001% to about 2.0% of a daylight fluor escent pigment.

12. The granular detergent composition of Claim 11 wherein the daylight fluorescent pigment provides at least about a 10% increase in intensity of fluorescence versus the corresponding common pigment.

13. The granular detergent composition of Claim 11 further com prising from about 0.001% to about 2.0% of a common pigment.

14. The granular detergent composition of Claim 13 wherein the weight ratio of said common pigment to said daylight fluores cent pigment is from about 1:10 to about 1:100.

15. The granular detergent composition of Claim 12 further com prising from about 5% to about 60% of a neutral or alkaline salt.

16. The granular detergent composition of Claim 15 wherein the neutral or alkaline salt is selected from the group consisting of sodium sulfate, sodium carbonate, and mixtures thereof.

17. The granular detergent composition of Claim 11 further comprising from about 5% to about 85% of a detergent builder selected from the group consisting of water-soluble, alkali metal, ammonium or substituted ammonium phosphates, poly phosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.

18. The granular detergent composition of Claim 17 further comprising from about 1% to about 10% by weight of the detergent composition of a fabric care agent selected from the group consisting of tertiary amines, cationic surfactants, and mixtures thereof.

19. The granular detergent composition of Claim 17 further comprising from about 4% to about 15% by weight of the detergent composition of smectite clay selected from the group consisting of sodium hectorite, potassium hectorite, lithium hectorite, magnesium hectorite, calcium hectorite, sodium montmorillonite, potassium montmorillonite, magnesium montmorillonite, calcium montmorillonite, sodium saponite, potassium saponite, lithium saponite, magnesium saponite, calcium saponite, and mixtures thereof.

20. The granular detergent composition of Claim 17 further comprising from about 0.1% to about 1.0% by weight of the detergent composition of enzyme.

21. The granular detergent composition of Claim 17 further comprising from about 1% to about 20% by weight of the detergent composition of percarboxylic acid bleaching agents or bleaching compositions containing peroxygen bleaches capable of yielding hydrogen peroxide in an aqueous solution and bleach activators.

22. The granular detergent composition of Claim 17 further comprising from about 0.01% to about 0.75% of a fluorescent brightener.