CA2081357A1 - Low ph granular laundry detergent compositions containing chlorine scavengers - Google Patents

Abstract

Low pH granular laundry detergent compositions contain a low level of chlorine scavenger, preferably an ammonium salt. The compositions minimize fading of pH-sensitive and chlorine-sensitive fabric dyes during laundering.

Description

WO 91/17234 PCr/US91/03101 Granular laundry detergent compositions containing chlorine scavengers Technical F~eld The present invention relates to low pH, granular laundry detergent compositions. Certain prefer,ed compositions herein contain a low level of a chlorine scavenger, preferab1y an ~10 ammonium salt. The compositions minimize Fading of fabric colors sensitive to higher wash water plls and to the low levels of chlorine present in ~he wash and rinse water. Other prefsrred compositions herein are dense, low or no phosphate detergents containing a specific aluminosilicato, ci ~,î ic acid 3nd carbonate builder system. Tnese compositiolls provide good cleaning performance while maintaining good physical properties.
Bac~qround Art Granular laundry detergents typically are formulated to provide a wash water pH of about 9.8 to 10.5. This pH range can cause fading of some fabric dyes after multiple laundry cycles.
When the wash solution is diluted in the rinse, the pH is lowered to a range of about 7 to 9 where some fabric dyes are generally less sensitive to pH.
Chlorine is used in many parts of the world to purify water.
To make sure that the water is safe, a small residual amount, typically about 1 part per million (ppm), of chlorine is left in the ~ater. It has been found that even this small amount of chlorine can cause fading of chlorine-sensitive fabric dyes. In a typical wash, there is usually enough soil on the fabrics to scavenge residual chlorine and minimize damage to chlorine-sensitive dyes. However, in the rinse the soil levels are greatly reduced, as is the pH, and chlorine-sensitive dyes can ~ fade-after multiple laundering cycles. Chlorine is also more ;~ aggressive to dyes at the lower pHs. Thus, fading of fabric colors over time is a result of both the high pH of typical ~ granular laundry detergents and the presence of residual chlorine -~ in the wash and rinse water.
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Delivering good cleaning performance from a low or no phosphate condensed detergent is difficult due to limitations in conventional spray dry processing. Additionally, trying to compensate i~ith higher levels of actives (surfactant and builder) is limited witnout signiFicantly diminishing product physical properties (solllbility, lumping/caking, scoopability).
Summar~/ or the invention The ~,es2nt in~ention encompasses granular laundry detergent composi.,ons co,i~prising:
(a) an e;;~c.ive amounL o; a chlorine scavenger; and (b) ~he balal1ce consiscing essentially of derergent components selected from the group consisting of .ntsnic, nonionic, ~.witterionis, ampholytic, and ~3tionic surfactan~s, de~ergellt builders, inert ; materials, detergent adjuvants, and mixtures thereof;and being essentially free of bleaches;
said composition having a pH of from about 7 to about 9.3 at a concentration of 1% by weight in water at 20-C.
; 20 The chlorine scavenger of the present composit10ns is ; employed in an effective amount to control residual chlorine in the wash and rinse water. The amount of chlorine scavenging material needed will vary, but only a small amount is used to avoid destroying 'nypochlori-te bleacn that may be added ' 25 deliberately to treat bleach-sensitive stains.
Detailed DescriDtion of the Invention The granular laundry detergent compositions of the present invention comprise a chlorine scavenger and detergent additives.
The compositions are formulated to provide a pH of from about 7 to about 9.3, preferably from about 8 to about 9.1, more preferably from about 8.5 to about 9.0, at a concentration of 1% by weight in ~ water at 20 C. The individual components of the compositions ;~ herein are described in detail below.
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Chlorine Scavenqer : 35 '~:
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` - 3 - ~ ~ ~. 2081~57 The chlorine scavengers should not be used in a large excess since they will interfere with normal hypochlorite bleaches added to the wash water for stain removal and whitening. Tne level should be from about 0.01% to about 10%, preferably from about 0.05% to about 5%, most preferably from about o.oa to about 2%, based on the molar amount equivalent to react with about 0.5 to about 2.5, typically about 1, ppm or available chlorine, per average rinse. If both the cation and t'ne anion of ths sca~/enger react ~ith chlorine,-which is desirable, ~he le~el is adjus'~ed to react with an equivalent amount Ot a`/ailable ÇhlOriile.
Suitable chlorine scavengers include che ,^oïlo~ing polym2rs ; which can be divided into four groups according to their structural construction: polysth~leneimlnss, pslyaml.nec, polyamineamides and polyacrylamides, o~ w,lich th2 polyethyleneimines, the polyamines and polyamineamides are especially preferred.
; Suitable polyethyleneimines are obtained by acid-catalyzed polymerkation of ethyleneimine and can be modified by urea and epichlorhydrin or dichlorethane. Polyethyleneimines can contain primary, secondary or tertiary amino groups as well as quaternary ammonium groups. Aqueous solutions of polyethyleneimines show basic reaction. The molecular weight can amount up to about 1, 000, 000 .
Polyamines are addition -or condensation products from multivalent aliphatic amines and compounds with several groups capable of reacting, for example, epichlorhydrin or alkylene dihalides. Therefore, they always contain several secondary, tertiary or even quaternary nitrogen atoms, as well as evencually also hydroxyl groups in the molecule. They are accordingly hydrophilic, polar compounds, which behave as polyelectrolytes and :~ are water soluble, inasmuch as they do not contain large hydrophobic groups in the molecule. The polyamines exhibit basic reaction in aqueous solution. Suitable compounds, for example, are described in U.S. Patent 2,969~302.

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W O 91/i7234 PCT/US91/03101 2o81357 - 4 -Polyamineamides contain amino- and amido groups in the molecule at the same time. T'ney are made, for example, by condensation of multibasic acids, for example, dibasic, saturated, aliphatic C3 to Cg acids and polyamines, as well as with compounds, which contain s~veral groups capable oF reacting, such as, for example, epichlorhydrin. These compounds also demonstrate basic reaction in aqueous SolUCiOIl. Suitable polyamineamidss are described, for exampl2, in IJ S Patent 2,925,l5~1.
Polyacrylainides having aimi"o g('OUpS aild molecular weights up to sev~ral million are suitable for use hersin. By building in carboxyl groups, 'il~iCi7 ~r~ ~ormed, ,or e:(ample, by partial hydrolysis, anionic polyacrylamides are obtained in addition to amido grouDs. "Ihile polyarrylamides ciontaining amin~ groups exhibit basic ,eûct-,on in aqueous solutiGn. Alnino groups can be ; introduced, for example, by reaction with alkali and hypobromite or hypochlorite.
It is common to all polymers that they are water soluble.
li Such polymers are cammercial products. Compounds especially well sui~ted as inserts to the detergents conforming to the d;scovery are the polyethyleneimines and polyamines, which exhibit strong basic reaction in water. Examples of commercially available polyethyleneimines, which are particularly appropriate, are 'iEpomin SP-003" rrom Mippon Sho'~ubai, "Lugalvan G20 and G35" from ;25 BASF, and "Ethyleneamine E-lOO" from Dow Chemical. These polymers can be added either alone or together with water soluble polymers ifrom melamine or urea and formaldehyde. Other polymers suitable for the detergents conforming to the discovery are, for example, ;~.
- the water soluble polymers based on alkyleneimines, acrylamides as well as melamine or urea and formaldehyde, which are described in the "Encyclopedia of Polymer Science and Technology", John Wiley &
Sons, Inc., New Yor~, 1968, Yol. 9, p. 762. An addition of these polymers to the detergents conforming to the discovery in combination with the amino- and/or amido group-containing polymers causes an intensification of the dy--protective effect.
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~, --. ' ' ,. . ~ . ~ , - 5 - : 20 ~1357 Preferred polymers for use .in the preferred anionic surfactant containing compositions herein are polyethyleneimines.
Polyethyleneimines are believed to be particularly efficient chlorine scavengers because they adsorb to cotton fibers. In an anionic surfactant matrix, ion pairing of the amines with surfactant or polymeric carboxylates tends to dramatically lower the solubility of the polymeric amine. The solubility oF 'L'ne polymeric amine complexes can be maintained by utilizing materi21s 0 of relatively low molecular weight. The molecular ,~eigh-t of tha chosen amine polymer should be control1?d co acnieve a rabric substantivity of preferably at least 50%. A Io~ s~bstantivity will not allow efficient carryover into the rinse. ~re;erred polyethyleneimines have a molecular ~eight of less ~han abolIt 800, more preferably from about 200 to about 400.
The cationic charge and the solubility of the polymeric amine allow the deposition of the polymer onto cotton fabric. The affinity the polymer has for fabric increases with lower pH, or higher molecular weight. Thus, a balance oi these properties (solubility, solution pH, and polymer molecular weight) controls the efficiency of the chlorine scavenger on fabric and in solution. The optimal composition will allow a balance of polymer on fabric (for carryover from wash to rinse) and in solution (for an efficiency rate of reaction with chlorinej.
Other chlorine scavengers herein are-anions selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, nitrite, etc. and antioxidants ~`~ like carbamate, ascorbate, etc. and mixtures thereof.
;~ Conventional non-chlorine scavenging anions like sulfate, bisulfate, carbonate, bicarbonate, nitrate, chloride, borate, - phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, salicylate, etc. and mixtures thereof can be used with ammonium cations.
Other chlorine scavengers useful herein include ammonium sulfate (preferred), and primary and secondary amines of low volatility such as ethanolamines, amino acids and their salts, polyamino acids and their saits, fatty amines, glucoseamine and ..:
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' :~ , W o 91/17234 PCT/VS91/03101 ~13~ 6 -other aminated sugars. Specific examples include tris(hydroxy-methyl) aminomethane, monoethanol amine, diethanol amine, sarcosine, glycine, iminodiacetic acid, lysine, ethylenediamine diacetic acid, 2,2,~5-tetramethyl piperinol, and 2,2,6,6-tetramethyl piperinone.
Other chlori ne scavens2rs i ncl ude phenol, phenol sulronate, 2,2-biphenol, tiron, and t-butyl h~droquinone. Preferred are meta-pol~phenols âuch as r sorcinol, resorcinol monoacetate, ; 10 2,4-dihydroxybenzoic acid, ~,5-dinydroxybenzoic acid, and 2,4-dihydroxyacetophenone.
Peroxide bleach sources, e.g perboratc, percarbonate and other persalts, can also be used in minor amounts (less 'ch2n 3~/~ by ~; weight, prererably 1ess ~hall abou~ 2'~',) as a ch10rine scav~ng2r herein. However, peroxides are not efficient chlorine scavengers because they cannot be used at high enough levels to carry over to ; the rinse water without risk of bleach damage to colors.
Detergent compositions comprising the chlorine scavenger and the detergent component can be provided having various ratios and proportions of these two materials. Of course, the amount of thè
~, chlorine scavenger can be varied, depending upon the level ofresidual chlorine expected by the formulator. Moreover, the amount of detergent component can be varied to provide either heavy-duty or light-duty products, as desired. This invention relates primarily to detergent compositions that contain essentially no additional ingredients which are chlorine .
scavengers. For example, the other materials present should not provide any substantial additional amounts of ammonium cations in ; the wash solution.
Deterqent Additives The amount of the detergent surfactant component can, as noted hereinabove, vary over a wide range which depends on the desires of the user. In general, the compositions contain from about 5% to about 50%, preferably from about 10% to about 30% by weight, of detergent surfactant, which preferably is an anionic ~ .
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`:-` 2~357 The detergent compositions of the instant invention can contain all manner of organic, water-soluble detergent surfactant compounds. A typical listing of the classes and species of 5detergent compounds useful herein appear in U.S. Patent 3,6~4,961, incorporated herein by reference. The following list of detergent compounds and mixtures which-can be used in the instant compo-sitions is representative of such materials, but is not intended to be limiting.
10Water-soluble salts of the higher fatty acids, i.e.~ "sGaps"~
are useful 2S the detergent component of the composition harein.
This class of detergents includes ordinary alkali metal soaps sucn as the sodium, potassium, salts of higher fatty acids containing from about 8 to about 24 carbon atoms and pre-,-erabl~ ,-ro"l about 10 to about 20 carbon atoms. Soaps can be made oy direct ; saponification of fats and oils or by the neutralization of fre~
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.
20Another class of de~ergents includes water-soluble salts, particularly the alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a 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 detergents which form a part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obt2ined by sulfating the higher ; alcohols (Cg-C1g carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and 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 United States ; Patents 2,220,099 and 2,477,383, incorporated herein by reference.
~ 35 Especially valuable are linear straight chain alkylbenzene , . . : . . :
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WO 91/17234 PCr/US91/03101 2Q~13~7 8 sulfonates in which the average of the alkyl groups is about 12 carbon atoms, abbreviat~d as C12 LA~-Other anionic detergent surfactant compounds herein include5 the sodium alkyl glyceryl ether sulfon2tes, especially those ethers of higher alcohols derived from tallo,w and coconut oil;
sodium coconut oil fatty acid munoglyceride sulfonates and sulfates; and sodium or potassium salts o~ alkyl phenol ethylene oxide ether sulfat2 containii1g frcln aoout 1 o about 10 units of 0 ethylene oxide per molerule and ~:lherein ~he alkyl groups contain about 8 to about 13 carbon atoms.
ater-soluble nonionic synlha~ic detergqnt surfactants are also useful as the deterrent component of the instant composition.
Such~ nonionic detergelt ma!~-,ial, ca,l b2 b~^Oadl~ ci2l^1n2d as compounds produced oy ~he condensa-cion oF etnylene oxide groups (hydrûphilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of ` the polyoxyethylene gro.up which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydroph;lic and hydrophobic elements.
For example~ a well-known class of nonionic synthetic deter-, gents is made available on the market under the trade name of"Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. Other suitable nonionic synthetic detergents 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 about 13 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 4 to about 15 moles of ethylene oxide per mole of alkyl phenol.
The water-soluble condensation products of aliphatic alcohols having from about 8 to about 22 carbon atoms, in either straight .: .

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chain or branched configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from about 3 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergent surfactants include ~ water-soluble amine oxides containing one alkyl moiety of from - about 10 to 20 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing ;rom 1 to about 3 carbon atoms; water-soluble phosphine o~ide detergents containing one alkyl moiety of from about 10 to 20 carbon atoms and 2 moieties selected from the group consisting of ~` al~yl groups and hydroxyalkyl groups containing from l to 2bout 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl or hydroxyalkyl moiety of from about 10 to about 20 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to about 3 carbon atoms.
Ampholytic detergent surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic ~oiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic detergent surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in ~hich the aliphatic moieties can be straight chain or branched, ; and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group. The quaternary compounds, themselves, e.g.
cetyltrimethyl ammonium bromide, can also be used herein.
Other useful detergent surfactant compounds herein include the ~ater-soluble salts of esters of alpha-sulfonated fatty acids `~ 35 containing from about 6 to about 20 carbon atoms in the fatty acid ~ ' ~ .

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group and from 1 to about 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alk3ne-l-sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 20 carbon atoms in the alkane moiety;
alkyl ether sulfates containing From abouc 10 to about 20 carbon atoms in the alkyl group and from about 1 to about 1~ moles of ethylene oxide; water-soluble salcs or 012;in sulfonates containing from about 12 to 20 -arbon atoms; ~nd beta-alkyloxy alkane sulfonates containing from abcll~ 1 ;o 3 carbon a-coms in ~he : alkyl group and from about ~ to Z0 carbon atoms in the al!~ane moiety.
Preferred water-soluble organic detergent compounds herein include linear alkylbenzen2 .;ulfona~s contai~ g r..,m abJut 11 to about l3 carbon atoms in the alkyl group; Cio l8 al~yl sulrates;
the C1o-l6 alkyl glyceryl sulfonates; Clo l~ 21kyl ether sulfates, especially wherein the alkyl moiety contains from about 14 to 1 carbon atoms and wherein the average degree of ethoxylation between 1 and 6; C10-l8 alkyl dimethyl amine oxides, especially wherein the alkyl group contains from about 11 to 16 carbon atoms;
; alkyldimethyl ammonio propane sulfonates and alkyldimethyl ammonio hydroxy propane sulfonates wherein the alkyl group in both types contains from 14 to 1~ carbon atoms; soaps, as hereinabove lj defined; and the condensation proàuct or C10-l8 fatty alcohols :, 25 with from about 3 to about 15 moles of ethylene oxides.
, . Specific preferred detergents for use herein include: sodium : linear C10 13 alkylbenzene sulfonates; sodium C12 18 alkyl sul-fates; sodium salts of sulfated condensation product of C12-i8 :: . alcohols with from about 1 to about 3 moles of ethylene oxide; the condensation product of a C1o-l8 fatty alcohols with from about 4 ~ . . to-about 10 moles of ethylene oxide; and the water-soluble sodium : and potassium salts of higher fatty acids containing from about 10 :~ to about 18 carbon atoms.

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It is to be recognized that aiy of the foregoing detergents can be used separately herein, or as mixtures. Examples of preferred detergent mixtures herein are as follo~s.
An especially preferred alkyl ether sulfate detergent compo-nent of the instant compositions is a mixture of alkyl ether sul-fates, said mixture having an average (arithmetic mean) carbon chain.length within the range of from about 12 to 16 carbon atoms, preferably From about 14 to 15 carbon atoms, and an a~lerage (arithmetic mean) degree of ethoxylation of from about 1 to ~
moles of ethylene oxide, preferably from about 1 to 3 moles of ethylene oxide.
The detergent compositions of the present invention can contain, in addition to the detergent surfactant, water-soluble or ~ water-insoluble builders such as those commonly taught for use in ; detergent compositions. Such auxiliary builders can be employed to sequester hardness ions and to help adjust the pH of the laundering liquor. Such builders can be employed in concentrations of from about 5Y. to about 95X by weight, preferably from about 10% to about 50% by weight, of the detergent compositions herein to provide their builder and pH-controlling functions. The builders herein include any of the conventional inorganic and organic water-soluble builder salts.
~ Such builders can be, for example, water-solub'.e salts of phosphates including tripolyphosphates, pyrophosphates, ortho-` phosphates, higher polyphosphates, carbonates, silicates, and organic polycarboxylates. Specific preferred examples of inorganic phosphate builders include sodium and potassium tripolyphosphates and pyrophosphates.
Nonphosphorus-containing materials can also be selected for use herein as builders.
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Specific examples of nonphosphorus, inorganic detergent ~ builder ingredients include water-soluble inorganic carbonate, -~ bicarbonate, and silicate salts. The alkali metal, e.g., sodium .
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, WO91/17234 PCI/l'S91/03101 .~:20~357 .,. ~z and potassium, carbonates, bicarbonates, and silicates are parti-cularly useful herein.
Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-ocrurrins aluminosilicates or synthetically derived. A me~hod for prqducing aluminosilicate ion exchange materials is discussed in U.S. Pat.
No. 3,985.669, Krummel et al, issued Oct. 12, 197r, incorr~rated herein by reference. Prererred synchecic crystalline aluminosilicate ion exchange materials userul h2rein are a~/ailable under the designations Zeolite A, Zeolite B, and Zeol~te X. In an especially preferred embodiment, the cr~st-allin? alei,~,nosilic3L.e ion exchange material in Zeolite A and has the i~3rmula Nal2[A102)12.(SiO2)l2]-xH2o wherein x is from about 20 to about 30, especially about 27.
Water-soluble, organic builders are also useful herein. For example, the alkali metal, polycarboxylates are useful in the present compositions. Specific examples of the polycarboxylate builder salts include sodium and potassium, salts of ethylene-diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, poly2crylic : acid, polymaleic acid, and citric acid.
Other desirable polycarboxylate builders are the builders set : forth in U.S. Patent 3,308,067, Diehl, incorporated herein by reference. Examples of such materials include the water-soluble salts of homo- and co-polymers of aliphatic carboxyllc acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid.
Other suitable polymeric polycarboxylates are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to Crutchfield et al, and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 to Crutchfield et al, both incorporated herein by reference. These polyacetal carboxylates can be prepared by :~
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, , 3~ PCI/US91/03101 `~ 2~,~13~7 ; 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, converted to the corresponding salt, and added to a surfactant.
Preferred builders herein are polycarbo~ylic acids, especially citric acid, which preferably are used at a level of From about 5% to about 10% by weight, and sodium acid pyrophosphate, which preferably is used at a level of irom about 5% to about 15% by weight. Such materials function as both builder and acid source to adjust pH to the desired range.
Deteraent Adiuvants The detergent compositions herein can contain all manner of additional materials, detergent adjuvants, commonly found in laundering and cleaning compositions. For example, the compositions can contain thickeners and soil-suspending agents such as carboxymethylcellulose and the like. Various enzymes, enzyme stabilizers, suds suppressors~, perfumes, optical bleaches, fillers, anticaking agents, fabric softeners and the like can be present in the compositions to provide the usual benefits occasioned by the use of such materials in detergent compositions.
Ihe compositions herein are essentially free of oxygen ;~ 25 bleaching agents, since if they are present, there is no need for ;~ the chlorine scavenger. Similarly, there should be no chlorine bleaching agent present since the chlorine scavenger wnuld not be ~ effective against a large amount of available chlorine.
A finished detergent composition of this invention can con-tain minor amounts of materials which make the product moreattractive. The following are mentioned by way of example: a tarnish inhibitor such as benzotriazole or ethylene thiourea can be added in amounts up to 2% by weight; fluorescers, perfumes and dyes, while not essential, can be added in small amounts. An alkaline material such as sodium or potassium carbonate or~
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hydroxide can be added in minor amounts as supplementary pH
adjusters. There may also be mentioned, as suitable addi~ives:
bacteriostats, bactericides, corrosion inhibitors such as soluble 5 alkali silicates (preferably sodium silicates having an SiO~/N220 ratio of from 1:1 to 2.8:1), and textile softening agents.
Particularly preferred compositions herqin are g,anular laundry detergents comprising by ~eight:
~` (a) from about 15% co about 25%, prel-erlDl~ -130U'C 13~, 50 about Z3%, of a mixture o~ a Cll-C13 (prq~
C12-C13) alkylben~ene sulfonate su.factan' and i C,~-C", (preferably C1~-C1s) al'~yl sulfate surfactant in weight ratio of sulfonatq surf~ctant to su',rate surfactant of from ~bout ':1 o bou- ': , ln., ~ra~)~
about 2 :1;
(b) from about 1% to about 3%, preferably about 1.5% to about 2.5%~ of an alkali metal (preferably sodium) si-licate having a molar ratio of SiO2 to alkali metal oxide of from about 1.0 to about 2.4, preferably about 1.4 to about 2.0;
(c) from about 20% to about 30%, preferably about 22% to about 28%, more preferably about 25% to about 28%, of a finely divided aluminosilicate ion exchange matPrial selected from the group consisting of:
(i) crystalline aluminosilicate material of the formula:
Naz[(A102)z. (SiO2)y] XH20 wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5 and x is from 10 to 264, said material having a particle size diameter of from about 0.1 micron to about 10 microns, a calcium ion exchange capacity of at least about 200 mg CaC03 eq./g and a calcium ion exchange rate of at least about 2 grains Ca++/gallon/min-ute/gram/gallon;
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W O 91/17?34 PC~r/US91/03101 2~1357 (ii) amorphous hydrated aluminosilicate material of the empirical formula:
M~(ZAlO2-YSio2) 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 ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate and a Mg++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon;
and mixturPs theroof;
~d) from about 4/0 to about 10%, preferably about 5% to about 8%, of citric acid;
(e) from about 5% to about 20X~ preferably fro~ about 8% to - about 12%, of an alkali metal (preferably sodium) carbonate;
said composition having a pH of from about 7 to about 9.3, preferably about 8 to about 9.1, mare preferably about 8.5 to about 9.0, at a concentration of 1% by weight in water at 20-C, and said composition having a density of from about 500 to about 600 grams per liter.
Preferred aluminosilicate ion exchange material is of the formula Nal2[(A102)12(SiO2)12].xH2o~ wherein x is from about 20 to about 30.
The above granular detergent compositions provide good cleaning performance due to the relatively high levels of anionic surfactants and aluminosilicate, citric acid, and carbonate . .
builders~ Despite having a density of from about 500 to about 600 ` grams per liter, the compositions have good physical properties, i.e., they are free-flowing and are readily soluble in the laundering solution. The citric acid and carbonate levels are 35 selected to obtain the required pH range and provide additional builder functioh to the aluminosilicate material.

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2~813~ - 16 -All percentages, parts and ratios herein are by weight unless otherwise specified.
The following examples illustrate the compositions herein.
EXAMPLES
Granular detergent compositions of the present in~ention - comprise the following ingredients:
Inqredient Percent (',~t~
II III
Sodium 12.3 linear alkyl benzene sulfonate 13.6 12.7 15.8 Sodium C14-C1s alkyl sulfate5.8 5.4 6.8 ` C12-C13 alcohol ethoxylate :~ (E0 6) 0 0 0.0 0.~
Citric acid 5.5 4.9 0.0 Sodium tripolyphosphate 0.0 0.0 6.8 Sodium pyrophosphate 0.0 0.0 13.1 Sodium acid pyrophosphate 0~0 0.0 12.4 Zeolite A, hydrate (1-10 micron size) 2C.9 27.3 0.0 Sodium carbonate 10.3 8.9 0.0 Sodium silicate (1.6 ratio NaO/SiO2) 2.2 2.1 7.6 Polyethylene glycol 8000 1.4 1.3 0.6 Sodium polyacrylate (MW 45003 3.2 3.0 3.4 Protease enzyme* 1.8 1.7 0.7 Sodium perborate tetrahydrate 0.0 0.0 1.9 Ammonium sulfate 2.0 2.0 0.0 ` ~ Sodium sulfate 18.3 17.1 14.4 : 30 Balance (including water, brightener, perfumej suds suppressor) ---------- to 100.0 -------pH 1% aqueous solution at 20~C 8.7 8.9 9.2 . *Activity of 1.8 Anson units per gram.
: Aqueous crutcher mixes of the detergent compositions are : 35 prepared and spray-dried, except for the citric acid, sodium acid ~ pyrophosphate, enzyme, perfume, and ammonium sulfate or perborale, :: .

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WO 91/17234 PCr/US91/03101 - 208~3~7 which are admixed, so that they contain the above ingredients at - the levels shown.
Fabrics laundered using the above compositions retain their color over time better than similar compositions not containing the chlorine scavenger or formulated to provide a higher wash pH.
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Claims (18)

WHAT IS CLAIMED IS:

1. A granular laundry detergent composition comprising:
(a) an effective amount of a chlorine scavenger; and (b) the balance consisting essentially of detergent components selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic, and cationic surfactants, detergent builders, inert materials, detergent adjuvants, and mixtures thereof, and being essentially free of bleaches;
said composition having a pH of from about 7 to about 9.3 at a concentration of 1% by weight in water at 20°C.

2. The composition of Claim 1 wherein said chlorine scavenger is an ammonium salt.

3. The composition of Claim 1 wherein said chlorine scavenger is a compatible salt of a sulfite, bisulfite, thiosulfite, thiosulfate, iodide, nitrite, carbamate or ascorbate anion or mixtures thereof.

4. The composition of Claim 1 wherein said chlorine scavenger is a polyethyleneimine having a molecular weight of less than 800.

5. The composition of Claim 4 wherein said chlorine scavenger is a polyethyleneimine having a molecular weight of from about 200 to about 400.

6. The composition or Claim 1 wherein said chlorine scavenger is a peroxide bleach.

7. The composition of Claim 1 wherein said composition has a pH of from about 8 to about 9.1 at a concentration of 1% by weight in water at 20°C.

8. The composition of claim 7 wherein said composition has a pH of from about 8.5 to about 9.0 at a concentration of 1% by weight in water at 20°C.

9. The composition of Claim 8 wherein said chlorine scavenger is an ammonium salt.

10. The composition of Claim 1 comprising from about 5% to about 50% detergent surfactant and from about 5% to about 95% by weight of detergent builder.

11. The composition of Claim 10 comprising from about 10% to about 30% detergent surfactant and from about 10% to about 50% of detergent builder.

12. The composition of Claim 11 comprising from about 5% to about 10% of citric acid builder.

13. The composition of Claim 11 comprising from about 5% to about 15% of sodium acid pyrophosphate builder.

14. The composition of Claim 12 wherein said chlorine scavenger is an ammonium salt.

15. The composition of Claim 14 wherein said ammonium salt is ammonium sulfate.

16. The composition of Claim 12 wherein said chlorine scavenger is polyethyleneimine having a molecular weight of from about 200 to about 400.

17. The composition of Claim 12 wherein said chlorine scavenger is perborate.

18. The composition of Claim 15 wherein said composition has a pH of from about 8.5 to about 9.0 at a concentration of 1% by weight in water at 20°C.