CA2192549A1 - Detergent composition containing anionic surfactants and water-soluble saccharides - Google Patents
Detergent composition containing anionic surfactants and water-soluble saccharidesInfo
- Publication number
- CA2192549A1 CA2192549A1 CA 2192549 CA2192549A CA2192549A1 CA 2192549 A1 CA2192549 A1 CA 2192549A1 CA 2192549 CA2192549 CA 2192549 CA 2192549 A CA2192549 A CA 2192549A CA 2192549 A1 CA2192549 A1 CA 2192549A1
- Authority
- CA
- Canada
- Prior art keywords
- detergent composition
- surfactant
- weight
- detergent
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
Abstract
A detergent composition in form of agglomerates is provided. The detergent composition contains from about 1 % to about 50 % by weight of a detersive surfactant system. The surfactant system itself includes, by weight of the surfactant system, at least about 30 % of a sulfated surfactant selected from alkyl sulfates, alkylethoxy sulfates, secondary alkyl sulfates and mixtures thereof. The detergent includes from about 0.1 % to about 5 % of a water-soluble saccharide selected from the group consisting of cellubiose, glucose, maltose, lactose, ribose, and lactulose mixtures thereof. Also, the detergent composition includes at least about 1 % by weight of a detergency builder to enhance cleaning. The surfactant system, saccharide and builder are agglomerated to form detergent agglomerates having a density of at least about 650 g/l. The anionic surfactants in the detergent composition have significantly improved dissolution in aqueous laundering solutions, especially those kept at cold temperatures, i.e. 5 ~C to 30 ~C.
Description
2~ 92549 ~ WO95135625 . . r~l~u.,.. ~i. 'gl DETERGENT COMPOSITION CONTAINING ANIONIC SURFACTANTS AND WATER-SOLUaLE
SACCHARIDES
S FIELD OF THE INVENTION
The poesent invention is generally directcd to an a,,~,' ' compact detergent composition having improved solubility in cold tcmperature laundering solutions. Morc particulsrly, the imvention is dircctcd to a detergent composition containing high levels of a sulfated surfactant selected from the group consisting of alkyl sulfates (also referenced herein as "AS"). alkyl ethoxy sulfates (also referenced heoein as "AES"), and secondary alL~I sulfates (also rcferenced herein as 'SAS") and mixtures thereof, and selected amounts of t~ater-soiuble saccharides, together tvhich rmprove the overall solubility o m ' , ' " x Or the cornposition in cold temperature washing solutions (e.g. 5~C to 30~C) and high water hardness conditions (e g, 7 _ '~, " ) For purposes of producing a high density, compact detcrgel1t composition, the detergent of the invention is in the form of detergent agglomerates rather than spray dried grtmules.
BACKGROUND OF T~ INVENTION
Typically, conventional detergent compositions contain mixtures of various surfactants In order to rcmove a ttide variety of soils and stains from surfaces. For example, various anionic surfactants, especially the alkyl benzcne sulfonates, are useful for removing particulate soils, and various nonionic smfact~mts, such as the alkyl ethoxylates and alkylphenol etho.xylatcs, are useful for removing greasy soils.
While thc art is rcplete with a ttide vanety of surfactants for those skilled in the art of dctergent formulation. most of the available surfactants are specialty chemicals which are not suitable for routine usc in low cost items such as home laundering ~ , Thc fact remains that many home-use laundry detergents still comprise one or more of the conventional alkyl benzenc sulfonates or primary alkyl sulfate surfactants. Another class of surfactants which has found use in various compositions whcre ' - is desired comprises the secondary alkyl sulfates. The convcntional sccondary alkyl sulfate smfactants are available as generally pasty, random mixtures of sulfatcd lincar and/or partially branched alkanes.
The limitcd solubility of alkyl sulfate surfactants including both primary and secondary alkyl sulfates is cspecially prcvalent in modern granular laundry detergents which are typically used m cold tempcrature (e.g. 5~C to 30~C) washing solutions and are formulated in "condensed" or "compact' form for low dosage usage. For the consumer, the smaller package sizc attendant with compact detergent prooucts protides tor casy storage snd l~andling. For the I ~ unit storage costs, shippmg costs and packaging costs are lowercd.
The manufacture of acceptable compact or condensed granular detergents has its difficulties. In a typical compact detergent formulation, the so~alled "incrt" ingredients such as ~0 9.'~/34625 -2~ 91 sodium suifate are substantiaily eliminmed. Hou~ever, such h~gredierlts do play a role in enhancing solubllity of conventionai detergcnts. As a consequence. cornpact detergents ofteil suffer from solubility problems, especially in cold tempernture laundering solutions. ~ioreovcr, conventionni compact or low density detergcnt granuies are usually prepared by spray drying proces~s v.~hich 5 result in extremely porous detergent particles that are quite amenable to bcing dissolved in aqueous washjng solutions. By contrnst, compact detergents are typically comprised of less porous, bigh density detergent pardcles which are less soluble, e.g. ~t~PJnn~ ~ Thus, since tho compact form ol granuiar detergents typicatly compn~ particles or granules which contain high levels of detersive ingredients with littie or no room for solubiliz.ing agents, and since such particies are intentionaily ~ ' at high br~k densities, the net result can be a substantial problem with regard to in-use solubility.
In the art of detergency, sugars have been to smne extent used to replace sodium siiicate for purposes of improving soiubility of spray dried granuiar detergents For example, one attempt in the past was directed to a spray-dried detergent composition cmltaillillg sugars and a seed crystai for 15 caicium carbonate to provide improved solubility. Howevcr, only ~spray-driedU detergent compositions ha~ing lov. e ' ' o f suifated snrfactants have been considered in the past.
Thus, the problems associated with modern day compac~ dctcrgents having densities vrhich are much higher (650 gli or more~ have not been addressed, as yet. Generally speaking, oniy the highiy densbled ~ ' detergcnt compositions encounter a much more difficult problem of 20 dissolving in cold temperature laundering solutions as compared to less dense spray-dried detergents.
Accordingly, despite thc disclosures in the art, there remains a need for art higb density detergent composition which has improved water solubilily, especiaily in cold temperature washing solutions. Tlus need is especiaily prevalent in the art of compact or high 25 density deterger ts currendy being used by consumers.
B~CKGROUND ART
The foiiowing patents dirrclo~ the use of sugars in detergents , ' ' Davies et ai, U.S. Pat. No. 4,908,159 (Lever Brothers Co.); Davies et al, U.S. Pat. No. 4,755,318 (Lever Brothers Co.); McCaiiion et al, U.S. Pat. No. 4~65~,782 (Lever Brothers Co.~; Cheng, U.S.
Pat. No. 4,414,130 (r' 1~ ~r ~ ~ . cO.); Finck, U.S. Pat. No. 3,821,118 (~ r ~ ~Co.l; IP Pat. No. 52094304 (Yukcn Kogyo iClC~, JP 58125797 (Shiseido KK); JP 60060196 (Kanebo KK); ~P 61238894 (S~mstar KK); JP 04146998 (Lion Corp.).
nte foliowing patent discloses secondary aikyl suifates: P~ossall ct ai, U.S. Patent No, 4,235~752, ~ W0 95134625 r~ n........................................ ~ 91 SUMMARY OF T~F. INVENTION
The prescm invention meets the needs iden~ified above by providhlg a detergent composition in the form of agglomerates vrllich exhibits improved solubility or dissolution of the anionic surfactants in cold temperaturc wasiling solutions as well as mlder iligh water hardness 5 conditions. The detergent composition comprises a surfactant system having a high level of a sulfated surfactant selected from the group of al~d sulfates, alkyl ethox~ sulfates, secondary alkyl sulfates and mixtures thereof, jD combination with a nater-soluble saccharide. Other adjunct detergent ingredients may also be included in the detergent t~_' which form the detergent composition. Additionall5~, the composition surprisingly exhibis imprwed water solubility despite 10 being in the form of high denr.~ty I __' and being subjected to cold temperature washing solutions.
As used herein, the phrase "improved solubility" mans that the solubility of the anionic surfactants of the detergent composition is enhanced by at least 5~~0 in the laundering soludon when employed in the manner of this invention, as compared to the solubility of the same anionic 15 surfactanB per se, umder the same test conditions (i.e. water temperature and pH, stimng speed and time, particle size, water hardness, and the like). As used herein, the term n ~ refers to particles formed by aw' " _ particles wluch typically have a smaller mean particle size than the formed w' All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documenB including patents and publications cited herein are incorporated 20 herein by reference.
In accordance v ith one aspect of the inventdon, a detergent composition in the forrn of agglomerates is provided herein. Tbe detergent composibon comprises from about 1~~u to 50~,~u by weight of a detersive surfactant system. The surfactant system itself comprises, by weight of the surfactant system, at least about 30~/0 of a sulfated surfactant selected from the group consisting of alkyl sulfates, 25 alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof. The detergent composition includes from about 0.1% to about 5YO of a ~ ' ' ' saccharide selected from the group consisting of cellobiose, ducose, maltose, lactose, ribose, and lactulose mi.~nures thereof Also, the detergent composibon includes at least about IYo by ~height of a detergency builder to enhance cleanmg. Tbe surfact;mt system, ~ ' ' ' saccharide, and builder are a_~' ' to form detergent 30 agglomerates having a density of at least about 650 g/l. The detergent composition has improYed solubility in aqueous taumdering solutions. Thus, the solubility of the sulfated surfactant (AS, AES
amdlor SAS~ is enhanced by at least 5YO, prefenably 10 to 50YO oYer those same surfactants alone under the same test conditions in aqueous washing solutions at cold ~ .e. 5DC to 30~C.
In amother embodiment of the invention. the sulfated surfactant is a mixture of alkyl sulfate 35 and alkyl ethoxy sulfate surfact;mts. Further, the detergcnt composition may include adjunct ingredienB selected from the group consisting of bleaches, bleach activators, suds suppressers and soil release agents.
~ 1 ~254~:~
W09s/~3462 i r~l~u..,.~ 2 )1 In a preferred embodiment, the detergency builder is selecled from the gruup Nnsisting of carbonates. zeolites and mi::tures thereof. The surfactan~ systern may f3mhcr comprise, by weight of the surfachnt system, from about 1% to about 50~/0 of a C lo-C 1~5 N~alkyi polyhydro: y fatty acid amide for use as an adjunct surfacttmt. In another embodmlent, t3ae comporition may include from about O.lC~o to about 15h of a linear alkylbenzene sulfonate surfactallt.
In a preferred embodiment of the invention, the detergem composition comprises: (a~ at least sbout 30~K by ueight of a suifated surfact33n~ seieaed from tl-e group consisting of atkyl ~ sulfates, alkyl etho.cy r~lfates, seNnd3ry alkyl sulfates and uli?;tures thereof; ~bi from about 0.1% to about 5~~0 by weight of sucrose; and (c) at least about 1% by weight of a detergency builder, wherein the surfactant system, saccharide and builder are a,,~ to form detergent agglomerates havirlg a denslty of at least 650 gli. The sulfated smfactant of the surfactant system has improved solubility in an aqueous hundenng solution aud the composition is substantially free of phosphates.
In accordance 7~ith anotber sspect of the ini entim3, a method for laundering soded fabrics is prosided. The method comprises the step of contacting soiled fabrics with an effective amount of a daergent composidon as desclibed herein in an aqueous laundenng solution. An offective amount is t~picslly on tho order of 1000 to 1500 ppm. Yet another embodiment of the invendon is di-ected to a laundry bar formed fmm compositions described herein.
Accordingly, it is an object of the present invention to provide a grtmuiar detergent Nmposition which has impmved solubility, especially in cold tempcr3rurc v ashing solutions. Il is also an object of the invention to provide such a detergent cmnposition which has impmved b: -i ~ - ' 7- ~ . These and other objects, fea{ures and attendant advantages of the prosent invendnn will become apparent to those skilled in the an from a reading of the foliowillg detailed descliption of the preferred embodiment and the tlppended claims.
D77TA7r .Fn D7~5CR~PT.70N OF rHE . REi E7.~RED E7~R( m~7NT
The invention is directed to a granular delergent composition ha~ing impmved solubility in cold temperature la7mdering solutions. A muititude of conrumers around the world launder soiled c othes in conventionai washing mschines unique to their particular geographic location. Tgpicaily, these conventionai washing macbines iaunder the soilod clothes in water supplied at rclatively oold for etuunple in range of 5~C to 30~C, and at high hudness e.g. 7 gtainslga7.10n lnch uith Ca and Mg ions). 7.~iost nf the nnodem day consumers aiso use compact or condensed laumdry detergents to accomplish their laundering needs. Undcr the r conditions, solubiliq of current detergents in agueous laundering solutions has been a problenL as montioned previously. This problem is especiaily exacerbated when the detergent composition has high le els of a kyl su7htos, a7kyl ethoxy Nlfate andlor secondary ahkyl suifates which ate not particularly a7nenable to dissolution jR cold aqueous laundcring solutions. Such rurfactantS aro particularly usefiR in modcrn hundry detergents since they minimiae or elin iMte the need for linear aikylbenzene suifate suRactants which gencrally have poor ' i ~ . 7M.oreover, ~1 925~9 ~ W0 9S/3462s P~ , .'C 62gl .~.
recenl compnct detergents have strived to limit or eliminate the use of phospllates uhicil are knoun to increase uater solubility, In view of this trend, the uater sohlbility problem is exacerbated further.
It has been foumd that highiy dense, ~ ' ' detergent compositions cnn experience 5 improved ~ , if selected nmounts of n wnter-soluble sncchnride nre included. Such detergent compositions prefernbly nlso include a smfnctant system wllich comprises at least 30~~0, prefernbly from about 35~/0 to about 90~/0, of n sulfated surfactallt selected frmll the group consisting of nlky' sulfntes, nikyl cthoxy suifates, secondary alicyl sulfates and mixlures thereof, Preferably. the detergent composition is in the form of 3=~' nnd hns nn overall densiy of 650 g/l or higher.
10 These fentures provide the rcompact" nature of the detergent composition i u nccordance u ith the invention, Preferably, the detergent composition of the invention also comprises nt lenst nbont 1%, preferably from about 10~/0 to nbout 40~~0, nnd most preferably from nbout 15~~0 to nbout 35~/0, of n detergency builder. The detergent composition may nlso include one or more of adjunct detergent ingredients. Noniimiting exnmples of the detergency surfnctant. wnter-soluble sncchnride.
15 detergency builder nnd ndjunct ingredients are described h1 detail hereinnfter.
For purposes of enhnncing b ~ v~ the delergent 1~' - wluch form the detergent composition of the invention preferably do not contnin phosphntes, Funher, it is impon~mt for the detergent Qmposidon to be in the forrn of " ==' " as opposed to spray dried grnnules. In addition to being nmenable for modern compact detergents, this is pardcuinrly 20 imponnnt since most sulfated smrfactants cannot be readily subjected to spray drying processes u ithout cnusing or creating extremely adverse plumes from the spray drying touvers.
The "improved solubiiity" achieved by the detergent composition is concerned with enhnnced solubility of the anionic surfactants contained in the surfactnnt system. i e. AS, ALS, SAS
or LAS if used. Preferably, the improvement represents at lenst n 5~~0 increase in solubiiity of these 25 nnionics in the wash solution over the solubility of the same surfactants if they were dissolved sione or without being contained in a detergent composition as defh~ed herein. More prefernbly, the solubiiiq improvement is from nbout 10% to nbout 50~~0 As those skilled in the art uill npprecinte, nmy compnrison of snionic smrfactant solubility should be completed under the same isundenng condidons, e.g. wntor temperature, hardness and pH, stirrhlg speed nnd time, and pnndcle sr2e.
30 Typicsi snior~ic surfsct~mt solubiliq , are set forth in thc Esamples hereinnfter.
Those skillcd in the srt should nlso npprecinte the numerous ~ays m which the nmount of the surfnctsnt system in the washing solution can be deterrnined For exmnple, in the so-csiled ~catS03~ titration technique, samples of the nqueous laundering solution containing the detergent composition c~m be tnken sfter one minute nnd filtered with 0.45 mm nylon filter HPLC, sfter which 35 the filtereri solution csn be dtrated with n cationic titrant, which can be "~ purchased, e.g. from Sigms Chemicni Company under the trnde nnme Hymnine, in the presence of anionic 2 1 9~54~ ~ ~
WO ~';t34625 i dyes. From thc foregoing, IhC amomlt of anionic surfict.ult which w3s dissolvcd in ~he uashing solution cnn be dcterrnined.
v;'nler-Soluble Sncchnride It has been foumd that the solubiiity of high-content alkyl sulfDte, al~yl etho~y suifate 5 amdlor secondary alicyl suUate ~"sulf3ted" surLIctnnt systcm) compact detergent composition in lhe form of agglomerates c~m bc increased by . ~ n water-soluble saccharide selected from the group consisting of glucose, mattose, cellobiose, Iactose, ribose, mld Inctulose mixtures thereof into the composition. Other mono-, di-, and poly- sacchnndes mld derivatives tbercof may be used in thc compositioms herein without departing from the scope of the invenbo:l. The snccharide repeating 10 m it can h~tve ns fev, as five cnrbon ntoms or as mnm,y as fift,v cnrbon ntoms consistent usth water solubiiity. To that end, the preferred detergent composition of the invention comprises from about 0 1% to about 5~~O more prefernbly from nbout 0.5~~O to nbout 4ffO, and most prefcrnbly from about 2% to about 4~~O by veiyht of the vater-soluble sacchande. The most preferred water-soluble saccharide is sucrose ~r its avnilability, i , ~ ., nnd performance. 8y "water-soluble" in 15 the presenl contest, it is meant thnt the sacchnnde is capnble of fomlillg a clear solution or a stable colloidai dispersion in distilled water nt room tempernture nt a ~ -- of 0.01 g/l.
Surfnctnnt Svstem The surfncLmt system in the detergent composition must include a suifated surfactant selected from the group consisting of alkyl suifates, alkyl ethoxy suifates, secondnry alkyl suifates, 20 and mi.ctures thereoL As mentioned previously. the nnionic surfnctnnts in the surl'nctnnt systcm of the invention. i.e. AS, AES, amd/or SAS, hnve improved solubility and more particularly, on the ordcr of 5~K or luigher. Optionnily, the surfactnnt system mny conlain onc or more of ndditionni surfac~mts, nonbmiting examples of which nre provided hereinnfter.
The surfar,tnnt system preferably includes com,entioR.Il prinLary alkyl suifJte suRaçtants 25 hnve the generai formula ROSO3-M+
wherem R is typicaily a linenr C to-C20 hydrocnrbyl group nnd M is a Ihaler-solubilizing çation.
'' ' '.,1~. primary alkyl sulfate surfaçtnnts (i.e.. I ' I c~n "PAS") hnving 10-20 cnrbon atoms am atsç be used hcrein; see, for c,sample. Europenn Patent Applicntion 43 9,316, Smith et ai, fiied 21.01.91, the disclosure of which is iucorporated herein by reference (Included in the term "atkyl" is tbe aikyl pordon of acyl groups). Included in the surfactnnt system are ~he C 10-C 18 alkyl nikoxy suifates ("AEiySn especinlly EO 1-7 ctllo ey sulfates).
Conventional secondary alkyl sulfate surfactnnts can also be used hercin and include those materials which have Ihe sulfate moiety distributed rmldomly along the hydrocarbyl "backbone" of 3 5 the molecutc. Such materials may be depicted by the structure CH3(CH2)n(CH0503 ~)(CH2)mCH3 ~ W095/.34625 r~"~
wherein m .md n arc integers of 2 or greatemllld the smll of m + n ~s tspicaily about 9 to 17, and M
is a ~ter-solubilizing cation.
More preferably, a sclected secondary (2,3) ali~l sulfate surfactant is used herein which compnses structures of formulas A and i3 (A~ CH3(CH2)y(CHOSO3~M+) CH3 ru~d (B) CH3(CH2)y(CHOSO3-M+)CH2CH3 for the 2-suifate and 3-suifate, respectively. Mixtures of the 2- and 3-sulfate can be used hc-rein. In formulas A and B, x and (y+l) are, respectively, integers of at least about 6, and an range from about 7 to about 20, prcferably about 10 to about 16. M is a cation, such as an alkali metai, ammonium,: " ' , aikaline earth metal, or Ihe like. Sodium is t~pical for use as M to prepare the ~ . ' ' ' (2,3) alkyl suifates, but I ' ' ~" ' ' potassium, ammonium, and the like, can also be used. It is preferred that the sccondr1ry (2,3) alkyl suifates be substantially free (i.e., contain less than about 20~/u, more preferably less than about 10%, most preferably less than about 5~/O) of such 0ndom secondary aikyl suifates.
The prcparation of the secondary (2,3) alk~l sulfates of the type useful herein can be carried out by the addition of H2SO4 to olefins. A typical synthesis using c~-olefims and suifunc acid is disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent 5,075,041, Lutz, granted December 24, 1991, both of which are incorporated herein by reference. The synthesis, conducted in solvents which afford the secondary (2,3) aikyl sulfates orl cooling, yields products which, when purified to remove the unreactcd materiais, randomly suifated matenals, unsuifiltcd by-products such as Clo and higher aicohols, secondary olefin sulfonates, and the like, are typically 90+~~u pure mi,Yturcs of 2- and 3-suifated materials (up to 10~~u sodimn suifate is typicaily present) and arc white, non-tacicy, apparentiy cr~stailine, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5U~u of the mixture of secondary (2,3) alkyl, ~r ' Such matenals are aYailable as under the name ~DAN", e.g., "DAN 200" from Shell Oil Company.
If increased solubility of the "crystalline" secondary (2,3) alkyl sulfate surfactants is desired, the formuiator may wish to employ mixtures of such surfactanus having a mixture of aiicyl chain lengths. Thus, a mixture of C12-ClS alkyl chains will provide an increase in solubility oYer a secondaty (2,3) aikyl sub'ate wberein the alkyl chain is, say, entirely C 16 The solubility of the secondary (2,3) aikyl sub'ates can aiso be enhanced by the addition thereto of other surfactants such as the materiai which decresses the crystallinity of tbe secondary (2,3) aikyl sulfates. Such .... .J " ~ , _ materiais are typically effecth!e at levels of 20U~o, or less, of the secondary ~2,3) aiicyl sub'ate.
Bui!der Tbe detergent composition of the in~enlion also includes a detergency builder material to assist in controlling minerai hardness. Inorgrmic as well as organic builders can be used. Builders 2 1 9 2 ~
Wo 95134i62.S -8- P~
are t,~pically used m fabric laundcrin_ compositiolls to assist in Ille rcmoval of pardculate soils.
Inorganic detergent builders include, but are not limited to, the alkali mctal, amlDonium and salts of phytic acid, silia!tes, carbonates (includhlg bicarbonates and ', sulphates. and _' ~
Examples of si licatc builders are the alkali met tl silicates, particulariy thosc having a SiO2:Na20 raho in uhc range 16:1 ~o 3,2:1 and layered silicates. such as the byered sodium siliallcs dcscribed in U.S. Patent 4,664.839, issued hSay 12, 1987 to H. P. Rieck. NnSKS-6 is tite Uademark ior a crystalline layered silhate marketcd by i{oechst (commonly abbrevinted herein 35 "SKS 6"), Uniike zeolite builders, the Na SKS-6 siliGtte builder does not contain aluminum, NaSKS-6 has thc deltrt-Na25iO5 morpholo ;y form of hlycrcd si licatc It can be prepared by mcthodssuchasthosedcscnbedinGermanDE-A-3,417,649alldDE-A-3,742,043, SKS-6isa highly preferred layered siliaate for use herehl, but other such layered silicales. such as those having uhc general formula Na~SSix02x+ 1 yH20 whcrein M is sodium or hydrogen. x is a numbcr from 1,9 to 4. prcferably 2, and y is a number from O to 20. prefcrably O can bs uscd herein, Various other layered silicates from Hoechst includc NaSKS-5. NaSKS-7 and NaSECS-I 1. as the aipha, beta and gamma forms. As noted above. thc delta-Na2SiO5 (NaSKS-6 foml~ is most preferrcd for trsc hercin. Other siliaatcs may also be uscful such as for e.~ample magnesium silicate. which Gan servG
as a crisping agcnt in granuiar formuiations, as a stabilizing agcnt for oxygell bleaches. and as a component of suds conUol systems, Examples of Garbonate builders are the alkaline earth and aikaii metai Garbonatcs as disclosed in Germ~m Patent AppliGation No. 2,321.001 publishcd on Novembcr 15, 1973 1~ ' ' builders are useful in the present invention, A ' ' builders arc of great importance in most currentiy marketed heavy duty granular dctcrgent ~ , , and can aiso be a signifiamt buiider ingredient in liquid detcrgcnt fommlatiolls. ~ ' ' builders includc those having the empiricai forrnuia:
Mz~zAlo2)yl ~' H20 wherein z and y are integers of at least 6. the molar ratio of z to y is in the range from 1.0 to about 0,5, and x is an integer fmm about 15 to about 264, Usefui ' - ione,;change materialsare '~ available. Titese 30 ~ ' Gan be crystailine or amorphous in structurc and can be naturally-occurring or synthetiG~Iily derived. A method for producing ' " ion c,cchange mnteriais is disclosed in U,S, Patent 3.955,669. Kruntmel. et al. issued October 12. 1976, Preferred synthetic crystalline ' ' ion exchanpe rnaterials useful hcreill are available umder Uhe designations Zeoiitc A, Zeolite P (Ei). Zeolite MAP and Zeolitc X. In an especially preferred 35 embodiment~ the crystatline ~ ' ion exchangc material has Ihe fonmuia:
Nal2¦~Al02)l2(5io2)l2l xH2o 2l q254~
e W0 9513462S , ~ ., ..'0~2ql whercin x is from about 20 to aboul 30, especially abou~ 27 This material is kuowll as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be uscd herein. Preferably, the ' "' has a panicle size of about 0.1 - 10 microns in diameter.
Organic detergent builders suitnble for the purposes of the present invention include, but 5 arc not rcstricted to, a uide variety of tJul~.,ad~v.~' compounds. As used herein, "poly-carboxylate" refers to compounds having a plurality of carboxylate groups, preferably at Icast 3 carboxylates. Po'~ubu,~' buildcr can generally be added to the composition in acid form, but cam also be added in the forrn of a neutralized Sâl~. When utilized Ul salt form, alkali metals, such as sodium, potassium, and iithium, or " ' sal~s are preferred.
Included among the t ul~ i,u,, ~ k,;~, builders are a variety of c itegories of useful materials.
One important category of ,uul~w~bu.~ ' builders encompasses ~he e~her uul~.d.l,uA~; , including o~ li,u~;...,;., as disclosed in Berg, U.S. Pa~eut 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 19?2. See also "TlvlS~TDS" builders of U.S. Patent 4,663,071, issued to Bush et ai, on May 5, 1987. Suitnble ether ,UUIJ~Ui/U.~ also include cyclic compounds, particularly alicyclic compomlds, such as those describcd in U.S. Patents 3,923,679; 3,835,163; 4,158,635: 4,120,874 and 4,102,903, Other useful detergency builders include the ether LJ;jlU.~ JlJ~ d~u~L t~ copolymers of rnaleic anhydride vith ethylenc or vinyl melhyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and ~ ub~ ',u: ,: ~ ' acid. the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ~.h,' ' ' tetraacetic acid and ~ acid, as ~vell as t~ulJ.,~ubu~' such as mellibc acid, succinic acid, u.~
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, u.l-hu.~ ' '(, ' ' acid, and soluble ssits thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodlum salt), are ,uul~ ' , ' builders of parbcular Importance for hea~y duty liouid detergent formulabons due to their availabllity from renewable resources and their h' ~ 81 r, Citrates can aiso be used, however, in granular , ' ' . especially in combination with zeolile and/or layered silicate builders. tl, " ~ are also especially use~u'i in such composibons amd ' ' Aiso suitable in the de~ergen~ compositions of ~he present invenbon are the 3,3-dicarboxy-4-oxa-1,~ ' ' and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Usehll succinic acid builders include tlle C5-C20 alkyl and aikenyl succinic acids and salts thereo~ A panicularly preferred compound of this type is ~' ' , ' aad, Speci~dc examples of succindte builders Include: hu~ ' ' 1..~ . i,l~ ' ' .
~ ' ,, d~ J , ' (preferred), 2-u...L,du~ ' , and the like.
35 1 ~' ~ are the preferred builders of tlus group, and are described in European Patent Appiicadon 86200690.5/0,200,263, published November 5, 1986. O~her suikable t~ul~ u~.~
~21~254 5 r~, U~ !dO 79l -ID-aredisclosedinU,S,Patent4,14~,226,Crulchf~eldctnl,isslledMarch 13, 1979andhlU.S.i'ate:lt 3,308,1367, Diehl, issued March 7, 1967. See also Diehl U.S. Patellt 3,723,322.
Fatty acids, e g., C12-C18 ' ~h,, acids, cnn also be incorporated into the Composihorls ah~ne, or hl combination ~vitll the nforesnid builders, especinlly citrate nnd'or the 5 sucanate buiiders, to provide additional builder activity, Such use of fntty acids v ill generaily roeuit in a dimdnudoo of sndsing, wilich shouid be taken into account by thc rormulator.
Adhmct Surfactants One or more adjunct surfactants nuay bc included generally at a les~l of from about 1% to about 50~fO by ureight of the surfnctmn system described herehl. Nonlimiting examples of 10 surfactants useful in conjunction with the surfnct~mts described hereill are the C lo-C 18 alkyl alkoxy ctrboxy!ates(especiaiiytheE01-5~tlluAr~ huA~' ',theC10 18glyceroletllers,theClo-Clx aikyl t,ul~bl~"u"l~,, auld their , ' _ sulfated t~~lY~ ~va;~i~5~ al d C12-C18 ~
fatty acid esters. if desired. the conventianal nonionic and amphoteric surfactants snch as the C12-Clg alkyl etho~ylates (nAE~) including Ihe so-called narrmi~ peaked alityl etitoxylates and C6 C12 aikyl phenol alkoxylates (especiaily ethoAylates m3d mi.Yed ~tl~ y/ulù~Ay), C12-C18 b~tain~s and suifobetaines ("suitainesn), can also be included in the overnli , ' ' The C lu-C 18 N-aikyl polyhydroYy fatty acid amides cnn also be used. T~ picai e.;amples include the C12-C1 8 N-', 'g' ' Sec WO 9,2û6, 154, Thc N-propyl througll N-he.Yy l C 1 2-C 18 glucamidcs can be used for low sndsing C lo-C20 conventional soaps mny also be uscd. If high sudsing is desircd, the 20 ; ' ': ' ~ Clo-C~6 soaps may bc used, AiSD included in the surfactant system is the conventional Cl l-C~8 nlkyl benzene suifonates (aiso referenced herein as ~LAS) Whiie the b: S L~ ~ 1 ' 1' r of the so-called "LAS"
surfactants have been the subject of somc concern, the surfactant system Iterein may inclnde an optimum level, from about 0.1Cfo to about 15% au~d more preferably frmn about 3~fO to about S~fO by 25 welght, for improving the overail solubility of the detergent composition ~vithout substantially decreasing the overaii ' ' ~ of the present detergent compositioll, Alten~ali~ely, the levd oELAS may bc included as fmm abont 1% to about 40~/O, more preferably frDm about IOC~G to abont 25%, by weight of the surfactant system in the detergent composition.
Thc surfactant system may aiso include an amine oAide surfactant. Noniimiting eYamples 30 include C 10-18 amine oxides, secondary aunine o.Yides such as dimethyl aunine oYidc, and tcrtiary anane o~ddes baving the general formnla RR'R"NO in whicll R is a primary alkyl group containdng 8 to 24 carbon atoms; R' is methyl, elhyl, or 2 '., ' , ', :, and R" is ' . ' '~ selected from methyi. cthyl, 2 ', ' , "~ amd primary aiicyl groups containing 8 to 24 carbon atoms.
Addidonaily, the tertiary amine oAide surfaannt may be in hydratcd form and have tùe general 35 formuia RR'R"NO ~i20 ~herein R R' and R" are the s:lme ~s abovo and n is I or 2 Ft~3uluples of other tertiary amines suitable for use herein include those containing one or twû short-chain gronps ' ', ' '~ selectedfrommethyl,ethyl,and2 '.,11u~j_',lgroups,withthercmainini3valenccs 2l 92s4q WO gS134625 P~
of the amino nitrogen being satisfied witll imlg-ch;lin grouys iul.r...l ..ll~ selected from primar,v alicyl groups cwntaining 8-24 carbons~ e.g., octyl, decyi, dodecs l, tetr;ldec~ I, hexadecyl, octadecyl, eicosyl, docosyl. and tetracosyl groups. The primary alkyl groups ma), be brallclled-clmin groups, but the preferred amines are those in ~hich at least most of the primarv ali<yl groups ha~e a straight ~ 5 chain.
Exempiary of these ten-amines are N-o.t~' '' ' J ' ' , N,N- iki.~,~' ', ' ' ~, N-decal-N~iud.~,~ ' h~ ' ' , N lu~ ' N ~ ' ~ Idi....~h, ' ' , N-tetradecyl-N-~lh,' ' ,' ' , N . ' ,; N c ' ,1-2-LJ~u.~ lJ' ' ~, N,N di t..-.~J.~I 2-h,liu.~ ' ' , N ' ' ~' " ' ,' ' N l; ~al~ ' '' 2~ .tli,' ' N-10 u.~~ ' ',' ' ,N,i~l:" ' ,I.tl.~' ' N-docosyl-N-2 h, IIUX~ J' '',' ', N-W ~ ,: , etc.
Additional amine oxide suriactants and methods of makillg the snnne, all of ~vhich are suitable for use herein, are disclosed by Borland et al, U. S . Patent No . 5.071,594 and Tosaka et ai, U.S. Patent No. 5,096,621, incorporated herein by reference.
Mi ctures of anionic and nonionic surfacolllts are especial ly useful. Other wnvendonai useful surfactants are listed in standard texts.
Deter~ent Adhmct lnaredients The detergent composition can also hlclude ally number of additional ingredients. These include detergency bleaches, bleach actiYators. suds boosters or suds suppressers, anti-tamish and 20 antiwrrosion agents. soil suspending agents, soil relcase agents, gemlicidcs, pE~ adjusting agents, non-builder alkaiinity sources, chelating agents, smectite clays, enzyllles, ~.~c~ ...., ' '-' ' ~ agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Basicerville, Ir. et al., inwrporated herein b,v reference. Aiso, fabnc conditioning agents may be mcluded as an adjunct materiai such as those described in U.S. Patent 4,861,502, issued August 29, 1989 to Casv.~ell, incwrpontted herein by 25 reference.
Bieaching agents and activators are described hl IJ.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hamnan, issued November 20, 1984, both of ~Yhich are imwrporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071, Bush et ai., from Column 17,1ine 54 through Column 18, line 68, incorporated hercin by reference.
30 Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued J;muary 20, 1976 to Bartoletta et ai., and 4,136,0 15, issued January 23, 1979 to Gault et ai., both incorporated herein by reference.
Suitable smectite clays for use herein are descnbed in U.S. Pa~ent 4,762,645, Tucker et ai, issued August 9, 1988, Column 6, line 3 through Column 7,1hle 24, hlcorporated herein by reference.
35 Suitable additionai detergency builders for use hereill are enumerated in the Basker~ille patent, Column 13, line 54 through Column 16, line 16, and hl U.S. Patent 4,663,071, Bush et ai, issued E~iay 5, 1987, both incorporated herein by reference.
WO 95J3~i625 p~,' '!r ?91 Enzymes cao be included in the formulatim~s lserebl for ~ ide ~anety of fabnc laundering purposes, including removal of ~, . ' 1. cnrbohydrme-based, or n ~ .. . id.-l,a..d stains, for example and for the prevention of refugec dye transfer, ;md for fabric restortttion. The ens~mcs to be incorporated inciude proteases. amylases, lipases~ cellulases, and peroxidases, as ~eli as nuxtures 5 thereo~ Other typa of cnzymes may also be included They nhiy be of any suitable origin, r,uch as segetabie, animai, bactenai, fnngal and ycdst origim i~ow~er, their choice is governed by severai factors such as pH-ac~ivity andfor stability optima, ' 'si " ~, stability versur. active detergcnts, buiiders and so on. ln tbis respect bacterial or fmlgal enrymes are preferred, such as bacteriri amyiases and proteases, and fimgal cellulases.
Suitablc examples of protcascs are lhe svbtilisf ns ~vhich are obtained from particular strains of B.s~btilis an~ B. IicbeniJorms. AnQther suitable protease is obtained from a straill of Bacillus, ha~-ingmaximumectiiit!,throughoutthepiir,u~geof8-12,developedQndsoldbyNovollidustries A!S under the registered trade namc ESPERASE, The preparQtion of Ihis enzyme and analogous enzymcs is describcd in British Patent Specification No 1,243,78i of Novo. Proleolytic enzymcs 15 suitabk for rcmoving p,t.; I ' stains that are "~ available include thosc sold undcr the trade names Ai CALASE and SAVINASE by Novo Industries A/S (Denmark j and MAXATASE by Intcrnational Bio-Synthetics. Inc. tThe Netherlands) Other prote sa include Protease A ~see European Patent Application 130,756, published Janudry 9, 198S) and Protease B
(see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130.756. Bott et al, published January 9, 1985).
Amylasa include. for e~ample, a-amylases descnbed Ul British Patent Specification No.
1,296,839 ~Novo), RAPIDASE. International Bio-Synthetics, Inc. and TERMAMYL, Noso Industries.
The oellulase usable in the preseot invelltion hlclude both bactenal or fungal oellulase Preferably. they will have a pH optimum of between 5 and 9.5. Swtable oellulases are disclosed in U.S. Patent 4.435.307, Barbagoard et al. issued March 6. 198S, whicll discloses fungal cellulase produoed from Humicola insolens and Mumicola strain DSM1800 or a cdluhlse 212-producing f~mgus bdongdng to the genus Aeromonss, amd oellulase e:;tracted from the ' , , of a marine nwllusk (Dolabella Auricula Solander) suitable cellulases are also disclosed in GB-A-2.075.02's GB-A-2.095.275andDE-05-2.2$7832.
Suitable lipase enzymes for det~gent usage hwlude those produced by , of thePseudomonasgroup,suchasPreudomomasstulzeriATCC 19.154,asdlr,closedinBritjshPatcnt 1.372,034. See also lipascs in Japanese Patent Application 53,20S87, laid open to public inspection on Febn ary 24, 1978. This lipase is avaihlble from Amallo P'- - - - ~ i ~ I Co. Ltd., Nagoya, 35 Japarl, umder the trade oame Lipase P "Amano,~ hereimlfter referred to as "Amsno-P. ~ Other conuncrcial lipasa include Amano-CES, lipasa ex C' ' viscosunt, e.g. t~hrn~h~ rrviscosum var. Iipolyticum NRRLB 3673, commercially availnble from Toyo rOzo Co., Tagata, 21 '~254'~
~ W095134625 P~lf~ 91 -Il-lapan: and further Chromobacter viscosmll lipnses frmll U.S. Biochelllical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipnses ex Pseudmllollas ghldioli. The LIPOLASE enzyme dem~ed from l .umicola lanuginosn and commercially nvail;lble from Noi o (see also EPO 341,g47) is a preferred lipase for use herein.
PeroxiLlse enzymes are used in combhlatioll ~ith ox~gen sources, e.g., p~rr~
perborate, persulfite, hydrogen pero.Yide, etc. They are used for ~'sohltioll blalching," i.e. to prevent Lransfer of dyes or pigments removed from substrates during ~vnsh operations to other substrates in the wash solution. Peroxidase enymes are known in the art, mld include, for example, horseradish peroxiLase, ligninase, and 1 ~ such as chloro- and bromo-peroYiLase. Pero.Yidase-containing detcrgent compositions are disclosed, for e.Y1mple, hl PCT International Application WO
89/099813, published October 19, 1989, by O. Kirk. assigned to Novo Indlls~ries A/S.
A v.ide range of enymc materials auld means for their ~ .s i into syntheLc detcrgcnt compositions arc also disclosed in U.S. Patellt 3,'J53, 139, issued January 5, 1971 to McCarty et al. Enymes are furtiler disclosed hl U.S. Pateot 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued Marcll 26, 1985, both. Enzyme materials usef for liquid detergent formulations, and their h~ ,lrliull into such formulations, are disclosed in U.S.Patent4,261,868,Horaetal,issuedApril14,1981. EnzymesforuseilldetergentscanbesLabilized by various techniques. Enzyme sLnbilization teclmiqlles are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, ~/enegas.
Enyme stabilization systems are also described, for ex,ample, hl U.S. Patent 3,519,570.
Additionally, dye transfer inhibiting agents may also be hlcluded, for example, J ~ f 't-, ' ' , polyamine N-oxide, copolymers oF N ~ " ' and N s ...~ " ' ' aro a suiLable dye transfer inhibidng polymers for use in the present detergent composition. The level of such additional dye transfcr inhibiting agents may var,v, but t~pically will be from about 0.0 IO~D tO about 10~~O by weight of the detergent composidon.
Al . 'r ' Process The follo~ving describes and exemplif as thc n, ,~ , process by which thc detergent composition of the inven don is produced. The parameters noted herein are exemplary only and should not be considered as limi~dng in any way.
Steo A - Preparation of Surfactant Paste - Tbe objeai-e is to combille the surfactants and liquid in thc compositions into a common mix in order to aid in surfactant ' ' "' ' and ~,,' ' In this Stcp, the surfactants and other liqmd components are mixed together in a Sigma Mixer at 140~F (60~C) at about 40 rpm to about 75 rpm for n period of from 15 minutes to about 30 minutes to provide a paste having the general consislency of 20,000-40,000 centipoise.
Once thoroughiy mixed, thc paste is stored at 140~F (60~C) until a2~,' ' Step f~B) is raidy to be conducted.
54 ~ ~ ~
WO f~C/3 ~625 P~ ~
SteD B - APol~ f~fif~n of Powders s ith Sllrfact:lm Paste - The purpose of this Step is to transform the base formula ingredients includfilg the wa~er-solllble stccharides descnbed herein into flowablc delergent aggdomerates lua h1g a n ean particle size rangc of froul about 800 microns to about 1600 microns. In this Stcp, Ihe powders (hlcludillg materials such as zeolite, citrate, citric 5 acid bnilder, la~ered silicate builder (as SKS-6~, rodimn cdrbmulte, ~Lh~' " " , magnesiwn sulfatc and opdcal brightener) are charged into the Eirich Mi.aer (R-Series~ and mixed brieffy (ca. 5 seconds - 10 seconds) at about 15a0 rpm to about 3000 rpm in order to mix the various dry powdcrs fully. The surfactant paste from Step A is then cluarged hlto the mixer and the mixinvg is continued at about 1500 rpm to about 3000 rpm for a period froul about I minute to about 10 10 minutes, preferably 1-3 minutes, at ambient temperature The miYing is stopped when coursc agglomeratcs (average particle size 800-1600 microns) are formcd.
SteD C - The pu-pose of this Step is to reduce the al_' ' stickiness by .,'d~J ' v moisture and to aid in panicle size reductloll to the target panicle size (in the mean particle size r~mge from about 800 to about 1600 microlls~ as measured by sieYe analysis). In 15 this Step, the i'f et agglomerates are charged imo a tiuidized bed at an ai r stream temperature of from about 41~C to about 60~C and dned to a final moisture cmltent of the particles from about 4~~O to abont 10%.
SteD D - Coat Aft~lomerates arld Add Free-Flow Aids - Tlte objective in this Step is to achieYe the fmat target agglomerate size range of from about 800 microns to about 1600 microos, 20 and to admQI materials which coat the 1__' ' , reduce the ~i.,bl' , 1 tendency of the particles and help maintain acceptable nowabiliq,. In this Step, the dried agglomcrates from Step C
are charged into the Eisich Mir~er (R-Series) and miYed at a rate of about 1500 rpm to about 3000 rpm while adding 1-6% Zeoiite A (median panicle size 2-5~"m) durfilg the mi.Ying. The mi,Ying is continocd until the desired median p~trticle size is acbieYed (typically trom abom 5 seconds to about 45 scconds) . At this pornt, from about 0. IYo to about I . 5~/O by w eight of precipltated silica (avcragc pardcle size 1-3 microns) is added as a flow aid and the mi.Ying is stopped.
Io order to make the present invention morc rcadily understood, referencc is madc to the following eYamples, whicù are intended to be illustrnive only and not mteltded to be limiting in scopc.
EXAMPLE I
Sevcrai detergcnt compositions ~A and B) are made in accordallce with the ~ ,,vi -- ~
process describcd above. Composidon B is within t he scope ot the in~ention and composition A is outside oF the invcndon and is presented for purposes of comparison as described in Example 11 hereinafter. The relativc proportions of compositions A and B, hl a~lomerate form, are listcd in Table I betow~
21 9254q ~ WO 9513462S P~ e.r ~ 1 t TABLE I
(U~ ei~htl Comr onent A B
C14 15 aiicyl sulfate 20.0 29.4 C16 aikyl etilo~ylate ~EO = 0.6~ sulfale 5.0 7.3 ~1 ' 4~.9 47.2 C12,13 lincaralicylbenzenesulfonate15.6 Sucrose -- 10 Sodiumcarbonate 1~,1 15.0 Minors (water, perfume, elC ) = O I
100.0 100.0 EXAitll'LE n This Esample illustrates the surpnsingly impros~ed sohlbility achieYed by the detergent composition of the invention Specifically, standard dosages of cmnpositimls A and B ~1170 ppm) are dissolved in an ;tqueous laundenng solution hai hig a s~ater temperatllre of 1 0~C and a water hardness of 7 grains/gallon (Ca i~lg ratio of 3 1 ) The lamldenng solution is condnuously agitated at a rate of 75 rpm and samples of the wash solution were taicen at various time intervals as showtt in Table I below, For purposes of illustrating the improved sohlbility of the detergent composihon according to the inYelltion, the amomlt of surfictant in the laundering solution is determined by conducdng the v, ell known "catS03" titration technique on the srlmples taken from hldiYidULil wash soludons containing one of the compositimls A or B In particular, the amount of anionic surfactant in the laundcring soludon is determined by filtering the samples through 0.45 nylon f lter paper to remove the insolublcs and thereafter~ titrating Ihe filtered solution to ~hich anionic dycs (dirnidium bromide) have been added with a cationic dtrant such as HyamineTM ' "~ availabte from Sigma Chemicai Company Accordingly, dhe relativc amomlt of anionic surfactant dissolved in d e w&sh solution atn be detcrmined This teclunique is ~vell knoH~n and others may be used if dcsired Thc results are shown in Table 11 below TABLE n (~/0 total of anionic dissolved) Time IMinutcs~ A B
1 26% 16C~u 3 38U~o 34%
42% 57%
~5% 71%
From dhe rcsults in Tablc 11, it is quite clcar that composition i3 whicll is within the scope of thc invention surprisingly has improved solubility over composition A which is outside the scope of dhe 25 invendon ~ I q~S~9 W095J34625 l~l/u.,._~r-E~I~IPLE 111 A laumdry bnr C suit~ble for ~ soiled fablics is prepared by a s~mdard e:strusiorl process and cornprises the follo~villg h~gredients listed iu Table 111:
(% - Cight) ~mE~ C
C14 ~ alkyl sulfs~e 20.0 C16 al~yl etho.sylato (E0 - 0.6~ sulfate 5.0 ~1 " J~.~
C12 13 lincar alkylbcnzene sulfonate 15.G
Sucrosc 1.0 Sodium carbonate 14.1 Minors twater, perfume, etc.) 0,4 I_ HaYing thus describcd the im~cntioll in detail, it will be clear to thosc skilled in the art that Yarious changes may be made Yfithout depnrting from tlle scope of the in~enlion and the h~Yention is not to be considered limited to Yrh;lt is described in the specification.
What is claimed is:
SACCHARIDES
S FIELD OF THE INVENTION
The poesent invention is generally directcd to an a,,~,' ' compact detergent composition having improved solubility in cold tcmperature laundering solutions. Morc particulsrly, the imvention is dircctcd to a detergent composition containing high levels of a sulfated surfactant selected from the group consisting of alkyl sulfates (also referenced herein as "AS"). alkyl ethoxy sulfates (also referenced heoein as "AES"), and secondary alL~I sulfates (also rcferenced herein as 'SAS") and mixtures thereof, and selected amounts of t~ater-soiuble saccharides, together tvhich rmprove the overall solubility o m ' , ' " x Or the cornposition in cold temperature washing solutions (e.g. 5~C to 30~C) and high water hardness conditions (e g, 7 _ '~, " ) For purposes of producing a high density, compact detcrgel1t composition, the detergent of the invention is in the form of detergent agglomerates rather than spray dried grtmules.
BACKGROUND OF T~ INVENTION
Typically, conventional detergent compositions contain mixtures of various surfactants In order to rcmove a ttide variety of soils and stains from surfaces. For example, various anionic surfactants, especially the alkyl benzcne sulfonates, are useful for removing particulate soils, and various nonionic smfact~mts, such as the alkyl ethoxylates and alkylphenol etho.xylatcs, are useful for removing greasy soils.
While thc art is rcplete with a ttide vanety of surfactants for those skilled in the art of dctergent formulation. most of the available surfactants are specialty chemicals which are not suitable for routine usc in low cost items such as home laundering ~ , Thc fact remains that many home-use laundry detergents still comprise one or more of the conventional alkyl benzenc sulfonates or primary alkyl sulfate surfactants. Another class of surfactants which has found use in various compositions whcre ' - is desired comprises the secondary alkyl sulfates. The convcntional sccondary alkyl sulfate smfactants are available as generally pasty, random mixtures of sulfatcd lincar and/or partially branched alkanes.
The limitcd solubility of alkyl sulfate surfactants including both primary and secondary alkyl sulfates is cspecially prcvalent in modern granular laundry detergents which are typically used m cold tempcrature (e.g. 5~C to 30~C) washing solutions and are formulated in "condensed" or "compact' form for low dosage usage. For the consumer, the smaller package sizc attendant with compact detergent prooucts protides tor casy storage snd l~andling. For the I ~ unit storage costs, shippmg costs and packaging costs are lowercd.
The manufacture of acceptable compact or condensed granular detergents has its difficulties. In a typical compact detergent formulation, the so~alled "incrt" ingredients such as ~0 9.'~/34625 -2~ 91 sodium suifate are substantiaily eliminmed. Hou~ever, such h~gredierlts do play a role in enhancing solubllity of conventionai detergcnts. As a consequence. cornpact detergents ofteil suffer from solubility problems, especially in cold tempernture laundering solutions. ~ioreovcr, conventionni compact or low density detergcnt granuies are usually prepared by spray drying proces~s v.~hich 5 result in extremely porous detergent particles that are quite amenable to bcing dissolved in aqueous washjng solutions. By contrnst, compact detergents are typically comprised of less porous, bigh density detergent pardcles which are less soluble, e.g. ~t~PJnn~ ~ Thus, since tho compact form ol granuiar detergents typicatly compn~ particles or granules which contain high levels of detersive ingredients with littie or no room for solubiliz.ing agents, and since such particies are intentionaily ~ ' at high br~k densities, the net result can be a substantial problem with regard to in-use solubility.
In the art of detergency, sugars have been to smne extent used to replace sodium siiicate for purposes of improving soiubility of spray dried granuiar detergents For example, one attempt in the past was directed to a spray-dried detergent composition cmltaillillg sugars and a seed crystai for 15 caicium carbonate to provide improved solubility. Howevcr, only ~spray-driedU detergent compositions ha~ing lov. e ' ' o f suifated snrfactants have been considered in the past.
Thus, the problems associated with modern day compac~ dctcrgents having densities vrhich are much higher (650 gli or more~ have not been addressed, as yet. Generally speaking, oniy the highiy densbled ~ ' detergcnt compositions encounter a much more difficult problem of 20 dissolving in cold temperature laundering solutions as compared to less dense spray-dried detergents.
Accordingly, despite thc disclosures in the art, there remains a need for art higb density detergent composition which has improved water solubilily, especiaily in cold temperature washing solutions. Tlus need is especiaily prevalent in the art of compact or high 25 density deterger ts currendy being used by consumers.
B~CKGROUND ART
The foiiowing patents dirrclo~ the use of sugars in detergents , ' ' Davies et ai, U.S. Pat. No. 4,908,159 (Lever Brothers Co.); Davies et al, U.S. Pat. No. 4,755,318 (Lever Brothers Co.); McCaiiion et al, U.S. Pat. No. 4~65~,782 (Lever Brothers Co.~; Cheng, U.S.
Pat. No. 4,414,130 (r' 1~ ~r ~ ~ . cO.); Finck, U.S. Pat. No. 3,821,118 (~ r ~ ~Co.l; IP Pat. No. 52094304 (Yukcn Kogyo iClC~, JP 58125797 (Shiseido KK); JP 60060196 (Kanebo KK); ~P 61238894 (S~mstar KK); JP 04146998 (Lion Corp.).
nte foliowing patent discloses secondary aikyl suifates: P~ossall ct ai, U.S. Patent No, 4,235~752, ~ W0 95134625 r~ n........................................ ~ 91 SUMMARY OF T~F. INVENTION
The prescm invention meets the needs iden~ified above by providhlg a detergent composition in the form of agglomerates vrllich exhibits improved solubility or dissolution of the anionic surfactants in cold temperaturc wasiling solutions as well as mlder iligh water hardness 5 conditions. The detergent composition comprises a surfactant system having a high level of a sulfated surfactant selected from the group of al~d sulfates, alkyl ethox~ sulfates, secondary alkyl sulfates and mixtures thereof, jD combination with a nater-soluble saccharide. Other adjunct detergent ingredients may also be included in the detergent t~_' which form the detergent composition. Additionall5~, the composition surprisingly exhibis imprwed water solubility despite 10 being in the form of high denr.~ty I __' and being subjected to cold temperature washing solutions.
As used herein, the phrase "improved solubility" mans that the solubility of the anionic surfactants of the detergent composition is enhanced by at least 5~~0 in the laundering soludon when employed in the manner of this invention, as compared to the solubility of the same anionic 15 surfactanB per se, umder the same test conditions (i.e. water temperature and pH, stimng speed and time, particle size, water hardness, and the like). As used herein, the term n ~ refers to particles formed by aw' " _ particles wluch typically have a smaller mean particle size than the formed w' All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documenB including patents and publications cited herein are incorporated 20 herein by reference.
In accordance v ith one aspect of the inventdon, a detergent composition in the forrn of agglomerates is provided herein. Tbe detergent composibon comprises from about 1~~u to 50~,~u by weight of a detersive surfactant system. The surfactant system itself comprises, by weight of the surfactant system, at least about 30~/0 of a sulfated surfactant selected from the group consisting of alkyl sulfates, 25 alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof. The detergent composition includes from about 0.1% to about 5YO of a ~ ' ' ' saccharide selected from the group consisting of cellobiose, ducose, maltose, lactose, ribose, and lactulose mi.~nures thereof Also, the detergent composibon includes at least about IYo by ~height of a detergency builder to enhance cleanmg. Tbe surfact;mt system, ~ ' ' ' saccharide, and builder are a_~' ' to form detergent 30 agglomerates having a density of at least about 650 g/l. The detergent composition has improYed solubility in aqueous taumdering solutions. Thus, the solubility of the sulfated surfactant (AS, AES
amdlor SAS~ is enhanced by at least 5YO, prefenably 10 to 50YO oYer those same surfactants alone under the same test conditions in aqueous washing solutions at cold ~ .e. 5DC to 30~C.
In amother embodiment of the invention. the sulfated surfactant is a mixture of alkyl sulfate 35 and alkyl ethoxy sulfate surfact;mts. Further, the detergcnt composition may include adjunct ingredienB selected from the group consisting of bleaches, bleach activators, suds suppressers and soil release agents.
~ 1 ~254~:~
W09s/~3462 i r~l~u..,.~ 2 )1 In a preferred embodiment, the detergency builder is selecled from the gruup Nnsisting of carbonates. zeolites and mi::tures thereof. The surfactan~ systern may f3mhcr comprise, by weight of the surfachnt system, from about 1% to about 50~/0 of a C lo-C 1~5 N~alkyi polyhydro: y fatty acid amide for use as an adjunct surfacttmt. In another embodmlent, t3ae comporition may include from about O.lC~o to about 15h of a linear alkylbenzene sulfonate surfactallt.
In a preferred embodiment of the invention, the detergem composition comprises: (a~ at least sbout 30~K by ueight of a suifated surfact33n~ seieaed from tl-e group consisting of atkyl ~ sulfates, alkyl etho.cy r~lfates, seNnd3ry alkyl sulfates and uli?;tures thereof; ~bi from about 0.1% to about 5~~0 by weight of sucrose; and (c) at least about 1% by weight of a detergency builder, wherein the surfactant system, saccharide and builder are a,,~ to form detergent agglomerates havirlg a denslty of at least 650 gli. The sulfated smfactant of the surfactant system has improved solubility in an aqueous hundenng solution aud the composition is substantially free of phosphates.
In accordance 7~ith anotber sspect of the ini entim3, a method for laundering soded fabrics is prosided. The method comprises the step of contacting soiled fabrics with an effective amount of a daergent composidon as desclibed herein in an aqueous laundenng solution. An offective amount is t~picslly on tho order of 1000 to 1500 ppm. Yet another embodiment of the invendon is di-ected to a laundry bar formed fmm compositions described herein.
Accordingly, it is an object of the present invention to provide a grtmuiar detergent Nmposition which has impmved solubility, especially in cold tempcr3rurc v ashing solutions. Il is also an object of the invention to provide such a detergent cmnposition which has impmved b: -i ~ - ' 7- ~ . These and other objects, fea{ures and attendant advantages of the prosent invendnn will become apparent to those skilled in the an from a reading of the foliowillg detailed descliption of the preferred embodiment and the tlppended claims.
D77TA7r .Fn D7~5CR~PT.70N OF rHE . REi E7.~RED E7~R( m~7NT
The invention is directed to a granular delergent composition ha~ing impmved solubility in cold temperature la7mdering solutions. A muititude of conrumers around the world launder soiled c othes in conventionai washing mschines unique to their particular geographic location. Tgpicaily, these conventionai washing macbines iaunder the soilod clothes in water supplied at rclatively oold for etuunple in range of 5~C to 30~C, and at high hudness e.g. 7 gtainslga7.10n lnch uith Ca and Mg ions). 7.~iost nf the nnodem day consumers aiso use compact or condensed laumdry detergents to accomplish their laundering needs. Undcr the r conditions, solubiliq of current detergents in agueous laundering solutions has been a problenL as montioned previously. This problem is especiaily exacerbated when the detergent composition has high le els of a kyl su7htos, a7kyl ethoxy Nlfate andlor secondary ahkyl suifates which ate not particularly a7nenable to dissolution jR cold aqueous laundcring solutions. Such rurfactantS aro particularly usefiR in modcrn hundry detergents since they minimiae or elin iMte the need for linear aikylbenzene suifate suRactants which gencrally have poor ' i ~ . 7M.oreover, ~1 925~9 ~ W0 9S/3462s P~ , .'C 62gl .~.
recenl compnct detergents have strived to limit or eliminate the use of phospllates uhicil are knoun to increase uater solubility, In view of this trend, the uater sohlbility problem is exacerbated further.
It has been foumd that highiy dense, ~ ' ' detergent compositions cnn experience 5 improved ~ , if selected nmounts of n wnter-soluble sncchnride nre included. Such detergent compositions prefernbly nlso include a smfnctant system wllich comprises at least 30~~0, prefernbly from about 35~/0 to about 90~/0, of n sulfated surfactallt selected frmll the group consisting of nlky' sulfntes, nikyl cthoxy suifates, secondary alicyl sulfates and mixlures thereof, Preferably. the detergent composition is in the form of 3=~' nnd hns nn overall densiy of 650 g/l or higher.
10 These fentures provide the rcompact" nature of the detergent composition i u nccordance u ith the invention, Preferably, the detergent composition of the invention also comprises nt lenst nbont 1%, preferably from about 10~/0 to nbout 40~~0, nnd most preferably from nbout 15~~0 to nbout 35~/0, of n detergency builder. The detergent composition may nlso include one or more of adjunct detergent ingredients. Noniimiting exnmples of the detergency surfnctant. wnter-soluble sncchnride.
15 detergency builder nnd ndjunct ingredients are described h1 detail hereinnfter.
For purposes of enhnncing b ~ v~ the delergent 1~' - wluch form the detergent composition of the invention preferably do not contnin phosphntes, Funher, it is impon~mt for the detergent Qmposidon to be in the forrn of " ==' " as opposed to spray dried grnnules. In addition to being nmenable for modern compact detergents, this is pardcuinrly 20 imponnnt since most sulfated smrfactants cannot be readily subjected to spray drying processes u ithout cnusing or creating extremely adverse plumes from the spray drying touvers.
The "improved solubiiity" achieved by the detergent composition is concerned with enhnnced solubility of the anionic surfactants contained in the surfactnnt system. i e. AS, ALS, SAS
or LAS if used. Preferably, the improvement represents at lenst n 5~~0 increase in solubiiity of these 25 nnionics in the wash solution over the solubility of the same surfactants if they were dissolved sione or without being contained in a detergent composition as defh~ed herein. More prefernbly, the solubiiiq improvement is from nbout 10% to nbout 50~~0 As those skilled in the art uill npprecinte, nmy compnrison of snionic smrfactant solubility should be completed under the same isundenng condidons, e.g. wntor temperature, hardness and pH, stirrhlg speed nnd time, and pnndcle sr2e.
30 Typicsi snior~ic surfsct~mt solubiliq , are set forth in thc Esamples hereinnfter.
Those skillcd in the srt should nlso npprecinte the numerous ~ays m which the nmount of the surfnctsnt system in the washing solution can be deterrnined For exmnple, in the so-csiled ~catS03~ titration technique, samples of the nqueous laundering solution containing the detergent composition c~m be tnken sfter one minute nnd filtered with 0.45 mm nylon filter HPLC, sfter which 35 the filtereri solution csn be dtrated with n cationic titrant, which can be "~ purchased, e.g. from Sigms Chemicni Company under the trnde nnme Hymnine, in the presence of anionic 2 1 9~54~ ~ ~
WO ~';t34625 i dyes. From thc foregoing, IhC amomlt of anionic surfict.ult which w3s dissolvcd in ~he uashing solution cnn be dcterrnined.
v;'nler-Soluble Sncchnride It has been foumd that the solubiiity of high-content alkyl sulfDte, al~yl etho~y suifate 5 amdlor secondary alicyl suUate ~"sulf3ted" surLIctnnt systcm) compact detergent composition in lhe form of agglomerates c~m bc increased by . ~ n water-soluble saccharide selected from the group consisting of glucose, mattose, cellobiose, Iactose, ribose, mld Inctulose mixtures thereof into the composition. Other mono-, di-, and poly- sacchnndes mld derivatives tbercof may be used in thc compositioms herein without departing from the scope of the invenbo:l. The snccharide repeating 10 m it can h~tve ns fev, as five cnrbon ntoms or as mnm,y as fift,v cnrbon ntoms consistent usth water solubiiity. To that end, the preferred detergent composition of the invention comprises from about 0 1% to about 5~~O more prefernbly from nbout 0.5~~O to nbout 4ffO, and most prefcrnbly from about 2% to about 4~~O by veiyht of the vater-soluble sacchande. The most preferred water-soluble saccharide is sucrose ~r its avnilability, i , ~ ., nnd performance. 8y "water-soluble" in 15 the presenl contest, it is meant thnt the sacchnnde is capnble of fomlillg a clear solution or a stable colloidai dispersion in distilled water nt room tempernture nt a ~ -- of 0.01 g/l.
Surfnctnnt Svstem The surfncLmt system in the detergent composition must include a suifated surfactant selected from the group consisting of alkyl suifates, alkyl ethoxy suifates, secondnry alkyl suifates, 20 and mi.ctures thereoL As mentioned previously. the nnionic surfnctnnts in the surl'nctnnt systcm of the invention. i.e. AS, AES, amd/or SAS, hnve improved solubility and more particularly, on the ordcr of 5~K or luigher. Optionnily, the surfactnnt system mny conlain onc or more of ndditionni surfac~mts, nonbmiting examples of which nre provided hereinnfter.
The surfar,tnnt system preferably includes com,entioR.Il prinLary alkyl suifJte suRaçtants 25 hnve the generai formula ROSO3-M+
wherem R is typicaily a linenr C to-C20 hydrocnrbyl group nnd M is a Ihaler-solubilizing çation.
'' ' '.,1~. primary alkyl sulfate surfaçtnnts (i.e.. I ' I c~n "PAS") hnving 10-20 cnrbon atoms am atsç be used hcrein; see, for c,sample. Europenn Patent Applicntion 43 9,316, Smith et ai, fiied 21.01.91, the disclosure of which is iucorporated herein by reference (Included in the term "atkyl" is tbe aikyl pordon of acyl groups). Included in the surfactnnt system are ~he C 10-C 18 alkyl nikoxy suifates ("AEiySn especinlly EO 1-7 ctllo ey sulfates).
Conventional secondary alkyl sulfate surfactnnts can also be used hercin and include those materials which have Ihe sulfate moiety distributed rmldomly along the hydrocarbyl "backbone" of 3 5 the molecutc. Such materials may be depicted by the structure CH3(CH2)n(CH0503 ~)(CH2)mCH3 ~ W095/.34625 r~"~
wherein m .md n arc integers of 2 or greatemllld the smll of m + n ~s tspicaily about 9 to 17, and M
is a ~ter-solubilizing cation.
More preferably, a sclected secondary (2,3) ali~l sulfate surfactant is used herein which compnses structures of formulas A and i3 (A~ CH3(CH2)y(CHOSO3~M+) CH3 ru~d (B) CH3(CH2)y(CHOSO3-M+)CH2CH3 for the 2-suifate and 3-suifate, respectively. Mixtures of the 2- and 3-sulfate can be used hc-rein. In formulas A and B, x and (y+l) are, respectively, integers of at least about 6, and an range from about 7 to about 20, prcferably about 10 to about 16. M is a cation, such as an alkali metai, ammonium,: " ' , aikaline earth metal, or Ihe like. Sodium is t~pical for use as M to prepare the ~ . ' ' ' (2,3) alkyl suifates, but I ' ' ~" ' ' potassium, ammonium, and the like, can also be used. It is preferred that the sccondr1ry (2,3) alkyl suifates be substantially free (i.e., contain less than about 20~/u, more preferably less than about 10%, most preferably less than about 5~/O) of such 0ndom secondary aikyl suifates.
The prcparation of the secondary (2,3) alk~l sulfates of the type useful herein can be carried out by the addition of H2SO4 to olefins. A typical synthesis using c~-olefims and suifunc acid is disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent 5,075,041, Lutz, granted December 24, 1991, both of which are incorporated herein by reference. The synthesis, conducted in solvents which afford the secondary (2,3) aikyl sulfates orl cooling, yields products which, when purified to remove the unreactcd materiais, randomly suifated matenals, unsuifiltcd by-products such as Clo and higher aicohols, secondary olefin sulfonates, and the like, are typically 90+~~u pure mi,Yturcs of 2- and 3-suifated materials (up to 10~~u sodimn suifate is typicaily present) and arc white, non-tacicy, apparentiy cr~stailine, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5U~u of the mixture of secondary (2,3) alkyl, ~r ' Such matenals are aYailable as under the name ~DAN", e.g., "DAN 200" from Shell Oil Company.
If increased solubility of the "crystalline" secondary (2,3) alkyl sulfate surfactants is desired, the formuiator may wish to employ mixtures of such surfactanus having a mixture of aiicyl chain lengths. Thus, a mixture of C12-ClS alkyl chains will provide an increase in solubility oYer a secondaty (2,3) aikyl sub'ate wberein the alkyl chain is, say, entirely C 16 The solubility of the secondary (2,3) aikyl sub'ates can aiso be enhanced by the addition thereto of other surfactants such as the materiai which decresses the crystallinity of tbe secondary (2,3) aikyl sulfates. Such .... .J " ~ , _ materiais are typically effecth!e at levels of 20U~o, or less, of the secondary ~2,3) aiicyl sub'ate.
Bui!der Tbe detergent composition of the in~enlion also includes a detergency builder material to assist in controlling minerai hardness. Inorgrmic as well as organic builders can be used. Builders 2 1 9 2 ~
Wo 95134i62.S -8- P~
are t,~pically used m fabric laundcrin_ compositiolls to assist in Ille rcmoval of pardculate soils.
Inorganic detergent builders include, but are not limited to, the alkali mctal, amlDonium and salts of phytic acid, silia!tes, carbonates (includhlg bicarbonates and ', sulphates. and _' ~
Examples of si licatc builders are the alkali met tl silicates, particulariy thosc having a SiO2:Na20 raho in uhc range 16:1 ~o 3,2:1 and layered silicates. such as the byered sodium siliallcs dcscribed in U.S. Patent 4,664.839, issued hSay 12, 1987 to H. P. Rieck. NnSKS-6 is tite Uademark ior a crystalline layered silhate marketcd by i{oechst (commonly abbrevinted herein 35 "SKS 6"), Uniike zeolite builders, the Na SKS-6 siliGtte builder does not contain aluminum, NaSKS-6 has thc deltrt-Na25iO5 morpholo ;y form of hlycrcd si licatc It can be prepared by mcthodssuchasthosedcscnbedinGermanDE-A-3,417,649alldDE-A-3,742,043, SKS-6isa highly preferred layered siliaate for use herehl, but other such layered silicales. such as those having uhc general formula Na~SSix02x+ 1 yH20 whcrein M is sodium or hydrogen. x is a numbcr from 1,9 to 4. prcferably 2, and y is a number from O to 20. prefcrably O can bs uscd herein, Various other layered silicates from Hoechst includc NaSKS-5. NaSKS-7 and NaSECS-I 1. as the aipha, beta and gamma forms. As noted above. thc delta-Na2SiO5 (NaSKS-6 foml~ is most preferrcd for trsc hercin. Other siliaatcs may also be uscful such as for e.~ample magnesium silicate. which Gan servG
as a crisping agcnt in granuiar formuiations, as a stabilizing agcnt for oxygell bleaches. and as a component of suds conUol systems, Examples of Garbonate builders are the alkaline earth and aikaii metai Garbonatcs as disclosed in Germ~m Patent AppliGation No. 2,321.001 publishcd on Novembcr 15, 1973 1~ ' ' builders are useful in the present invention, A ' ' builders arc of great importance in most currentiy marketed heavy duty granular dctcrgent ~ , , and can aiso be a signifiamt buiider ingredient in liquid detcrgcnt fommlatiolls. ~ ' ' builders includc those having the empiricai forrnuia:
Mz~zAlo2)yl ~' H20 wherein z and y are integers of at least 6. the molar ratio of z to y is in the range from 1.0 to about 0,5, and x is an integer fmm about 15 to about 264, Usefui ' - ione,;change materialsare '~ available. Titese 30 ~ ' Gan be crystailine or amorphous in structurc and can be naturally-occurring or synthetiG~Iily derived. A method for producing ' " ion c,cchange mnteriais is disclosed in U,S, Patent 3.955,669. Kruntmel. et al. issued October 12. 1976, Preferred synthetic crystalline ' ' ion exchanpe rnaterials useful hcreill are available umder Uhe designations Zeoiitc A, Zeolite P (Ei). Zeolite MAP and Zeolitc X. In an especially preferred 35 embodiment~ the crystatline ~ ' ion exchangc material has Ihe fonmuia:
Nal2¦~Al02)l2(5io2)l2l xH2o 2l q254~
e W0 9513462S , ~ ., ..'0~2ql whercin x is from about 20 to aboul 30, especially abou~ 27 This material is kuowll as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be uscd herein. Preferably, the ' "' has a panicle size of about 0.1 - 10 microns in diameter.
Organic detergent builders suitnble for the purposes of the present invention include, but 5 arc not rcstricted to, a uide variety of tJul~.,ad~v.~' compounds. As used herein, "poly-carboxylate" refers to compounds having a plurality of carboxylate groups, preferably at Icast 3 carboxylates. Po'~ubu,~' buildcr can generally be added to the composition in acid form, but cam also be added in the forrn of a neutralized Sâl~. When utilized Ul salt form, alkali metals, such as sodium, potassium, and iithium, or " ' sal~s are preferred.
Included among the t ul~ i,u,, ~ k,;~, builders are a variety of c itegories of useful materials.
One important category of ,uul~w~bu.~ ' builders encompasses ~he e~her uul~.d.l,uA~; , including o~ li,u~;...,;., as disclosed in Berg, U.S. Pa~eut 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 19?2. See also "TlvlS~TDS" builders of U.S. Patent 4,663,071, issued to Bush et ai, on May 5, 1987. Suitnble ether ,UUIJ~Ui/U.~ also include cyclic compounds, particularly alicyclic compomlds, such as those describcd in U.S. Patents 3,923,679; 3,835,163; 4,158,635: 4,120,874 and 4,102,903, Other useful detergency builders include the ether LJ;jlU.~ JlJ~ d~u~L t~ copolymers of rnaleic anhydride vith ethylenc or vinyl melhyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and ~ ub~ ',u: ,: ~ ' acid. the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ~.h,' ' ' tetraacetic acid and ~ acid, as ~vell as t~ulJ.,~ubu~' such as mellibc acid, succinic acid, u.~
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, u.l-hu.~ ' '(, ' ' acid, and soluble ssits thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodlum salt), are ,uul~ ' , ' builders of parbcular Importance for hea~y duty liouid detergent formulabons due to their availabllity from renewable resources and their h' ~ 81 r, Citrates can aiso be used, however, in granular , ' ' . especially in combination with zeolile and/or layered silicate builders. tl, " ~ are also especially use~u'i in such composibons amd ' ' Aiso suitable in the de~ergen~ compositions of ~he present invenbon are the 3,3-dicarboxy-4-oxa-1,~ ' ' and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Usehll succinic acid builders include tlle C5-C20 alkyl and aikenyl succinic acids and salts thereo~ A panicularly preferred compound of this type is ~' ' , ' aad, Speci~dc examples of succindte builders Include: hu~ ' ' 1..~ . i,l~ ' ' .
~ ' ,, d~ J , ' (preferred), 2-u...L,du~ ' , and the like.
35 1 ~' ~ are the preferred builders of tlus group, and are described in European Patent Appiicadon 86200690.5/0,200,263, published November 5, 1986. O~her suikable t~ul~ u~.~
~21~254 5 r~, U~ !dO 79l -ID-aredisclosedinU,S,Patent4,14~,226,Crulchf~eldctnl,isslledMarch 13, 1979andhlU.S.i'ate:lt 3,308,1367, Diehl, issued March 7, 1967. See also Diehl U.S. Patellt 3,723,322.
Fatty acids, e g., C12-C18 ' ~h,, acids, cnn also be incorporated into the Composihorls ah~ne, or hl combination ~vitll the nforesnid builders, especinlly citrate nnd'or the 5 sucanate buiiders, to provide additional builder activity, Such use of fntty acids v ill generaily roeuit in a dimdnudoo of sndsing, wilich shouid be taken into account by thc rormulator.
Adhmct Surfactants One or more adjunct surfactants nuay bc included generally at a les~l of from about 1% to about 50~fO by ureight of the surfnctmn system described herehl. Nonlimiting examples of 10 surfactants useful in conjunction with the surfnct~mts described hereill are the C lo-C 18 alkyl alkoxy ctrboxy!ates(especiaiiytheE01-5~tlluAr~ huA~' ',theC10 18glyceroletllers,theClo-Clx aikyl t,ul~bl~"u"l~,, auld their , ' _ sulfated t~~lY~ ~va;~i~5~ al d C12-C18 ~
fatty acid esters. if desired. the conventianal nonionic and amphoteric surfactants snch as the C12-Clg alkyl etho~ylates (nAE~) including Ihe so-called narrmi~ peaked alityl etitoxylates and C6 C12 aikyl phenol alkoxylates (especiaily ethoAylates m3d mi.Yed ~tl~ y/ulù~Ay), C12-C18 b~tain~s and suifobetaines ("suitainesn), can also be included in the overnli , ' ' The C lu-C 18 N-aikyl polyhydroYy fatty acid amides cnn also be used. T~ picai e.;amples include the C12-C1 8 N-', 'g' ' Sec WO 9,2û6, 154, Thc N-propyl througll N-he.Yy l C 1 2-C 18 glucamidcs can be used for low sndsing C lo-C20 conventional soaps mny also be uscd. If high sudsing is desircd, the 20 ; ' ': ' ~ Clo-C~6 soaps may bc used, AiSD included in the surfactant system is the conventional Cl l-C~8 nlkyl benzene suifonates (aiso referenced herein as ~LAS) Whiie the b: S L~ ~ 1 ' 1' r of the so-called "LAS"
surfactants have been the subject of somc concern, the surfactant system Iterein may inclnde an optimum level, from about 0.1Cfo to about 15% au~d more preferably frmn about 3~fO to about S~fO by 25 welght, for improving the overail solubility of the detergent composition ~vithout substantially decreasing the overaii ' ' ~ of the present detergent compositioll, Alten~ali~ely, the levd oELAS may bc included as fmm abont 1% to about 40~/O, more preferably frDm about IOC~G to abont 25%, by weight of the surfactant system in the detergent composition.
Thc surfactant system may aiso include an amine oAide surfactant. Noniimiting eYamples 30 include C 10-18 amine oxides, secondary aunine o.Yides such as dimethyl aunine oYidc, and tcrtiary anane o~ddes baving the general formnla RR'R"NO in whicll R is a primary alkyl group containdng 8 to 24 carbon atoms; R' is methyl, elhyl, or 2 '., ' , ', :, and R" is ' . ' '~ selected from methyi. cthyl, 2 ', ' , "~ amd primary aiicyl groups containing 8 to 24 carbon atoms.
Addidonaily, the tertiary amine oAide surfaannt may be in hydratcd form and have tùe general 35 formuia RR'R"NO ~i20 ~herein R R' and R" are the s:lme ~s abovo and n is I or 2 Ft~3uluples of other tertiary amines suitable for use herein include those containing one or twû short-chain gronps ' ', ' '~ selectedfrommethyl,ethyl,and2 '.,11u~j_',lgroups,withthercmainini3valenccs 2l 92s4q WO gS134625 P~
of the amino nitrogen being satisfied witll imlg-ch;lin grouys iul.r...l ..ll~ selected from primar,v alicyl groups cwntaining 8-24 carbons~ e.g., octyl, decyi, dodecs l, tetr;ldec~ I, hexadecyl, octadecyl, eicosyl, docosyl. and tetracosyl groups. The primary alkyl groups ma), be brallclled-clmin groups, but the preferred amines are those in ~hich at least most of the primarv ali<yl groups ha~e a straight ~ 5 chain.
Exempiary of these ten-amines are N-o.t~' '' ' J ' ' , N,N- iki.~,~' ', ' ' ~, N-decal-N~iud.~,~ ' h~ ' ' , N lu~ ' N ~ ' ~ Idi....~h, ' ' , N-tetradecyl-N-~lh,' ' ,' ' , N . ' ,; N c ' ,1-2-LJ~u.~ lJ' ' ~, N,N di t..-.~J.~I 2-h,liu.~ ' ' , N ' ' ~' " ' ,' ' N l; ~al~ ' '' 2~ .tli,' ' N-10 u.~~ ' ',' ' ,N,i~l:" ' ,I.tl.~' ' N-docosyl-N-2 h, IIUX~ J' '',' ', N-W ~ ,: , etc.
Additional amine oxide suriactants and methods of makillg the snnne, all of ~vhich are suitable for use herein, are disclosed by Borland et al, U. S . Patent No . 5.071,594 and Tosaka et ai, U.S. Patent No. 5,096,621, incorporated herein by reference.
Mi ctures of anionic and nonionic surfacolllts are especial ly useful. Other wnvendonai useful surfactants are listed in standard texts.
Deter~ent Adhmct lnaredients The detergent composition can also hlclude ally number of additional ingredients. These include detergency bleaches, bleach actiYators. suds boosters or suds suppressers, anti-tamish and 20 antiwrrosion agents. soil suspending agents, soil relcase agents, gemlicidcs, pE~ adjusting agents, non-builder alkaiinity sources, chelating agents, smectite clays, enzyllles, ~.~c~ ...., ' '-' ' ~ agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Basicerville, Ir. et al., inwrporated herein b,v reference. Aiso, fabnc conditioning agents may be mcluded as an adjunct materiai such as those described in U.S. Patent 4,861,502, issued August 29, 1989 to Casv.~ell, incwrpontted herein by 25 reference.
Bieaching agents and activators are described hl IJ.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hamnan, issued November 20, 1984, both of ~Yhich are imwrporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071, Bush et ai., from Column 17,1ine 54 through Column 18, line 68, incorporated hercin by reference.
30 Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued J;muary 20, 1976 to Bartoletta et ai., and 4,136,0 15, issued January 23, 1979 to Gault et ai., both incorporated herein by reference.
Suitable smectite clays for use herein are descnbed in U.S. Pa~ent 4,762,645, Tucker et ai, issued August 9, 1988, Column 6, line 3 through Column 7,1hle 24, hlcorporated herein by reference.
35 Suitable additionai detergency builders for use hereill are enumerated in the Basker~ille patent, Column 13, line 54 through Column 16, line 16, and hl U.S. Patent 4,663,071, Bush et ai, issued E~iay 5, 1987, both incorporated herein by reference.
WO 95J3~i625 p~,' '!r ?91 Enzymes cao be included in the formulatim~s lserebl for ~ ide ~anety of fabnc laundering purposes, including removal of ~, . ' 1. cnrbohydrme-based, or n ~ .. . id.-l,a..d stains, for example and for the prevention of refugec dye transfer, ;md for fabric restortttion. The ens~mcs to be incorporated inciude proteases. amylases, lipases~ cellulases, and peroxidases, as ~eli as nuxtures 5 thereo~ Other typa of cnzymes may also be included They nhiy be of any suitable origin, r,uch as segetabie, animai, bactenai, fnngal and ycdst origim i~ow~er, their choice is governed by severai factors such as pH-ac~ivity andfor stability optima, ' 'si " ~, stability versur. active detergcnts, buiiders and so on. ln tbis respect bacterial or fmlgal enrymes are preferred, such as bacteriri amyiases and proteases, and fimgal cellulases.
Suitablc examples of protcascs are lhe svbtilisf ns ~vhich are obtained from particular strains of B.s~btilis an~ B. IicbeniJorms. AnQther suitable protease is obtained from a straill of Bacillus, ha~-ingmaximumectiiit!,throughoutthepiir,u~geof8-12,developedQndsoldbyNovollidustries A!S under the registered trade namc ESPERASE, The preparQtion of Ihis enzyme and analogous enzymcs is describcd in British Patent Specification No 1,243,78i of Novo. Proleolytic enzymcs 15 suitabk for rcmoving p,t.; I ' stains that are "~ available include thosc sold undcr the trade names Ai CALASE and SAVINASE by Novo Industries A/S (Denmark j and MAXATASE by Intcrnational Bio-Synthetics. Inc. tThe Netherlands) Other prote sa include Protease A ~see European Patent Application 130,756, published Janudry 9, 198S) and Protease B
(see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130.756. Bott et al, published January 9, 1985).
Amylasa include. for e~ample, a-amylases descnbed Ul British Patent Specification No.
1,296,839 ~Novo), RAPIDASE. International Bio-Synthetics, Inc. and TERMAMYL, Noso Industries.
The oellulase usable in the preseot invelltion hlclude both bactenal or fungal oellulase Preferably. they will have a pH optimum of between 5 and 9.5. Swtable oellulases are disclosed in U.S. Patent 4.435.307, Barbagoard et al. issued March 6. 198S, whicll discloses fungal cellulase produoed from Humicola insolens and Mumicola strain DSM1800 or a cdluhlse 212-producing f~mgus bdongdng to the genus Aeromonss, amd oellulase e:;tracted from the ' , , of a marine nwllusk (Dolabella Auricula Solander) suitable cellulases are also disclosed in GB-A-2.075.02's GB-A-2.095.275andDE-05-2.2$7832.
Suitable lipase enzymes for det~gent usage hwlude those produced by , of thePseudomonasgroup,suchasPreudomomasstulzeriATCC 19.154,asdlr,closedinBritjshPatcnt 1.372,034. See also lipascs in Japanese Patent Application 53,20S87, laid open to public inspection on Febn ary 24, 1978. This lipase is avaihlble from Amallo P'- - - - ~ i ~ I Co. Ltd., Nagoya, 35 Japarl, umder the trade oame Lipase P "Amano,~ hereimlfter referred to as "Amsno-P. ~ Other conuncrcial lipasa include Amano-CES, lipasa ex C' ' viscosunt, e.g. t~hrn~h~ rrviscosum var. Iipolyticum NRRLB 3673, commercially availnble from Toyo rOzo Co., Tagata, 21 '~254'~
~ W095134625 P~lf~ 91 -Il-lapan: and further Chromobacter viscosmll lipnses frmll U.S. Biochelllical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipnses ex Pseudmllollas ghldioli. The LIPOLASE enzyme dem~ed from l .umicola lanuginosn and commercially nvail;lble from Noi o (see also EPO 341,g47) is a preferred lipase for use herein.
PeroxiLlse enzymes are used in combhlatioll ~ith ox~gen sources, e.g., p~rr~
perborate, persulfite, hydrogen pero.Yide, etc. They are used for ~'sohltioll blalching," i.e. to prevent Lransfer of dyes or pigments removed from substrates during ~vnsh operations to other substrates in the wash solution. Peroxidase enymes are known in the art, mld include, for example, horseradish peroxiLase, ligninase, and 1 ~ such as chloro- and bromo-peroYiLase. Pero.Yidase-containing detcrgent compositions are disclosed, for e.Y1mple, hl PCT International Application WO
89/099813, published October 19, 1989, by O. Kirk. assigned to Novo Indlls~ries A/S.
A v.ide range of enymc materials auld means for their ~ .s i into syntheLc detcrgcnt compositions arc also disclosed in U.S. Patellt 3,'J53, 139, issued January 5, 1971 to McCarty et al. Enymes are furtiler disclosed hl U.S. Pateot 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued Marcll 26, 1985, both. Enzyme materials usef for liquid detergent formulations, and their h~ ,lrliull into such formulations, are disclosed in U.S.Patent4,261,868,Horaetal,issuedApril14,1981. EnzymesforuseilldetergentscanbesLabilized by various techniques. Enzyme sLnbilization teclmiqlles are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, ~/enegas.
Enyme stabilization systems are also described, for ex,ample, hl U.S. Patent 3,519,570.
Additionally, dye transfer inhibiting agents may also be hlcluded, for example, J ~ f 't-, ' ' , polyamine N-oxide, copolymers oF N ~ " ' and N s ...~ " ' ' aro a suiLable dye transfer inhibidng polymers for use in the present detergent composition. The level of such additional dye transfcr inhibiting agents may var,v, but t~pically will be from about 0.0 IO~D tO about 10~~O by weight of the detergent composidon.
Al . 'r ' Process The follo~ving describes and exemplif as thc n, ,~ , process by which thc detergent composition of the inven don is produced. The parameters noted herein are exemplary only and should not be considered as limi~dng in any way.
Steo A - Preparation of Surfactant Paste - Tbe objeai-e is to combille the surfactants and liquid in thc compositions into a common mix in order to aid in surfactant ' ' "' ' and ~,,' ' In this Stcp, the surfactants and other liqmd components are mixed together in a Sigma Mixer at 140~F (60~C) at about 40 rpm to about 75 rpm for n period of from 15 minutes to about 30 minutes to provide a paste having the general consislency of 20,000-40,000 centipoise.
Once thoroughiy mixed, thc paste is stored at 140~F (60~C) until a2~,' ' Step f~B) is raidy to be conducted.
54 ~ ~ ~
WO f~C/3 ~625 P~ ~
SteD B - APol~ f~fif~n of Powders s ith Sllrfact:lm Paste - The purpose of this Step is to transform the base formula ingredients includfilg the wa~er-solllble stccharides descnbed herein into flowablc delergent aggdomerates lua h1g a n ean particle size rangc of froul about 800 microns to about 1600 microns. In this Stcp, Ihe powders (hlcludillg materials such as zeolite, citrate, citric 5 acid bnilder, la~ered silicate builder (as SKS-6~, rodimn cdrbmulte, ~Lh~' " " , magnesiwn sulfatc and opdcal brightener) are charged into the Eirich Mi.aer (R-Series~ and mixed brieffy (ca. 5 seconds - 10 seconds) at about 15a0 rpm to about 3000 rpm in order to mix the various dry powdcrs fully. The surfactant paste from Step A is then cluarged hlto the mixer and the mixinvg is continued at about 1500 rpm to about 3000 rpm for a period froul about I minute to about 10 10 minutes, preferably 1-3 minutes, at ambient temperature The miYing is stopped when coursc agglomeratcs (average particle size 800-1600 microns) are formcd.
SteD C - The pu-pose of this Step is to reduce the al_' ' stickiness by .,'d~J ' v moisture and to aid in panicle size reductloll to the target panicle size (in the mean particle size r~mge from about 800 to about 1600 microlls~ as measured by sieYe analysis). In 15 this Step, the i'f et agglomerates are charged imo a tiuidized bed at an ai r stream temperature of from about 41~C to about 60~C and dned to a final moisture cmltent of the particles from about 4~~O to abont 10%.
SteD D - Coat Aft~lomerates arld Add Free-Flow Aids - Tlte objective in this Step is to achieYe the fmat target agglomerate size range of from about 800 microns to about 1600 microos, 20 and to admQI materials which coat the 1__' ' , reduce the ~i.,bl' , 1 tendency of the particles and help maintain acceptable nowabiliq,. In this Step, the dried agglomcrates from Step C
are charged into the Eisich Mir~er (R-Series) and miYed at a rate of about 1500 rpm to about 3000 rpm while adding 1-6% Zeoiite A (median panicle size 2-5~"m) durfilg the mi.Ying. The mi,Ying is continocd until the desired median p~trticle size is acbieYed (typically trom abom 5 seconds to about 45 scconds) . At this pornt, from about 0. IYo to about I . 5~/O by w eight of precipltated silica (avcragc pardcle size 1-3 microns) is added as a flow aid and the mi.Ying is stopped.
Io order to make the present invention morc rcadily understood, referencc is madc to the following eYamples, whicù are intended to be illustrnive only and not mteltded to be limiting in scopc.
EXAMPLE I
Sevcrai detergcnt compositions ~A and B) are made in accordallce with the ~ ,,vi -- ~
process describcd above. Composidon B is within t he scope ot the in~ention and composition A is outside oF the invcndon and is presented for purposes of comparison as described in Example 11 hereinafter. The relativc proportions of compositions A and B, hl a~lomerate form, are listcd in Table I betow~
21 9254q ~ WO 9513462S P~ e.r ~ 1 t TABLE I
(U~ ei~htl Comr onent A B
C14 15 aiicyl sulfate 20.0 29.4 C16 aikyl etilo~ylate ~EO = 0.6~ sulfale 5.0 7.3 ~1 ' 4~.9 47.2 C12,13 lincaralicylbenzenesulfonate15.6 Sucrose -- 10 Sodiumcarbonate 1~,1 15.0 Minors (water, perfume, elC ) = O I
100.0 100.0 EXAitll'LE n This Esample illustrates the surpnsingly impros~ed sohlbility achieYed by the detergent composition of the invention Specifically, standard dosages of cmnpositimls A and B ~1170 ppm) are dissolved in an ;tqueous laundenng solution hai hig a s~ater temperatllre of 1 0~C and a water hardness of 7 grains/gallon (Ca i~lg ratio of 3 1 ) The lamldenng solution is condnuously agitated at a rate of 75 rpm and samples of the wash solution were taicen at various time intervals as showtt in Table I below, For purposes of illustrating the improved sohlbility of the detergent composihon according to the inYelltion, the amomlt of surfictant in the laundering solution is determined by conducdng the v, ell known "catS03" titration technique on the srlmples taken from hldiYidULil wash soludons containing one of the compositimls A or B In particular, the amount of anionic surfactant in the laundcring soludon is determined by filtering the samples through 0.45 nylon f lter paper to remove the insolublcs and thereafter~ titrating Ihe filtered solution to ~hich anionic dycs (dirnidium bromide) have been added with a cationic dtrant such as HyamineTM ' "~ availabte from Sigma Chemicai Company Accordingly, dhe relativc amomlt of anionic surfactant dissolved in d e w&sh solution atn be detcrmined This teclunique is ~vell knoH~n and others may be used if dcsired Thc results are shown in Table 11 below TABLE n (~/0 total of anionic dissolved) Time IMinutcs~ A B
1 26% 16C~u 3 38U~o 34%
42% 57%
~5% 71%
From dhe rcsults in Tablc 11, it is quite clcar that composition i3 whicll is within the scope of thc invention surprisingly has improved solubility over composition A which is outside the scope of dhe 25 invendon ~ I q~S~9 W095J34625 l~l/u.,._~r-E~I~IPLE 111 A laumdry bnr C suit~ble for ~ soiled fablics is prepared by a s~mdard e:strusiorl process and cornprises the follo~villg h~gredients listed iu Table 111:
(% - Cight) ~mE~ C
C14 ~ alkyl sulfs~e 20.0 C16 al~yl etho.sylato (E0 - 0.6~ sulfate 5.0 ~1 " J~.~
C12 13 lincar alkylbcnzene sulfonate 15.G
Sucrosc 1.0 Sodium carbonate 14.1 Minors twater, perfume, etc.) 0,4 I_ HaYing thus describcd the im~cntioll in detail, it will be clear to thosc skilled in the art that Yarious changes may be made Yfithout depnrting from tlle scope of the in~enlion and the h~Yention is not to be considered limited to Yrh;lt is described in the specification.
What is claimed is:
Claims (16)
1. A detergent composition comprising:
(a) from about 1% to about 50% by weight of a detersive surfactant system comprising at least about 30%, by weight of said surfactant system, of a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof;
(b) from about 0.1% to about 5% by weight of a water-soluble saccharide selected from the group consisting of cellubiose, glucose, maltose, lactose, ribose, and lactulose mixtures thereof; and (c) at least about 1% by weight of a detergency builder;
wherein said surfactant system, said saccharide and said builder are agglomerated to form detergent agglomerates having a density of at least 650 g/l; wherein said sulfated surfactant of said surfactant system has improved solubility in an aqueous laundering solution.
(a) from about 1% to about 50% by weight of a detersive surfactant system comprising at least about 30%, by weight of said surfactant system, of a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof;
(b) from about 0.1% to about 5% by weight of a water-soluble saccharide selected from the group consisting of cellubiose, glucose, maltose, lactose, ribose, and lactulose mixtures thereof; and (c) at least about 1% by weight of a detergency builder;
wherein said surfactant system, said saccharide and said builder are agglomerated to form detergent agglomerates having a density of at least 650 g/l; wherein said sulfated surfactant of said surfactant system has improved solubility in an aqueous laundering solution.
2. The detergent composition of claim 1 wherein said secondary alkyl sulfate surfactant is a secondary (2,3) alkyl sulfate.
3. The detergent composition of claim 1 wherein said detergency builder is in an amount from about 10% to about 40% by weight.
4. The detergent composition of claim 1 wherein said sulfated surfactant is a mixture of alkyl sulfate and alkyl ethoxy sulfate surfactants.
5. The detergent composition of claim 1 wherein said saccharide is sucrose.
6. The detergent composition of claim 1 further comprising adjunct ingredients selected from the group consisting of bleaches, bleach activators, suds suppressers and soil release agents.
7. The detergent composition of claim 1 wherein said detergency builder is selected from the group consisting of carbonates, zeolites and mixtures thereof.
8. The detergent composition of claim 1 wherein said surfactant system further comprises, by weight of said surfactant system, from about 1% to about 50% of a C10-C18 N-alkyl polyhydroxy fatty acid amide for use as an adjunct surfactant.
9. The detergent composition of claim 1 wherein said sulfate surfactant is at least 5% more soluble in said detergent composition as compared to said sulfate surfactant dissolved alone in said aqueous laundering solution.
10. The detergent composition of claim 1 further comprising from about 0.1% to about 15% of a linear alkylbenzene sulfonate surfactant.
11. The detergent composition of claim 1 wherein said saccharide is present in amount from about 2% to about 4%.
12. The detergent composition of claim 1 wherein said detergent composition is substantially free of phosphates.
13. A detergent composition according to claim 1 wherein said detergent composition is in the form of a laundry bar.
14. A method for laundering soiled fabrics comprising the step of contacting said soiled fabrics with an effective amount of a detergent composition according to claim 1 in an aqueous laundering solution.
15. A detergent composition comprising:
(a) at least about 30% by weight of a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof;
(b) from about 0.1% to about 5% by weight of sucrose; and (c) at least about 1% by weight of a detergency builder;
wherein said surfactant system, said saccharide and said builder are agglomerated to form detergent agglomerates having a density of at least 650 g/l; wherein said sulfated surfactant of said surfactant system has improved solubility in an aqueous laundering solution and said composition is substantially free of phosphates.
(a) at least about 30% by weight of a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof;
(b) from about 0.1% to about 5% by weight of sucrose; and (c) at least about 1% by weight of a detergency builder;
wherein said surfactant system, said saccharide and said builder are agglomerated to form detergent agglomerates having a density of at least 650 g/l; wherein said sulfated surfactant of said surfactant system has improved solubility in an aqueous laundering solution and said composition is substantially free of phosphates.
16. A method for laundering soiled fabrics comprising the step of contacting said soiled fabrics with an effective amount of a detergent composition according to claim 15 in an aqueous laundering solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25880894A | 1994-06-13 | 1994-06-13 | |
| US258,808 | 1994-06-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2192549A1 true CA2192549A1 (en) | 1995-12-21 |
Family
ID=22982215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2192549 Abandoned CA2192549A1 (en) | 1994-06-13 | 1995-05-18 | Detergent composition containing anionic surfactants and water-soluble saccharides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0765378A1 (en) |
| JP (1) | JPH10504329A (en) |
| CA (1) | CA2192549A1 (en) |
| MX (1) | MX9606350A (en) |
| WO (1) | WO1995034625A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19620364A1 (en) * | 1996-05-22 | 1997-11-27 | Basf Ag | Use of at least trihydric alcohols and their alkoxylation products to increase the dissolution rate of particulate detergent formulations in water |
| ES2162337T3 (en) * | 1996-11-18 | 2001-12-16 | Basf Ag | POLIVALENT ALCOHOLS AND THEIR ALCOXYLATE PRODUCTS IN WASHING AGENTS IN THE FORM OF PARTICLES FOR INCREASING THE DISSOLUTION SPEED. |
| BR9914747A (en) * | 1998-10-23 | 2001-10-02 | Procter & Gamble | Color care method for fabrics |
| DE19911570A1 (en) * | 1999-03-16 | 2000-09-28 | Henkel Kgaa | Anionic surfactant granules |
| US7012053B1 (en) | 1999-10-22 | 2006-03-14 | The Procter & Gamble Company | Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent |
| DE10015661A1 (en) * | 2000-03-29 | 2001-10-31 | Henkel Kgaa | Detergent tablets, include surfactant granules containing sugars, sugar acids and/or sugar acid salts for improved stability and solubility |
| US10287531B2 (en) * | 2013-07-18 | 2019-05-14 | Galaxy Surfactants Ltd. | Free-flowing, solid, high active alkyl ether sulfates |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5294304A (en) * | 1976-02-03 | 1977-08-08 | Yuken Kagaku Kougiyou Kk | Detergent composition |
| US4414130A (en) * | 1976-08-17 | 1983-11-08 | Colgate Palmolive Company | Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them |
| JPS6060196A (en) * | 1983-09-14 | 1985-04-06 | カネボウ株式会社 | Solid detergent |
| JPS61238894A (en) * | 1985-04-17 | 1986-10-24 | サンスタ−株式会社 | Detergent composition |
| GB2174712B (en) * | 1985-05-10 | 1988-10-19 | Unilever Plc | Detergent granules |
| GB8522621D0 (en) * | 1985-09-12 | 1985-10-16 | Unilever Plc | Detergent powder |
| EP0622454A1 (en) * | 1993-04-30 | 1994-11-02 | The Procter & Gamble Company | Structuring liquid nonionic surfactants prior to granulation process |
-
1995
- 1995-05-18 CA CA 2192549 patent/CA2192549A1/en not_active Abandoned
- 1995-05-18 EP EP95920527A patent/EP0765378A1/en not_active Withdrawn
- 1995-05-18 WO PCT/US1995/006291 patent/WO1995034625A1/en not_active Application Discontinuation
- 1995-05-18 MX MX9606350A patent/MX9606350A/en unknown
- 1995-05-18 JP JP8502172A patent/JPH10504329A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0765378A1 (en) | 1997-04-02 |
| MX9606350A (en) | 1997-03-29 |
| WO1995034625A1 (en) | 1995-12-21 |
| JPH10504329A (en) | 1998-04-28 |
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