CA2232956A1 - Detergent composition based on zeolite-bicarbonate builder mixture - Google Patents
Detergent composition based on zeolite-bicarbonate builder mixture Download PDFInfo
- Publication number
- CA2232956A1 CA2232956A1 CA 2232956 CA2232956A CA2232956A1 CA 2232956 A1 CA2232956 A1 CA 2232956A1 CA 2232956 CA2232956 CA 2232956 CA 2232956 A CA2232956 A CA 2232956A CA 2232956 A1 CA2232956 A1 CA 2232956A1
- Authority
- CA
- Canada
- Prior art keywords
- builder
- zeolite
- detergent composition
- bicarbonate
- composition according
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38609—Protease or amylase in solid compositions only
Abstract
A detergent composition is provided which contains a zeolite builder having a particle size, d50, of less than 1.0 micrometres; and a bicarbonate builder.
Optionally, low levels of carbonate builder may be present such that the weight ratio of any carbonate builder to the bicarbonate builder is less than 4:1.
Optionally, low levels of carbonate builder may be present such that the weight ratio of any carbonate builder to the bicarbonate builder is less than 4:1.
Description
CA 02232956 l998-03-25 DETERGENT COMPOSITION BASED ON ZEOLITE-BICARBONATE BUILDER MIXTURE ' The present invention relates to a detergent composition comprising both zeolite as a seque~tering agent for water hardness and bicarbonate builder.
<
Detergent compositions for fabric washing conventionally contain detergency builders which lower the concellL~alion of c~ m and m~gnPci.lm water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soft water.
Conventionah r~ i"organic phosphates, such as sodium tripolyphosphate, have beenused as builder3 for laundry detergents. More recently, aLkali metal ~lllminosilicate iori--e:~h~rlgers, particularly crystalline sodium ~lllminosi~ te zeolite A, have been proposed as repl~-Pm~ntc for the il-OI ~ iC phosph:~tPC
For cA~Iple, EP 21 491A (Procter & Gamble) ~ sps d.,t~,.g,t..l compositions co..~ a building system which in~l~ldes zeolite A, X or P (B) or a mixture thereof. EP 384070A (IJnilever) discloses specific zeolite P materials having anespecially low silicon to ~1~...;.,;.,~., ratio not greater than 1.33 (ht.t;illaller lere--~to as zeolite MAP) and des~;. ~es its use as a det~ ,n~iy builder.
Zeolite builders are typically used in detergent compositions with cobuilders toprovide o~,ti,.,u-~ building capacity for the detergent composition as a whole.
Ca l,onale is a particularly commonly used cob--ildPr, which is favoured in part, for its ability to provide both building capacity and ~ inity to a wash solution.
The Applicants have now surprisingly found that a p.o~' may occur when a water insoluble zeolite having a small particle size, is used as a dcte-~.,ncy builder in a fabric laundering detergent composition also co..~ p. relatively high levels of c~hl,olla~e cobuilder. The problem has been found to be particularly pronounced when the zeolite builder is zeolite MAP.
The choice of a small particle size for a zeolite MAP co,--polle--l, that is to say particles having a particle size, measured as a dso value, of up to 1.0 micrometres has previously been taught to be ple~-.~,d in the art, as rep,~ 1, for example, by EP 384070 A.
The problem relates to the aforemçntit)ned detergent compositions having a marked incompatibility with printed cotton fabrics. In particular, it has been found that the use of detergent compositions co~ g smaU particle size zeolite tends to lead to the removal of printed pigment from a printed cotton fabric surface. The presence of relatively high levels of carbonate cobuilder has been found to eA~I ~ebale this effect.
The Applicant has surprisingly found that this p~c,bl~l.l can be ameliorated by the partial or complete repl~cPmPnt of the c~l,onale component of the detergent composition by a bicarbonate builder co...ponent.
The present invention is thus based on the u~l~,A~c~,led finding that the printed cotton fabric care profile of a detergent composition co-lll,-isiilg zeolite of small particle size, bic~l,ona~e builder and relatively low levels of carbonate builder is superior to that of cO---~l&-ably aL~caline and built compositions co~ g p.i.~ipally carbonate cobuilder.
This finding allows the fonnulation of dt;l~ ~,e"l compositions providing both eYcPIIPnt rle~ning and printed fabric care plope.lies on cotton fabrics.
Whilst the prior art, as lep-~nled for ~ -~-..ple by European Patent Aplications, EP
384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP 544492 A, EP 552053 A, and EP 552054 A has envisaged the use of cobuilders in conlbinal~on with zeolite in laundry d~ ,c;..l compositions, none of these prior art doc~mPn~ specificallydisclose the use of bicall~onale cobuilder with a small particle size zeolite component. Fu~lL_.mor~" none of these prior art doc~ i provides any te~ching relating to the printed cotton fabric care pr~bl addressed by the current invention, nor of any solution thereto involving the selection of a particular bicarbonate cobuilder co-l,pone.ll.
Thus, the present i~e.llion provides a dele.~,t;..l composition co.,~ ;n~
(a) a zeolite builder having a particle size, dso, of less than 1.0 rnicrometres;
~b) a bicalboilale builder; and optionally (c) a carbonate builder wherein the weight ratio any carbonate builder to the bic~l,ona~e builder is less than 4:1.
In a p,t;re-lled embodiment of the invention the zeolite builder comprises zeolite P
having a silcon to ~ minillm ratio of not greater than 1.33 (zeolite MAP).
In a further plt;rellc;d embodiment the detergent composition according to the invention is form--l~ted to be espeçi~lly useful in the laundering of coloured fabrics and p,~,rel~bly is free of bleach. Accol~ g to another aspect of the invention, the composition is subs~ ially free of an optical brightf n~r.
Zeolite builder The first P ss~ l co",pon~ of the present invention is an alllmino.cili~te zeolite builder.
The zeolite builder is typically present at a level of from 1% to 80%, more plt;Çel~bly from 15% to 40% by weight ofthe cc"~.po~;~;ons Suitable ~hlminosilis~te zeolites have the unit cell formula Naz[(A102)z(SiO2)y].
XH2O wh~ z and y are at least 6; the molar ratio of z to y is from 1.0 to 0. 5 and x is at least 5, pr~f~ bly from 7.5 to 276, more plerél~bly from 10 to 264. The alllminosiliss~te m~trri~l are in hydrated form and are p,~f~ bly crystalline, cc,..~ 5 from 10% to 28%, more prt;r~ bly from 18% to 22% water in bound form.
The ~hlminocilir~qte zeolites can be naturally occurnng materials, but are preferably synth~ti~lly derived. Synthetic crystalline ~lllminocili~te ion ~ .~hange materials are available under the d~ci~. l;onc Zeolite A, Zeolite B, Zeolite P, Zeolite X Zeolite MAP, Zeolite HS and ~-~lur,s thereo~
Zeolite A has the formula Na 12 ~AlO2) 12 (SiO2)l2] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(Alo2)86(sio2)lo6] 276 H20.
Zeo1ite MAP is described in EP 384070A (Unilever). It is defned as an alkali metal mino-silicate of the zeolite P type having a silicon to ~ minillrn ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0 9 to 1.2.
Of particular interest is zeolite MAP having a silicon to ~In.. : .. ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:AI ratio of 1.33 or less may be p~epalcd by the following steps:
(i) mixing together a sodium ~IIlmin~te having a mole ratio Na2O:A12O3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio SiO2:Na2O within the range of from 0.8 to 3 4 with vigorous stirring at a tc,~ re within the range of from 25~C to boiling point usually 95~C, to give a gel having the following composition; A12O3: (1.75-3.5) SiO2: (2.3-7.5) Na2O :P (80-450)H20;
(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to Shours, at a tClll~ tUl~, within the range of from 70~C to boiling point, usually to 95~C, with s~fficiPnt stirnng to ~"ai~ any solids present in su;.~ n;
(iii) S~p~aling the crystalline sodium ~ minosilic~te thus formed, washing to a pH within the range of from 10 to 12.5, and drying, ~f~,fe.ably at a tc~ ,.alure not ~ -~,ee~ g 150~C, to a moisture content of not less than S wt.%.
Pleîcll~,d drying methods are spray-drying and fiash-drying. It ap~ that oven drying at too high a t~ lpe.~ re may adversely affect the calcium binding capacity of the product under certain c;l ~ S
CGIIUII~C;dI sodium metasilicate pentahydrate dissolved in water and collu"e.,ial sodium silicate solution (waLel~lass) are both suitable silica sources for the ~ CA 02232956 1998-03-25 WO 97/12025 PCT~US96/15452 production of zeolite P in accordance with the invention. The re~ct~ntc may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95~C) both give the desired product.
Vigorous stirring of the gel during the ~d~liti~n of the re~cf~ntc and at least moderate stirring during the subsequPnt ageing step, however, appear to be ~cct~nti:~l for the forrnation of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a c~ m binding capacity of at least 150 mg CaO per g of a~ ous ~ mint~silc~te, as measured by the standard method described in GB
1473201 (Henkel). The calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
.~lthough zeolite MAP like other zeolites co..~aills water of hydration, for thepurposes of the present invention amollntC and pc.c~ gçs of zeolite are cA~Jle i~d in terms of the notional a~ dru-ls material.
The amount of water present in hydrated zeolite MAP at ~l)ienl telllp~ re and humidity is generally about 20 wt.%.
The ~olite builder used in the present invention has a particle size dso of less than 1.0 mi~lull~ell~s~ pr~,ably from 0.05 to 0.9 miclo"~elles~ most preferably from 0.2 to 0.7 micrc~ ,L~.,s. The dso value i~ le9 that 50% by weight of the particles have a ti;a~ t~ srnaller than that figure. The particle size may be determined by conv~nfion~l analytical teçhnitlues such as, for example, microscopic del~,.llfinalion ili7ing a S ;a ~ g el~, o- 11~ uscopC or by means of a laser granulometer.
Zeolite builder having the r~uired particle size acco.-li"g to the present invention can, for ~ , 'e, be p.ep~ed by the conventional techn:ques as dese~ ed above while adop~ g one or more of the following steps:-a) de ~ lg cryst~ tion time;
b) decreasing the size of the seed crystals used to produce the zeolite;
c) screening the zeolite product to remove coarse material.
An article by D. Vucelic, published in Progr Colloid Polymer Science, 1994, Volume 95, pages 14 - 38 desc,ibes methods for the synthesis of zeolite particles, and in particular how to jnfl~lence the particle size characteristics of the zeolites by modification of the synthesis process steps.
Brcarl~nate builder In addition to zeolite, the dt:le.~ compositions contain bicarbonate builder. Bybicarbonate builder it is meant herein any compound capable of rçleAsing bicarbonate ions to a wash solution.
Prère~llèd bicarbonate builders include the alkali and alkaline earth bicall,ona~e salts, particularly sodium bic~hbonale.
The bica,l,onale builder is typically present at a level of from 0.5% to 60%, ~lert~ably from 2% to 40%, most pref~.ably from 3% to 20% by weight of the detergent composition.
The bicarbonate builder is p~fc.ably present at a weight ratio of zeolite builder to bi- l,onale builder of from 20:1 to 1:5, more ~ ,f~,.ably from 10:1 to 2:1, mostp. ~,re~ ably from 5 :1 to 1:1.
Other builders The d.,le. ~ccnl co...pos;lions may contain other organic or inorganic builders.
In an f/~ ;AI aspect the level of any c~l,ohale builder, that is of inorganic compound capable of rPlp~cing carbonate ions into a wash solution, is kept relatively low. In particular, any carbonate builder is present only at a level wh~.ei-~ the weight ratio of the carbonate builder to the b:~r bonale builder is less than 4:1, ~le~.ably less than 2:1, more prere ably less than 1:1. Most pr~relably the de composition is free from ca,l,Gnale builder.
Suitable organic cob~ rs can be ...ono~....ic or polymeric carboxylates such as citrates or polymers of acrylic, methArrylic and/or maleic acids in neutralised form.
Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.
Suitable crystalline layered eilic~tes have the composition:
NaMSix02x+l . yH20 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No.
4664839; No. 4728443 and No. 4820439 (Hoechst AG). F..epeçi~lly plèfclled are compounds in which x = 2 and y = O. The synthetic material is co.lllllel.,;ally availab1e from Hoechst AG as o -Na2 Si2Os (SKS6) and is de~l;bed in US Patent No. 4664830.
The total amount of dGlel~ency builder in the granular composition typically ranges from 10 to 80 wt.%, more plcfcl~Lbly from 15 to 60 wt% and most plefGIably from 10 to 45 wt.%.
-Additional dc~ components The detergent composition accordillg to the invention may contain other delecolllponel~ls such as surf~Gt~nte ble~h~c~ fluol~,scc.~, antiredeposition agents, ~llOI~alLC salts such as sodium sulphate, other el~llles, lather control agents, fabric softening agents, pi~rn~nte, coloured speckles and perfumes.
Surfactant The d~,t~e.ll composition according to the invention pl er~l ~bl" includes a surfactant s~lect~i from anionics, nonionics, zwitterionics, ampholytics and ç~ti~ ~ --s The surfactant is p~Gfel~bly present in the detergent compositions at a level of from 1% to 50%, pl~f~,.ably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.
Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Dt;~l2;ellls" Volumes I and II by Scl-w~ 4 Perry and Berch).
Examples of suitable additional anionic surf~ctAntc include anionic sl-lf~tes, olefin sulphonates, alkyl xylene sulphonates, diallcyl~lrhos Ic~ cs, and fatty acid ester sulphonates. Sodium salts are generally plt;~..~d.
Anion~c suLfate .,ulr~;l~ll Anionic sulfate surfactants suitable for use herein include the linear and branched prirnary alkyl s-llf~tes, aL~cyl ethoxys-llf~t~e, fatty oleoyl glycerol sl-lf~tçe, alkyl phenol ethylene oxide ether s~lf~tes~ the Cs-C17 acyl-N-(Cl-C4 alkyl) and -N-(Cl-C2 hydroxyalkyl) ~ c~mine slllf~tçe, and sulfates of aL~cylpolysaccharides such as the suLfates of alkylpolyglucoside (the nonionic non~.llri.~ccl compounds being described herein).
-Alkyl ethoxysulfate surf~t~nts are pl.,f~ bly s--lected from the group consisting of the C6-C1g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per mole lle More plef~.~ly, the allcyl ~ilhu~y.,L~lfate surfactant is a C6-Clg alkyl sulfate which has been ethoxylated with from 0.5 to 20, pltifel~blyfrom 0.5 to 5, moles of ethylene oxide per mole llç
Anionic sulfonate surfactant Anionic sulfon~te s~rf~ct~nt!c suitable for use herein include the salts of Cs-C20 linear allylb~ e s~llron~ ,s, alkyl ester sl-lfon~t~e, C6-C22 pl~ll~y or second~uy aLtcane sulrona~es, C6-C24 olefin sulfonates, s~llro~ eA polyc~l.u~ylic acids, aL~cyl glycerol s ~lro~ c~ fatty acyl glycerol s~lr~n~t~s~ fatty oleyl glycerol sulronales, and any mixtures thereo~
Nonionic surfactant The n~niQnic sulr~ is pl~fe ~bly a Ly-ilophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a h~drophilic lipophilic balance (hlb) value of < 9.5, more ~,ert .~ly < 10.5.
Examples of suitable hydrophobic alkoxylated nonionic surf~ct~nts include alkoxylated ~dd~lr,tC of fatty alcohols co..~ g an average of less than 5 alkylene oxide groups per molecule.
The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
r~Çelled alkylene oxide ~dclt1ct~ of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
R-O~(CnH2nO)yH
whele.l~ R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
Plerell~d nonionic surf~ct~nts include p---~ Cll-Cls ~liph~tic alcoholscon~nced with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, prerel~blyfrom 25% to less than 50% by weight.
A particularly pre~..ed ~liph~tic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain conden-ce~ with an average of three ethoxy groups per mole of alcohol.
.~perifir, examples of suitable alkoxylated ~ductc of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-Cls alcohol with about three ethylene oxide groups per mole ~le and F.mpil~n KB3 (ex Marchon), which is lauric alcohol 3EO.
Another class of nonjonic s~f~ntc CGIll~Jli~S alkyl polygluco~ e compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from gl~r~se; R is a saturated l,~d,~,phobic alkylgroup that co..l; ;..~ from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds in~ ing less than 10% unreacted fatty alcohol and CA 02232956 l99X-03-25 less than 50% short chain allyl polyglucosides Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 00941 18 Bleach Detergent compositions acco~ d.llg to the invention may also contain a bleach system Where present, this preferably CO.Il~l ;SCS one or more peroxy bleach compounds, for cA~Ill~le, h~or~g~.c persalts or organic pe~u~yacids, which may be employed in conjunction with bleach precursors to improve bl~- chin~ action at low te.~l~,e.dl~lres The bleach system p,~rw~bly comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor Suitable persalts include sodium pclbGIaLe monohydrate and tetrahydrate and sodium p~,..,&l,ona~e, with sodium pe.~l,onate being most prere-.~d.
~ Pl~:felr.,d bleach precursors are peracetic acid plecu-sors, such as tetraacety~lethylene e (TAED); I:Je ~y~ ,OiC acid precursors In one pref~ d aspect, the detergent col.lpo~;~ions are free of bleach and of particular utility in the washing of loads CQ~ g brightly coloured fabrics I,ow pH~lk~linity del~ al conlpos;lions P~.f~.l~l d~l~,.~nl compositions accol~ g to the invention are .,h~ ised by having a pH measured as a 1% solution of the detergent composition in ~ tilled water at 25~C of C 10 5, plef~.ably < 10.4, most preferably ~10 3 It has ~een found that compositions having a low level of reserve ~ lini~y are adv~nt~geol-~ in that they have a further reduced ten~lenCy to cause the removal of printed p;g. .~ .l from printed cotton fabncs. Reserve ~ik~linity is ~"~pl.,sse;i as g of NaOH per 100 g of composition as d~f ...i~f~ by acid titration of a sample, as 1%
solution in ~lictill~l water to a pH of 9 5 Pl.,fe.,~d values of reserve ~ inity are <
8 0 g p~erei~ably < 5 0 g, most pL~ ably < 3 0 g NaOH per 100g of composition Physical form The detergent composition acco~-Lng to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositionsare p-crclled.
Making process The dele~genl compositions of the invention may be pleparcd by any suitable method. The particulate detergent compositions are suitably p.~l,ared by any tower (spray-drying) or non-tower process.
In processes based around a spray-drying tower, a base powder is first p-~,p~hed by spray-drying a slurry and then other co---ponenls lln.cllit~ble for processing via the slurry can be sprayed on or ~1mixed (postdosed).
The zeolite builder is suitable for in~ n in the slurly, although it may be ~ advantageous for procçCcing reasons for part of the zeolite builder to be incGl~o.aled post-tower. The crystalline layered silicate, where this is employed, is also illco,~ ed via a non-tower process and is pl~,f~,.ably post<lose~
Alternatively, particulate detergent compositions in accordd~ce with the invention may be pr ~ ,d by wholly non-tower processes such as granulation.
The ~..llar d~,tclg~,nt compositions of the invention may be pl~paled to any suitable buL~c density. The compositions p-,f~ bly have a buL~c density of at least 400 gA prcrcl~bly at least 550 g/l, most pl~,r~,~ly at least 700 gA and, with particular pr~f.,rence at least 800 gA.
The benefits of the present invention are particularly evident in powders of high bulk density, for; l~ '-, of 700 gA or above. Such powders may be plel)~ed either by post-tower ~ n.cifie~tion of spray-dried powder, or by wholly non-tower methods such as dry mixing and gr~mll~fion; in both cases a high-speed mixer/granulator may adv~nt~geously be used. E'locesses using high-speed mixer/granulators are f~i.c~.ioseA, for; , '~, in EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
The detergent composition of the invention may be form~ ted as a liquid detergent composition which may be aqueous or anhydrous. The term "liquid" used herein in~ es pasty viscous formulations such as gels. The liquid detergent compositiongenerally has a pH offrom 6.5 to 10.5.
The total amount of detergency builder in the liquid composition is p,efe.~bly from 5 to 70% ofthe total liquid composition.
Illustrative co...pos;l;- ns according to the present invention are presented in the following Ex~mp'cs. In the dele. ~enl compocition~ the abbreviated component identifi~tions have the following ...~ni 24AS : Sodium alkyl sulfate surfactant co predollfi"al~lly C12 and C14 aLkyl chains TAS : Sodium aL~yl sulfate :~u~ra~ co............ l;~i.. il~g predol.~in~lly C16 - Clg alkyl chains derived from tallow oil.
24AE3S : C12-C14 alkyl e~ y~LIlfate co~ an average of three ethoxy groups per mole 35E3 : A C13 15 primary alcohol con~n-~ with an average of 3 moles of ethylene oxide 25E3 : A C12-C15 pll~ y alcohol con~ n~ with an average of 3 moles of ethylene oxide C~l,on~.le : Anhydrous sodium carbonate Bicaul,vnale : Anhydrous sodium bic~bonale P~,.l,o,~le : Sodium p~.b~ale tetrahydrate TAED : Tetraacetyl ethylene ~
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio normally follows) SKS6 : Crystalline layered silicate available from Hoechst AG
as SKS6 (tr~.~len~mP) Zeolite MAP : Hydrated sodium ~ minosilicate zeolite MAP
having a silicon to ~lllminium ratio of 1.07 having a particle size, CA~I ~;.sed as a dso value, of 0.7 mi~, ul"el. ~ s ZeoliteA : Hydrated sodium ~lllminosilicate zeolite A having a particle size, c ~ ssed as a dso value, of 0.6 mi.,lu",el,~,s MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
-Alcalase : rro~eolytic enzyme sold under the tr~d~n~me Alcalase by Novo Industries A/S (approx 1% enzyme activity by weight) BSA : Amylolytic enzyme sold under the tr~ n~me LE17 by Novo T.~ c A/S (approx 1% enzyme activity) F,Y~m~
The following granular laundry delel-~e.ll compositions were p,~,~,~ed (parts byweight) in acco. dauce with the invention.
A B C D E
24AS 7.6 6.5 4.8 6.8 TAS - - - - 8.6 24AE3S 2.4 - 1.2 1.7 25E3 3.26 - - - 6.3 35E3 - 5.0 5.0 5.0 Zeolite MAP 20 0 25 0 25 0 - 16 0 Zeolite A - - - 25 0 15 0 SKS6 70 5.0 100 Carbonate 3 0 3 0 Bicarbonate 3 0 4.0 4 0 8 0 5 0 Perborate 160 160 160 160 200 TAED 5 0 5 0 5.0 5 0 6 7 Alcalase 0.2 0 5 0 3 0 2 0 1 Protease 0 04 0 08 - 0 05 0 05 Silicate (2 0 4 0 - - 4 0 3 0 ratio) Water and micc~ neous (Tnclll-1ing suds sl.ppl~,ssor, sodium sulphate, perfume) to balance The detergent compositions accoldi.,~ to the invention, which co,..l"ise zeolitebuilder of larger particle size and bic~l,ol.~te builder optionally with relatively low levels of c~bollale builder, show good results in stain removal and lower printed cotton fabric damage as co---pa,t;d with a co---p~bly ~Ik~lin~ and built bicarbonate-free composition comprising small particle size zeolite and p..n~ ,ally carbonate builder
<
Detergent compositions for fabric washing conventionally contain detergency builders which lower the concellL~alion of c~ m and m~gnPci.lm water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soft water.
Conventionah r~ i"organic phosphates, such as sodium tripolyphosphate, have beenused as builder3 for laundry detergents. More recently, aLkali metal ~lllminosilicate iori--e:~h~rlgers, particularly crystalline sodium ~lllminosi~ te zeolite A, have been proposed as repl~-Pm~ntc for the il-OI ~ iC phosph:~tPC
For cA~Iple, EP 21 491A (Procter & Gamble) ~ sps d.,t~,.g,t..l compositions co..~ a building system which in~l~ldes zeolite A, X or P (B) or a mixture thereof. EP 384070A (IJnilever) discloses specific zeolite P materials having anespecially low silicon to ~1~...;.,;.,~., ratio not greater than 1.33 (ht.t;illaller lere--~to as zeolite MAP) and des~;. ~es its use as a det~ ,n~iy builder.
Zeolite builders are typically used in detergent compositions with cobuilders toprovide o~,ti,.,u-~ building capacity for the detergent composition as a whole.
Ca l,onale is a particularly commonly used cob--ildPr, which is favoured in part, for its ability to provide both building capacity and ~ inity to a wash solution.
The Applicants have now surprisingly found that a p.o~' may occur when a water insoluble zeolite having a small particle size, is used as a dcte-~.,ncy builder in a fabric laundering detergent composition also co..~ p. relatively high levels of c~hl,olla~e cobuilder. The problem has been found to be particularly pronounced when the zeolite builder is zeolite MAP.
The choice of a small particle size for a zeolite MAP co,--polle--l, that is to say particles having a particle size, measured as a dso value, of up to 1.0 micrometres has previously been taught to be ple~-.~,d in the art, as rep,~ 1, for example, by EP 384070 A.
The problem relates to the aforemçntit)ned detergent compositions having a marked incompatibility with printed cotton fabrics. In particular, it has been found that the use of detergent compositions co~ g smaU particle size zeolite tends to lead to the removal of printed pigment from a printed cotton fabric surface. The presence of relatively high levels of carbonate cobuilder has been found to eA~I ~ebale this effect.
The Applicant has surprisingly found that this p~c,bl~l.l can be ameliorated by the partial or complete repl~cPmPnt of the c~l,onale component of the detergent composition by a bicarbonate builder co...ponent.
The present invention is thus based on the u~l~,A~c~,led finding that the printed cotton fabric care profile of a detergent composition co-lll,-isiilg zeolite of small particle size, bic~l,ona~e builder and relatively low levels of carbonate builder is superior to that of cO---~l&-ably aL~caline and built compositions co~ g p.i.~ipally carbonate cobuilder.
This finding allows the fonnulation of dt;l~ ~,e"l compositions providing both eYcPIIPnt rle~ning and printed fabric care plope.lies on cotton fabrics.
Whilst the prior art, as lep-~nled for ~ -~-..ple by European Patent Aplications, EP
384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP 544492 A, EP 552053 A, and EP 552054 A has envisaged the use of cobuilders in conlbinal~on with zeolite in laundry d~ ,c;..l compositions, none of these prior art doc~mPn~ specificallydisclose the use of bicall~onale cobuilder with a small particle size zeolite component. Fu~lL_.mor~" none of these prior art doc~ i provides any te~ching relating to the printed cotton fabric care pr~bl addressed by the current invention, nor of any solution thereto involving the selection of a particular bicarbonate cobuilder co-l,pone.ll.
Thus, the present i~e.llion provides a dele.~,t;..l composition co.,~ ;n~
(a) a zeolite builder having a particle size, dso, of less than 1.0 rnicrometres;
~b) a bicalboilale builder; and optionally (c) a carbonate builder wherein the weight ratio any carbonate builder to the bic~l,ona~e builder is less than 4:1.
In a p,t;re-lled embodiment of the invention the zeolite builder comprises zeolite P
having a silcon to ~ minillm ratio of not greater than 1.33 (zeolite MAP).
In a further plt;rellc;d embodiment the detergent composition according to the invention is form--l~ted to be espeçi~lly useful in the laundering of coloured fabrics and p,~,rel~bly is free of bleach. Accol~ g to another aspect of the invention, the composition is subs~ ially free of an optical brightf n~r.
Zeolite builder The first P ss~ l co",pon~ of the present invention is an alllmino.cili~te zeolite builder.
The zeolite builder is typically present at a level of from 1% to 80%, more plt;Çel~bly from 15% to 40% by weight ofthe cc"~.po~;~;ons Suitable ~hlminosilis~te zeolites have the unit cell formula Naz[(A102)z(SiO2)y].
XH2O wh~ z and y are at least 6; the molar ratio of z to y is from 1.0 to 0. 5 and x is at least 5, pr~f~ bly from 7.5 to 276, more plerél~bly from 10 to 264. The alllminosiliss~te m~trri~l are in hydrated form and are p,~f~ bly crystalline, cc,..~ 5 from 10% to 28%, more prt;r~ bly from 18% to 22% water in bound form.
The ~hlminocilir~qte zeolites can be naturally occurnng materials, but are preferably synth~ti~lly derived. Synthetic crystalline ~lllminocili~te ion ~ .~hange materials are available under the d~ci~. l;onc Zeolite A, Zeolite B, Zeolite P, Zeolite X Zeolite MAP, Zeolite HS and ~-~lur,s thereo~
Zeolite A has the formula Na 12 ~AlO2) 12 (SiO2)l2] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(Alo2)86(sio2)lo6] 276 H20.
Zeo1ite MAP is described in EP 384070A (Unilever). It is defned as an alkali metal mino-silicate of the zeolite P type having a silicon to ~ minillrn ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0 9 to 1.2.
Of particular interest is zeolite MAP having a silicon to ~In.. : .. ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:AI ratio of 1.33 or less may be p~epalcd by the following steps:
(i) mixing together a sodium ~IIlmin~te having a mole ratio Na2O:A12O3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio SiO2:Na2O within the range of from 0.8 to 3 4 with vigorous stirring at a tc,~ re within the range of from 25~C to boiling point usually 95~C, to give a gel having the following composition; A12O3: (1.75-3.5) SiO2: (2.3-7.5) Na2O :P (80-450)H20;
(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to Shours, at a tClll~ tUl~, within the range of from 70~C to boiling point, usually to 95~C, with s~fficiPnt stirnng to ~"ai~ any solids present in su;.~ n;
(iii) S~p~aling the crystalline sodium ~ minosilic~te thus formed, washing to a pH within the range of from 10 to 12.5, and drying, ~f~,fe.ably at a tc~ ,.alure not ~ -~,ee~ g 150~C, to a moisture content of not less than S wt.%.
Pleîcll~,d drying methods are spray-drying and fiash-drying. It ap~ that oven drying at too high a t~ lpe.~ re may adversely affect the calcium binding capacity of the product under certain c;l ~ S
CGIIUII~C;dI sodium metasilicate pentahydrate dissolved in water and collu"e.,ial sodium silicate solution (waLel~lass) are both suitable silica sources for the ~ CA 02232956 1998-03-25 WO 97/12025 PCT~US96/15452 production of zeolite P in accordance with the invention. The re~ct~ntc may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95~C) both give the desired product.
Vigorous stirring of the gel during the ~d~liti~n of the re~cf~ntc and at least moderate stirring during the subsequPnt ageing step, however, appear to be ~cct~nti:~l for the forrnation of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a c~ m binding capacity of at least 150 mg CaO per g of a~ ous ~ mint~silc~te, as measured by the standard method described in GB
1473201 (Henkel). The calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
.~lthough zeolite MAP like other zeolites co..~aills water of hydration, for thepurposes of the present invention amollntC and pc.c~ gçs of zeolite are cA~Jle i~d in terms of the notional a~ dru-ls material.
The amount of water present in hydrated zeolite MAP at ~l)ienl telllp~ re and humidity is generally about 20 wt.%.
The ~olite builder used in the present invention has a particle size dso of less than 1.0 mi~lull~ell~s~ pr~,ably from 0.05 to 0.9 miclo"~elles~ most preferably from 0.2 to 0.7 micrc~ ,L~.,s. The dso value i~ le9 that 50% by weight of the particles have a ti;a~ t~ srnaller than that figure. The particle size may be determined by conv~nfion~l analytical teçhnitlues such as, for example, microscopic del~,.llfinalion ili7ing a S ;a ~ g el~, o- 11~ uscopC or by means of a laser granulometer.
Zeolite builder having the r~uired particle size acco.-li"g to the present invention can, for ~ , 'e, be p.ep~ed by the conventional techn:ques as dese~ ed above while adop~ g one or more of the following steps:-a) de ~ lg cryst~ tion time;
b) decreasing the size of the seed crystals used to produce the zeolite;
c) screening the zeolite product to remove coarse material.
An article by D. Vucelic, published in Progr Colloid Polymer Science, 1994, Volume 95, pages 14 - 38 desc,ibes methods for the synthesis of zeolite particles, and in particular how to jnfl~lence the particle size characteristics of the zeolites by modification of the synthesis process steps.
Brcarl~nate builder In addition to zeolite, the dt:le.~ compositions contain bicarbonate builder. Bybicarbonate builder it is meant herein any compound capable of rçleAsing bicarbonate ions to a wash solution.
Prère~llèd bicarbonate builders include the alkali and alkaline earth bicall,ona~e salts, particularly sodium bic~hbonale.
The bica,l,onale builder is typically present at a level of from 0.5% to 60%, ~lert~ably from 2% to 40%, most pref~.ably from 3% to 20% by weight of the detergent composition.
The bicarbonate builder is p~fc.ably present at a weight ratio of zeolite builder to bi- l,onale builder of from 20:1 to 1:5, more ~ ,f~,.ably from 10:1 to 2:1, mostp. ~,re~ ably from 5 :1 to 1:1.
Other builders The d.,le. ~ccnl co...pos;lions may contain other organic or inorganic builders.
In an f/~ ;AI aspect the level of any c~l,ohale builder, that is of inorganic compound capable of rPlp~cing carbonate ions into a wash solution, is kept relatively low. In particular, any carbonate builder is present only at a level wh~.ei-~ the weight ratio of the carbonate builder to the b:~r bonale builder is less than 4:1, ~le~.ably less than 2:1, more prere ably less than 1:1. Most pr~relably the de composition is free from ca,l,Gnale builder.
Suitable organic cob~ rs can be ...ono~....ic or polymeric carboxylates such as citrates or polymers of acrylic, methArrylic and/or maleic acids in neutralised form.
Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.
Suitable crystalline layered eilic~tes have the composition:
NaMSix02x+l . yH20 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No.
4664839; No. 4728443 and No. 4820439 (Hoechst AG). F..epeçi~lly plèfclled are compounds in which x = 2 and y = O. The synthetic material is co.lllllel.,;ally availab1e from Hoechst AG as o -Na2 Si2Os (SKS6) and is de~l;bed in US Patent No. 4664830.
The total amount of dGlel~ency builder in the granular composition typically ranges from 10 to 80 wt.%, more plcfcl~Lbly from 15 to 60 wt% and most plefGIably from 10 to 45 wt.%.
-Additional dc~ components The detergent composition accordillg to the invention may contain other delecolllponel~ls such as surf~Gt~nte ble~h~c~ fluol~,scc.~, antiredeposition agents, ~llOI~alLC salts such as sodium sulphate, other el~llles, lather control agents, fabric softening agents, pi~rn~nte, coloured speckles and perfumes.
Surfactant The d~,t~e.ll composition according to the invention pl er~l ~bl" includes a surfactant s~lect~i from anionics, nonionics, zwitterionics, ampholytics and ç~ti~ ~ --s The surfactant is p~Gfel~bly present in the detergent compositions at a level of from 1% to 50%, pl~f~,.ably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.
Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Dt;~l2;ellls" Volumes I and II by Scl-w~ 4 Perry and Berch).
Examples of suitable additional anionic surf~ctAntc include anionic sl-lf~tes, olefin sulphonates, alkyl xylene sulphonates, diallcyl~lrhos Ic~ cs, and fatty acid ester sulphonates. Sodium salts are generally plt;~..~d.
Anion~c suLfate .,ulr~;l~ll Anionic sulfate surfactants suitable for use herein include the linear and branched prirnary alkyl s-llf~tes, aL~cyl ethoxys-llf~t~e, fatty oleoyl glycerol sl-lf~tçe, alkyl phenol ethylene oxide ether s~lf~tes~ the Cs-C17 acyl-N-(Cl-C4 alkyl) and -N-(Cl-C2 hydroxyalkyl) ~ c~mine slllf~tçe, and sulfates of aL~cylpolysaccharides such as the suLfates of alkylpolyglucoside (the nonionic non~.llri.~ccl compounds being described herein).
-Alkyl ethoxysulfate surf~t~nts are pl.,f~ bly s--lected from the group consisting of the C6-C1g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per mole lle More plef~.~ly, the allcyl ~ilhu~y.,L~lfate surfactant is a C6-Clg alkyl sulfate which has been ethoxylated with from 0.5 to 20, pltifel~blyfrom 0.5 to 5, moles of ethylene oxide per mole llç
Anionic sulfonate surfactant Anionic sulfon~te s~rf~ct~nt!c suitable for use herein include the salts of Cs-C20 linear allylb~ e s~llron~ ,s, alkyl ester sl-lfon~t~e, C6-C22 pl~ll~y or second~uy aLtcane sulrona~es, C6-C24 olefin sulfonates, s~llro~ eA polyc~l.u~ylic acids, aL~cyl glycerol s ~lro~ c~ fatty acyl glycerol s~lr~n~t~s~ fatty oleyl glycerol sulronales, and any mixtures thereo~
Nonionic surfactant The n~niQnic sulr~ is pl~fe ~bly a Ly-ilophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a h~drophilic lipophilic balance (hlb) value of < 9.5, more ~,ert .~ly < 10.5.
Examples of suitable hydrophobic alkoxylated nonionic surf~ct~nts include alkoxylated ~dd~lr,tC of fatty alcohols co..~ g an average of less than 5 alkylene oxide groups per molecule.
The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
r~Çelled alkylene oxide ~dclt1ct~ of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
R-O~(CnH2nO)yH
whele.l~ R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
Plerell~d nonionic surf~ct~nts include p---~ Cll-Cls ~liph~tic alcoholscon~nced with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, prerel~blyfrom 25% to less than 50% by weight.
A particularly pre~..ed ~liph~tic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain conden-ce~ with an average of three ethoxy groups per mole of alcohol.
.~perifir, examples of suitable alkoxylated ~ductc of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-Cls alcohol with about three ethylene oxide groups per mole ~le and F.mpil~n KB3 (ex Marchon), which is lauric alcohol 3EO.
Another class of nonjonic s~f~ntc CGIll~Jli~S alkyl polygluco~ e compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from gl~r~se; R is a saturated l,~d,~,phobic alkylgroup that co..l; ;..~ from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds in~ ing less than 10% unreacted fatty alcohol and CA 02232956 l99X-03-25 less than 50% short chain allyl polyglucosides Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 00941 18 Bleach Detergent compositions acco~ d.llg to the invention may also contain a bleach system Where present, this preferably CO.Il~l ;SCS one or more peroxy bleach compounds, for cA~Ill~le, h~or~g~.c persalts or organic pe~u~yacids, which may be employed in conjunction with bleach precursors to improve bl~- chin~ action at low te.~l~,e.dl~lres The bleach system p,~rw~bly comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor Suitable persalts include sodium pclbGIaLe monohydrate and tetrahydrate and sodium p~,..,&l,ona~e, with sodium pe.~l,onate being most prere-.~d.
~ Pl~:felr.,d bleach precursors are peracetic acid plecu-sors, such as tetraacety~lethylene e (TAED); I:Je ~y~ ,OiC acid precursors In one pref~ d aspect, the detergent col.lpo~;~ions are free of bleach and of particular utility in the washing of loads CQ~ g brightly coloured fabrics I,ow pH~lk~linity del~ al conlpos;lions P~.f~.l~l d~l~,.~nl compositions accol~ g to the invention are .,h~ ised by having a pH measured as a 1% solution of the detergent composition in ~ tilled water at 25~C of C 10 5, plef~.ably < 10.4, most preferably ~10 3 It has ~een found that compositions having a low level of reserve ~ lini~y are adv~nt~geol-~ in that they have a further reduced ten~lenCy to cause the removal of printed p;g. .~ .l from printed cotton fabncs. Reserve ~ik~linity is ~"~pl.,sse;i as g of NaOH per 100 g of composition as d~f ...i~f~ by acid titration of a sample, as 1%
solution in ~lictill~l water to a pH of 9 5 Pl.,fe.,~d values of reserve ~ inity are <
8 0 g p~erei~ably < 5 0 g, most pL~ ably < 3 0 g NaOH per 100g of composition Physical form The detergent composition acco~-Lng to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositionsare p-crclled.
Making process The dele~genl compositions of the invention may be pleparcd by any suitable method. The particulate detergent compositions are suitably p.~l,ared by any tower (spray-drying) or non-tower process.
In processes based around a spray-drying tower, a base powder is first p-~,p~hed by spray-drying a slurry and then other co---ponenls lln.cllit~ble for processing via the slurry can be sprayed on or ~1mixed (postdosed).
The zeolite builder is suitable for in~ n in the slurly, although it may be ~ advantageous for procçCcing reasons for part of the zeolite builder to be incGl~o.aled post-tower. The crystalline layered silicate, where this is employed, is also illco,~ ed via a non-tower process and is pl~,f~,.ably post<lose~
Alternatively, particulate detergent compositions in accordd~ce with the invention may be pr ~ ,d by wholly non-tower processes such as granulation.
The ~..llar d~,tclg~,nt compositions of the invention may be pl~paled to any suitable buL~c density. The compositions p-,f~ bly have a buL~c density of at least 400 gA prcrcl~bly at least 550 g/l, most pl~,r~,~ly at least 700 gA and, with particular pr~f.,rence at least 800 gA.
The benefits of the present invention are particularly evident in powders of high bulk density, for; l~ '-, of 700 gA or above. Such powders may be plel)~ed either by post-tower ~ n.cifie~tion of spray-dried powder, or by wholly non-tower methods such as dry mixing and gr~mll~fion; in both cases a high-speed mixer/granulator may adv~nt~geously be used. E'locesses using high-speed mixer/granulators are f~i.c~.ioseA, for; , '~, in EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
The detergent composition of the invention may be form~ ted as a liquid detergent composition which may be aqueous or anhydrous. The term "liquid" used herein in~ es pasty viscous formulations such as gels. The liquid detergent compositiongenerally has a pH offrom 6.5 to 10.5.
The total amount of detergency builder in the liquid composition is p,efe.~bly from 5 to 70% ofthe total liquid composition.
Illustrative co...pos;l;- ns according to the present invention are presented in the following Ex~mp'cs. In the dele. ~enl compocition~ the abbreviated component identifi~tions have the following ...~ni 24AS : Sodium alkyl sulfate surfactant co predollfi"al~lly C12 and C14 aLkyl chains TAS : Sodium aL~yl sulfate :~u~ra~ co............ l;~i.. il~g predol.~in~lly C16 - Clg alkyl chains derived from tallow oil.
24AE3S : C12-C14 alkyl e~ y~LIlfate co~ an average of three ethoxy groups per mole 35E3 : A C13 15 primary alcohol con~n-~ with an average of 3 moles of ethylene oxide 25E3 : A C12-C15 pll~ y alcohol con~ n~ with an average of 3 moles of ethylene oxide C~l,on~.le : Anhydrous sodium carbonate Bicaul,vnale : Anhydrous sodium bic~bonale P~,.l,o,~le : Sodium p~.b~ale tetrahydrate TAED : Tetraacetyl ethylene ~
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio normally follows) SKS6 : Crystalline layered silicate available from Hoechst AG
as SKS6 (tr~.~len~mP) Zeolite MAP : Hydrated sodium ~ minosilicate zeolite MAP
having a silicon to ~lllminium ratio of 1.07 having a particle size, CA~I ~;.sed as a dso value, of 0.7 mi~, ul"el. ~ s ZeoliteA : Hydrated sodium ~lllminosilicate zeolite A having a particle size, c ~ ssed as a dso value, of 0.6 mi.,lu",el,~,s MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
-Alcalase : rro~eolytic enzyme sold under the tr~d~n~me Alcalase by Novo Industries A/S (approx 1% enzyme activity by weight) BSA : Amylolytic enzyme sold under the tr~ n~me LE17 by Novo T.~ c A/S (approx 1% enzyme activity) F,Y~m~
The following granular laundry delel-~e.ll compositions were p,~,~,~ed (parts byweight) in acco. dauce with the invention.
A B C D E
24AS 7.6 6.5 4.8 6.8 TAS - - - - 8.6 24AE3S 2.4 - 1.2 1.7 25E3 3.26 - - - 6.3 35E3 - 5.0 5.0 5.0 Zeolite MAP 20 0 25 0 25 0 - 16 0 Zeolite A - - - 25 0 15 0 SKS6 70 5.0 100 Carbonate 3 0 3 0 Bicarbonate 3 0 4.0 4 0 8 0 5 0 Perborate 160 160 160 160 200 TAED 5 0 5 0 5.0 5 0 6 7 Alcalase 0.2 0 5 0 3 0 2 0 1 Protease 0 04 0 08 - 0 05 0 05 Silicate (2 0 4 0 - - 4 0 3 0 ratio) Water and micc~ neous (Tnclll-1ing suds sl.ppl~,ssor, sodium sulphate, perfume) to balance The detergent compositions accoldi.,~ to the invention, which co,..l"ise zeolitebuilder of larger particle size and bic~l,ol.~te builder optionally with relatively low levels of c~bollale builder, show good results in stain removal and lower printed cotton fabric damage as co---pa,t;d with a co---p~bly ~Ik~lin~ and built bicarbonate-free composition comprising small particle size zeolite and p..n~ ,ally carbonate builder
Claims (11)
1. A detergent composition containing (a) a zeolite builder having a particle size, d50, of less than 1.0 micrometres;
(b) a bicarbonate builder; and optionally (c) a carbonate builder wherein the weight ratio any carbonate builder to the bicarbonate builder is less than 4:1.
(b) a bicarbonate builder; and optionally (c) a carbonate builder wherein the weight ratio any carbonate builder to the bicarbonate builder is less than 4:1.
2. A detergent composition according to claim 1, wherein the zeolite builder has a particle size d50 of from 0.05 to 0.9 micrometres.
3. A detergent composition according to either of claims 1 or 2, wherein the zeolite builder comprises zeolite P having a silcon to aluminium ratio of not greater than 1.33 (zeolite MAP).
4. A detergent composition according to claim 3, wherein the zeolite MAP has a silicon to aluminium ratio not greater than 1.15.
5. A detergent composition according to any one of claims 1 to 4, which comprises from 1 to 80% by weight of the zeolite builder.
6. A detergent composition according to any of claims 1 to 5, wherein said bicarbonate builder is present at a level of from 0.5% to 60% by weight of the detergent composition.
7. A detergent composition according to any of claims 1 to 6, wherein the weight ratio of zeolite builder to bicarbonate builder is from 20:1 to 1:5.
8. A detergent composition according to any of claims 1 to 7, wherein the bicarbonate builder is sodium bicarbonate.
9. A detergent composition according to any of claims 1 to 8, which is free from carbonate builder.
10. A detergent composition according to any of claims 1 to 9, wherein the composition has a reserve alkalinity (expressed as g of NaOH per 100 g of composition as determined by acid titration of a sample as 1% solution in distilled water to a pH of 9.5) of less than 8.0 g.
11. A detergent composition according to any of claims 1 to 10, which is free of bleach or optical brightener.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9519607.7A GB9519607D0 (en) | 1995-09-26 | 1995-09-26 | Detergent composition |
| GB9519607.7 | 1995-09-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2232956A1 true CA2232956A1 (en) | 1997-04-03 |
Family
ID=10781288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2232956 Abandoned CA2232956A1 (en) | 1995-09-26 | 1996-09-26 | Detergent composition based on zeolite-bicarbonate builder mixture |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0863973A4 (en) |
| BR (1) | BR9610735A (en) |
| CA (1) | CA2232956A1 (en) |
| GB (1) | GB9519607D0 (en) |
| WO (1) | WO1997012025A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6638902B2 (en) * | 2001-02-01 | 2003-10-28 | Ecolab Inc. | Stable solid enzyme compositions and methods employing them |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666740A (en) * | 1976-12-02 | 1987-05-19 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
| GB9305599D0 (en) * | 1993-03-18 | 1993-05-05 | Unilever Plc | Detergent compositions |
| GB9313878D0 (en) * | 1993-07-05 | 1993-08-18 | Unilever Plc | Detergent composition or component containing anionic surfactant and process for its preparation |
| EP0653481A1 (en) * | 1993-11-11 | 1995-05-17 | The Procter & Gamble Company | Granular detergent composition |
| MA23390A1 (en) * | 1993-12-07 | 1995-07-01 | Procter & Gamble | DETERGENT COMPOSITION CONTAINING AN OXIDE-AMINE SURFACTANT IN THE FORM OF AGGLOMERATES |
-
1995
- 1995-09-26 GB GBGB9519607.7A patent/GB9519607D0/en active Pending
-
1996
- 1996-09-26 EP EP96933155A patent/EP0863973A4/en not_active Withdrawn
- 1996-09-26 CA CA 2232956 patent/CA2232956A1/en not_active Abandoned
- 1996-09-26 BR BR9610735A patent/BR9610735A/en not_active Application Discontinuation
- 1996-09-26 WO PCT/US1996/015452 patent/WO1997012025A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0863973A1 (en) | 1998-09-16 |
| EP0863973A4 (en) | 1999-02-10 |
| GB9519607D0 (en) | 1995-11-29 |
| WO1997012025A1 (en) | 1997-04-03 |
| BR9610735A (en) | 1999-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5078916A (en) | Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds | |
| IE52685B1 (en) | Enzyme detergent composition | |
| JPH0948995A (en) | Detergent and cleaner containing iminodisuccinate | |
| US20030045440A1 (en) | Detergent compositions | |
| US6534464B1 (en) | Compositions containing α-sulfofatty acid ester and polyalkoxylated alkanolamide and methods of making and using the same | |
| US5958871A (en) | Detergent composition based on zeolite-bicarbonate builder mixture | |
| CA2232956A1 (en) | Detergent composition based on zeolite-bicarbonate builder mixture | |
| EP0808356A1 (en) | Detergent compositions comprising zeolite map and clay mineral | |
| GB2287948A (en) | Laundry detergent composition | |
| EP0754216B1 (en) | Detergent compositions comprising aldobionamides | |
| GB2303858A (en) | Detergent composition | |
| WO1997012026A1 (en) | Detergent composition comprising zeolite and proteolytic enzyme | |
| US6440922B1 (en) | Detergent composition comprising zeolite and amylase enzyme | |
| GB2288187A (en) | Detergent composition | |
| CA2210646C (en) | Detergent composition comprising zeolite map and amylase enzymes | |
| GB2294269A (en) | Detergent composition | |
| EP0859824A1 (en) | Detergent composition | |
| MXPA98002408A (en) | Deterge composition | |
| EP0964907A1 (en) | Detergent composition containing particulate zeolite builder and lubricant therefor | |
| MXPA98002410A (en) | Detergent composition based on an improving mixture of detergence of zeolite and bicarbon | |
| CA2209667A1 (en) | Detergent composition | |
| MXPA98002409A (en) | Detergent composition comprising zeolite and enzyme proteolit | |
| MXPA98002501A (en) | Detergent composition containing a zeolite detergent improvement and a lubricant for elmi | |
| CA2210293C (en) | Detergent composition | |
| MXPA97002939A (en) | Deterge composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |