CA2184363A1 - Detergent composition comprising zeolite map builder - Google Patents
Detergent composition comprising zeolite map builderInfo
- Publication number
- CA2184363A1 CA2184363A1 CA 2184363 CA2184363A CA2184363A1 CA 2184363 A1 CA2184363 A1 CA 2184363A1 CA 2184363 CA2184363 CA 2184363 CA 2184363 A CA2184363 A CA 2184363A CA 2184363 A1 CA2184363 A1 CA 2184363A1
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- CA
- Canada
- Prior art keywords
- detergent composition
- zeolite
- zeolite map
- composition according
- micrometres
- 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
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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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A detergent composition is disclosed comprising a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof and a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP) and having a particle size , d50, of from 2.0 to 10.0 micrometres, preferably 2.25 to 5 micrometres. The detergent composition is in one aspect preferably free of bleach. Granular and liquid detergent compositions are preferred. Methods of making the compositions are disclosed.
Description
WO9~/27027 2 1 84363 pCT"S95tO2698 DETERGENT COMPOSITION COMPRISING ZEOLITE MAP BUILDER
The present invention relates to a deterge.ll composition and, in particular, toimprovements in the detergency pe~rolll.allce of laundry dete.~ellt compositions comprising zeolites as a sequestering agent for water hardness.
Detergent compositions for fabric washing conventionally contain detergency builders which lower the conce~ alion of calcium and magnesium water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soflc water.
Conventionally, inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry detergellts. More recently, alkali metal aluminosilicate ion-exchangers, particularly crystalline sodium nosilicate zeolite A, have been proposed as replacements for the inorganic phosph~tes.
For example, EP 21 491A (Procter & Gamble) discloses detel~,elll compositions col-t~ g a building system which includes zeolite A, X or P
(B) or a ll~ u e thereof. EP 384070A (IJnilever) discloses specific zeolite P materials having an especially low silicon to ~ ;ulll ratio not greater than 1.33 (he~e~ler refelled to as zeolite MAP) and describes its use as a det~,r~;e.lcy builder. To date, however, zeolite A is the prefelled nosilicate delelge~cy builder in commercially available products.
EP 384,070A (Unilever) suggest~ that zeolite MAP has advantages as a deterge~cy builder over other zeolites. The preferred zeolite MAP in accordance with the disclosure of EP 384070A has a dso (as defined he~ ller) within the range of from 0.1 to 5.0 micrometres, prefe,ably within the range of from 0.1 to 1.0 microme~es and more plererably within the range of from 0.4 to 0.7 micrometres. The 4ual~tily "dso" in~lic~tes that 50% by weight of the particles have a diameter smaller than that figure.
WogS/27027 2 1 8 4 3 6 3 PCT/US95/02698 We have found that detergent compositions comprising zeolite MAP as detergency builder have a marked incomp~tibility with printed cotton fabrics as compared with conventional detergent compositions comprising other zeolites such as zeolite A. In particular, it has been found that detergent compositions co..l~;..il.~ zeolite MAP reduce the substantivity of printed pigment on a cotton fabric surface, thereby sho1l~,~ing fabric lifetime, as co111~a~ed with dete~g~1lt compositions comprising zeolite A.
We have surprisingly found that these problems can be subst~nt~ y overcome by using7 as the deterge.1cy builder, a zeolite MAP having a particle size dso somewhat larger than the l .cre,1ed particle size ranges prevlously proposed.
Thus, the present invention provides a deter~;e,ll composition comprising:
a) a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic dete,ge,lt-active compounds and 1~ clures thereof; and b) a detergency builder comprising zeolite P having a silicon to alun~ ium ratio not ~eater than 1.33 (zeolite MAP) and having a particle size, dso, of from 2.0 to 10.0 micrometres.
Accordi~g to a l,refe~1ed embo-liment the zeolite MAP has a particle size dso of from 2.25 to 5 micrometres.
In one pref~1ed aspect the deterg~"lt composition according to the present invention is form~ ted to be especially suited to the l~m-lering of bleach sensitive fabrics and cont~ins no bleach.
The dete,ge1l~ composition according to the invention conlaills, as an essen~i~l ingredient, one or more surfactants selecte~ from anionic, nonionic, cationic, amphoteric and zwitterionic deterge~ active compounds and mi~ es thereo Such surfactants are well known and described in the ~il~lu~e, for example, in "Surface-Active Agents and Detergehts", Volumes I and II by Schwartz, Perry and Berch.
W O 95/27027 PC~rrUS95/02698 -Examples of suitable anionic surfactants include alkylbenzene sulphonates, particularly sodiurn linear alkylbenzene s~llphon~tes having an alkyl chain length of C8-C15; Cl2-cl5 primary alkyl s~lph~te~; olefin sulphonates;
alkyl xylene sulphonates; diaLkyl sulphosuccin~tes; and fatty acid ester sulphon~tes. Sodium salts are generally prefe.-ed.
Examples of suitable nonionic surf~ct~nt~ include alkoxylated adducts of fatty alcohols co..~ an average of less than S alkylene oxide groups per molecule, for example less than 4 alkylene oxide groups per molecule e.g.
3.5 and usefully 3 alkylene oxide groups per molecule or less and usefully also ~ater than 0.5, or l, or 2 alkylene oxide groups per molecule.
A particularly ~Jrefelled aliphatic alcohol ethoxylate is a plil~y alcohol having an average of 12 to 15 carbon atoms in the aLkyl chain con~l~n~e~
with an average of three ethoxy groups per mole of alcohol.
Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-Cls alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
Another class of nonionic surf~ct~nts comprises alkyl polyglucoside compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a s~ ated hydrophobic alkyl group that cont~in~ 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 including less than 10%
unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in deter~ent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
The surf~ct~nt will generally be included in the deterge.lt composition in an amount of S to 60% by weight, ~refelably 5 to 40% by weight and most 2 1 8 4 3 6 3 PCT/USgSI`~2~3~
y~ferably from 10 to 25% by weight of the composition.
According to the present invention the deterge,lcy builder system is based on zeolite MAP, optionally in conjunction with one or more supplementary builders. The amount of zeolite MAP employed may range, for example, from 1 to 80 wt %, ~lefe~dbly from 5 to 60 wt.%, more prere,dbly from 10 to40wt.%.
Zeolite MAP is described in EP 384070A (IJnilever). It is defined as an alkali metal ~lllmino-silicate of the zeolite P type having a silicon to ~1".";";"." ratio not ~aler than 1.33, ~rere,ably wi~hin the range from 0.9 to 1.33 and more prefe.dbly within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to al!~";";l~ ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:Al ratio of 1.33 or less may be yre~ared by the following steps:
(i) mixing together a sodium alllmin~te having a mole ratio Na20:A1203 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 tempe,dl lre within the range of from 25C to boiling point usually 95C, to give a gel having the following composition;
A123: (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, l,lefe~ably 2 to 5 hours, at a tempe,~dlur~ within the range of from 70C to boiling point, usually to 95C, with sufficient stirring to m~int~in any solids present in suspension;
(iii) sepaldtillg the crys~lline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying, preferably at a te~erdlule not excee~ling 150C, to a moisture content of not less than 5 wt.%.
WO95/27027 2 1 84363 p~tUS95t02698 -Plefelled drying methods are spray-drying and flash drying. It appears that oven drying at too high a tempc,alure may adversely affect the calcium binding capacity of the product under certain circllm~tances.
Commercial so~limn metasilicate pentahydrate dissolved in water and comrnercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention.
The re~ct~nt~ may be added together in any order either rapidly or slowly.
Rapid addition at ambient temperalu.e, and slow addition at elevated tempcralule (90-95C) both give the desired product.
Vigorous stirnng of the gel during the addition of the reactants, and at least moderate stirring during the subsequent ageing step, however, appear to be essenti~l for the formation of pure zeolite P. In the absence of stirring, various ~ es of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous ~lllminosilicate, as me~nred 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.
Although zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percell~ages of zeolite are expressed in terms of the notional anhydrous material. The amount of water present in hydlated zeolite MAP at ambient temper~lule and humidity is generally about 20 wt.%.
The zeolite MAP used in the present invention has a particle size dso of from 2.0 to 10.0 micrometres, plefe;ably from 2.2S to 5 micrometres, most plefer~bly from 2.75 to 5 micrometres. The particle size is deterrnined by conventional analytical techniques -such as, for example, microscopic detel",i..;1l;on lltili7ing a sc~nnin~ electron microscope or by means of a laser granulometer.
Zeolite MAP having the required particle size according to the present invention can be pre~ared by the conventional tecllniques as described WO95/27027 21 ~4363 PCT/US95tO2698 above while adopting one or more of the following steps:-a) increasing cryst~llic~tion time;
b) increasing the size of the seed crystals used to produce the zeolite;
c) feeding the ~hlminosilicate gels into the cryst~ tion stage immediately after they form (i.e. elimin~te ageing of gels);
d) screening the zeolite product to remove fine material.
An article by D. Vucelic, published in Progr Colloid Polymer Science, 1994, Volume 95, pages 14 - 38 describes methods for the synth~si~ of zeolite particles, and in particular how to influence the particle size characteristics of the zeolites by modification of the synthesi~ process steps.
The delerge,l~ composition according to the invention generally contains zeolite MAP in an amount of 1 to 80% by weight of the composition, plefer~bly S to 60% and most prefe,ably lO to 40% by weight of the composition.
According to the invention zeolite MAP may be the sole builder component or it may be used in combination with an organic or inorganic cobuilder.
According to a particular embodiment of the invention, zeolite MAP is the principal builder component.
Suitable organic cobuilders can be monomeric or polymeric carboxylates such as cillates or polymers of acrylic, methacrylic and/or maleic acids in - neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline lamellar sodium silica~es.
Suitable silicates have the composition:
NaMSix02x+l, YH20 where M is sodium or hydrogen, l,refc.ably 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
rate.lls No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
Especially prer~,lled are compounds in which x = 2 and y = O. The synthetic material is commercially available from Hoechst AG as ~-Na2 Si2Os (SKS6) and is described in US Patent No. 4664830.
The total amount of detergency builder in the granular composition ranges from 1 to 80 wt%, more l,~feldbly from 10 to 60 wt% and most p,efelably from 15 to 45 wt%.
The detergent composition according to the invention may include the conventional deter~,~nl materials. However, prereldbly the composition is free of bleach. Other optional materials which may be present include, for example, enzymes, fluorescers, antiredeposition ~gent~, inorganic salts such as sodium snlrh~te, lather control agents, fabric softenin~ ~gentc, pigments, coloured speckles and perfumes.
The detergent compositions of the invention may be of any physical type, for example, powders, tablets, liquids and gels. However, granular and liquid compositions are ~f~.ed.
The detergent compositions of the invention may be l,r~aled by any suitable method. The particulate det~gent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
In processes based around a spray-drying tower, a base powder is first prepaled by spray-drying a slurry and then o~er components lmcllit~ble for proce~sing via the slurry can be sprayed on or admixed (postdosed).
The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower.
Alternatively, particulate detergelll compositions in accord~lce with the invention may be l ,e~aled by wholly non-tower processes such as gr~nlll~ion.
W O 95t27027 PC~rrUS95/02698 The granular detergent compositions of the invention may be prepared to any suitable bulk density. The compositions yrefe~ably have a bulk density of at least 400 g/l ~,e~,ably at least 550 g/l, most l,lefelably at least 700 g/l and, with particular pre~rence at least 800 g/l.
The bPn~fitc of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be ~le~ared either by post-tower ~lencification of spray-dried powder, or by wholly non-tower methods such as dry mixing and gr~m-l~tion; in both cases a high-speed mixer/gr~nul~tor may advantageously be used. Processes using high-speed mixer/gr~n-ll~tors are disclosed, for example, in EP340 013A, EP
367 339A, EP 390 251A and EP 420 317A (Unilever).
According to one aspect of the invention there is provided a granular detergent composition comprising:
a) from 5 to 60 wt%, l.~felably 5 to 40 wt%, of one or more surfactants selecteA from anionic, nonionic, cationic, ~mphoteric and zwitterionic detergent-active compounds and ~ es thereof, and b) from 10 to 80 wt% of a detergency builder comprising zeolite P having a silicon to al.~ ratio not gleater than 1.33 (zeolite MAP) and having a particle size dso of from 2.0 to 10.0 micrometres, l,refelably from 2.25 to 5 micrometres.
According to another embo~limPnt of the invention there is provided a liquid d~t~g~l composition, prefeYably a heavy duty liquid d&t~gent composition, comprising from 5 to 60 wt% of component (a) above and ~om 5 to 40 wt%
of component (b) above.
According to this embodiment the liquid detergellt composition may be of any convenient physical form which may be aqueous or anhydrous. The term "liquid" used herein includes partly viscous fonn~ tion~ such as gels.
The liquid detergen~ composition generally has a pH of from 6.5 to 10.5.
The total amount of detergency builder in the liquid composition is prefelably from 5 to 70% of the total liquid composition.
According to a further aspect, the invention provides use of zeolite MAP
having a particle size dso of 2.0 to 10.0 micrometres, plefe~bly from 2.25 to 5 micrometres as an additive for a detergent composition.
The following Example provides an illustration of a deter~e~lt composition according to the present invention.
The following abbreviations have been used:
AS :- sodiumalkylsulphate AEs :- tallow alcohol ethoxylated with 5 ethoxy groups per mole alcohol AE45 :- tallow alcohol ethoxylated with 4 to 5 ethoxy groups per mole alcohol CMC :- sodium carboxymethyl cellulose EDTMP :- ethylene ~ mine tetramethylene phosphon~te PVP :- polyvinyl pyrrolidone MA/AA copolymer :- copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000 TAED :- tetracetyl ethylene ~i~mine WO 95/27027 2 1 8 4 3 6 3 rC~tU$95tO2698 Component Proportion (bY wt) zeolite MLA~P (d50 = 3 0 40 % 38.5 %
micrometers Carbonate 7% 7.2%
Silicate 2.0R 5 % 5.8 %
Citrate 15 %
C14 - C 15 A S 7 %
C 12 - C14 A S 5.6 %
A E5 12%
A E45 - 11.5 %
Citric Acid 3 % 3.0 %
Silicone Antifoam 0.5 %
Soap - 1.0%
Hyfac 1.0%
Wax 0.5%
MLA/A A copolymer 1.5 % 1.8 %
Savinase (2.0 KNPU) 2.0% 2.0%
Lipolase(100,000 LU/l) 0.4% 0.2%
CMC 0.8%
Optical Brightener 0.2%
PVP 1.0%
EDTMP 0.8% 0.1%
TAED - 2.5%
Sodium rerc~l,onate - 14.0%
Moisture& balance balance Miscellaneous 100% 100%
The present invention relates to a deterge.ll composition and, in particular, toimprovements in the detergency pe~rolll.allce of laundry dete.~ellt compositions comprising zeolites as a sequestering agent for water hardness.
Detergent compositions for fabric washing conventionally contain detergency builders which lower the conce~ alion of calcium and magnesium water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soflc water.
Conventionally, inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry detergellts. More recently, alkali metal aluminosilicate ion-exchangers, particularly crystalline sodium nosilicate zeolite A, have been proposed as replacements for the inorganic phosph~tes.
For example, EP 21 491A (Procter & Gamble) discloses detel~,elll compositions col-t~ g a building system which includes zeolite A, X or P
(B) or a ll~ u e thereof. EP 384070A (IJnilever) discloses specific zeolite P materials having an especially low silicon to ~ ;ulll ratio not greater than 1.33 (he~e~ler refelled to as zeolite MAP) and describes its use as a det~,r~;e.lcy builder. To date, however, zeolite A is the prefelled nosilicate delelge~cy builder in commercially available products.
EP 384,070A (Unilever) suggest~ that zeolite MAP has advantages as a deterge~cy builder over other zeolites. The preferred zeolite MAP in accordance with the disclosure of EP 384070A has a dso (as defined he~ ller) within the range of from 0.1 to 5.0 micrometres, prefe,ably within the range of from 0.1 to 1.0 microme~es and more plererably within the range of from 0.4 to 0.7 micrometres. The 4ual~tily "dso" in~lic~tes that 50% by weight of the particles have a diameter smaller than that figure.
WogS/27027 2 1 8 4 3 6 3 PCT/US95/02698 We have found that detergent compositions comprising zeolite MAP as detergency builder have a marked incomp~tibility with printed cotton fabrics as compared with conventional detergent compositions comprising other zeolites such as zeolite A. In particular, it has been found that detergent compositions co..l~;..il.~ zeolite MAP reduce the substantivity of printed pigment on a cotton fabric surface, thereby sho1l~,~ing fabric lifetime, as co111~a~ed with dete~g~1lt compositions comprising zeolite A.
We have surprisingly found that these problems can be subst~nt~ y overcome by using7 as the deterge.1cy builder, a zeolite MAP having a particle size dso somewhat larger than the l .cre,1ed particle size ranges prevlously proposed.
Thus, the present invention provides a deter~;e,ll composition comprising:
a) a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic dete,ge,lt-active compounds and 1~ clures thereof; and b) a detergency builder comprising zeolite P having a silicon to alun~ ium ratio not ~eater than 1.33 (zeolite MAP) and having a particle size, dso, of from 2.0 to 10.0 micrometres.
Accordi~g to a l,refe~1ed embo-liment the zeolite MAP has a particle size dso of from 2.25 to 5 micrometres.
In one pref~1ed aspect the deterg~"lt composition according to the present invention is form~ ted to be especially suited to the l~m-lering of bleach sensitive fabrics and cont~ins no bleach.
The dete,ge1l~ composition according to the invention conlaills, as an essen~i~l ingredient, one or more surfactants selecte~ from anionic, nonionic, cationic, amphoteric and zwitterionic deterge~ active compounds and mi~ es thereo Such surfactants are well known and described in the ~il~lu~e, for example, in "Surface-Active Agents and Detergehts", Volumes I and II by Schwartz, Perry and Berch.
W O 95/27027 PC~rrUS95/02698 -Examples of suitable anionic surfactants include alkylbenzene sulphonates, particularly sodiurn linear alkylbenzene s~llphon~tes having an alkyl chain length of C8-C15; Cl2-cl5 primary alkyl s~lph~te~; olefin sulphonates;
alkyl xylene sulphonates; diaLkyl sulphosuccin~tes; and fatty acid ester sulphon~tes. Sodium salts are generally prefe.-ed.
Examples of suitable nonionic surf~ct~nt~ include alkoxylated adducts of fatty alcohols co..~ an average of less than S alkylene oxide groups per molecule, for example less than 4 alkylene oxide groups per molecule e.g.
3.5 and usefully 3 alkylene oxide groups per molecule or less and usefully also ~ater than 0.5, or l, or 2 alkylene oxide groups per molecule.
A particularly ~Jrefelled aliphatic alcohol ethoxylate is a plil~y alcohol having an average of 12 to 15 carbon atoms in the aLkyl chain con~l~n~e~
with an average of three ethoxy groups per mole of alcohol.
Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-Cls alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
Another class of nonionic surf~ct~nts comprises alkyl polyglucoside compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a s~ ated hydrophobic alkyl group that cont~in~ 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 including less than 10%
unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in deter~ent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
The surf~ct~nt will generally be included in the deterge.lt composition in an amount of S to 60% by weight, ~refelably 5 to 40% by weight and most 2 1 8 4 3 6 3 PCT/USgSI`~2~3~
y~ferably from 10 to 25% by weight of the composition.
According to the present invention the deterge,lcy builder system is based on zeolite MAP, optionally in conjunction with one or more supplementary builders. The amount of zeolite MAP employed may range, for example, from 1 to 80 wt %, ~lefe~dbly from 5 to 60 wt.%, more prere,dbly from 10 to40wt.%.
Zeolite MAP is described in EP 384070A (IJnilever). It is defined as an alkali metal ~lllmino-silicate of the zeolite P type having a silicon to ~1".";";"." ratio not ~aler than 1.33, ~rere,ably wi~hin the range from 0.9 to 1.33 and more prefe.dbly within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to al!~";";l~ ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:Al ratio of 1.33 or less may be yre~ared by the following steps:
(i) mixing together a sodium alllmin~te having a mole ratio Na20:A1203 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 tempe,dl lre within the range of from 25C to boiling point usually 95C, to give a gel having the following composition;
A123: (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, l,lefe~ably 2 to 5 hours, at a tempe,~dlur~ within the range of from 70C to boiling point, usually to 95C, with sufficient stirring to m~int~in any solids present in suspension;
(iii) sepaldtillg the crys~lline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying, preferably at a te~erdlule not excee~ling 150C, to a moisture content of not less than 5 wt.%.
WO95/27027 2 1 84363 p~tUS95t02698 -Plefelled drying methods are spray-drying and flash drying. It appears that oven drying at too high a tempc,alure may adversely affect the calcium binding capacity of the product under certain circllm~tances.
Commercial so~limn metasilicate pentahydrate dissolved in water and comrnercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention.
The re~ct~nt~ may be added together in any order either rapidly or slowly.
Rapid addition at ambient temperalu.e, and slow addition at elevated tempcralule (90-95C) both give the desired product.
Vigorous stirnng of the gel during the addition of the reactants, and at least moderate stirring during the subsequent ageing step, however, appear to be essenti~l for the formation of pure zeolite P. In the absence of stirring, various ~ es of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous ~lllminosilicate, as me~nred 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.
Although zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percell~ages of zeolite are expressed in terms of the notional anhydrous material. The amount of water present in hydlated zeolite MAP at ambient temper~lule and humidity is generally about 20 wt.%.
The zeolite MAP used in the present invention has a particle size dso of from 2.0 to 10.0 micrometres, plefe;ably from 2.2S to 5 micrometres, most plefer~bly from 2.75 to 5 micrometres. The particle size is deterrnined by conventional analytical techniques -such as, for example, microscopic detel",i..;1l;on lltili7ing a sc~nnin~ electron microscope or by means of a laser granulometer.
Zeolite MAP having the required particle size according to the present invention can be pre~ared by the conventional tecllniques as described WO95/27027 21 ~4363 PCT/US95tO2698 above while adopting one or more of the following steps:-a) increasing cryst~llic~tion time;
b) increasing the size of the seed crystals used to produce the zeolite;
c) feeding the ~hlminosilicate gels into the cryst~ tion stage immediately after they form (i.e. elimin~te ageing of gels);
d) screening the zeolite product to remove fine material.
An article by D. Vucelic, published in Progr Colloid Polymer Science, 1994, Volume 95, pages 14 - 38 describes methods for the synth~si~ of zeolite particles, and in particular how to influence the particle size characteristics of the zeolites by modification of the synthesi~ process steps.
The delerge,l~ composition according to the invention generally contains zeolite MAP in an amount of 1 to 80% by weight of the composition, plefer~bly S to 60% and most prefe,ably lO to 40% by weight of the composition.
According to the invention zeolite MAP may be the sole builder component or it may be used in combination with an organic or inorganic cobuilder.
According to a particular embodiment of the invention, zeolite MAP is the principal builder component.
Suitable organic cobuilders can be monomeric or polymeric carboxylates such as cillates or polymers of acrylic, methacrylic and/or maleic acids in - neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline lamellar sodium silica~es.
Suitable silicates have the composition:
NaMSix02x+l, YH20 where M is sodium or hydrogen, l,refc.ably 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
rate.lls No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
Especially prer~,lled are compounds in which x = 2 and y = O. The synthetic material is commercially available from Hoechst AG as ~-Na2 Si2Os (SKS6) and is described in US Patent No. 4664830.
The total amount of detergency builder in the granular composition ranges from 1 to 80 wt%, more l,~feldbly from 10 to 60 wt% and most p,efelably from 15 to 45 wt%.
The detergent composition according to the invention may include the conventional deter~,~nl materials. However, prereldbly the composition is free of bleach. Other optional materials which may be present include, for example, enzymes, fluorescers, antiredeposition ~gent~, inorganic salts such as sodium snlrh~te, lather control agents, fabric softenin~ ~gentc, pigments, coloured speckles and perfumes.
The detergent compositions of the invention may be of any physical type, for example, powders, tablets, liquids and gels. However, granular and liquid compositions are ~f~.ed.
The detergent compositions of the invention may be l,r~aled by any suitable method. The particulate det~gent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
In processes based around a spray-drying tower, a base powder is first prepaled by spray-drying a slurry and then o~er components lmcllit~ble for proce~sing via the slurry can be sprayed on or admixed (postdosed).
The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower.
Alternatively, particulate detergelll compositions in accord~lce with the invention may be l ,e~aled by wholly non-tower processes such as gr~nlll~ion.
W O 95t27027 PC~rrUS95/02698 The granular detergent compositions of the invention may be prepared to any suitable bulk density. The compositions yrefe~ably have a bulk density of at least 400 g/l ~,e~,ably at least 550 g/l, most l,lefelably at least 700 g/l and, with particular pre~rence at least 800 g/l.
The bPn~fitc of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be ~le~ared either by post-tower ~lencification of spray-dried powder, or by wholly non-tower methods such as dry mixing and gr~m-l~tion; in both cases a high-speed mixer/gr~nul~tor may advantageously be used. Processes using high-speed mixer/gr~n-ll~tors are disclosed, for example, in EP340 013A, EP
367 339A, EP 390 251A and EP 420 317A (Unilever).
According to one aspect of the invention there is provided a granular detergent composition comprising:
a) from 5 to 60 wt%, l.~felably 5 to 40 wt%, of one or more surfactants selecteA from anionic, nonionic, cationic, ~mphoteric and zwitterionic detergent-active compounds and ~ es thereof, and b) from 10 to 80 wt% of a detergency builder comprising zeolite P having a silicon to al.~ ratio not gleater than 1.33 (zeolite MAP) and having a particle size dso of from 2.0 to 10.0 micrometres, l,refelably from 2.25 to 5 micrometres.
According to another embo~limPnt of the invention there is provided a liquid d~t~g~l composition, prefeYably a heavy duty liquid d&t~gent composition, comprising from 5 to 60 wt% of component (a) above and ~om 5 to 40 wt%
of component (b) above.
According to this embodiment the liquid detergellt composition may be of any convenient physical form which may be aqueous or anhydrous. The term "liquid" used herein includes partly viscous fonn~ tion~ such as gels.
The liquid detergen~ composition generally has a pH of from 6.5 to 10.5.
The total amount of detergency builder in the liquid composition is prefelably from 5 to 70% of the total liquid composition.
According to a further aspect, the invention provides use of zeolite MAP
having a particle size dso of 2.0 to 10.0 micrometres, plefe~bly from 2.25 to 5 micrometres as an additive for a detergent composition.
The following Example provides an illustration of a deter~e~lt composition according to the present invention.
The following abbreviations have been used:
AS :- sodiumalkylsulphate AEs :- tallow alcohol ethoxylated with 5 ethoxy groups per mole alcohol AE45 :- tallow alcohol ethoxylated with 4 to 5 ethoxy groups per mole alcohol CMC :- sodium carboxymethyl cellulose EDTMP :- ethylene ~ mine tetramethylene phosphon~te PVP :- polyvinyl pyrrolidone MA/AA copolymer :- copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000 TAED :- tetracetyl ethylene ~i~mine WO 95/27027 2 1 8 4 3 6 3 rC~tU$95tO2698 Component Proportion (bY wt) zeolite MLA~P (d50 = 3 0 40 % 38.5 %
micrometers Carbonate 7% 7.2%
Silicate 2.0R 5 % 5.8 %
Citrate 15 %
C14 - C 15 A S 7 %
C 12 - C14 A S 5.6 %
A E5 12%
A E45 - 11.5 %
Citric Acid 3 % 3.0 %
Silicone Antifoam 0.5 %
Soap - 1.0%
Hyfac 1.0%
Wax 0.5%
MLA/A A copolymer 1.5 % 1.8 %
Savinase (2.0 KNPU) 2.0% 2.0%
Lipolase(100,000 LU/l) 0.4% 0.2%
CMC 0.8%
Optical Brightener 0.2%
PVP 1.0%
EDTMP 0.8% 0.1%
TAED - 2.5%
Sodium rerc~l,onate - 14.0%
Moisture& balance balance Miscellaneous 100% 100%
Claims (11)
1. A detergent composition comprising:
a) a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof; and b) a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP) and having a particle size, d50, of from 2.0 to 10 micrometres.
a) a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof; and b) a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP) and having a particle size, d50, of from 2.0 to 10 micrometres.
2. A detergent composition according to claim 1, wherein the zeolite MAP
has a particle size, d50, of from 2.25 to 5 micrometres.
has a particle size, d50, of from 2.25 to 5 micrometres.
3. A detergent composition according to claim 1 or 2, which contains no bleach.
4. A detergent composition according to any one of claims 1 to 3, wherein the detergency builder (b) comprises the zeolite MAP as the principal detergent builder component.
5. A detergent composition according to any one of claims 1 to 3, wherein the detergency builder (b) comprises the zeolite MAP and a cobuilder selected from monomeric and polymeric carboxylates, polymers of acrylic, methacrylic and/or maleic acids in neutralised form, and carbonates.
6. A detergent composition according to any one of claims 1 to 5, which comprises 1 to 80 wt% of the zeolite MAP.
7. A detergent composition according to claim 6, which comprises from 10 to 40 wt% of the zeolite MAP.
8. A detergent composition as claimed in any one of claims 1 to 6, wherein the zeolite MAP has a silicon to aluminium ratio not greater than 1.07.
9. A granular detergent composition according to any of claims 1 to 8, comprising from 5 to 60 wt% of component (a) and from 10 to 80 wt%
of the component (b).
of the component (b).
10. A liquid detergent composition according to any one of claims 1 to 8, comprising from 5 to 60 wt% of component (a) and from 5 to 40 wt%
of component (b).
of component (b).
11. Use of zeolite P having a silicon to aluminium ratio not greater than 1.33 and having a particle size, d50, of from 2.0 to 10.0 micrometres as an additive for a detergent composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9406567A GB2288187A (en) | 1994-03-31 | 1994-03-31 | Detergent composition |
| GB9406567.9 | 1994-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2184363A1 true CA2184363A1 (en) | 1995-10-12 |
Family
ID=10752942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2184363 Abandoned CA2184363A1 (en) | 1994-03-31 | 1995-03-01 | Detergent composition comprising zeolite map builder |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0753042A4 (en) |
| JP (1) | JPH09511269A (en) |
| CN (1) | CN1168690A (en) |
| CA (1) | CA2184363A1 (en) |
| GB (1) | GB2288187A (en) |
| WO (1) | WO1995027027A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2296919A (en) * | 1995-01-12 | 1996-07-17 | Procter & Gamble | Detergent composition |
| GB9605534D0 (en) * | 1996-03-15 | 1996-05-15 | Unilever Plc | Detergent compositions |
| DE19723616A1 (en) * | 1997-06-05 | 1998-12-10 | Henkel Kgaa | Granular detergent |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2001927C (en) * | 1988-11-03 | 1999-12-21 | Graham Thomas Brown | Aluminosilicates and detergent compositions |
| JP3583152B2 (en) * | 1991-01-24 | 2004-10-27 | 株式会社アマダ | Bar loading / unloading device |
| GB9113675D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Particulate detergent composition or component |
| GB9113674D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Detergent compositions |
| SK278834B6 (en) * | 1992-01-17 | 1998-03-04 | Unilever Nv | Detergent whitening mixture containing particles |
| CZ280593B6 (en) * | 1992-01-17 | 1996-02-14 | Unilever Nv | Particulate bleaching detergent mixture and the use of map zeolite in such mixture |
| WO1994000545A1 (en) * | 1992-06-25 | 1994-01-06 | Unilever N.V. | Machine dishwashing composition |
-
1994
- 1994-03-31 GB GB9406567A patent/GB2288187A/en not_active Withdrawn
-
1995
- 1995-03-01 CN CN 95192364 patent/CN1168690A/en active Pending
- 1995-03-01 WO PCT/US1995/002698 patent/WO1995027027A1/en not_active Application Discontinuation
- 1995-03-01 JP JP7525691A patent/JPH09511269A/en active Pending
- 1995-03-01 CA CA 2184363 patent/CA2184363A1/en not_active Abandoned
- 1995-03-01 EP EP95913548A patent/EP0753042A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995027027A1 (en) | 1995-10-12 |
| CN1168690A (en) | 1997-12-24 |
| JPH09511269A (en) | 1997-11-11 |
| GB2288187A (en) | 1995-10-11 |
| GB9406567D0 (en) | 1994-05-25 |
| EP0753042A4 (en) | 1998-05-06 |
| EP0753042A1 (en) | 1997-01-15 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Dead |